CN115414963B - Catalyst for removing VOCs and preparation method and application thereof - Google Patents
Catalyst for removing VOCs and preparation method and application thereof Download PDFInfo
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- CN115414963B CN115414963B CN202211151384.8A CN202211151384A CN115414963B CN 115414963 B CN115414963 B CN 115414963B CN 202211151384 A CN202211151384 A CN 202211151384A CN 115414963 B CN115414963 B CN 115414963B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 79
- 239000012855 volatile organic compound Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title abstract description 24
- 239000002808 molecular sieve Substances 0.000 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 claims abstract description 67
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 16
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000010457 zeolite Substances 0.000 claims abstract description 16
- 238000011068 loading method Methods 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 20
- 239000002243 precursor Substances 0.000 claims description 18
- 229910002651 NO3 Inorganic materials 0.000 claims description 15
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 15
- 229910052697 platinum Inorganic materials 0.000 claims description 15
- 238000002390 rotary evaporation Methods 0.000 claims description 15
- 150000003839 salts Chemical class 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000005245 sintering Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 229910052763 palladium Inorganic materials 0.000 claims description 7
- 239000012266 salt solution Substances 0.000 claims description 6
- 238000010025 steaming Methods 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 4
- 229910000510 noble metal Inorganic materials 0.000 abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 13
- 229910052799 carbon Inorganic materials 0.000 abstract description 9
- 230000002195 synergetic effect Effects 0.000 abstract description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 35
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 29
- 230000003197 catalytic effect Effects 0.000 description 17
- 230000003647 oxidation Effects 0.000 description 17
- 238000007254 oxidation reaction Methods 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 16
- 238000001179 sorption measurement Methods 0.000 description 16
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 229910052710 silicon Inorganic materials 0.000 description 8
- 239000010703 silicon Substances 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 230000008021 deposition Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 238000011031 large-scale manufacturing process Methods 0.000 description 3
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical group [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 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
- 239000003513 alkali Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000002149 hierarchical pore Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/74—Noble metals
- B01J29/7415—Zeolite Beta
-
- 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
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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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
-
- 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
-
- 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
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- Biomedical Technology (AREA)
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- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
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Abstract
The invention provides a catalyst for removing VOCs, a preparation method and application thereof. The catalyst comprises zeolite molecular sieve loading and active components loaded on the zeolite molecular sieve; the zeolite molecular sieve comprises Beta molecular sieve with silicon-aluminum molar ratio of 6-500, and the active component comprises Pt and/or Pd. The catalyst provided by the invention can efficiently adsorb VOCs under the room temperature condition by combining Beta molecular sieve with specific silicon-aluminum ratio with noble metal and performing synergistic effect, and can effectively catalyze and oxidize VOCs under the low temperature condition, and has long service life and carbon deposit resistance.
Description
Technical Field
The invention belongs to the technical field of catalysts, and relates to a catalyst for removing VOCs, and a preparation method and application thereof.
Background
Volatile Organic Compounds (VOCs) are directly harmful to human health, and are also important precursors for forming ozone and dust haze, so that atmospheric environmental pollution is caused. Removal of VOCs has been the focus of research. The removal technology of VOCs mainly comprises adsorption, catalytic oxidation and the like. Adsorption technology can remove VOCs at normal temperature, and activated carbon is a common adsorption material, but has poor thermal stability.
CN111617633a discloses a preparation method of multi-shell photocatalyst and active carbon composite degradation VOCs, comprising the following steps: s1 preparation of three-layer hollow SiO 2 Nanospheres, S2 is SiO 2 Adding a titanium source into a template, and performing hydrothermal reaction to prepare multi-shell photocatalyst TiO 2 S3 is in multi-shell TiO 2 The upper loadNoble metal with a certain proportion, S4 is TiO loaded with noble metal 2 And uniformly mixing with active carbon with proper proportion to obtain the composite material. In this document, adsorption is performed by activated carbon, and there is a problem that certain thermal stability is poor.
Molecular sieves are improved adsorbent materials in recent years, and can improve the performance of adsorbing VOCs. The catalytic oxidation technology can thoroughly oxidize and remove VOCs at medium and low temperatures. The molecular sieve loaded noble metal catalyst can reduce the catalytic oxidation temperature of VOCs and realize the removal of VOCs under the condition of lower temperature. However, the molecular sieve supported noble metal catalyst has the problems of easy carbon deposition, short service life and the like. Developing a molecular sieve with high adsorption capacity at normal temperature and high catalytic oxidation performance at low temperature to effectively remove VOCs becomes a new challenge.
