CN106925255A - A kind of photochemical catalyst of room temperature catalytic decomposition formaldehyde and preparation method thereof - Google Patents
A kind of photochemical catalyst of room temperature catalytic decomposition formaldehyde and preparation method thereof Download PDFInfo
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- CN106925255A CN106925255A CN201710235929.6A CN201710235929A CN106925255A CN 106925255 A CN106925255 A CN 106925255A CN 201710235929 A CN201710235929 A CN 201710235929A CN 106925255 A CN106925255 A CN 106925255A
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- formaldehyde
- photochemical catalyst
- room temperature
- titanium dioxide
- rare earth
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- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 239000003054 catalyst Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims description 22
- 238000003421 catalytic decomposition reaction Methods 0.000 title description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 74
- 239000000463 material Substances 0.000 claims abstract description 49
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 37
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims abstract description 33
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims abstract description 29
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 22
- 150000001875 compounds Chemical class 0.000 claims abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 56
- 239000000843 powder Substances 0.000 claims description 40
- 239000011343 solid material Substances 0.000 claims description 32
- 238000001354 calcination Methods 0.000 claims description 26
- 230000004913 activation Effects 0.000 claims description 24
- 239000011259 mixed solution Substances 0.000 claims description 24
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 18
- 239000011505 plaster Substances 0.000 claims description 16
- 239000010802 sludge Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 9
- 229910021529 ammonia Inorganic materials 0.000 claims description 9
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- 239000010936 titanium Substances 0.000 claims description 9
- 238000003763 carbonization Methods 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 8
- 238000010926 purge Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000013049 sediment Substances 0.000 claims description 7
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 claims description 6
- 229910003447 praseodymium oxide Inorganic materials 0.000 claims description 6
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 6
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 5
- 244000060011 Cocos nucifera Species 0.000 claims description 5
- 229910052691 Erbium Inorganic materials 0.000 claims description 5
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 5
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims description 5
- 239000010903 husk Substances 0.000 claims description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims description 5
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 5
- WPCMRGJTLPITMF-UHFFFAOYSA-I niobium(5+);pentahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[Nb+5] WPCMRGJTLPITMF-UHFFFAOYSA-I 0.000 claims description 5
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 5
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 5
- WYOIGGSUICKDNZ-UHFFFAOYSA-N 2,3,5,6,7,8-hexahydropyrrolizin-1-one Chemical compound C1CCC2C(=O)CCN21 WYOIGGSUICKDNZ-UHFFFAOYSA-N 0.000 claims description 4
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 4
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 4
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 4
- 239000011425 bamboo Substances 0.000 claims description 4
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 claims description 4
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 3
- YBYGDBANBWOYIF-UHFFFAOYSA-N erbium(3+);trinitrate Chemical compound [Er+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YBYGDBANBWOYIF-UHFFFAOYSA-N 0.000 claims description 3
- SYDXSHCNMKOQFW-UHFFFAOYSA-H erbium(3+);trisulfate Chemical compound [Er+3].[Er+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O SYDXSHCNMKOQFW-UHFFFAOYSA-H 0.000 claims description 3
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical compound [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 claims description 3
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 3
- XNHGKSMNCCTMFO-UHFFFAOYSA-D niobium(5+);oxalate Chemical compound [Nb+5].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XNHGKSMNCCTMFO-UHFFFAOYSA-D 0.000 claims description 3
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 3
- 239000002023 wood Substances 0.000 claims description 3
- WFNBSLYTFHMPBY-UHFFFAOYSA-N acetic acid;erbium Chemical compound [Er].CC(O)=O WFNBSLYTFHMPBY-UHFFFAOYSA-N 0.000 claims description 2
- VQEHIYWBGOJJDM-UHFFFAOYSA-H lanthanum(3+);trisulfate Chemical compound [La+3].[La+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VQEHIYWBGOJJDM-UHFFFAOYSA-H 0.000 claims 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 claims description 2
- HWZAHTVZMSRSJE-UHFFFAOYSA-H praseodymium(iii) sulfate Chemical compound [Pr+3].[Pr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O HWZAHTVZMSRSJE-UHFFFAOYSA-H 0.000 claims description 2
- 244000082204 Phyllostachys viridis Species 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 6
