CN116328818A - Carrier modified catalyst and preparation method and application thereof - Google Patents
Carrier modified catalyst and preparation method and application thereof Download PDFInfo
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- CN116328818A CN116328818A CN202310229430.XA CN202310229430A CN116328818A CN 116328818 A CN116328818 A CN 116328818A CN 202310229430 A CN202310229430 A CN 202310229430A CN 116328818 A CN116328818 A CN 116328818A
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- Prior art keywords
- carrier
- noble metal
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- catalyst
- roasting
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- 239000003054 catalyst Substances 0.000 title claims abstract description 86
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 239000003607 modifier Substances 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000007787 solid Substances 0.000 claims abstract description 25
- 238000002156 mixing Methods 0.000 claims abstract description 24
- 239000011259 mixed solution Substances 0.000 claims abstract description 21
- 239000000243 solution Substances 0.000 claims abstract description 21
- 239000011973 solid acid Substances 0.000 claims abstract description 20
- 239000002243 precursor Substances 0.000 claims abstract description 18
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 17
- 238000000746 purification Methods 0.000 claims abstract description 15
- 239000002808 molecular sieve Substances 0.000 claims abstract description 13
- 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 13
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000002425 crystallisation Methods 0.000 claims abstract description 8
- 230000008025 crystallization Effects 0.000 claims abstract description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 63
- 238000000034 method Methods 0.000 claims description 26
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 22
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 20
- 239000010881 fly ash Substances 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 17
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 15
- 229910052707 ruthenium Inorganic materials 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 14
- 239000012855 volatile organic compound Substances 0.000 claims description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 229910052763 palladium Inorganic materials 0.000 claims description 11
- 229910052697 platinum Inorganic materials 0.000 claims description 10
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 9
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 9
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 9
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 239000003446 ligand Substances 0.000 claims description 7
- 125000001477 organic nitrogen group Chemical group 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 239000012670 alkaline solution Substances 0.000 claims description 4
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 4
- 229910052878 cordierite Inorganic materials 0.000 claims description 4
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 4
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000000908 ammonium hydroxide Substances 0.000 claims description 3
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052863 mullite Inorganic materials 0.000 claims 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 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 claims description 2
- 235000019743 Choline chloride Nutrition 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 claims description 2
- 229960003178 choline chloride Drugs 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- 238000005554 pickling Methods 0.000 claims 1
- 239000007789 gas Substances 0.000 abstract description 9
- 239000010815 organic waste Substances 0.000 abstract description 5
- 238000004806 packaging method and process Methods 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 16
- 239000008367 deionised water Substances 0.000 description 15
- 229910021641 deionized water Inorganic materials 0.000 description 15
- 239000011248 coating agent Substances 0.000 description 14
- 238000000576 coating method Methods 0.000 description 14
- 125000004429 atom Chemical group 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000460 chlorine Substances 0.000 description 8
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 230000000670 limiting effect Effects 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- 238000001354 calcination Methods 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 239000003344 environmental pollutant Substances 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- 238000001914 filtration Methods 0.000 description 3
- -1 polytetrafluoroethylene Polymers 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 239000002912 waste gas Substances 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000012080 ambient air Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000007084 catalytic combustion reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000006255 coating slurry Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002345 surface coating layer Substances 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- 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
- B01J29/064—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing iron group metals, noble metals or copper
- B01J29/068—Noble metals
-
- 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
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/40—Special temperature treatment, i.e. other than just for template removal
-
- 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
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/42—Addition of matrix or binder particles
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Analytical Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Biomedical Technology (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention provides a carrier modified catalyst and a preparation method and application thereof, wherein the carrier modified catalyst comprises a modified carrier and solid acid of packaging noble metal single atoms grafted on the surface of the modified carrier; the preparation method comprises the following steps: 1) Mixing the main carrier, the solid modifier and water, and obtaining a modified carrier through hydrothermal reaction; 2) Mixing the modified carrier with the prepared noble metal precursor mixed solution, and sequentially carrying out crystallization reaction and roasting to obtain a molecular sieve catalyst encapsulated with noble metal monoatoms; 3) Reacting the molecular sieve catalyst encapsulated with noble metal monoatoms with an ammonium nitrate solution, and roasting to obtain a solid acid catalyst encapsulated with noble metal monoatoms; the carrier modified catalyst remarkably improves the overall performance of the catalyst by comprehensively improving and optimizing the original carrier and the active components, is widely applicable to the purification treatment of various complex organic waste gases, and has good application prospect.
Description
Technical Field
The invention belongs to the technical field of environment-friendly catalysis, and particularly relates to a carrier modified catalyst and a preparation method and application thereof.
Background
Volatile organic compounds (Volatile Organic Compounds, VOCs) are a common type of industrial waste gas, mainly from the industries of medicines, rubber, plastics, pesticides, dyes and the like. The emission of such exhaust gases can cause serious environmental problems, including ozone pollution and PM2.5 anomalies. In recent years, with the continuous promotion of green sustainable development, engineering construction for VOCs waste gas is one of important means for improving the quality of ambient air. The catalytic oxidation method is a purification technology for directionally removing target pollutants by using a catalyst at high temperature, and has the characteristics of low energy consumption, remarkable effect and the like. The method is characterized in that the method designs and develops the catalyst with high mechanical strength, good catalytic performance, low price and less secondary pollutant.
