CN114669296B - Blocky Ru-Pt organic waste gas purifying catalyst and preparation method thereof - Google Patents
Blocky Ru-Pt organic waste gas purifying catalyst and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 80
- 239000007789 gas Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000010815 organic waste Substances 0.000 title claims abstract description 24
- 239000011248 coating agent Substances 0.000 claims abstract description 36
- 238000000576 coating method Methods 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000000919 ceramic Substances 0.000 claims abstract description 20
- 229910052878 cordierite Inorganic materials 0.000 claims abstract description 19
- 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 abstract description 19
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 16
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 12
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 55
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 26
- 239000007788 liquid Substances 0.000 claims description 20
- 239000000843 powder Substances 0.000 claims description 18
- 238000011068 loading method Methods 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000011148 porous material Substances 0.000 claims description 12
- 239000002002 slurry Substances 0.000 claims description 11
- 229910052681 coesite Inorganic materials 0.000 claims description 9
- 229910052906 cristobalite Inorganic materials 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- 229910052682 stishovite Inorganic materials 0.000 claims description 9
- 229910052905 tridymite Inorganic materials 0.000 claims description 9
- 239000004576 sand Substances 0.000 claims description 8
- 238000005470 impregnation Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 229920000875 Dissolving pulp Polymers 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 5
- 238000010521 absorption reaction Methods 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000000354 decomposition reaction Methods 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 3
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- 238000013329 compounding Methods 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 claims description 2
- 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 2
- GTCKPGDAPXUISX-UHFFFAOYSA-N ruthenium(3+);trinitrate Chemical compound [Ru+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GTCKPGDAPXUISX-UHFFFAOYSA-N 0.000 claims description 2
- 230000004913 activation Effects 0.000 claims 1
- 125000004122 cyclic group Chemical group 0.000 claims 1
- 229910000510 noble metal Inorganic materials 0.000 abstract description 12
- 239000002131 composite material Substances 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 9
- 239000002351 wastewater Substances 0.000 abstract description 6
- 239000002912 waste gas Substances 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000007084 catalytic combustion reaction Methods 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000012855 volatile organic compound Substances 0.000 description 6
- 238000011282 treatment Methods 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 3
- 239000000920 calcium hydroxide Substances 0.000 description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000006255 coating slurry Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 229910002848 Pt–Ru Inorganic materials 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N CuO Inorganic materials [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 229910002621 H2PtCl6 Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 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
- 238000004458 analytical method Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- OYJSZRRJQJAOFK-UHFFFAOYSA-N palladium ruthenium Chemical compound [Ru].[Pd] OYJSZRRJQJAOFK-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000012041 precatalyst Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/63—Platinum group metals with rare earths or actinides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
- F23G7/06—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
- F23G7/07—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases in which combustion takes place in the presence of catalytic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G2209/00—Specific waste
- F23G2209/14—Gaseous waste or fumes
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The invention relates to a massive Ru-Pt organic waste gas purifying catalyst and a preparation method thereof, wherein a thin-wall cordierite ceramic honeycomb body is coated with a layer of composite oxide of r-Al 2O3、CeO2, caO and SiO to form a catalyst carrier, and noble metals Ru and Pt are used as main active components. The total mass of the composite oxide coating accounts for 2.0-5.0% of the mass of the carrier. Preferably, the mass ratio of r-Al 2O3、CeO2, caO and SiO is 1: 0.2-0.5:0.05-0.1:0.05-0.1. The total load of the active component Ru-Pt is 0.1-0.5g/L, and the mol ratio of Ru to Pt is 2-10: 1. the blocky Ru-Pt organic waste gas purifying catalyst prepared by the method is relatively low in raw material cost, excellent in catalyst performance, high in activity and good in stability. The whole process of the catalyst preparation process has no waste water and waste gas emission which are harmful to the environment, and is easy for industrial production.
Description
Technical Field
The invention relates to a massive Ru-Pt organic waste gas purifying catalyst and a preparation method thereof. The product is applied to the catalytic purification of industrial organic waste gas, eliminates the harm of organic pollutants to the environment and human health, and belongs to an environment-friendly product. The preparation method and the application thereof belong to the technical field of catalysts.