- 229930040373 Paraformaldehyde Natural products 0.000 abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 4
- 239000001301 oxygen Substances 0.000 abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 abstract description 4
- 229920002866 paraformaldehyde Polymers 0.000 abstract description 4
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract description 3
- HBBATKAUXPHIQN-UHFFFAOYSA-N [Cl].[Ti] Chemical compound [Cl].[Ti] HBBATKAUXPHIQN-UHFFFAOYSA-N 0.000 abstract description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 2
- -1 hydroxyl radical free radical Chemical class 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract description 2
- 230000008961 swelling Effects 0.000 abstract description 2
- 230000009466 transformation Effects 0.000 abstract description 2
- 230000001699 photocatalysis Effects 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- 230000002045 lasting effect Effects 0.000 description 7
- 238000006555 catalytic reaction Methods 0.000 description 6
- 239000003344 environmental pollutant Substances 0.000 description 6
- 231100000719 pollutant Toxicity 0.000 description 6
- 238000007146 photocatalysis Methods 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 241001330002 Bambuseae Species 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 3
- 238000004887 air purification Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- HGWOWDFNMKCVLG-UHFFFAOYSA-N [O--].[O--].[Ti+4].[Ti+4] Chemical compound [O--].[O--].[Ti+4].[Ti+4] HGWOWDFNMKCVLG-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 210000003739 neck Anatomy 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000006057 reforming reaction Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 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
- B01J23/20—Vanadium, niobium or tantalum
-
- 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
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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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/10—Inorganic adsorbents
- B01D2253/102—Carbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/206—Rare earth metals
- B01D2255/2063—Lanthanum
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
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- B01D2255/206—Rare earth metals
- B01D2255/2066—Praseodymium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20707—Titanium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/209—Other metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/80—Type of catalytic reaction
- B01D2255/802—Photocatalytic
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Abstract
A kind of room temperature of the invention is catalytically decomposed the photochemical catalyst of formaldehyde, including carrier and active component, active component is carried on carrier, and described active component includes rare earth oxide, niobium pentaoxide and titanium dioxide, the ability of the capture light induced electron of the energy high system of adulterating of three；The compound of doping system two-by-two can effectively be suppressed to bury in oblivion；Rare earth oxide can enter in the lattice of titanium dioxide, niobium pentaoxide can be with the lattice of stabilized chlorine titanium composite rare-earth oxide, so lattice can be stablized in certain swelling state, the transformation of titanium dioxide crystalline phase and the increase of particle diameter are inhibited, so as to extend the catalytic life of photochemical catalyst；The doping of three causes that the hydroxyl of titanium dioxide distortion of lattice, material surface absorption increases, it is easy to produce hydroxyl radical free radical；And Lattice Oxygen is easy to depart from, and forms the state of Lacking oxygen；Three's system PARA FORMALDEHYDE PRILLS(91,95) has extremely strong adsorption capacity, and especially rare earth oxide has the suction exoergic power of formaldehyde material.
Description
Technical field
The present invention relates to a kind of catalyst of the formaldehyde of photocatalysis Decomposition at ambient temperature and preparation method thereof, belong to indoor
Purification of air administers field.
Background technology
With social civilization and expanding economy, inhabitation and operating environment requirements more and more higher of the people to oneself, but with
This simultaneously, the development of industrial economy so that the surrounding environment of people also becomes worse and worse.This contradiction just generates demand,
Wherein, people have led to the appearance of Techniques for Indoor Air Purification and products thereof to the demand of good indoor environment.
Indoor air pollutants include three aspects：First pollutant is gaseous contaminant, and gaseous contaminant is included
The gas with foreign flavor such as machine gaseous contaminant and ammonia, wherein typical pollutant is formaldehyde (HCHO), formaldehyde have penetrating odor and
Can cause a disease with it is carcinogenic, can all have the formaldehyde of higher concentration in the indoor environment such as newly-decorated house and office space, formaldehyde is
Pollutant widest in area is paid close attention in current indoor air purification；Other two pollutants are the solid-state pollution as representative with dust
The microorganism such as thing and bacterium.