CN113426458A discloses a catalyst for catalytic combustion of halogen-containing volatile organic compounds, which comprises a monolithic or granular carrier, and a high-viscosity coating, an auxiliary agent and an active component coating supported on the carrier, wherein the high-viscosity coating is obtained by coating an inorganic oxide carrier with an alumina sol and then calcining, and the active component is precipitated on the surface of the high-viscosity coating by adopting a redox method. The catalyst has good stability, reproducibility and high moisture resistance, has high conversion efficiency on halogen-containing volatile organic compounds, and has low preparation cost, and the active coating is firmly combined with the monolithic or granular inorganic oxide carrier.
However, the monolithic catalysts currently used for purifying VOCs exhaust gas still have the following problems: 1) The cheap modifier is selected to modify the catalyst carrier so as to solve the problems of low carrier microroughness, small specific surface area and poor compatibility with active components, thereby expanding the application scene of the catalyst carrier under complex and severe working conditions; 2) How to develop an integral catalyst with low noble metal loading rate on the basis of ensuring high VOCs conversion rate, thereby realizing the purpose of reducing catalyst cost; 3) How to avoid the phenomenon of activity reduction caused by migration, agglomeration, volatilization, loss, poisoning and the like of noble metal species in the reaction process, and prolong the service life of the catalyst; 4) For specific chlorine-containing waste gas treatment, how to inhibit the generation of secondary organic chlorine-containing pollutants with stronger toxicity and greater harm in the reaction process; 5) Aiming at different VOCs waste gas working conditions, how to accurately design and prepare the high-performance catalyst, and avoid the loss of materials and equipment caused by repeated trial and error.
In view of the foregoing, it is currently highly desirable to develop a catalyst that solves the above-mentioned problems.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention aims to provide a carrier modified catalyst, a preparation method and application thereof, wherein the carrier modified catalyst remarkably improves the overall performance of the catalyst by comprehensively improving and optimizing an original carrier and active components, is widely applicable to the purification treatment of various complex organic waste gases, has remarkable advantages in the treatment of organic waste gases containing hetero atoms such as Cl and the like, and has good application prospect.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a carrier modified catalyst comprising a modified carrier and a solid acid encapsulating a noble metal monoatom grafted to the surface of the modified carrier;
the modified carrier comprises a main carrier modified by a solid modifier.
The following technical scheme is a preferred technical scheme of the invention, but is not a limitation of the technical scheme provided by the invention, and the technical purpose and beneficial effects of the invention can be better achieved and realized through the following technical scheme.
As a preferred embodiment of the present invention, the main support comprises cordierite or mullite.
Preferably, the main components of the solid modifier include Si, O, al and Mg, which are similar in cost to the main support.
Preferably, the solid modifier comprises fly ash.
As a preferred embodiment of the present invention, the noble metal comprises any one or a combination of at least two of platinum, ruthenium or palladium, and typical but non-limiting examples of such combinations are: platinum and ruthenium combinations, ruthenium and palladium combinations, platinum, ruthenium and palladium combinations, and the like.
In a second aspect, the present invention provides a method for preparing the carrier modified catalyst according to the first aspect, the method comprising the steps of:
(1) Mixing the pretreated main carrier and the pretreated solid modifier with water, and carrying out hydrothermal reaction to obtain a modified carrier;
(2) Mixing the modified carrier in the step (1) with the prepared noble metal precursor mixed solution, and sequentially carrying out crystallization reaction and roasting to obtain a molecular sieve catalyst encapsulated with noble metal monoatoms;
(3) And (3) reacting the molecular sieve catalyst encapsulated with the noble metal monoatoms in the step (2) with an ammonium nitrate solution, and roasting to obtain the solid acid catalyst encapsulated with the noble metal monoatoms.
As a preferred technical solution of the present invention, the method for pretreating the master carrier in step (1) includes: mixing the main carrier with alkali solution, performing hydrothermal reaction, and then washing and drying sequentially to obtain the pretreated main carrier.
Preferably, the alkaline solution comprises sodium hydroxide solution and/or potassium hydroxide solution.
Preferably, the concentration of the alkaline solution is 10-20wt%, such as 10wt%, 12wt%, 14wt%, 16wt%, 18wt%, or 20wt%, etc., but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the temperature of the hydrothermal reaction during the pretreatment of the main carrier is 120-150 ℃, for example 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃, 150 ℃, etc.; the time is 10-16 hours, such as 10 hours, 12 hours, 14 hours or 16 hours, etc., but is not limited to the recited values, and other non-recited values within the range are equally applicable.
As a preferred technical scheme of the present invention, the method for pretreating the solid modifier in the step (1) includes: and (3) sequentially carrying out acid washing and drying on the solid modifier, mixing the solid modifier with an alkaline substance, and then grinding and roasting to obtain the pretreated solid modifier.
Preferably, the acid solution used for the acid washing comprises hydrochloric acid.
Preferably, the hydrochloric acid has a concentration of 1 to 10mol/L, for example, 10mol/L, or 10mol/L, etc., but is not limited to the recited values, and other non-recited values within the range of the recited values are equally applicable.