Background
Industrial organic waste gas is widely involved, and can be generated in the production process of organic chemical industry, pharmaceutical chemical industry, petrochemical industry, paint, coating, printing, automobile, machinery, electronics, furniture and the like. The organic waste gas refers to a gas containing volatile organic matters (Volatile Organic Compounds) (abbreviated as VOC S), such as aromatic hydrocarbons, alkanes, alkenes, ketones, alcohols, aldehydes, acids, esters and organic matters containing Cl, N and S, which are directly harmful to human health if discharged into the atmosphere without treatment, and are also major factors for producing haze and photochemical pollution, so that various methods are necessary for treatment. One of the most effective treatments is the catalytic combustion method-! The catalytic combustion has high purification rate, no secondary pollution, low energy consumption, energy conservation and emission reduction. Catalytic combustion processes for purifying organic exhaust gases are widely accepted and employed technologies, the core of which is a catalyst.
Catalytic combustion catalysts are defined from the main active component as two broad categories, noble metal type and non-noble metal type. The organic waste gas purifying catalyst actually applied in the market at present is a supported catalyst mainly of noble metal type, which takes Pt, pd or a combination of Pt and Pd, or a combination of Pt, pd and Ph (such as a ternary catalyst for purifying automobile tail gas) as an active component, and has a block shape and a particle shape. Because of high activity and good stability, and wide adaptability (broad spectrum) to different types of VOCs, the method is long-lived and does not decline-! However, because of scarce resources and high price, the materials are also easy to be poisoned by Cl, S, as, P, pb and other elements, therefore, the application is also limited and restricted to a certain extent,
Scientists engaged in catalyst research are in a thousand ways searching for assistants and substitute elements of noble metals or innovative preparation process, aiming at reducing the content of noble metals and providing a catalyst with high activity and stability. As early as 80 th century, modified natural mordenite is used as a carrier to load trace (0.02-0.05%) of Pt or Pd to prepare a catalyst with excellent performance, and the catalyst can be widely popularized and applied in the tin printing and coating industries and is exported to Japan in batches of 87 years.
The research and development of noble metal catalysts have been many since this century, and the patent application is not few, and the patent selection of some disclosed massive noble metal organic waste gas purifying catalysts can be generally seen:
[ CN106378132A ] cordierite ceramic honeycomb bodies supported catalysts examples 4-7 had Pd contents of 0.09 to 0.18wt% and Pt of 0.12 to 0.27wt%. And nitrate such as Zr, K, rh, ca, mg, na and the like are respectively added as auxiliary agents.
[ CN107876050A ] Pd, pt, ph 0.6-2.0 g/L.
[ CN10831472A ] Pd, the total mass of Pt is 0.5-2.5g/L.
[ CN103831104A ] Pd, the total Pt content was 0.55g/L.
Ru has less application reports in catalytic combustion catalysts. [ CN1251322A ] example 3, the active component is 0.06% Pt-Pd-Ru, example 4, the active component is 0.1% Pd-Ru, and the preparation method is relatively complex when being applied to the treatment of CO, organic wastewater COD and NH 3 -N respectively.
In the embodiment 10 in the [ CN113996291A ], the Pt-Ru catalyst loaded on the CuO and TiO 2,Al2O3,SiO2 composite oxide carrier has high catalytic activity on dichloromethane and bromomethane, the loading amount of Pt-Ru is higher than 1%, the mass ratio of Pt to Ru is 4:1, the Pt is taken as a main material, the production process is complex, and the problems of waste gas and waste water are caused.
The information shows that the loading of noble metal in the prior art is relatively high, even if the minimum amount of noble metal is 500g per cubic meter of catalyst, if the maximum amount of noble metal is 2500g, the useful weight percentage is usually 0.09-0.27wt% or higher, the useful amount is even more than 1%, the raw material cost is high, and the preparation process is complex. Some of the support or coating materials are selected from nitrates of the relevant metal elements, such as cerium nitrate, zirconium nitrate, copper nitrate, manganese nitrate, aluminum chloride, and the like. The noble metal active components are reduced by alkaline solution such as (NaOH and KOH) reducing agent after being immersed, and are required to be washed to be neutral, and the problems of waste gas and waste water are unavoidable in industrial mass production.
The monolithic industrial application catalyst which takes Ru-Pt mainly as an active component and has broad-spectrum excellent catalytic activity under low load is not discovered up to the present.