Photocatalyst has largely been reported both at home and abroad for the research of room temperature photocatalysis Decomposition formaldehyde, wherein, titanium dioxide is to grind
Studying carefully must compare many photochemical catalysts, but, when researcher has found simple titanium dioxide as photochemical catalyst, the light of PARA FORMALDEHYDE PRILLS(91,95)
Catalytic decomposition activity is limited, and after use a period of time, its stability can also decline, therefore, entered based on titanium dioxide
The research of the modified photochemical catalyst of row is more in recent years.
There is researcher to find that the oxide of transition metal niobium there is catalysis well to live the decomposition and inversion of organic molecule
Property, the especially organic molecule such as formaldehyde, therefore, niobium pentaoxide is studied for organic catalytic reaction, many organic catalysis
Niobium pentaoxide can be used as co-catalyst in reforming reaction, the doping of niobium pentaoxide can be obviously improved organic catalyst
Activity.
Although rare earth element is used to improve photocatalytic activity and also have been reported that, suitable rare earth element and rationally is chosen
Process conditions (particularly calcination condition), to obtaining the catalysis material of high activity crystalline structure and its important.
In addition to the organic pollutions such as formaldehyde are catalytically decomposed using photochemical catalyst, the adsorbent such as activated carbon is also used to inhale
Attached formaldehyde, different from photochemical catalyst, the material such as activated carbon is have very strong adsorption capacity to organic molecule, by organic molecule
Absorption is not decomposed or eliminated inside duct.
The content of the invention
The technical problems to be solved by the invention are for above-mentioned existing technology status, by rare earth oxide, dioxy
Change titanium to be combined with each other with niobium pentaoxide, by the adjustment and the interaction of three class materials of preparation technology, can be formed
Uniform doping system, improves the photocatalytic activity of titanium dioxide, while by active component load on the activated carbon, formation both had
Have adsorption capacity has catalysis activity again so that the photochemical catalyst that formaldehyde removal ability is improved.
A kind of room temperature is catalytically decomposed the photochemical catalyst of formaldehyde, and it includes carrier and active component, and active component is carried on load
On body, described active component includes rare earth oxide, niobium pentaoxide and titanium dioxide.Rare earth oxide, niobium pentaoxide
Can be interacted with titanium dioxide three, compared to one of which material or adulterating two-by-two with being used alone, 1) three mixes
It is miscellaneous can be high the ability of the capture light induced electron of system；2) the compound of system that can effectively suppress to adulterate two-by-two is buried in oblivion；3) rare earth
Oxide can enter in the lattice of titanium dioxide, and niobium pentaoxide can be with the crystalline substance of stabilized chlorine titanium composite rare-earth oxide
Lattice, such lattice can be stablized in certain swelling state, it is suppressed that the transformation of titanium dioxide crystalline phase and the increase of particle diameter, so that
Extend the catalytic life of photochemical catalyst；4) doping of three causes titanium dioxide distortion of lattice, the hydroxyl of surfacing absorption
Increase, it is easy to produce hydroxyl radical free radical；And Lattice Oxygen is easy to depart from, and forms Lacking oxygen；5) three's system PARA FORMALDEHYDE PRILLS(91,95) has extremely strong
Adsorption capacity, especially rare earth oxide has the suction exoergic power of formaldehyde material.Therefore, three's system compared to be used alone its
A kind of middle material or two-by-two system have photocatalysis efficiency and the longer life-span higher.
Further, the carrier of this patent is activated carbon.Activated carbon can effective formaldehyde adsorption, by with native oxide,
Niobium pentaoxide and titanium dioxide mixing after formed highdensity hole under conditions of ultraviolet source decomposing formaldehyde so that
Further increase the capacity of decomposition of formaldehyde.
Further, the rare earth oxide of this patent is the one kind in lanthanum, praseodymium, the oxide of erbium.Compared to other rare earths
Oxide, lanthanum, praseodymium, the oxide of erbium have abundant energy level and electron transition characteristic, are also easy to produce polyelectron configuration, and crystal formation
Many, adsorptive selectivity is strong, electron type electric conductivity and thermal stability are good, can effectively improve niobium pentaoxide and titanium dioxide
Photocatalytic activity and life-span.