Preferably, the mass ratio of the solid modifier to the acid solution is 1 (1-10), such as 1:1, 1:2, 1:4, 1:6, 1:8 or 1:10, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the alkaline substance comprises any one or a combination of at least two of sodium hydroxide, sodium carbonate, potassium hydroxide or potassium carbonate, typical but non-limiting examples of which are: a combination of sodium hydroxide and potassium hydroxide, and a combination of sodium carbonate and potassium carbonate.
Preferably, the mass ratio of the solid modifier to the alkaline substance is 1 (0.5-3), such as 1:0.5, 1:1, 1:1.5, 1:2, 1:2.5 or 1:3, etc., but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the solid modifier is pre-treated at 400-900 deg.c, such as 400 deg.c, 500 deg.c, 600 deg.c, 700 deg.c, 800 deg.c, 900 deg.c, etc; the time is 1 to 5 hours, for example, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, etc., and the above-mentioned values are not limited to the listed values, and other non-listed values are equally applicable within the respective value ranges.
As a preferred embodiment of the present invention, the mass ratio of the pretreated solid modifier to water in step (1) is 1 (2-20), such as 1:2, 1:4, 1:6, 1:8, 1:10, 1:12, 1:14, 1:18 or 1:20, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the temperature of the hydrothermal reaction in the step (1) is 80 to 200 ℃, for example 80 ℃, 100 ℃, 120 ℃, 160 ℃, 180 ℃, 200 ℃ or the like, but is not limited to the recited values, and other non-recited values within the range of the recited values are equally applicable.
Preferably, the hydrothermal reaction in step (1) is performed for a period of time ranging from 4 to 24 hours, such as 4 hours, 8 hours, 12 hours, 16 hours, 20 hours, or 24 hours, etc., but is not limited to the recited values, and other non-recited values within the range are equally applicable.
As a preferable technical scheme of the invention, the method for preparing the noble metal precursor mixed solution in the step (2) comprises the following steps: and mixing the noble metal precursor, the organic nitrogen-containing ligand, the template agent, the aluminum source, the sodium hydroxide, the silicon source and water to obtain a noble metal precursor mixed solution.
Preferably, the noble metal precursor and the organic nitrogen-containing ligand are fully dissolved and mixed, then the template agent, the aluminum source and the sodium hydroxide are added, then the silicon source is slowly added, and the mixed solution is obtained after vigorous stirring.
Preferably, the molar ratio of the noble metal precursor to the organic nitrogen-containing ligand is 1 (20-50), such as 1:20, 1:25, 1:30, 1:35, 1:40, 1:45, or 1:50, etc., but is not limited to the recited values, as other non-recited values within the range of values are equally applicable.
Preferably, the molar ratio of the aluminum source, water, sodium hydroxide, templating agent, and silicon source is 1 (100-1000): (1-10): (5-200): (10-50), such as 1:100:1:5:10, 1:200:4:40:30, 1:400:7:100:40, 1:300:2:200:50, or 1:100:10:180:12, etc., but is not limited to the recited values, as are other non-recited values within this range.
Preferably, the molar ratio of the noble metal precursor to the water is 1 (20000-80000), such as 1:20000, 1:30000, 1:40000, 1:50000, 1:60000, 1:70000, or 1:80000, etc., but is not limited to the recited values, as other non-recited values within the range of values are equally applicable.
Preferably, the noble metal precursor comprises any one or a combination of at least two of chloroplatinic acid, platinum nitrate, tetraammineplatinum nitrate, ruthenium nitrosylnitrate, ruthenium chloride, palladium nitrate, or tetraamminepalladium nitrate, typical but non-limiting examples of such combinations are: a combination of chloroplatinic acid and platinum nitrate, a combination of chloroplatinic acid and ruthenium chloride, a combination of ruthenium chloride and palladium chloride, and the like.
Preferably, the organic nitrogen-containing ligand comprises ethylenediamine and/or diethylenetriamine.
Preferably, the templating agent comprises any one or a combination of at least two of N, N-trimethyl-1-adamantane-ammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, or choline chloride, typical but non-limiting examples of such combinations being: a combination of N, N, N-trimethyl-1-adamantane-ammonium hydroxide and tetraethylammonium hydroxide, a combination of tetraethylammonium hydroxide and tetrapropylammonium hydroxide, and the like.
Preferably, the aluminum source comprises any one or a combination of at least two of sodium metaaluminate, aluminum sulfate, aluminum nitrate, or aluminum isopropoxide, typical but non-limiting examples of which are: a combination of sodium metaaluminate and aluminum sulfate, a combination of aluminum sulfate and aluminum nitrate, and the like.
Preferably, the silicon source comprises any one or a combination of at least two of white carbon black, ethyl orthosilicate, silica sol or methyl orthosilicate, typical but non-limiting examples of such combinations are: a combination of ethyl orthosilicate and silica sol, and the like.
Preferably, the crystallization reaction in step (2) is carried out at a temperature of 120 to 200 ℃, for example 120 ℃, 140 ℃, 160 ℃, 180 ℃, 200 ℃ or the like, but is not limited to the values recited, and other values not recited in the range are equally applicable.