CN113275034a discloses a hierarchical pore molecular sieve catalyst for eliminating VOCs and a preparation method thereof. The preparation of the catalyst comprises the following steps: (1) Mixing a silicon source, an aluminum source, an alkali source and water together, uniformly stirring, and removing alcohol organic matters generated by decomposition to obtain gel; (2) Transferring the gel into a reaction kettle for sealing and crystallizing to obtain white powdery solid, namely a ZSM-5 molecular sieve carrier; (3) The ZSM-5 molecular sieve carrier is immersed in an aqueous solution containing noble metal soluble salt, and the multistage pore molecular sieve catalyst loaded with noble metal is obtained through ultrasonic treatment, stirring, standing, drying and roasting, and the problems of easy carbon deposition, short service life and the like exist in the collocation in the literature to a certain extent.
Therefore, how to obtain a catalyst with high adsorption capacity at normal temperature and high catalytic oxidation performance at low temperature for effectively removing VOCs is a technical problem to be solved.
Disclosure of Invention
The invention aims to provide a catalyst for removing VOCs, and a preparation method and application thereof. The catalyst provided by the invention can efficiently adsorb VOCs under the room temperature condition by combining Beta molecular sieve with specific silicon-aluminum ratio with noble metal and performing synergistic effect, and can effectively catalyze and oxidize VOCs under the low temperature condition, and has long service life and carbon deposit resistance.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a catalyst for removing VOCs, the catalyst comprising a zeolite molecular sieve support and an active component supported on the zeolite molecular sieve; the zeolite molecular sieve comprises Beta molecular sieve with a silicon to aluminum molar ratio of 6-500, and the active component comprises Pt and/or Pd, for example, the silicon to aluminum ratio may be 6, 8, 10, 20, 50, 80, 100, 130, 150, 180, 200, 230, 250, 280, 300, 330, 350, 380, 400, 430, 450, 480, 500, or the like.
According to the catalyst provided by the invention, beta molecular sieve with specific silicon-aluminum ratio is combined with noble metal, and the regulation and control of pore channel structure, acidity-alkalinity and hydroxyl functional groups on noble metal valence state, dispersity and active site distribution position are utilized, so that the synergistic effect of physical and chemical adsorption and catalytic oxidation is exerted, the catalyst can efficiently adsorb VOCs at room temperature, and the catalyst can effectively catalyze and oxidize VOCs at low temperature, and has long service life and carbon deposit resistance.
Beta molecular sieve with silicon-aluminum ratio of 6-500 is compounded with specific platinum and/or palladium, and the Beta molecular sieve and the specific platinum and/or palladium are cooperated to realize high catalytic oxidation performance of the catalyst at low temperature, and molecular sieves (such as all-silicon type molecular sieves) within the silicon-aluminum ratio range provided by the invention cannot realize the regulation and control of noble metal valence state, dispersity and active site distribution position, and cannot realize the purpose of low-temperature high-efficiency catalytic oxidation of VOCs if the Beta molecular sieve is other active components.
In the invention, if the molar ratio of silicon to aluminum is too large, exceeding 500 can lead to noble metal agglomeration and activity reduction.
Preferably, the mass of the active component is 0.1 to 10wt%, such as 0.1wt%, 0.5wt%, 1wt%, 2wt%, 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt%, etc. of the catalyst.
Preferably, the silicon to aluminum molar ratio is 200 to 500, such as 200, 230, 250, 280, 300, 330, 350, 380, 400, 430, 450, 480, 500, or the like.
In the invention, the silicon-aluminum molar ratio exceeds 200, which is more beneficial to improving the performances of adsorbing and catalytically oxidizing VOCs
In a second aspect, the present invention provides a method for preparing a catalyst for removing VOCs according to the first aspect, the catalyst comprising the steps of:
mixing and impregnating the precursor salt solution and the zeolite molecular sieve, loading by adopting a rotary steaming method, and sintering to obtain the catalyst for removing VOCs;
wherein the metal element in the precursor salt comprises Pt and/or Pd, and the zeolite molecular sieve comprises Beta molecular sieve with a silicon-aluminum ratio of 6-500.
In the invention, the active components are loaded by adopting a method of spin evaporation after impregnation, so that the loading of platinum and/or palladium on the molecular sieve can be better realized, and the preparation method is simple, does not need complex operation steps, and is suitable for large-scale production.
Preferably, the precursor salt comprises nitrate and/or tetrammine nitrate.
