CN114887655B - Nanometer NiO-VO X /TiO 2 Molecular sieve composite catalyst and preparation method and application thereof - Google Patents
Nanometer NiO-VO X /TiO 2 Molecular sieve composite catalyst and preparation method and application thereof Download PDFInfo
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- 229910010413 TiO 2 Inorganic materials 0.000 title claims abstract description 109
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 67
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 239000003054 catalyst Substances 0.000 title claims abstract description 48
- 239000002131 composite material Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000012855 volatile organic compound Substances 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 13
- 230000008569 process Effects 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims description 49
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000008367 deionised water Substances 0.000 claims description 25
- 229910021641 deionized water Inorganic materials 0.000 claims description 25
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 15
- 238000000227 grinding Methods 0.000 claims description 12
- 239000002202 Polyethylene glycol Substances 0.000 claims description 11
- 229920001223 polyethylene glycol Polymers 0.000 claims description 11
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 9
- 229960000583 acetic acid Drugs 0.000 claims description 9
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000012362 glacial acetic acid Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 239000004094 surface-active agent Substances 0.000 claims description 9
- 238000003786 synthesis reaction Methods 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 230000003301 hydrolyzing effect Effects 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000000643 oven drying Methods 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 42
- 230000000694 effects Effects 0.000 abstract description 9
- 230000015556 catabolic process Effects 0.000 abstract description 7
- 238000006731 degradation reaction Methods 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 230000010354 integration Effects 0.000 abstract description 3
- 238000013329 compounding Methods 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 28
- 239000007789 gas Substances 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000003795 desorption Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
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- 238000012360 testing method Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
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- FLDSMVTWEZKONL-AWEZNQCLSA-N 5,5-dimethyl-N-[(3S)-5-methyl-4-oxo-2,3-dihydro-1,5-benzoxazepin-3-yl]-1,4,7,8-tetrahydrooxepino[4,5-c]pyrazole-3-carboxamide Chemical compound CC1(CC2=C(NN=C2C(=O)N[C@@H]2C(N(C3=C(OC2)C=CC=C3)C)=O)CCO1)C FLDSMVTWEZKONL-AWEZNQCLSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
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- 150000002148 esters Chemical class 0.000 description 1
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- 238000002474 experimental method Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000004408 titanium dioxide 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
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- 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
- 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
- B01D53/8678—Removing components of undefined structure
- B01D53/8687—Organic components
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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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/847—Vanadium, niobium or tantalum or polonium
- B01J23/8472—Vanadium
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- B01J35/23—
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/708—Volatile organic compounds V.O.C.'s
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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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
The invention belongs to the technical field of environmental treatment, and discloses a nano NiO-VO X /TiO 2 Molecular sieve composite catalyst, preparation method and application thereof, and nano NiO-VO X /TiO 2 The molecular sieve composite catalyst consists of hollow mesoporous nano TiO 2 And compounding Ni and V oxide with molecular sieve. Nanometer NiO-VO X /TiO 2 Has a mesoporous structure, a larger specific surface area, good adsorption performance and high catalytic degradation performance on VOCs. The composite catalyst can effectively degrade VOCs while adsorbing the VOCs, greatly improves the adsorption efficiency and the treatment effect of the molecular sieve on the VOCs, realizes the integration of adsorption and degradation, and simplifies the process flow of VOCs treatment.
Description
Technical Field
The invention belongs to the technical field of environmental treatment, and in particular relates to a nano NiO-VO X /TiO 2 -molecular sieve composite catalyst, and preparation method and application thereof.
Background
Volatile Organic Compounds (VOCs) generally refer to organic compounds having boiling points between 50 and 260 ℃ at 101.325kPa, and mainly include hydrocarbons, esters, alcohols, aldehydes, benzene compounds, halogenated hydrocarbons, and the like. The sources of VOCs in the air are wide, and mainly comprise industrial sources, living sources, agricultural sources and the like. Excessive VOCs in the environment can cause serious harm to human bodies, and can also cause direct influence on the ecological environment, such as ozone generation, PM2.5 pollution and the like.