Preferably, the crystallization reaction in step (2) is performed for 72-200 hours, for example, 72 hours, 80 hours, 90 hours, 100 hours, 120 hours, 140 hours, 180 hours or 200 hours, etc., but the crystallization reaction is not limited to the recited values, and other non-recited values within the range of the recited values are equally applicable.
Preferably, the temperature of the calcination in step (2) is 450-650 ℃, such as 450 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃ or the like, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the time of the calcination in step (2) is 2-8 hours, such as 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours or 8 hours, etc., but is not limited to the recited values, and other non-recited values within the range are equally applicable.
As a preferred embodiment of the present invention, the concentration of the ammonium nitrate solution in the step (3) is 2 to 3mol// L, for example, 2mol// L, 2.2mol// L, 2.4mol// L, 2.6mol// L, 2.8mol// L or 3mol// L, etc., but not limited to the recited values, and other non-recited values within the range of the recited values are equally applicable.
Preferably, the temperature of the reaction in step (3) is 70-80 ℃, for example 70 ℃, 72 ℃, 74 ℃, 76 ℃, 78 ℃, 80 ℃ or the like, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the reaction time in step (3) is 2-6 hours, such as 2 hours, 3 hours, 4 hours, 5 hours or 6 hours, etc., but is not limited to the recited values, and other non-recited values within the range are equally applicable.
Preferably, the temperature of the calcination in step (3) is 450-650 ℃, such as 450 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃ or the like, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the time of the calcination in step (3) is 1-8 hours, such as 1h, 2h, 3h, 4h, 5h, 6h, 7h or 8h, etc., but is not limited to the recited values, and other non-recited values within the range are equally applicable.
In a third aspect, the present invention provides the use of a carrier modified catalyst according to the first aspect for purification of VOCs.
Compared with the prior art, the invention has the following beneficial effects:
(1) Compared with the original catalyst carrier, the carrier modified catalyst disclosed by the invention has the advantages that the solid modifier close to the carrier component is adopted to modify the surface of the catalyst, so that the micro roughness and the specific surface area of the carrier can be obviously increased, the subsequent in-situ grafting of the solid acid packaged with noble metal single atoms on the modified carrier surface is facilitated, the problems of poor compatibility of active components and the carrier, more coating slurry loss, high coating falling rate and the like in the preparation of the integral catalyst by the traditional wet coating production process are solved, the mechanical strength of the integral catalyst is improved, and the application scene of the catalyst under complex and severe working conditions such as high humidity and high airspeed is expanded;
(2) Compared with the traditional noble metal nanoparticle catalyst, the carrier modified catalyst has a unique valence electronic structure and ideal noble metal utilization rate, and can reduce the noble metal loading rate on the basis of ensuring high VOCs conversion rate, thereby realizing the purpose of reducing the catalyst cost; on the other hand, noble metals are packaged in solid acid in a monoatomic dispersion mode, so that migration and agglomeration phenomena of the noble metals in a high-temperature environment can be inhibited, volatilization, loss and poisoning of the noble metals can be avoided, the purification stability of the catalyst is ensured, and the service life of the catalyst is prolonged;
(3) The solid acid catalyst surface of the present invention has a large number of
Acid sites, when processing chlorine-containing VOCs under special working conditions, can provide enough protons to combine with chlorine to generate HCl, and avoid the generation of Cl with high reactivity and oxidability in the reaction process 2 Thereby inhibiting the generation of secondary organic chlorine-containing pollutants with stronger toxicity and greater harm;
(4) The invention establishes a target guiding strategy of 'working condition-noble metal combination-catalyst', and meets the purpose of accurately designing the high-performance catalyst applied to complex exhaust gas working conditions.
Detailed Description
For better illustrating the present invention, the technical scheme of the present invention is convenient to understand, and the present invention is further described in detail below. The following examples are merely illustrative of the present invention and are not intended to represent or limit the scope of the invention as defined in the claims.
The following are exemplary but non-limiting examples of the invention:
example 1:
the embodiment provides a preparation method of a carrier modified catalyst, which comprises the following steps:
s101, repeatedly washing and drying a main carrier (honeycomb cordierite) by deionized water, transferring the main carrier and 10wt% sodium hydroxide solution into a hydrothermal reaction kettle, reacting for 14 hours at 120 ℃, and after the reaction is finished, washing and drying to obtain a pretreatment carrier;
s102, mixing the fly ash and 5mol/L hydrochloric acid solution according to a mass ratio of 1:5, and then stirring, filtering and drying sequentially to obtain a dried product; mixing and grinding the dried product and sodium hydroxide according to the mass ratio of 1:1, and roasting at 800 ℃ for 3 hours to obtain pretreated fly ash; then mixing and stirring the pretreated fly ash and deionized water according to a mass ratio of 1:5 to obtain a first mixed solution; transferring the first mixed solution and the pretreated carrier in the step (1) into a hydrothermal reaction kettle, reacting for 15 hours at 120 ℃, and washing and drying after the reaction is finished to obtain a fly ash modified carrier;
s103, mixing chloroplatinic acid, ethylenediamine and deionized water according to a molar ratio of 1:25:20000, stirring, then adding tetrapropylammonium hydroxide, sodium metaaluminate and sodium hydroxide for ultrasonic stirring, then slowly adding tetraethoxysilane, and stirring vigorously to obtain a second mixed solution (wherein the molar ratio of sodium metaaluminate to tetraethoxysilane, deionized water, sodium hydroxide and tetrapropylammonium hydroxide is 1:10:200:3:30); transferring the second mixed solution and the fly ash modified carrier into a reaction kettle with a polytetrafluoroethylene lining, crystallizing at 150 ℃ for 98 hours, washing and drying after the reaction is finished, and roasting at 550 ℃ for 5 hours to obtain a molecular sieve catalyst encapsulated with platinum monoatoms;
s104, transferring the prepared molecular sieve catalyst encapsulated with platinum single atoms into an ammonium nitrate solution with the concentration of 2mol/L, reacting for 3 hours at 80 ℃, washing and drying, and roasting for 5 hours at 550 ℃ to obtain the solid acid catalyst encapsulated with platinum single atoms.