Disclosure of Invention
The invention aims to provide a massive Ru-Pt organic waste gas purifying catalyst and a preparation method thereof, aiming at the defects of the prior art. The invention takes Ru as the main component, adds a small amount of Pt, takes Ru-Pt as the main active component, is loaded on the carrier of the thin-wall cordierite ceramic honeycomb body coated with the r-Al 2O3、CeO2、CaO、SiO2 composite oxide, can obtain the industrial practical catalyst with high activity, good stability and broad spectrum under low loading, and has simple and environment-friendly preparation method.
The technical scheme adopted by the invention is as follows:
a monolithic Ru-Pt organic waste gas purifying catalyst uses a commercial thin-wall cordierite ceramic honeycomb body (preferably with a pore density of 200-300 pores/inch 2) coated with a composite oxide coating as a catalyst carrier, wherein the oxide coating comprises r-Al 2O3、CeO2, caO and SiO 2, and the total mass of the oxide coating is 2.0-5.0% of the mass of the catalyst carrier. Active components Ru and Pt are loaded on the catalyst carrier, the total loading capacity of the active components is 0.1-0.5g/L, and the molar ratio of Ru to Pt is 2-10: 1.
Wherein, the mass ratio of the r-Al 2O3、CeO2、CaO、SiO2 is 1: 0.2-0.5:0.05-0.1:0.05-0.1
The method for preparing the massive Ru-Pt organic waste gas purifying catalyst is prepared by adopting the physical processes of powder sanding into slurry and coating by an impregnation method, and is environment-friendly, and the method specifically comprises the following steps:
1) Preparation of the coating: weighing micron-sized r-Al 2O3 powder, micron-sized Ce (OH) 3、Ca(OH)2 and H 2 O in a sand mill, circularly grinding for a certain time, discharging and standing for more than 24 hours, and enabling dissolving pulp to be basically uniform up and down without layering and sinking;
2) And (3) coating preparation: adjusting the concentration of the obtained dissolving pulp of 1) according to the requirements of the water absorption rate and the coating load capacity of the cordierite ceramic honeycomb body, and adding neutral silica sol to ensure that the dissolving pulp density d=1.04-1.09; dipping the cordierite ceramic honeycomb body into the solution for 30-60 sec, taking out the slurry which is blown off by compressed air and remains around the honeycomb body pore canal and is recycled, standing and drying in the shade for 12-24h;
3) Coating bonding: placing the cordierite ceramic honeycomb body obtained in the step 2) in a high-temperature oven, heating to 100-120 ℃ and preserving heat for 1-2h, heating to 450-550 ℃ and preserving heat for 3-5h, and cooling to obtain a catalyst carrier;
4) Loading active components: immersing the catalyst carrier obtained in the step 3) in precursor liquid of active components Ru and Pt for 3-5sec, and taking out liquid (recycling) remained in the pore canal and around by blowing compressed air.
In the above scheme, further, the r-Al 2O3 powder is formed by compounding three types of r-Al 2O3 powder with three different crystallinity degrees, different fineness and different viscosity, and the three types are micron-sized r-Al 2O3 powder 404, 401 and 409 which is specially used for coating and is produced by Jiangsu crystal new material Co., ltd; in the coating manufacturing process, the properties, proportion and uniformity of oxide powder and coating slurry influence the bonding strength, temperature resistance, specific surface area and space structure of the coating, and finally influence the dispersity and electronic structure of active components and the synergistic effect of acid-base property.
Further, the rotational speed of the sand mill in the step 1) is 1100-1600 rpm, and the sand mill is circularly ground for 60-120min.
Further, the precursor of the active components Ru and Pt in 4) can be ruthenium chloride, ruthenium nitrate, chloroplatinic acid, platinum chloride and platinum nitrate. Ruthenium chloride and chloroplatinic acid are preferred.
Further, in the step 4), after the active component precursor liquid is immersed, the active component precursor liquid is taken out and is heated, decomposed and activated by microwaves, or is taken out and is kept stand for 8-24 hours, and then is placed in a high-temperature oven at 100-120 ℃ for heat preservation for 1-2 hours, and is then heated to 400-500 ℃ for heat preservation for 3-5 hours, so that the catalyst is obtained. Preferably, the microwave heating decomposition is carried out, the output power of the microwave is usually 5-25 KW, the holding time is 5-15 min, and the power and the residence time of the microwave can be set according to the treatment amount. The precursor solution of the active component is immersed and loaded on the catalyst carrier and decomposed by microwave heating, which is more beneficial to the coupling of Ru and Pt in the high-dispersity space structure, electronic structure and acid-base generated by the r-Al 2O3、CeO2、CaO、SiO2 composite oxide coating, thus constructing the catalytic active group. The rate of supplying [ O ] (active oxygen) and the recovery rate of [ O ] of the active group in the catalytic combustion reaction process are balanced, so that the catalytic combustion reaction process runs stably.