The efficient treatment technology of VOCs is widely focused, and mainly comprises two modes of capturing (condensation, absorption, adsorption, membrane separation and the like) and destroying (thermal incineration, thermal catalysis, plasma, photocatalysis and the like), wherein the destroying technology needs to capture and enrich the low-concentration VOCs gas in the air. The adsorption method is the most widely applied VOCs trapping technology at present, and has the advantages of high maturity, simple operation process and relatively low economic cost. The technical core of the adsorption method is the development of a high-performance adsorbent which has high adsorption capacity of VOCs, controllable desorption and easy regeneration. Currently, adsorbents used for the trapping of VOCs gases are mainly porous materials such as activated carbon, activated carbon fibers, diatomaceous earth, mesoporous silica, metal Organic Frameworks (MOFs), molecular sieves, and the like. Activated carbon and activated carbon fiber belong to carbon-based porous materials with large adsorption capacity, acid and alkali resistance and low cost, but abundant surface groups are easy to chemically adsorb VOCs molecules or form stable hydrogen bonds, desorption/desorption is not thorough, and the carbon-based materials are not resistant to high temperature, so that regeneration is difficult; the diatomite has poor hydrothermal stability and a main macroporous structure, which is not beneficial to the adsorption of VOCs gas under low concentration; mesoporous silica is limited by mesoporous channels with larger self, has relatively weak adsorption binding force on VOCs molecules with smaller kinetic diameters, and has poor capability of enriching low-concentration VOCs gas; the metal organic framework compound has higher adsorption capacity to VOCs molecules, but the precursor preparation cost is high, and the metal organic framework compound is still in the basic research and development stage at present; the molecular sieve is highly ordered in molecular size, has microporous channels with adjustable aperture, has rich skeleton structure and good thermal stability, has been widely used in industrial adsorption/separation processes, wherein the molecular sieve runner technology has been successfully applied to adsorption and trapping of industrial exhaust VOCs gas, the molecular sieve adsorption runner generally adopts a honeycomb substrate profile formed by inorganic fiber paper, hydrophobic molecular sieve is coated/grown on the surface of a channel of the honeycomb porous structure, and finally the integral molecular sieve adsorption runner is manufactured through sintering, but the integral molecular sieve adsorption runner is easy to adsorb and saturated, so that the adsorption efficiency is reduced, and the technological processes of desorption, oxidization and the like after adsorption are complex.
Disclosure of Invention
In view of the above, the present invention aims to provide a nano NiO-VO X /TiO 2 The catalyst realizes the degradation of VOCs while the molecular sieve adsorbs the VOCs, greatly improves the adsorption efficiency and the treatment effect of the molecular sieve on the VOCs, realizes the integration of adsorption and degradation, and simplifies the process flow of the VOCs treatment.
The technical scheme provided by the invention is as follows:
nanometer NiO-VO X /TiO 2 -a process for the preparation of a molecular sieve composite catalyst, characterized in that it comprises the following steps:
s1, mesoporous hollow nano TiO 2 Is synthesized by the following steps: dissolving butyl titanate in absolute ethyl alcohol, adding surfactant CTAB and nano C, dropwise adding a mixture of absolute ethyl alcohol, glacial acetic acid and deionized water under stirring, hydrolyzing to form sol, continuously stirring to form gel, standing for 2-3 days, vacuum drying at 80-100 ℃ for 8-10 hours, grinding, and roasting to obtain mesoporous hollow nano TiO 2 ；
S2, nanometer NiO-VO X /TiO 2 Is synthesized by the following steps: NH is added to 4 VO 3 And Ni (NO) 3 ) 2 ·6H 2 Adding O into deionized water at 60-70deg.C, stirring to dissolve, adding the mesoporous hollow nanometer TiO 2 Stirring for 5-10 min, adding citric acid and polyethylene glycol, stirring, heating to 80-100deg.C, stirring to form gel, oven drying, grinding, and calcining to obtain nanometer NiO-VO X /TiO 2 ；
S3, nanometer NiO-VO X /TiO 2 -synthesis of molecular sieve composite catalyst: subjecting the nano NiO-VO to X /TiO 2 Adding the nanometer NiO-VO and molecular sieve into deionized water, performing ultrasonic dispersion, stirring for 4-6h, and drying to obtain nanometer NiO-VO X /TiO 2 -molecular sieve composite catalyst.