In the solid acid catalyst encapsulated with platinum single atoms obtained in this example, the shedding rate of the carrier surface coating was 0.5wt%, at 10000h -1 Under the space velocity condition, the purification efficiency of toluene reaches 99% at 330 ℃; after 20h of operation at 350℃the activity of the catalyst obtained was reduced by 0.5%.
Comparative example 1:
this comparative example provides a preparation method of a carrier modified catalyst, which is different from that in example 1 only in that: step S102 is not carried out, namely the main carrier is not modified by the fly ash, and the rest is unchanged.
In the solid acid catalyst encapsulated with platinum single atoms obtained in this comparative example, the shedding rate of the surface coating layer of the carrier reached 10.3wt%, at 10000h -1 Under the space velocity condition, the purification efficiency of toluene reaches 99% at 360 ℃; after 20h of operation at 350℃the activity decreased by 5.1%.
Example 2:
the embodiment provides a preparation method of a carrier modified catalyst, which comprises the following steps:
s101, repeatedly washing and drying a main carrier (honeycomb mullite) by deionized water, transferring the main carrier and a 10wt% potassium hydroxide solution into a hydrothermal reaction kettle, reacting for 11 hours at 130 ℃, and after the reaction is finished, washing and drying to obtain a pretreated carrier;
s102, mixing the fly ash and 5mol/L hydrochloric acid solution according to a mass ratio of 1:5, and then stirring, filtering and drying sequentially to obtain a dried product; mixing and grinding the dried product and sodium hydroxide according to the mass ratio of 1:1, and roasting at 700 ℃ for 4 hours to obtain pretreated fly ash; then mixing and stirring the pretreated fly ash and deionized water according to a mass ratio of 1:5 to obtain a first mixed solution; transferring the first mixed solution and the pretreated carrier in the step (1) into a hydrothermal reaction kettle, reacting for 12 hours at 150 ℃, and washing and drying after the reaction is finished to obtain a fly ash modified carrier;
s103, mixing and stirring palladium nitrate, ethylenediamine and deionized water according to a molar ratio of 1:25:30000, then adding tetrapropylammonium hydroxide, sodium metaaluminate and sodium hydroxide for ultrasonic stirring, then slowly adding tetraethoxysilane, and vigorously stirring to obtain a second mixed solution (wherein the molar ratio of the sodium metaaluminate to the tetraethoxysilane, the deionized water, the sodium hydroxide and the tetrapropylammonium hydroxide is 1:10:300:3:40); transferring the second mixed solution and the fly ash modified carrier into a reaction kettle with a polytetrafluoroethylene lining, crystallizing for 120 hours at 130 ℃, washing and drying after the reaction is finished, and roasting for 4 hours at 600 ℃ to obtain the molecular sieve catalyst packed with palladium monoatoms;
s104, transferring the prepared molecular sieve catalyst encapsulated with palladium single atoms into an ammonium nitrate solution with the concentration of 2mol/L, reacting for 3 hours at 80 ℃, washing and drying, and roasting for 5 hours at 550 ℃ to obtain the solid acid catalyst encapsulated with palladium single atoms.
In the solid acid catalyst encapsulated with palladium single atoms obtained in this example, the shedding rate of the surface coating of the support was 0.6wt%, at 10000h -1 Under the condition of airspeed, the purification efficiency of chlorobenzene reaches 99% at 427 ℃; after 20h of operation at 500℃the activity of the catalyst obtained was reduced by 0.4%.
Comparative example 2:
this comparative example provides a preparation method of a carrier modified catalyst, which is different from the preparation method in example 2 only in that: in S103, the use amount of palladium nitrate and ethylenediamine is increased to 40 times, namely, the molar ratio of palladium nitrate to ethylenediamine to deionized water is 40:1000:30000, and the rest conditions are unchanged, so that the solid acid catalyst encapsulated with palladium nano particles is obtained.
In the solid acid catalyst encapsulated with palladium nano particles obtained in the comparative example, the shedding rate of the surface coating of the carrier reaches 1.5 weight percent, and 10000 hours -1 Under the condition of airspeed, the purification efficiency of chlorobenzene reaches 99 percent at 435 ℃; after 20h of operation at 500℃the activity decreased by 4.5%.