The beneficial effects of the invention are as follows:
1. Ru and Pt are used as active components, ru is used as a main component in the active components, a layer of r-Al 2O3、CeO2、CaO、SiO2 composite oxide is coated on a thin-wall cordierite ceramic honeycomb body as a catalyst carrier, and the active components are impregnated and loaded; obtaining a catalyst; in the catalyst, ru-Pt has co-catalysis effect, the loading of the composite oxide is only 2.0-5.0% of that of the catalyst carrier, more importantly, the total loading of active component Ru-Pt in the catalyst is only 0.1-0.5g/L (less than 500g per cubic meter of catalyst and equivalent to 0.016-0.085wt% after conversion), and Ru is taken as the main component in Ru-Pt, so that the catalyst cost can be greatly reduced.
2. The invention has low active component load, and the prepared catalyst has high catalytic activity against various industrial organic waste gases such as toluene, normal hexane, cyclohexanone, ethyl acetate and butanol, has low initial reaction temperature for the complete oxidation of different types of VOCs, and has quite good catalytic activity. The prepared catalyst is a very practical industrial organic waste gas purifying catalyst with broad spectrum.
3. The catalyst disclosed by the invention has no emission of waste such as waste gas and waste water which are harmful to the environment in the preparation process, and is different from the existing catalyst preparation method, and the existing catalyst preparation process usually generates emission of waste water or waste gas as described in the previous background materials.
Detailed Description
In the following examples, the catalyst activity was evaluated by selecting the common pollutants of industrial organic waste gas, such as toluene, n-hexane, cyclohexanone, ethyl acetate and butanol, as representative examples. But the effectiveness is not limited to these ingredients.
Airspeed: 20000h -1
Concentration: 2000-6000mg/m 3
The catalyst dosage is 20-25ml. Taking a block from the massive catalyst, making the block into a cylinder, putting the cylinder into a stainless steel tube, and heating the stainless steel tube in a tube furnace.
The analysis method of the organic matters comprises the following steps:
Gas chromatograph, capillary chromatographic column separation, hydrogen flame ionization detection.
And (3) data processing: an N2000 type data processing station.
Example 1
1. Preparing a coating slurry: the micron-sized r-Al 2O3 powder 404 and 401 are weighed into 200g and 409 respectively: 100g, micron-sized Ce (OH) 3：120g,Ca(OH)2：10g,H2 O:5000g is placed in a charging basket of a sand mill, the rotation speed of the sand mill is started to 1300 revolutions per minute, the sand mill is circularly sanded for 90 minutes, the sand mill is discharged for 24 hours, the coating slurry is not layered and is not sunk, and the upper and lower parts are basically uniform.
2. And (3) preparing a coating:
① The cordierite ceramic honeycomb body (200 holes/inch 2) [100 x 50]10 pieces are weighed to be 2650.8g in total mass, 265.1g in average mass, immersed in clean water for 30 minutes, taken out, and the residual water quantity in the pore channels and the periphery of the honeycomb body is blown out by compressed air, and the total mass is weighed to be 3233.1g, the increment is 582.3g, and the average water absorption rate is 22.0%.
② Taking 1/2 of the total sol in the step 1, regulating the density of the sol to about 1.06 by using H 2 O, adding 100ml of neutral silica sol, and fully and uniformly stirring.
③ 10 Cordierite ceramic honeycomb bodies were immersed in the sol slurry obtained by ② for 30-60sec and taken out, and the residual slurry around the honeycomb channels and the periphery was blown off (recycled) with compressed air. And (5) placing in the shade and drying for 24 hours.
④ Coating bonding: and (3) placing the ceramic honeycomb body which is coated with r-Al 2O3,Ce(OH)3,Ca(OH)2, silica sol slurry and dried in the shade and is obtained by ③ in a high-temperature furnace, heating to 120 ℃, preserving heat for 2 hours, heating to 500 ℃, preserving heat for 4 hours, and cooling to obtain the catalyst carrier. The total mass of the alloy is as follows: 2716.4g, increment of 65.6g, and total mass of the average r-Al 2O3、CeO2、CaO、SiO2 composite oxide accounting for 2.5% of the carrier.