In the step S1, the mol ratio of the butyl titanate to the absolute ethyl alcohol to the glacial acetic acid to the deionized water to the surfactant CTAB to the nano C is 1 (20-40): 1-2.5): 2-6): 0.022:2.
Further, in step S1, the baking is air baking in a muffle furnace at 500 ℃ for 3 hours.
Further, in step S2, citric acid and NH 4 VO 3 And Ni (NO) 3 ) 2 ·6H 2 The molar ratio of O is 4:1:1; the NiO-VO X /TiO 2 In NiO-VO X The mass percentage of the polyethylene glycol to the citric acid is 1-10%, preferably 6%, and the mass ratio of the polyethylene glycol to the citric acid is 1:10.
Further, the steps ofIn the step S2, the mass of the deionized water is mesoporous hollow nano TiO 2 2-5 times of the mass.
Further, in step S3, the molecular sieve is ZSM-5, beta-type molecular sieve or Y-5A.
Further, in step S3, the mass of the deionized water is NiO-VO X /TiO 2 3-5 times of the sum of the molecular sieve mass.
Further, the molecular sieve is ZSM-5.
Further, in step S2, the temperature of the drying is 120 ℃, and the baking is air baking for 3.5 hours at 500 ℃ in a muffle furnace.
The invention also provides the nano NiO-VO prepared by the preparation method X /TiO 2 -molecular sieve composite catalyst.
The invention also provides the nano NiO-VO X /TiO 2 -use of a molecular sieve composite catalyst in the removal of VOCs.
The invention also provides a VOCs treating agent, which comprises the nano NiO-VO X /TiO 2 -molecular sieve composite catalyst.
Compared with the prior art, the invention has the following beneficial effects:
1) Nanometer NiO-VO X /TiO 2 The mesoporous nano NiO-VO has a mesoporous structure, a large specific surface area, a short pore passage, good VOCs adsorption performance, no influence on adsorption of the molecular sieve after being compounded with the molecular sieve with a microporous structure and a high specific surface area, and a mesoporous structure at the same time of compounding X /TiO 2 And the porous structure and the molecular sieve with the microporous structure form multistage holes, so that the pore channels are reduced, and the adsorption efficiency of the composite catalyst on VOCs is improved.
2) Nanometer NiO-VO X /TiO 2 Middle Ni 2+ Formation of NiO deposited on TiO 2 V of (2) 5+ Forming VO of different valence states of various structures X Species, V in V 4+ And V 5+ In the form of NiO and VO X Has stronger interaction and improves NiO-V 5+ The quality of the catalyst is improved, and the surface of the catalyst has high activity and OH concentrationMaking NiO-VO X /TiO 2 Has higher catalytic degradation performance of VOCs. TiO (titanium dioxide) 2 With vacancies on the surface, V during firing 5+ Into TiO 2 Lattice, partially substituted for Ti 4+ Form Ti-O-V bond, reduce TiO 2 Improves the band gap energy of the nanometer NiO-VO X /TiO 2 Is used for the catalytic performance of the catalyst. V (V) 5+ The photo-generated electrons are consumed to form a shallow potential trap of the photo-generated electrons, so that the electron hole separation efficiency is improved, and the nano NiO-VO X /TiO 2 The activity is improved. The synergistic effect of the nanometer NiO-VO X /TiO 2 Has higher catalytic degradation performance on VOCs.
3) Realizes the integration of adsorption and catalysis, improves the adsorption efficiency and the treatment effect of the molecular sieve, and simplifies the VOCs treatment process flow.
Drawings
FIG. 1 is an XPS plot of V2p for the catalyst of example 4;
FIG. 2 shows ZSM-5 and example 4 nano NiO-VO X /TiO 2 Molecular sieve composite catalyst adsorption capacity test results.
Detailed Description
For a further understanding of the present invention, preferred embodiments of the invention are described below in conjunction with the examples, but it should be understood that these descriptions are merely intended to illustrate further features and advantages of the invention, and are not limiting of the claims of the invention.
All the raw materials of the present invention are not particularly limited in their sources, and may be purchased on the market or prepared according to conventional methods well known to those skilled in the art.