Example 3:
the embodiment provides a preparation method of a carrier modified catalyst, which comprises the following steps:
s101, repeatedly washing and drying a main carrier (honeycomb cordierite) by deionized water, transferring the main carrier and 10wt% sodium hydroxide solution into a hydrothermal reaction kettle, reacting for 14 hours at 120 ℃, and after the reaction is finished, washing and drying to obtain a pretreatment carrier;
s102, mixing the fly ash and 5mol/L hydrochloric acid solution according to a mass ratio of 1:5, and then stirring, filtering and drying sequentially to obtain a dried product; mixing and grinding the dried product and sodium hydroxide according to the mass ratio of 1:1, and roasting at 800 ℃ for 3 hours to obtain pretreated fly ash; then mixing and stirring the pretreated fly ash and deionized water according to a mass ratio of 1:5 to obtain a first mixed solution; transferring the first mixed solution and the pretreated carrier in the step (1) into a hydrothermal reaction kettle, reacting for 15 hours at 120 ℃, and washing and drying after the reaction is finished to obtain a fly ash modified carrier;
s103, mixing ruthenium chloride, ethylenediamine, diethylenetriamine and deionized water according to a molar ratio of 1:20:20:50000, stirring, then adding tetrapropylammonium hydroxide, sodium metaaluminate and sodium hydroxide for ultrasonic stirring, then slowly adding tetraethoxysilane, and stirring vigorously to obtain a second mixed solution (wherein the molar ratio of sodium metaaluminate to tetraethoxysilane, deionized water, sodium hydroxide and tetrapropylammonium hydroxide is 1:10:600:6:50); transferring the second mixed solution and the fly ash modified carrier into a reaction kettle with a polytetrafluoroethylene lining, crystallizing for 110 hours at 160 ℃, washing and drying after the reaction is finished, and roasting for 4 hours at 550 ℃ to obtain the molecular sieve catalyst encapsulated with ruthenium monoatoms;
s104, transferring the prepared molecular sieve catalyst encapsulated with ruthenium single atoms into an ammonium nitrate solution with the concentration of 2mol/L, reacting for 3 hours at 80 ℃, washing and drying, and roasting for 5 hours at 550 ℃ to obtain the solid acid catalyst encapsulated with ruthenium single atoms.
The seal obtained in this exampleIn the solid acid catalyst containing ruthenium single atom, the shedding rate of the surface coating of the carrier is 0.4 weight percent, and 10000h -1 Under the condition of airspeed, the purification efficiency of chlorobenzene reaches 99% at 425 ℃; in the range of 400-500 ℃, selectivity of HCl>85%, the activity was reduced by 0.2% after running at 500℃for 20 h.
Comparative example 3:
this comparative example provides a preparation method of a carrier modified catalyst, which is different from the preparation method in example 3 only in that: s104 is not performed, and the rest are the same.
In the molecular sieve catalyst encapsulated with ruthenium monoatoms obtained in the comparative example, the shedding rate of the surface coating of the carrier reaches 1.1 weight percent, and 10000 hours -1 Under the condition of airspeed, the purification efficiency of chlorobenzene reaches 99% at 439 ℃; in the range of 400-500 ℃, selectivity of HCl<50%, the activity was reduced by 3.2% after running at 500℃for 20 h.
Example 4:
this example provides a method for preparing a carrier-modified catalyst, which is different from the method of example 1 only in that: in S103, when preparing the second mixed solution, chloroplatinic acid, ruthenium nitrosylnitrate, ethylenediamine and deionized water are mixed according to the molar ratio of 0.5:0.5:25:30000, namely, two noble metal precursors are introduced, and the rest are unchanged.
In the solid acid catalyst encapsulated with platinum/ruthenium single atoms obtained in this example, the shedding rate of the support surface coating was 0.3wt%, at 10000h -1 Under the space velocity condition, the purification efficiency of the methylene dichloride reaches 99 percent at 411 ℃.
Example 5:
this example provides a method for preparing a carrier-modified catalyst, which is different from the method of example 2 only in that: in S103, when preparing the second mixed solution, palladium nitrate, ruthenium chloride, ethylenediamine and deionized water are mixed according to the molar ratio of 0.4:0.6:30:30000, namely, two noble metal precursors are introduced, and the rest is unchanged.
In the solid acid catalyst packed with palladium/ruthenium monoatoms obtained in this example, the surface of the support was coated withThe falling rate of (C) is 0.65wt%, and 10000h -1 Under the space velocity condition, the purification efficiency of the trichloroethylene reaches 99 percent at 395 ℃.
It can be seen from the above examples and comparative examples that the carrier modified catalyst of the present invention significantly improves the overall performance of the catalyst by comprehensively improving and optimizing the original carrier and the active components, is widely applicable to the purification treatment of various complex organic waste gases, and has significant advantages, especially in the treatment of organic waste gases containing heteroatoms such as Cl, and has good application prospects.
The present invention is illustrated by the above examples as products and detailed methods, but the present invention is not limited to the above products and detailed methods, i.e., it is not meant that the present invention must be practiced with the above products and detailed methods. It should be apparent to those skilled in the art that any modifications, equivalent substitutions for operation of the present invention, addition of auxiliary operations, selection of specific modes, etc., are intended to fall within the scope of the present invention and the scope of the disclosure.
Claims (10)
1. The carrier modified catalyst is characterized by comprising a modified carrier and solid acid grafted on the surface of the modified carrier and encapsulating noble metal monoatoms;
the modified carrier comprises a main carrier modified by a solid modifier.