In the invention, nitrate and/or tetrammine nitrate are selected as precursors, so that low-temperature catalytic oxidation of VOCs can be better realized, and if other kinds of metal salts such as chloroplatinic acid and the like are selected, noble metal valence states can be influenced, and the activities of adsorption and catalytic oxidation of VOCs under the same experimental conditions are reduced.
Preferably, the rotary steaming method comprises:
the mixed impregnated solution was subjected to rotary evaporation, which was accompanied by stirring and drying.
Preferably, the temperature of the rotary evaporation is 60 ℃ or less, for example 60 ℃,50 ℃,45 ℃, 40 ℃, 35 ℃, 30 ℃, 25 ℃, 20 ℃ or the like.
In the invention, too high temperature of rotary evaporation can lead to the reduction of the dispersity of noble metals and reduce the performance of catalytic oxidation of VOCs.
Preferably, the time of the rotary evaporation is 1 to 2 hours, for example 1 hour, 1.3 hours, 1.5 hours, 1.8 hours or 2 hours, etc.
Preferably, the temperature rising rate during the sintering is 1 to 10 ℃ per minute, for example 1 ℃ per minute, 2 ℃ per minute, 3 ℃ per minute, 4 ℃ per minute, 5 ℃ per minute, 6 ℃ per minute, 7 ℃ per minute, 8 ℃ per minute, 9 ℃ per minute or 10 ℃ per minute, etc.
In the invention, the temperature rising rate is too low, which is not beneficial to retaining OH functional groups in the molecular sieve, reducing the functions of adsorbing VOCs and dispersing noble metals, and the temperature rising rate is too high, which can influence the water content in the molecular sieve and the regulation and control of the valence state of the noble metals.
Preferably, the sintering temperature is 400 to 800 ℃, for example 400 ℃, 430 ℃, 450 ℃, 480 ℃, 500 ℃, 530 ℃, 550 ℃, 580 ℃, 600 ℃, 630 ℃, 650 ℃, 680 ℃, 700 ℃, 730 ℃, 750 ℃, 780 ℃, 800 ℃, or the like.
As a preferred technical scheme, the preparation method comprises the following steps:
mixing and impregnating the precursor salt solution and the zeolite molecular sieve, performing rotary evaporation on the mixed and impregnated solution for 1-2 h in an environment less than or equal to 60 ℃, stirring and drying the mixed and impregnated solution in the rotary evaporation process, and heating the mixed and impregnated solution to 400-800 ℃ at a heating rate of 1-10 ℃/min to sinter the mixed and impregnated solution to obtain the catalyst for removing VOCs;
wherein the precursor salt comprises nitrate and/or tetrammine nitrate, the metal element in the precursor salt comprises Pt and/or Pd, and the zeolite molecular sieve comprises Beta molecular sieve with a silicon-aluminum ratio of 6-500.
In a third aspect, the invention also provides the use of a catalyst for the removal of VOCs, the use comprising using a catalyst according to the first aspect for the removal of VOCs.
Compared with the prior art, the invention has the following beneficial effects:
the catalyst provided by the invention adopts a method of spin steaming after impregnation to load active components on a molecular sieve, the obtained catalyst has the molecular sieve with specific silicon-aluminum ratio and the active components of the specific active components, the effect that the catalyst can efficiently adsorb VOCs under the room temperature condition and can effectively catalyze and oxidize the VOCs under the low temperature condition is realized through the synergistic effect of the molecular sieve and the active components, the service life of the catalyst is long, and carbon deposition is also prevented, so that the catalyst is suitable for large-scale production and use. The catalyst provided by the invention has the silicon-aluminum ratio in the Beta molecular sieve of 200-500, and when the active component contains platinum, the penetration time for adsorbing toluene can reach 320min or more, and 90% of toluene is catalyzed and oxidized to CO 2 The required temperature is lowThe toluene conversion rate after 60 hours of continuous reaction was reduced to less than 8% by the reaction at a temperature below 156 ℃.
Drawings
FIG. 1 is a graph showing the permeation of toluene by the catalyst provided in example 1 and examples 6 to 7.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides a catalyst for removing VOCs, which comprises a Beta molecular sieve with a silicon-aluminum molar ratio of 280 and platinum loaded on the molecular sieve, wherein the mass ratio of the platinum in the catalyst is 1wt%.
The preparation method of the catalyst comprises the following steps:
adding Beta molecular sieve with silicon aluminum molar ratio of 280 into tetramine platinum nitrate solution for soaking, performing rotary evaporation (accompanied by stirring) at 50 ℃ for 2h, drying at 100 ℃ for 12h, and then heating at 550 ℃ at the heating rate of 5 ℃/min for sintering for 3h to obtain the catalyst.