Example 1
(1) Mesoporous hollow nano TiO 2 Is synthesized by the following steps: dissolving 17mL of butyl titanate in 22mL of absolute ethyl alcohol, adding 0.4g of surfactant CTAB and 1.2g of nano C, dropwise adding a mixture of 22mL of absolute ethyl alcohol, 3.6mL of glacial acetic acid and 3.6mL of deionized water under stirring, hydrolyzing to form sol, continuing stirring, standing for 2-3 days after gel is formed, vacuum drying at 80 ℃ for 8-10 hours, grinding the obtained powder, and roasting in a muffle furnace at 500 ℃ for 3 hours to obtain 4g of mesoporous hollow nano TiO 2 。
(2) Nanometer NiO-VO X /TiO 2 Is synthesized by the following steps: first 0.0285g of NH 4 VO 3 And 0.0597g of Ni (NO) 3 ) 2 ·6H 2 Adding O into 10mL of deionized water at 60-70 ℃, stirring and dissolving, and adding 4g of mesoporous hollow nano TiO prepared in the step (1) 2 After stirring for 5-10 minutes, 0.0947g of citric acid and 0.0095g of polyethylene glycol are added, stirring is accelerated, the temperature is increased to 80 ℃, and stirring is continued until gel is formed. Drying the gel at 120deg.C, grinding, and air roasting in a muffle furnace at 500deg.C for 3.5 hr to obtain 4.04g NiO-VO X In NiO-VO X /TiO 2 Nano NiO-VO with mass ratio of 1% X /TiO 2 。
(3) Nanometer NiO-VO X /TiO 2 -synthesis of molecular sieve composite catalyst: 1g of NiO-VO synthesized in the step (2) is reacted with X /TiO 2 Dispersing with 4g ZSM-5 molecular sieve with 20mL deionized water, performing ultrasonic stirring for 4h, and drying at 100deg.C to obtain NiO-VO X /TiO 2 Nanometer NiO-VO with mass ratio of 1:4 with ZSM-5 molecular sieve X /TiO 2 -molecular sieve composite catalyst.
Example 2
(1) Mesoporous hollow nano TiO 2 Is synthesized by the following steps: dissolving 17mL of butyl titanate in 22mL of absolute ethyl alcohol, adding 0.4g of surfactant CTAB and 1.2g of nano C, dropwise adding a mixture of 22mL of absolute ethyl alcohol, 3.6mL of glacial acetic acid and 3.6mL of deionized water under stirring, hydrolyzing to form sol, continuing stirring, standing for 2-3 days after gel is formed, vacuum drying at 80 ℃ for 8-10 hours, grinding the obtained powder, and roasting in a muffle furnace at 500 ℃ for 3 hours to obtain 4g of mesoporous hollow nano TiO 2 。
(2) Nanometer NiO-VO X /TiO 2 Is synthesized by the following steps: 0.0576g of NH was first of all 4 VO 3 And 0.1206g of Ni (NO) 3 ) 2 ·6H 2 Adding O into 10mL of deionized water at 60-70 ℃, stirring and dissolving, and adding 4g of mesoporous hollow nano TiO prepared in the step (1) 2 After stirring for 5-10 minutes, 0.1894g of citric acid and 0.0189g of polyethylene glycol were added, stirring was accelerated, the temperature was raised to 80 ℃, and stirring was continued until a gel formed. Drying the gel at 120deg.C, and grindingRoasting the mixture in the muffle furnace at 500 ℃ for 3.5h to obtain 4.08g of NiO-VO X In NiO-VO X /TiO 2 The mass ratio of the nanometer NiO-VO is 2 percent X /TiO 2 。
(3) Nanometer NiO-VO X /TiO 2 -synthesis of molecular sieve composite catalyst: 1g of NiO-VO synthesized in the step (2) is reacted with X /TiO 2 Dispersing with 3g ZSM-5 molecular sieve with 20mL deionized water, performing ultrasonic stirring for 4h, and drying at 100deg.C to obtain NiO-VO X /TiO 2 Nanometer NiO-VO with mass ratio of 1:3 with ZSM-5 molecular sieve X /TiO 2 -molecular sieve composite catalyst.