2. The carrier-modified catalyst according to claim 1, wherein the primary carrier comprises cordierite or mullite;
preferably, the main components of the solid modifier include Si, O, al and Mg;
preferably, the solid modifier comprises fly ash.
3. The support modified catalyst of claim 1 or 2, wherein the noble metal comprises any one or a combination of at least two of platinum, ruthenium, or palladium.
4. A method for preparing the carrier-modified catalyst as claimed in any one of claims 1 to 3, comprising the steps of:
(1) Mixing the pretreated main carrier and the pretreated solid modifier with water, and carrying out hydrothermal reaction to obtain a modified carrier;
(2) Mixing the modified carrier in the step (1) with the prepared noble metal precursor mixed solution, and sequentially carrying out crystallization reaction and roasting to obtain a molecular sieve catalyst encapsulated with noble metal monoatoms;
(3) And (3) reacting the molecular sieve catalyst encapsulated with the noble metal monoatoms in the step (2) with an ammonium nitrate solution, and roasting to obtain the solid acid catalyst encapsulated with the noble metal monoatoms.
5. The method for preparing a modified catalyst on a carrier as claimed in claim 4, wherein the method for pretreating the main carrier in the step (1) comprises: mixing the main carrier with an alkali solution, performing hydrothermal reaction, and then sequentially washing and drying to obtain a pretreated main carrier;
preferably, the alkaline solution comprises sodium hydroxide solution and/or potassium hydroxide solution;
preferably, the concentration of the alkaline solution is 10-20wt%;
preferably, in the pretreatment process of the main carrier, the temperature of the hydrothermal reaction is 120-150 ℃ and the time is 10-16h.
6. The method for preparing a carrier-modified catalyst according to claim 4 or 5, wherein the method for pretreating the solid modifier of step (1) comprises: sequentially carrying out acid washing and drying on the solid modifier, mixing with an alkaline substance, and then grinding and roasting to obtain a pretreated solid modifier;
preferably, the acid solution used for pickling comprises hydrochloric acid;
preferably, the concentration of the hydrochloric acid is 1-10mol/L;
preferably, the mass ratio of the solid modifier to the acid liquor is 1 (1-10);
preferably, the alkaline substance comprises any one or a combination of at least two of sodium hydroxide, sodium carbonate, potassium hydroxide or potassium carbonate;
preferably, the mass ratio of the solid modifier to the alkaline substance is 1 (0.5-3);
preferably, in the pretreatment process of the solid modifier, the roasting temperature is 400-900 ℃ and the time is 1-5h.
7. The method for producing a carrier-modified catalyst as claimed in any one of claims 4 to 6, wherein the mass ratio of the pretreated solid modifier to water in the step (1) is 1 (2 to 20);
preferably, the temperature of the hydrothermal reaction in the step (1) is 80-200 ℃;
preferably, the hydrothermal reaction in step (1) takes 4 to 24 hours.
8. The method of any one of claims 4 to 7, wherein the method of preparing the noble metal precursor mixture in step (2) comprises: mixing a noble metal precursor, an organic nitrogen-containing ligand, a template agent, an aluminum source, sodium hydroxide, a silicon source and water to obtain a noble metal precursor mixed solution;
preferably, the molar ratio of the noble metal precursor to the organic nitrogen-containing ligand is 1 (20-50);
preferably, the molar ratio of the aluminum source to the water to the sodium hydroxide to the template agent to the silicon source is 1 (100-1000): (1-10): (5-200): (10-50);
preferably, the molar ratio of the noble metal precursor to the water is 1 (20000-80000);
preferably, the noble metal precursor comprises any one or a combination of at least two of chloroplatinic acid, platinum nitrate, tetraammineplatinum nitrate, ruthenium nitrosylnitrate, ruthenium chloride, palladium nitrate or tetraamminepalladium nitrate;
preferably, the organic nitrogen-containing ligand comprises ethylenediamine and/or diethylenetriamine;
preferably, the template comprises any one or a combination of at least two of N, N-trimethyl-1-adamantane-ammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide or choline chloride;
preferably, the aluminum source comprises any one or a combination of at least two of sodium metaaluminate, aluminum sulfate, aluminum nitrate or aluminum isopropoxide;
preferably, the silicon source comprises any one or a combination of at least two of white carbon black, ethyl orthosilicate, silica sol or methyl orthosilicate;
preferably, the temperature of the crystallization reaction in the step (2) is 120-200 ℃;
preferably, the crystallization reaction time in the step (2) is 72-200h;
preferably, the roasting temperature in the step (2) is 450-650 ℃;
preferably, the roasting time in the step (2) is 2-8h.
9. The method according to any one of claims 4 to 8, wherein the concentration of the ammonium nitrate solution in step (3) is 2 to 3mol// L;
preferably, the temperature of the reaction in step (3) is 70-80 ℃;
preferably, the reaction time of step (3) is 2-6 hours;
preferably, the roasting temperature in the step (3) is 450-650 ℃;
preferably, the roasting time in the step (3) is 1-8h.