3. Preparation of active liquid: according to Ru: mole ratio of Pt 4:1 RuCl 3,H2PtCl6 is weighed to prepare active liquid with concentration of 0.30 percent.
4. Loading of active liquid: and (3) immersing the cordierite ceramic honeycomb carrier prepared in the step (2) in the active liquid prepared in the step (3) for 3-5sec, taking out, and blowing off residual liquid around the pore channels of the honeycomb carrier by using compressed air (recycling). Decomposing by microwave heating. Based on the theoretical amount of the configuration (the same in each example below), the total Ru-Pt loading was 0.35g/L.
5. The activity of the catalyst was summarized according to the above-mentioned process conditions and evaluation results.
Example 2
The catalyst carrier was the same as in example 1, and the active liquid preparation method was the same as in example 1, except that the active component Ru: the molar ratio of Pt is 3:1, and the concentration of the active liquid is 0.20%. The impregnation method was carried out in the same manner as in example 1, except that the total loading of Ru-Pt was 0.23g/L.
Example 3
The catalyst support, active component solution formulation, loading method and drying decomposition were the same as in example 1, except that the active component Ru: the Pt molar ratio was 5:1, the concentration of the active solution is 0.38%, and the total load of Ru-Pt is 0.44g/L.
Example 4
The catalyst support was prepared in the same manner as in example 1, except that the sol slurry remaining in example 1 was applied twice, and the thickness of the coating was increased so that the total mass of r-Al 2O3、CeO2、CaO、SiO2 was 4.6% of the support. The preparation method of the active solution, the impregnation loading and the dry decomposition method are the same as in example 1, ru: the molar ratio of Pt is 2:1, the concentration of the active liquid is 0.25%, and the total Ru-Pt load is 0.29g/L.
Example 5
The catalyst carrier was the same as in example 4. Unlike example 4, ru: the molar ratio of Pt is 4:1, the concentration of the active liquid is 0.16%, and the total load of Ru and Pt is 0.19g/L.
Example 6
The preparation method of the catalyst carrier is the same as in example 1, except that the micron-sized r-Al 2O3 is changed to 400g, the micron-sized Ce (OH) 3 is changed to 200g, the slurry density is adjusted to d=1.08, and the total mass of the coating r-Al 2O3、CeO2、CaO、SiO2 accounts for 3.2% of the carrier. The active solution was formulated, impregnated, dry decomposed as in example 1, except for Ru: the molar ratio of Pt is 6:1, the concentration of the active liquid is 0.2%, and the total load of Ru-Pt is 0.25g/L.
Example 7
The catalytic support was the same as in example 6, except for Ru: the molar ratio of Pt was 8:1, the concentration of the active liquid is 0.25%, and the total load of Ru-Pt is 0.30g/L.
Results of evaluation of catalyst Activity, summary of removal rate of VOCs
* DEG C refers to the pre-heat temperature of the simulated exhaust, i.e., the pre-catalyst inlet temperature.
As can be seen from the table, the massive Ru-Pt organic waste gas purifying catalyst has low initial reaction temperature for the complete oxidation of different types of VOCs, and has quite good catalyst activity. Small batches of products with preferable formulas are applied and inspected in relevant factories for treating organic waste gas.
Claims (9)
1. A massive Ru-Pt organic waste gas purifying catalyst is characterized in that:
The catalyst takes a thin-wall cordierite ceramic honeycomb body coated with an oxide coating as a catalyst carrier, wherein the oxide coating comprises r-Al 2O3、CeO2, caO and SiO 2, the total mass of the oxide coating is 2.0-5.0% of the mass of the catalyst carrier, active components Ru and Pt are loaded on the catalyst carrier, the total loading of the active components is 0.1-0.5g/L, and the molar ratio of Ru to Pt is 2-10: 1, a step of; the preparation method of the coating adopts a physical process of powder sanding into slurry and coating by an impregnation method, and specifically comprises the following steps:
1) Preparation of the coating: weighing micron-sized r-Al 2O3 powder, micron-sized Ce (OH) 3 powder, ca (OH) 2 powder and H 2 O, circularly grinding for a certain time at a high speed, discharging and standing for more than 24 hours, wherein the dissolving pulp is not layered and does not sink, and is basically uniform up and down;
2) And (3) coating preparation: according to the requirements of the water absorption rate and the coating load of the cordierite ceramic honeycomb body, adding neutral silica sol and H 2 O into the obtained solution, so that the solution density d=1.04-1.09; dipping the cordierite ceramic honeycomb body into the solution for 30-60 sec, taking out the slurry which is blown off by compressed air and remains around the honeycomb body pore canal, standing and drying in the shade for 12-24h;
3) Coating bonding: placing the cordierite ceramic honeycomb body obtained in the step 2) into a high-temperature oven, heating to 100-120 ℃ and preserving heat for 1-2h, heating to 450-550 ℃ and preserving heat for 3-5h, and cooling to obtain a catalyst carrier;
4) Loading active components: immersing the catalyst carrier obtained in the step 3) in precursor liquid of active components Ru and Pt for 3-5sec, and taking out liquid remained in pore channels and around by using compressed air.