Example 3
(1) Mesoporous hollow nano TiO 2 Is synthesized by the following steps: dissolving 17mL of butyl titanate in 22mL of absolute ethyl alcohol, adding 0.4g of surfactant CTAB and 1.2g of nano C, dropwise adding a mixture of 22mL of absolute ethyl alcohol, 3.6mL of glacial acetic acid and 3.6mL of deionized water under stirring, hydrolyzing to form sol, continuing stirring, standing for 2-3 days after gel is formed, vacuum drying at 80 ℃ for 8-10 hours, grinding the obtained powder, and roasting in a muffle furnace at 500 ℃ for 3 hours to obtain 4g of mesoporous hollow nano TiO 2 。
(2) Nanometer NiO-VO X /TiO 2 Is synthesized by the following steps: 0.1176g of NH was first of all 4 VO 3 And 0.2463g of Ni (NO) 3 ) 2 ·6H 2 Adding O into 10mL of deionized water at 60-70 ℃, stirring and dissolving, and adding 4g of mesoporous hollow nano TiO prepared in the step (1) 2 After stirring for 5-10 minutes, 0.3867g of citric acid and 0.0387g of polyethylene glycol were added, stirring was accelerated, the temperature was raised to 80 ℃, and stirring was continued until a gel formed. Drying the gel at 120deg.C, grinding, and air roasting in a muffle furnace at 500deg.C for 3.5 hr to obtain 4.167g NiO-VO X In NiO-VO X /TiO 2 Nano NiO-VO with mass ratio of 4% X /TiO 2 。
(3) Nanometer NiO-VO X /TiO 2 -synthesis of molecular sieve composite catalyst: 1g of NiO-VO synthesized in the step (2) is reacted with X /TiO 2 Dispersing with 10g ZSM-5 molecular sieve with 50mL deionized water, performing ultrasonic stirring for 4h, and drying at 100deg.C to obtain NiO-VO X /TiO 2 With ZSM-5 molecular sieveNanometer NiO-VO with mass ratio of 1:10 X /TiO 2 -molecular sieve composite catalyst.
Example 4
(1) Mesoporous hollow nano TiO 2 Is synthesized by the following steps: dissolving 17mL of butyl titanate in 22mL of absolute ethyl alcohol, adding 0.4g of surfactant CTAB and 1.2g of nano C, dropwise adding a mixture of 22mL of absolute ethyl alcohol, 3.6mL of glacial acetic acid and 3.6mL of deionized water under stirring, hydrolyzing to form sol, continuing stirring, standing for 2-3 days after gel is formed, vacuum drying at 80 ℃ for 8-10 hours, grinding the obtained powder, and roasting in a muffle furnace at 500 ℃ for 3 hours to obtain 4g of mesoporous hollow nano TiO 2 。
(2) Nanometer NiO-VO X /TiO 2 Is synthesized by the following steps: 0.1802g of NH was first of all 4 VO 3 And 0.3773g of Ni (NO) 3 ) 2 ·6H 2 Adding O into 10mL of deionized water at 60-70 ℃, stirring and dissolving, and adding 4g of mesoporous hollow nano TiO prepared in the step (1) 2 After stirring for 5-10 minutes, 0.5924g of citric acid and 0.0592g of polyethylene glycol are added, stirring is accelerated, the temperature is increased to 80 ℃, and stirring is continued until gel is formed. Drying the gel at 120deg.C, grinding, and air roasting in a muffle furnace at 500deg.C for 3.5 hr to obtain 4.255g NiO-VO X In NiO-VO X /TiO 2 Nano NiO-VO with mass ratio of 6% X /TiO 2 。
(3) Nanometer NiO-VO X /TiO 2 -synthesis of molecular sieve composite catalyst: 1g of NiO-VO synthesized in the step (2) is reacted with X /TiO 2 Dispersing with 8g ZSM-5 molecular sieve with 40mL deionized water, performing ultrasonic treatment, stirring for 4h, and drying at 100deg.C to obtain NiO-VO X /TiO 2 Nanometer NiO-VO with mass ratio of 1:8 with ZSM-5 molecular sieve X /TiO 2 -molecular sieve composite catalyst.