Further, the mol ratio of the active component rare earth elements, titanium elements and niobium element of this patent is 1:(1~6):
1, it is preferred that the weight sum of the rare earth oxide, niobium pentaoxide and titanium dioxide of this patent accounts for the 5% of total catalyst weight
To 25%.Matched more than interval, enable to the coordinating effect between three's system to reach most preferably, its photocatalytic activity with
Life-span is relatively good.
A kind of preparation method of the photochemical catalyst of room temperature catalytic decomposition formaldehyde, it comprises the following steps：
1) presoma of the presoma of rare earth oxide, the presoma of niobium pentaoxide and titanium dioxide is mixed and is dissolved
Yu Shuizhong, obtains mixed solution；
2) form heavy to 9 to 11, in mixed solution using the pH value of 20% to 30% ammonia spirit regulation mixed solution
Starch, filters to obtain sludge thing；
3) support powder and water are mixed and continue stirring until mud paste, add step 2) obtained by sludge thing,
It is lasting to mix, obtain mud plaster material；
4) mud plaster material is sealed old at ambient temperature, the old time be 12 to 24 hours, it is old after carry out
Dried 12 to 24 hours under 80 to 120 degree celsius temperatures, obtain solid material；
5) solid material is calcined, calcining heat is 280 to 500 degrees Celsius, calcination time is 1 to 4 hour, calcining
After naturally cool to normal temperature, obtain carbonized solid material；
6) sieved after carbonized solid material is ground, obtain powder material；
7) powder material is activated, activation temperature is 100 to 200 degrees Celsius, soak time is 12 to 24 hours, living
Keep inert gas to the purging of powder material during change, the photochemical catalyst that room temperature is catalytically decomposed formaldehyde is obtained after activation.
Further, the presoma of the rare earth oxide of this patent includes compound as follows：The presoma of lanthanum-oxides
Including the one kind in lanthanum nitrate, lanthanum acetate, lanthanum sulfate；The presoma of praseodymium oxide is included in praseodymium nitrate, praseodymium acetate, praseodymium sulfate
It is a kind of；The presoma of Er oxide includes the one kind in erbium nitrate, acetic acid erbium, erbium sulfate.
Further, the presoma of the niobium pentaoxide of this patent is the one kind in niobium oxalate, niobium hydroxide or columbium pentachloride.
Further, the presoma of the titanium dioxide of this patent is in butyl titanate, titanyl sulfate, titanium tetrachloride
Kind.
Further, the support powder of this patent is active carbon powder, and it is by one or more in bamboo chip, coconut husk, wood chip
Gained is crushed after carbonization.
In the structure of this patent photochemical catalyst system, by selecting suitable rare earth element and rational technique above
The steps such as condition, the order for especially mixing, calcination condition, activation, are obtained in that with highlight catalytic active crystalline structure
Catalysis material.
In sum, the advantage of the invention is that：1) active component is with rare earth oxide, niobium pentaoxide and titanium dioxide
It is combined with each other and is prepared from, the introducing of rare earth oxide and niobium pentaoxide so that the photocatalytic activity of titanium dioxide is able to
Improve, relative to traditional photochemical catalyst individually using titanium dioxide and two-by-two system as active component, three of the invention
System photocatalyst activity is higher.
2) using activated carbon as the carrier of photochemical catalyst, by active component rare earth oxide, niobium pentaoxide and titanium dioxide
Titanium it is composite oxide supported onto activated carbon, synergy can be formed between activated carbon and active component, and form hole
Effect, activated carbon PARA FORMALDEHYDE PRILLS(91,95) has good suction-operated, when formaldehyde molecule is adsorbed to activated carbon surface, will be by hole
Active component catalytic decomposition fall, activated carbon can play dual parts of carry active component and adsorption reaction thing.
Specific embodiment
To describe technology contents of the invention, structural feature, the objects and the effects in detail, below in conjunction with implementation method
It is explained in detail.