2. The bulk Ru-Pt organic exhaust gas purifying catalyst as claimed in claim 1, wherein the mass ratio of r-Al 2O3、CeO2、CaO、SiO2 is 1: 0.2-0.5:0.05-0.1:0.05-0.1.
3. The bulk Ru-Pt organic exhaust gas purifying catalyst of claim 1, wherein said thin wall cordierite ceramic honeycomb body has a pore density of from 200 to 300 pores per inch 2.
4. The method for preparing the massive Ru-Pt organic waste gas purifying catalyst according to claim 1, wherein the preparation method of the coating is prepared by adopting a physical process of powder sanding into slurry and coating by a dipping method, and specifically comprises the following steps:
1) Preparation of the coating: weighing micron-sized r-Al 2O3 powder, micron-sized Ce (OH) 3 powder, ca (OH) 2 powder and H 2 O, circularly grinding for a certain time at a high speed, discharging and standing for more than 24 hours, wherein the dissolving pulp is not layered and does not sink, and is basically uniform up and down;
2) And (3) coating preparation: according to the requirements of the water absorption rate and the coating load of the cordierite ceramic honeycomb body, adding neutral silica sol and H 2 O into the obtained solution, so that the solution density d=1.04-1.09; dipping the cordierite ceramic honeycomb body into the solution for 30-60 sec, taking out the slurry which is blown off by compressed air and remains around the honeycomb body pore canal, standing and drying in the shade for 12-24h;
3) Coating bonding: placing the cordierite ceramic honeycomb body obtained in the step 2) into a high-temperature oven, heating to 100-120 ℃ and preserving heat for 1-2h, heating to 450-550 ℃ and preserving heat for 3-5h, and cooling to obtain a catalyst carrier;
4) Loading active components: immersing the catalyst carrier obtained in the step 3) in precursor liquid of active components Ru and Pt for 3-5sec, and taking out liquid remained in pore channels and around by using compressed air.
5. The method for preparing the massive Ru-Pt organic waste gas purifying catalyst according to claim 4, wherein the r-Al 2O3 powder is formed by compounding three types of r-Al 2O3 powder with different crystallinity, fineness and viscosity in a micron level, and the three types are micron-level r-Al 2O3 powder 404, 401 and 409 specially used for coating and produced by Jiangsu crystal new materials.
6. The method for preparing a bulk Ru-Pt organic exhaust gas purifying catalyst according to claim 4, wherein 1) the rotation speed of the sand mill is 1100-1600 rpm, and the cyclic grinding is performed for 60-120 min.
7. The method for preparing a monolithic Ru-Pt organic waste gas purifying catalyst as claimed in claim 4, wherein the precursors of Ru and Pt as the active components in 4) are selected from ruthenium chloride, ruthenium nitrate and chloroplatinic acid, platinum chloride, and platinum nitrate.
8. The method for preparing a block-shaped Ru-Pt organic waste gas purifying catalyst according to claim 4, wherein in 4), after the impregnation of the active component precursor liquid, the catalyst is prepared by taking out, performing microwave heating decomposition and activation, or taking out, standing for 8-24h after the impregnation, placing in a high-temperature oven at 100-120 ℃ for 1-2h, and then heating to 400-500 ℃ for 3-5 h.
9. The method for preparing a bulk Ru-Pt organic waste gas purifying catalyst as claimed in claim 8, wherein the microwave output power is 5-25 KW and the residence time is 5-15 min.
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