Example 5
(1) Mesoporous hollow nano TiO 2 Is synthesized by the following steps: 17mL of butyl titanate is dissolved in 22mL of absolute ethyl alcohol, 0.4g of surfactant CTAB and 1.2g of nano C are added, a mixture of 22mL of absolute ethyl alcohol, 3.6mL of glacial acetic acid and 3.6mL of deionized water is added dropwise under stirring, the mixture is hydrolyzed to form sol, stirring is continued, standing is carried out for 2-3 days after gel is formed, and vacuum drying is carried out at 80 DEG CGrinding the powder obtained after 8-10 hours of drying, and roasting in a muffle furnace at 500 ℃ for 3 hours to obtain 4g mesoporous hollow nano TiO 2 。
(2) Nanometer NiO-VO X /TiO 2 Is synthesized by the following steps: 0.3137g of NH was first of all 4 VO 3 And 0.6567g of Ni (NO) 3 ) 2 ·6H 2 Adding O into 12mL of deionized water at 60-70 ℃, stirring and dissolving, and adding 4g of mesoporous hollow nano TiO prepared in the step (1) 2 After stirring for 5-10 minutes, 1.0312g of citric acid and 0.1031g of polyethylene glycol were added, stirring was accelerated, the temperature was raised to 80 ℃, and stirring was continued until a gel formed. Drying the gel at 120deg.C, grinding, and air roasting in a muffle furnace at 500deg.C for 3.5 hr to obtain 4.444g NiO-VO X In NiO-VO X /TiO 2 The mass ratio of the nanometer NiO-VO is 10 percent X /TiO 2 。
(3) Nanometer NiO-VO X /TiO 2 -synthesis of molecular sieve composite catalyst: 1g of NiO-VO synthesized in the step (2) is reacted with X /TiO 2 Dispersing with 20g ZSM-5 molecular sieve with 80mL deionized water, performing ultrasonic treatment, stirring for 4h, and drying at 100deg.C to obtain NiO-VO X /TiO 2 Nanometer NiO-VO with mass ratio of 1:20 with ZSM-5 molecular sieve X /TiO 2 -molecular sieve composite catalyst.
Using N 2 TiO by adsorption-desorption method 2 Nanometer NiO-VO X /TiO 2 ZSM-5, nano NiO-VO prepared in example 4 X /TiO 2 The specific surface area, pore volume, pore diameter and particle size of the ZSM-5 composite catalyst are shown in Table 1.
TABLE 1
It can be seen that TiO 2 Nanometer NiO-VO X /TiO 2 Nanometer NiO-VO X /TiO 2 The ZSM-5 composite catalysts all have larger specific surface area and TiO 2 Nanometer NiO-VO X /TiO 2 NiO-VO with mesoporous structure and ZSM-5 composite structure X /TiO 2 The ZSM-5 composite catalyst still has larger pore volume, and the adsorption effect of the ZSM-5 is not greatly influenced by the composite catalyst.
FIG. 1 is an XPS plot of V2p for the catalyst of example 4. As can be seen in FIG. 1, V is at 515.79eV and 516.94eV, respectively 4+ And V 5+ Characteristic peaks of (2) indicating VO X V is V in the middle 4+ And V 5+ Is in the form of V 4+ And V 5+ The ratio of NiO to VO is 1:3-4 X Between them and the carrier TiO 2 Strong interactions between them.
The test of the removal effect of VOCs was performed in a fixed bed reactor with a gas chromatograph attached using common VOCs toluene as a reference. The gas chromatograph front detector is equipped with a hydrogen flame ion detector and a thermal conductivity detector. During test experiments, 100mg of ZSM-5 and nano NiO-VO X /TiO 2 The molecular sieve composite catalyst is respectively put into a reaction tube, and is treated for 12 hours at 200 ℃ before the adsorption reaction so as to remove water and impurities in the catalyst. Toluene was evaporated by heating at a rate of 100mL/min to give a toluene concentration of 400ppm. The toluene saturation adsorption time and saturation adsorption capacity were measured. Adsorption capacity calculation formula:
wherein:
f is the flow rate of toluene
C 0 For initial toluene concentration mg/m 3
C t Toluene concentration mg/m after t minutes 3
t is adsorption time
t s For saturation adsorption time
FIG. 2 and Table 2 show ZSM-5 and example 4 nano NiO-VO X /TiO 2 Molecular sieve composite catalyst adsorption capacity test results.