Embodiment 1：A kind of room temperature is catalytically decomposed the photochemical catalyst of formaldehyde, and it includes activated carbon and active component, activearm
Divide and be carried on activated carbon, described active component includes praseodymium oxide, niobium pentaoxide and titanium dioxide, praseodymium in active component
The mol ratio of element, titanium elements and niobium element is 1:1:1.The weight sum of praseodymium oxide, niobium pentaoxide and titanium dioxide is accounted for
The 25% of total catalyst weight.
Embodiment 2：A kind of room temperature is catalytically decomposed the photochemical catalyst of formaldehyde, and it includes activated carbon and active component, activearm
Divide and be carried on activated carbon, described active component includes lanthanum-oxides, niobium pentaoxide and titanium dioxide, lanthanum in active component
The mol ratio of element, titanium elements and niobium element is 1:6:1.The weight sum of lanthanum-oxides, niobium pentaoxide and titanium dioxide is accounted for
The 5% of total catalyst weight.
Embodiment 3：A kind of room temperature is catalytically decomposed the photochemical catalyst of formaldehyde, and it includes activated carbon and active component, activearm
Divide and be carried on activated carbon, described active component includes Er oxide, niobium pentaoxide and titanium dioxide, erbium in active component
The mol ratio of element, titanium elements and niobium element is 1:3:1.The weight sum of Er oxide, niobium pentaoxide and titanium dioxide is accounted for
The 20% of total catalyst weight.
Embodiment 4：A kind of room temperature is catalytically decomposed the photochemical catalyst of formaldehyde, and it includes activated carbon and active component, activearm
Divide and be carried on activated carbon, described active component includes praseodymium oxide, niobium pentaoxide and titanium dioxide, praseodymium in active component
The mol ratio of element, titanium elements and niobium element is 1:2:1.The weight sum of praseodymium oxide, niobium pentaoxide and titanium dioxide is accounted for
The 10% of total catalyst weight.
Embodiment 5：A kind of room temperature is catalytically decomposed the photochemical catalyst of formaldehyde, and it includes activated carbon and active component, activearm
Divide and be carried on activated carbon, described active component includes lanthanum-oxides, niobium pentaoxide and titanium dioxide, lanthanum in active component
The mol ratio of element, titanium elements and niobium element is 1:4:1.The weight sum of lanthanum-oxides, niobium pentaoxide and titanium dioxide is accounted for
The 15% of total catalyst weight.
Embodiment 6：A kind of room temperature is catalytically decomposed the photochemical catalyst of formaldehyde, and it includes activated carbon and active component, activearm
Divide and be carried on activated carbon, described active component includes Er oxide, niobium pentaoxide and titanium dioxide, erbium in active component
The mol ratio of element, titanium elements and niobium element is 1:5:1.The weight sum of Er oxide, niobium pentaoxide and titanium dioxide is accounted for
The 18% of total catalyst weight.
Preparation example 1：A kind of preparation method of the photochemical catalyst of room temperature catalytic decomposition formaldehyde, it comprises the following steps：
1) lanthanum nitrate, niobium oxalate and butyl titanate are mixed and is dissolved in the water, obtain mixed solution；
2) pH value of mixed solution is adjusted to 9 using 20% ammonia spirit, sediment is formed in mixed solution, filtered
Sludge thing；
3) support powder and water are mixed and continue stirring until mud paste, add step 2) obtained by sludge thing,
It is lasting to mix, obtain mud plaster material；
4) mud plaster material is sealed old at ambient temperature, the old time be 12 hours, it is old after taken the photograph 80
Dried 12 hours at a temperature of family name's degree, obtain solid material；
5) solid material is calcined, calcining heat is 280 degrees Celsius, calcination time is 1 hour, naturally cold after calcining
But to normal temperature, carbonized solid material is obtained；
6) sieved after carbonized solid material is ground, obtain powder material；
7) powder material is activated, activation temperature is 100 degrees Celsius, and soak time is 12 hours, is kept during activation
Inert gas obtains the photochemical catalyst that room temperature is catalytically decomposed formaldehyde to the purging of powder material after activation.
Support powder is active carbon powder, and it is crushed gained by bamboo chip after carbonization.