Example 2
The embodiment provides a catalyst for removing VOCs, which comprises a Beta molecular sieve with a silicon-aluminum molar ratio of 500 and platinum loaded on the molecular sieve, wherein the mass ratio of the platinum in the catalyst is 5wt%.
The preparation method of the catalyst comprises the following steps:
adding Beta molecular sieve with silicon aluminum molar ratio of 500 into platinum nitrate solution for soaking, performing rotary evaporation (accompanied by stirring) at 45 ℃ for 1.5h, drying at 120 ℃ for 10h, and then heating at 800 ℃ for 3h at the heating rate of 10 ℃/min to obtain the catalyst.
Example 3
The embodiment provides a catalyst for removing VOCs, which comprises a Beta molecular sieve with a silicon-aluminum molar ratio of 200 and platinum loaded on the molecular sieve, wherein the mass ratio of the platinum in the catalyst is 10wt%.
The preparation method of the catalyst comprises the following steps:
adding Beta molecular sieve with silicon aluminum molar ratio of 200 into tetramine platinum nitrate solution for soaking, performing rotary evaporation (accompanied by stirring) at 50 ℃ for 2h, drying at 100 ℃ for 12h, and then heating at 400 ℃ at the heating rate of 1 ℃/min for sintering for 5h to obtain the catalyst.
Example 4
The difference between this example and example 1 is that in this example the active component is palladium and the precursor salt is tetraammine palladium nitrate.
The remaining preparation methods and parameters were consistent with example 1.
Example 5
This example differs from example 1 in that the active components in this example are palladium and platinum, each of which constitutes 1wt% of the mass of the catalyst. The precursor salts are palladium tetrammine nitrate and platinum tetrammine nitrate.
The remaining preparation methods and parameters were consistent with example 1.
Example 6
The difference between this example and example 1 is that the mole ratio of silica to alumina of the Beta molecular sieve in this example is 6.
The remaining preparation methods and parameters were consistent with example 1.
Example 7
The difference between this example and example 1 is that the mole ratio of silica to alumina of the Beta molecular sieve in this example is 40.
The remaining preparation methods and parameters were consistent with example 1.
Fig. 1 shows the permeation curves of the catalyst adsorption toluene provided in examples 1 and 6-7, and as can be seen from the permeation curves of the catalyst para-toluene in fig. 1, the permeation time of the catalyst para-toluene is prolonged and the adsorption amount is increased as the silicon-aluminum ratio is increased.
Example 8
The difference between this example and example 1 is that the precursor salt in this example is chloroplatinic acid.
The remaining preparation methods and parameters were consistent with example 1.
Example 9
The difference between this example and example 1 is that the temperature rise rate in this example is 15℃per minute.
The remaining preparation methods and parameters were consistent with example 1.
Comparative example 1
The difference between this comparative example and example 1 is that the mole ratio of silicon to aluminum of the Beta molecular sieve in this comparative example is 600.
The remaining preparation methods and parameters were consistent with example 1.
Comparative example 2
The difference between this comparative example and example 1 is that the Beta molecular sieve in this comparative example is an all-silica molecular sieve.
The remaining preparation methods and parameters were consistent with example 1.
Comparative example 3
The difference between this comparative example and example 1 is that the active component in this comparative example is iridium and the precursor salt is iridium tetrammine nitrate.
The remaining preparation methods and parameters were consistent with example 1.
Comparative example 4
The difference between this comparative example and example 4 is that the Beta molecular sieve in this comparative example is an all-silica molecular sieve.
The remaining preparation methods and parameters were consistent with example 4.
The catalysts provided in examples 1-9 and comparative examples 1-4 were subjected to adsorption of toluene and catalytic oxidation of toluene to CO 2 Specific test conditions are as follows: a quartz tube flow reactor with an inner diameter of 4mm and 100mg of catalyst was used, the initial concentration of toluene was 200ppm, the air flow rate was 100mL/min, toluene and CO 2 The concentration was detected by gas chromatography. The results are shown in Table 1.
TABLE 1
From the data of examples 1-5, the catalyst provided by the invention has high adsorption capacity, good catalytic oxidation performance at low temperature and good stability.
From the data of examples 1 and 6 and 7, it is clear that the molar ratio of Si to Al is too low, below 200, which is detrimental to adsorption and catalytic oxidation of VOCs.
From the data of examples 1 and 8, it is clear that the use of other types of salt solutions results in reduced activity and stability of the catalytically oxidized VOCs.