TABLE 2
| Catalyst | Adsorption capacity (mg/g) |
| ZSM-5 | 121.8 |
| Example 4NiO-VO X /TiO 2 -ZSM-5 | 146.5 |
Table 2 shows that ZSM-5 has an adsorption capacity of 121.8mg/g for p-toluene and nano NiO-VO X /TiO 2 The adsorption capacity of the ZSM-5 composite catalyst is 146.5mg/g, which is improved by 20.3 percent compared with the adsorption capacity of ZSM-5.
FIG. 2 shows that ZSM-5 has an adsorption saturation time of 21 minutes, while nano NiO-VO X /TiO 2 The saturation adsorption time of the molecular sieve composite catalyst is 52 minutes, and after the adsorption saturation is reached, the nano NiO-VO X /TiO 2 The increase rate of the toluene concentration in the reaction tube after the molecular sieve composite catalyst is adsorbed is smaller than ZSM-5, which shows that the nano NiO-VO X /TiO 2 Has better catalytic degradation effect on toluene.
FIG. 2 and Table 2 show the results of nano NiO-VO X /TiO 2 The molecular sieve composite catalyst has better treatment effect on VOCs, and improves the adsorption efficiency of the molecular sieve.
While the fundamental and principal features of the invention and advantages of the invention have been shown and described, it will be apparent to those skilled in the art that the invention is not limited to the details of the foregoing exemplary embodiments, but may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (7)
1. Nanometer NiO-VO for removing VOCs X /TiO 2 -a process for the preparation of a molecular sieve composite catalyst, characterized in that it comprises the following steps:
s1, mesoporous hollow nano TiO 2 Is synthesized by the following steps: dissolving butyl titanate in absolute ethyl alcohol, adding surfactant CTAB and nano C, dropwise adding a mixture of absolute ethyl alcohol, glacial acetic acid and deionized water under stirring, hydrolyzing to form sol, continuously stirring to form gel, standing for 2-3 days, vacuum drying at 80-100 ℃ for 8-10 hours, grinding, and air roasting in a muffle furnace at 500 ℃ for 3 hours to obtain mesoporous hollow nano TiO 2 ；
S2, nanometer NiO-VO X /TiO 2 Is synthesized by the following steps: NH is added to 4 VO 3 And Ni (NO) 3 ) 2 •6H 2 Adding O into deionized water at 60-70deg.C, stirring to dissolve, adding the mesoporous hollow nanometer TiO 2 Stirring for 5-10 min, adding citric acid and polyethylene glycol, stirring, heating to 80-100deg.C, stirring to form gel, oven drying, grinding, and calcining to obtain nanometer NiO-VO X /TiO 2 The method comprises the steps of carrying out a first treatment on the surface of the The temperature of the drying is 120 ℃, and the roasting is 3.5h of a muffle furnace at 500 ℃;
s3, nanometer NiO-VO X /TiO 2 -synthesis of molecular sieve composite catalyst: subjecting the nano NiO-VO to X /TiO 2 Adding the nanometer NiO-VO and molecular sieve into deionized water, performing ultrasonic dispersion, stirring for 4-6h, and drying to obtain nanometer NiO-VO X /TiO 2 -molecular sieve composite catalyst, said molecular sieve being ZSM-5, beta-type molecular sieve or Y-5A.
2. The preparation method of claim 1, wherein in the step S1, the molar ratio of the butyl titanate, the absolute ethyl alcohol, the glacial acetic acid, the deionized water, the surfactant CTAB and the nano C is 1 (20-40): 1-2.5): 2-6): 0.022:2.
3. The method according to claim 1, wherein in step S2, citric acid and NH are added 4 VO 3 And Ni (NO) 3 ) 2 •6H 2 The molar ratio of O is 4:1:1; the NiO-VO X /TiO 2 In NiO-VO X The mass percentage of the polyethylene glycol to the citric acid is 1-10%, and the mass ratio of the polyethylene glycol to the citric acid is 1:10.
4. The method of claim 1, wherein the molecular sieve is ZSM-5.
5. The nano NiO-VO for removing VOCs prepared by the preparation method of any one of claims 1-4 X /TiO 2 -molecular sieve composite catalyst.
6. The nano NiO-VO for removing VOCS of claim 5 X /TiO 2 -use of a molecular sieve composite catalyst in the removal of VOCs.
7. A VOCs treating agent, comprising the nano NiO-VO for removing VOCs according to claim 5 X /TiO 2 -molecular sieve composite catalyst.
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