Preparation example 2：A kind of preparation method of the photochemical catalyst of room temperature catalytic decomposition formaldehyde, it comprises the following steps：
1) praseodymium acetate, niobium hydroxide and titanyl sulfate are mixed and is dissolved in the water, obtain mixed solution；
2) pH value of mixed solution is adjusted to 11 using 30% ammonia spirit, sediment is formed in mixed solution, filtered
Obtain sludge thing；
3) support powder and water are mixed and continue stirring until mud paste, add step 2) obtained by sludge thing,
It is lasting to mix, obtain mud plaster material；
4) mud plaster material is sealed old at ambient temperature, the old time be 24 hours, it is old after taken the photograph 120
Dried 24 hours at a temperature of family name's degree, obtain solid material；
5) solid material is calcined, calcining heat is 500 degrees Celsius, calcination time is 4 hours, naturally cold after calcining
But to normal temperature, carbonized solid material is obtained；
6) sieved after carbonized solid material is ground, obtain powder material；
7) powder material is activated, activation temperature is 200 degrees Celsius, and soak time is 24 hours, is kept during activation
Inert gas obtains the photochemical catalyst that room temperature is catalytically decomposed formaldehyde to the purging of powder material after activation.
Support powder is active carbon powder, and it is crushed gained by coconut husk after carbonization.
Preparation example 3：A kind of preparation method of the photochemical catalyst of room temperature catalytic decomposition formaldehyde, it comprises the following steps：
1) erbium nitrate, columbium pentachloride and titanium tetrachloride are mixed and is dissolved in the water, obtain mixed solution；
2) pH value of mixed solution is adjusted to 10 using 25% ammonia spirit, sediment is formed in mixed solution, filtered
Obtain sludge thing；
3) support powder and water are mixed and continue stirring until mud paste, add step 2) obtained by sludge thing,
It is lasting to mix, obtain mud plaster material；
4) mud plaster material is sealed old at ambient temperature, the old time be 18 hours, it is old after taken the photograph 100
Dried 18 hours at a temperature of family name's degree, obtain solid material；
5) solid material is calcined, calcining heat is 400 degrees Celsius, calcination time is 3 hours, naturally cold after calcining
But to normal temperature, carbonized solid material is obtained；
6) sieved after carbonized solid material is ground, obtain powder material；
7) powder material is activated, activation temperature is 150 degrees Celsius, and soak time is 18 hours, is kept during activation
Inert gas obtains the photochemical catalyst that room temperature is catalytically decomposed formaldehyde to the purging of powder material after activation.
Support powder is active carbon powder, and it is crushed gained by wood chip after carbonization.
Preparation example 4：A kind of preparation method of the photochemical catalyst of room temperature catalytic decomposition formaldehyde, it comprises the following steps：
1) lanthanum acetate, niobium hydroxide, titanium tetrachloride are mixed and is dissolved in the water, obtain mixed solution；
2) pH value of mixed solution is adjusted to 9 using 23% ammonia spirit, sediment is formed in mixed solution, filtered
Sludge thing；
3) support powder and water are mixed and continue stirring until mud paste, add step 2) obtained by sludge thing,
It is lasting to mix, obtain mud plaster material；
4) mud plaster material is sealed old at ambient temperature, the old time be 13 hours, it is old after taken the photograph 90
Dried 15 hours at a temperature of family name's degree, obtain solid material；
5) solid material is calcined, calcining heat is 450 degrees Celsius, calcination time is 2 hours, naturally cold after calcining
But to normal temperature, carbonized solid material is obtained；
6) sieved after carbonized solid material is ground, obtain powder material；
7) powder material is activated, activation temperature is 120 degrees Celsius, and soak time is 20 hours, is kept during activation
Inert gas obtains the photochemical catalyst that room temperature is catalytically decomposed formaldehyde to the purging of powder material after activation.
Support powder is active carbon powder, and it is crushed gained by bamboo chip after carbonization.