10. Use of a carrier-modified catalyst as claimed in any one of claims 1 to 3 for the purification of VOCs.
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Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5783515A (en) * | 1993-09-24 | 1998-07-21 | N.E. Chemcat Corporation | Catalyst for treating exhaust gases containing dioxines, production process for the catalyst and method of treating the exhaust gases |
| JPH1147604A (en) * | 1997-08-06 | 1999-02-23 | Tosoh Corp | Catalyst for combustion and removal of organic compound containing halogen, and combusting and removing method |
| JPH11165073A (en) * | 1997-12-05 | 1999-06-22 | Sumitomo Metal Mining Co Ltd | Oxidation catalyst and production thereof |
| JP2001246253A (en) * | 2000-03-08 | 2001-09-11 | Natl Inst Of Advanced Industrial Science & Technology Meti | Catalyst composition for hydrogenating aromatic hydrocarbon |
| US20150336090A1 (en) * | 2014-05-21 | 2015-11-26 | Council Of Scientific & Industrial Research | Novel oxidation catalyst, the process for the preparation thereof and green process for selective aerobic oxidation |
| CN106362787A (en) * | 2016-08-06 | 2017-02-01 | 浙江大学 | Preparation method for zeolite-immobilized photocatalyst |
| WO2017141132A1 (en) * | 2016-02-18 | 2017-08-24 | Sabic Global Technologies B.V. | Hollow zeolite type catalysts with varying framework and zeolite topologies |
| CN107983401A (en) * | 2017-11-23 | 2018-05-04 | 太原理工大学 | A kind of monoatomic layer Pd catalyst of ZSM-5 encapsulation and its preparation method and application |
| CN113559916A (en) * | 2021-08-27 | 2021-10-29 | 中国科学院山西煤炭化学研究所 | Molecular sieve encapsulated noble metal catalyst and preparation method and application thereof |
| CN114950542A (en) * | 2022-06-02 | 2022-08-30 | 江苏扬农化工集团有限公司 | Bimetal supported molecular sieve catalyst and preparation method and application thereof |
| CN115430427A (en) * | 2022-09-05 | 2022-12-06 | 安庆市长三角未来产业研究院 | Photo-thermal synergistic catalyst for efficiently degrading low-concentration VOCs (volatile organic compounds), and preparation method and application thereof |
-
2023
- 2023-03-10 CN CN202310229430.XA patent/CN116328818A/en active Pending
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5783515A (en) * | 1993-09-24 | 1998-07-21 | N.E. Chemcat Corporation | Catalyst for treating exhaust gases containing dioxines, production process for the catalyst and method of treating the exhaust gases |
| JPH1147604A (en) * | 1997-08-06 | 1999-02-23 | Tosoh Corp | Catalyst for combustion and removal of organic compound containing halogen, and combusting and removing method |
| JPH11165073A (en) * | 1997-12-05 | 1999-06-22 | Sumitomo Metal Mining Co Ltd | Oxidation catalyst and production thereof |
| JP2001246253A (en) * | 2000-03-08 | 2001-09-11 | Natl Inst Of Advanced Industrial Science & Technology Meti | Catalyst composition for hydrogenating aromatic hydrocarbon |
| US20150336090A1 (en) * | 2014-05-21 | 2015-11-26 | Council Of Scientific & Industrial Research | Novel oxidation catalyst, the process for the preparation thereof and green process for selective aerobic oxidation |
| WO2017141132A1 (en) * | 2016-02-18 | 2017-08-24 | Sabic Global Technologies B.V. | Hollow zeolite type catalysts with varying framework and zeolite topologies |
| CN106362787A (en) * | 2016-08-06 | 2017-02-01 | 浙江大学 | Preparation method for zeolite-immobilized photocatalyst |
| CN107983401A (en) * | 2017-11-23 | 2018-05-04 | 太原理工大学 | A kind of monoatomic layer Pd catalyst of ZSM-5 encapsulation and its preparation method and application |
| CN113559916A (en) * | 2021-08-27 | 2021-10-29 | 中国科学院山西煤炭化学研究所 | Molecular sieve encapsulated noble metal catalyst and preparation method and application thereof |
| CN114950542A (en) * | 2022-06-02 | 2022-08-30 | 江苏扬农化工集团有限公司 | Bimetal supported molecular sieve catalyst and preparation method and application thereof |
| CN115430427A (en) * | 2022-09-05 | 2022-12-06 | 安庆市长三角未来产业研究院 | Photo-thermal synergistic catalyst for efficiently degrading low-concentration VOCs (volatile organic compounds), and preparation method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| SILVIYA BOYCHEVA ET AL.: "Plasma-Modified Coal Fly Ash Zeolites with Enhanced Catalytic Efficiency toward the Total Oxidation of Volatile Organic Compounds as Low-Cost Substitutes for Platinum Group Metals Catalysts", 《PHYS. STATUS SOLIDI A》, vol. 219, no. 15, 22 January 2022 (2022-01-22), pages 1 - 11 * |
| YEMIN ZHAO ET AL.: "Ru-based monolithic catalysts for the catalytic oxidation of chlorinated volatile organic compound", 《RSC ADV.》, vol. 13, 1 March 2023 (2023-03-01), pages 7037 - 7044 * |
| 陆强 等: "粉煤灰活化及其制备多孑L催化材料的研究进展", 《洁净煤技术》, vol. 27, no. 3, 5 May 2021 (2021-05-05), pages 1 - 12 * |
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