From the data in examples 1 and 9, it is clear that too fast a temperature rise rate affects adsorption and catalytic oxidation of VOCs.
From the data of example 1 and comparative example 1, it is understood that too large a molar ratio of silicon to aluminum of the molecular sieve, exceeding 500, results in a decrease in the performance of adsorbing and catalytically oxidizing VOCs.
From the data of examples 1 and 2 and 4, it is evident that the use of other types of molecular sieves also results in decreased adsorption and catalytic oxidation of VOCs.
From the data of examples 1 and comparative examples 1-3 and example 4 and comparative example 4, the catalyst provided by the invention requires the synergistic effect of molecular sieve with specific silicon-aluminum molar ratio and specific active component to realize high-efficiency adsorption and low-temperature catalytic oxidation of VOCs and increase the service life of the catalyst.
In summary, the catalyst provided by the invention adopts a method of spin steaming after impregnation to load active components on a molecular sieve, the obtained catalyst has the molecular sieve with a specific silicon-aluminum ratio and the active components of the specific active components, the effect that the catalyst can efficiently adsorb VOCs under the condition of room temperature and effectively catalyze and oxidize the VOCs under the condition of low temperature is realized through the synergistic effect of the molecular sieve and the active components, the service life of the catalyst is long, and carbon deposition is also prevented, so that the catalyst is suitable for large-scale production and use. The catalyst provided by the invention has the silicon-aluminum ratio in the Beta molecular sieve within 200-500, and when the active component contains platinum, the penetration of the adsorbed tolueneThe time can reach 320min and above, and 90% of toluene is catalyzed and oxidized to CO 2 The required temperature is as low as 156 ℃, and the toluene conversion rate is reduced by less than 8% after 60 hours of continuous reaction.
The applicant declares that the above is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that are easily conceivable within the technical scope of the present invention disclosed by the present invention fall within the scope of the present invention and the disclosure.
Claims (9)
1. A catalyst for removing VOCs, said catalyst comprising a zeolite molecular sieve and an active component supported on said zeolite molecular sieve; the zeolite molecular sieve comprises a Beta molecular sieve with a silicon-aluminum molar ratio of 280-500, and the active component comprises Pt or Pt and Pd;
the catalyst is prepared by the following method, which comprises the following steps:
mixing and impregnating the precursor salt solution and the zeolite molecular sieve, loading by adopting a rotary steaming method, and sintering to obtain the catalyst for removing VOCs;
wherein the precursor salt comprises nitrate and/or tetrammine nitrate, and the heating rate in the sintering process is 1-10 ℃/min.
2. The catalyst for removing VOCs according to claim 1, wherein the mass of the active component is 0.1 to 10wt% of the mass of the catalyst.
3. A method of preparing the catalyst for removing VOCs according to claim 1 or 2, wherein said catalyst comprises the steps of:
mixing and impregnating the precursor salt solution and the zeolite molecular sieve, loading by adopting a rotary steaming method, and sintering to obtain the catalyst for removing VOCs;
wherein the precursor salt comprises nitrate and/or tetrammine nitrate, and the heating rate in the sintering process is 1-10 ℃/min.
4. The method for preparing a catalyst for removing VOCs according to claim 3, wherein said rotary evaporation method comprises:
the mixed impregnated solution was subjected to rotary evaporation, which was accompanied by stirring and drying.
5. The method for preparing a catalyst for removing VOCs according to claim 4, wherein the temperature of the rotary evaporation is 60 ℃.
6. The method for preparing a catalyst for removing VOCs according to claim 4, wherein the time of the rotary evaporation is 1 to 2 hours.
7. The method for preparing a catalyst for removing VOCs according to claim 3, wherein the sintering temperature is 400 to 800 ℃.
8. The method for preparing a catalyst for removing VOCs according to claim 3, comprising the steps of:
mixing and impregnating the precursor salt solution and the zeolite molecular sieve, performing rotary evaporation on the mixed and impregnated solution for 1-2 h in an environment less than or equal to 60 ℃, stirring and drying the mixed and impregnated solution in the rotary evaporation process, and heating the mixed and impregnated solution to 400-800 ℃ at a heating rate of 1-10 ℃/min to sinter the mixed and impregnated solution to obtain the catalyst for removing VOCs;
wherein the precursor salt comprises nitrate and/or tetrammine nitrate.
9. Use of a catalyst for the removal of VOCs, characterized in that the use comprises using the catalyst according to claim 1 or 2 for the removal of VOCs.
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