Preparation example 5：A kind of preparation method of the photochemical catalyst of room temperature catalytic decomposition formaldehyde, it comprises the following steps：
1) praseodymium acetate, niobium hydroxide, titanium tetrachloride are mixed and is dissolved in the water, obtain mixed solution；
2) pH value of mixed solution is adjusted to 11 using 28% ammonia spirit, sediment is formed in mixed solution, filtered
Obtain sludge thing；
3) support powder and water are mixed and continue stirring until mud paste, add step 2) obtained by sludge thing,
It is lasting to mix, obtain mud plaster material；
4) mud plaster material is sealed old at ambient temperature, the old time be 22 hours, it is old after taken the photograph 110
Dried 16 hours at a temperature of family name's degree, obtain solid material；
5) solid material is calcined, calcining heat is 380 degrees Celsius, and calcination time is 3.5 hours, natural after calcining
Normal temperature is cooled to, carbonized solid material is obtained；
6) sieved after carbonized solid material is ground, obtain powder material；
7) powder material is activated, activation temperature is 160 degrees Celsius, and soak time is 22 hours, is kept during activation
Inert gas obtains the photochemical catalyst that room temperature is catalytically decomposed formaldehyde to the purging of powder material after activation.
Support powder is active carbon powder, and it is crushed gained by coconut husk after carbonization.
Preparation example 6：A kind of preparation method of the photochemical catalyst of room temperature catalytic decomposition formaldehyde, it comprises the following steps：
1) erbium sulfate, columbium pentachloride, titanium tetrachloride are mixed and is dissolved in the water, obtain mixed solution；
2) pH value of mixed solution is adjusted to 9 using 23% ammonia spirit, sediment is formed in mixed solution, filtered
Sludge thing；
3) support powder and water are mixed and continue stirring until mud paste, add step 2) obtained by sludge thing,
It is lasting to mix, obtain mud plaster material；
4) mud plaster material is sealed old at ambient temperature, the old time be 23 hours, it is old after taken the photograph 90
Dried 16 hours at a temperature of family name's degree, obtain solid material；
5) solid material is calcined, calcining heat is 490 degrees Celsius, and calcination time is 2.5 hours, natural after calcining
Normal temperature is cooled to, carbonized solid material is obtained；
6) sieved after carbonized solid material is ground, obtain powder material；
7) powder material is activated, activation temperature is 160 degrees Celsius, and soak time is 17 hours, is kept during activation
Inert gas obtains the photochemical catalyst that room temperature is catalytically decomposed formaldehyde to the purging of powder material after activation.
Support powder is active carbon powder, and it is crushed gained by coconut husk after carbonization.
Test example：With reference to《The photocatalysis removal experiment of indoor pollutant formaldehyde》,《Urban environment and urban ecology》2006
The 3rd phase of year, Li Wencai etc. write, and build the photocatalysis removal experiment porch of indoor pollutant formaldehyde, measure each embodiment formaldehyde 1 small
When purifying rate, see the table below 1：
The 1 hour purifying rate of each embodiment formaldehyde of table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | |
| 1 hour purifying rate | 76.8% | 88.3% | 85.4% |
| Embodiment 5 | Embodiment 6 | Embodiment 3 | |
| 1 hour purifying rate | 80.3% | 83.2% | 78.9% |
Embodiments of the invention are the foregoing is only, scope of patent protection of the invention, every utilization is not thereby limited
Equivalent structure or equivalent flow conversion that description of the invention is made, or directly or indirectly it is used in other related technology necks
Domain, is included within the scope of the present invention.
Claims (10)
1. a kind of room temperature is catalytically decomposed the photochemical catalyst of formaldehyde, it is characterised in that：It includes carrier and active component, active component
It is carried on carrier, described active component includes rare earth oxide, niobium pentaoxide and titanium dioxide.
2. a kind of room temperature according to claim 1 is catalytically decomposed the photochemical catalyst of formaldehyde, it is characterised in that：Described carrier
It is activated carbon.
3. a kind of room temperature according to claim 1 is catalytically decomposed the photochemical catalyst of formaldehyde, it is characterised in that：Described rare earth
Oxide is the one kind in lanthanum, praseodymium, the oxide of erbium.
4. a kind of room temperature according to claim 3 is catalytically decomposed the photochemical catalyst of formaldehyde, it is characterised in that：In active component
The mol ratio of rare earth element, titanium elements and niobium element is 1:(1~6):1.
5. any one room temperature according to Claims 1-4 is catalytically decomposed the photochemical catalyst of formaldehyde, it is characterised in that：Institute
The weight sum of rare earth oxide, niobium pentaoxide and the titanium dioxide stated accounts for the 5% to 25% of total catalyst weight.
6. a kind of room temperature is catalytically decomposed the preparation method of the photochemical catalyst of formaldehyde, it is characterised in that：It comprises the following steps：
1) presoma of the presoma of rare earth oxide, the presoma of niobium pentaoxide and titanium dioxide is mixed and is dissolved in water
In, obtain mixed solution；
2) pH value of mixed solution is adjusted to 9 to 11 using 20% to 30% ammonia spirit, sediment is formed in mixed solution,
Filter to obtain sludge thing；
3) support powder and water are mixed and continue stirring until mud paste, add step 2) obtained by sludge thing, continue
Mix, obtain mud plaster material；
4) mud plaster material is sealed old at ambient temperature, the old time be 12 to 24 hours, it is old after carry out 80 to
Dried 12 to 24 hours under 120 degree celsius temperatures, obtain solid material；
5) solid material is calcined, calcining heat is 280 to 500 degrees Celsius, and calcination time is 1 to 4 hour, after calcining certainly
Normal temperature so is cooled to, carbonized solid material is obtained；
6) sieved after carbonized solid material is ground, obtain powder material；
7) powder material is activated, activation temperature is 100 to 200 degrees Celsius, and soak time is 12 to 24 hours, during activation
Keep inert gas to the purging of powder material, the photochemical catalyst that room temperature is catalytically decomposed formaldehyde is obtained after activation.
7. a kind of room temperature according to claim 6 is catalytically decomposed the preparation method of the photochemical catalyst of formaldehyde, it is characterised in that：
The presoma of rare earth oxide includes compound as follows：
The presoma of lanthanum-oxides includes the one kind in lanthanum nitrate, lanthanum acetate, lanthanum sulfate；
The presoma of praseodymium oxide includes the one kind in praseodymium nitrate, praseodymium acetate, praseodymium sulfate；
The presoma of Er oxide includes the one kind in erbium nitrate, acetic acid erbium, erbium sulfate.
8. a kind of room temperature according to claim 6 is catalytically decomposed the preparation method of the photochemical catalyst of formaldehyde, it is characterised in that：
The presoma of described niobium pentaoxide is the one kind in niobium oxalate, niobium hydroxide or columbium pentachloride.
9. a kind of room temperature according to claim 6 is catalytically decomposed the preparation method of the photochemical catalyst of formaldehyde, it is characterised in that：
The presoma of described titanium dioxide is the one kind in butyl titanate, titanyl sulfate, titanium tetrachloride.
10. a kind of room temperature according to claim 6 is catalytically decomposed the preparation method of the photochemical catalyst of formaldehyde, and its feature exists
In：Described support powder is active carbon powder, and it crushes institute by one or more in bamboo chip, coconut husk, wood chip after carbonization
.
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| CN117000227A (en) * | 2023-10-08 | 2023-11-07 | 琥崧科技集团股份有限公司 | Nanometer titanium dioxide composite material and preparation method thereof |
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| CN108126709A (en) * | 2017-12-19 | 2018-06-08 | 如皋六维环境科技有限公司 | A kind of support type formaldehyde catalyst and preparation method thereof |
| CN110841627A (en) * | 2019-11-09 | 2020-02-28 | 上海纳米技术及应用国家工程研究中心有限公司 | Rare earth modified adsorption enrichment-catalytic oxidation bifunctional catalyst and preparation method and application thereof |
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| CN115475616B (en) * | 2021-06-16 | 2024-03-26 | 中国石油化工股份有限公司 | Wet oxidation catalyst and preparation method and application thereof |
| CN117000227A (en) * | 2023-10-08 | 2023-11-07 | 琥崧科技集团股份有限公司 | Nanometer titanium dioxide composite material and preparation method thereof |
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