CN115106101A - Low-carbon oxygen-containing organic waste gas ruthenium-based noble metal combustion catalyst and preparation method and application thereof - Google Patents
Low-carbon oxygen-containing organic waste gas ruthenium-based noble metal combustion catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 93
- 239000007789 gas Substances 0.000 title claims abstract description 55
- 239000010815 organic waste Substances 0.000 title claims abstract description 37
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 28
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 22
- 238000002485 combustion reaction Methods 0.000 title claims abstract description 19
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000007084 catalytic combustion reaction Methods 0.000 claims abstract description 23
- 239000002131 composite material Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 19
- 238000011068 loading method Methods 0.000 claims abstract description 14
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 14
- 229910002848 Pt–Ru Inorganic materials 0.000 claims abstract description 11
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 4
- 229910052802 copper Inorganic materials 0.000 claims abstract description 4
- SKEYZPJKRDZMJG-UHFFFAOYSA-N cerium copper Chemical group [Cu].[Ce] SKEYZPJKRDZMJG-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000010949 copper Substances 0.000 claims description 33
- 239000000203 mixture Substances 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical group O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 claims description 10
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical group O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 150000000703 Cerium Chemical class 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 150000001879 copper Chemical class 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- BIXNGBXQRRXPLM-UHFFFAOYSA-K ruthenium(3+);trichloride;hydrate Chemical group O.Cl[Ru](Cl)Cl BIXNGBXQRRXPLM-UHFFFAOYSA-K 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 3
- 230000032683 aging Effects 0.000 claims description 3
- 150000004687 hexahydrates Chemical class 0.000 claims description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000005457 ice water Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 13
- 238000007254 oxidation reaction Methods 0.000 abstract description 7
- 230000003647 oxidation Effects 0.000 abstract description 6
- 238000002372 labelling Methods 0.000 abstract description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 11
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 229910052763 palladium Inorganic materials 0.000 description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 7
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 239000006004 Quartz sand Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000010718 Oxidation Activity Effects 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 3
- CFQCIHVMOFOCGH-UHFFFAOYSA-N platinum ruthenium Chemical compound [Ru].[Pt] CFQCIHVMOFOCGH-UHFFFAOYSA-N 0.000 description 3
- 239000012855 volatile organic compound Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910000929 Ru alloy Inorganic materials 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- CSJDCSCTVDEHRN-UHFFFAOYSA-N methane;molecular oxygen Chemical compound C.O=O CSJDCSCTVDEHRN-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910001260 Pt alloy Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- OYJSZRRJQJAOFK-UHFFFAOYSA-N palladium ruthenium Chemical compound [Ru].[Pd] OYJSZRRJQJAOFK-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/894—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 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
-
- 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
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- 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
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- Chemical Kinetics & Catalysis (AREA)
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- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
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Abstract
The invention discloses a low-carbon oxygen-containing organic waste gas ruthenium-based noble metal combustion catalyst, and a preparation method and application thereof, wherein the catalyst is a copper-cerium composite oxide CuCeO x Loading Ru and Pt active components on carrier as carrier, and labeling it as Pt-Ru/CuCeO x A catalyst; wherein, CuCeO x The molar weight of Ce element in the carrier is 90-99% of the sum of the molar weights of Cu and Ce, the loading amount of Pt in the catalyst is 0.01-0.2 wt%, and the loading amount of Ru is 0.1-1.0 wt%. The catalyst prepared by the method is particularly suitable for low-temperature catalytic combustion of ethylene oxide, the complete oxidation temperature of the catalyst is only about 120 ℃, the catalyst has good catalytic activity on various low-carbon oxygen-containing organic waste gases, and the catalyst has great industrial application potential and value.
Description
Technical Field
The invention relates to the technical field of catalytic combustion of low-carbon oxygen-containing organic waste gas, in particular to a ruthenium-based noble metal combustion catalyst for low-carbon oxygen-containing organic waste gas and a preparation method and application thereof.
Background
The low-carbon oxygen-containing organic waste gas is a part of oxygen-containing volatile organic compounds (OVOCs), such as: methanol, formaldehyde, ethylene oxide, ethyl acetate, butanone, etc., which play an important role in atmospheric photochemical circulation, can be further oxidized to form secondary atmospheric pollution, such as ozone (O) 3 ) And Secondary Organosols (SOA).
At present, the treatment of oxygen-containing volatile organic compounds mainly comprises a direct combustion method, an adsorption method, an absorption method, a hydration method and the like, but the treatment method has certain safety problems and economic problems due to the characteristics of extremely low boiling point, flammability, explosiveness and the like of some low-carbon oxygen-containing organic waste gases. The catalytic combustion technology is an effective method for degrading VOCs, and the core of the technology is a catalytic oxidation catalyst. The low-carbon oxygen-containing organic exhaust gas catalytic oxidation catalyst widely used at present is a noble metal catalyst and a composite oxide catalyst which take Pt and Pd as active components, wherein the noble metal platinum (Pt) and palladium (Pd) catalysts show very excellent activity, for example, patent CN110743545A discloses an ethylene oxide double-active site combustion catalyst and preparation and application thereof, one of single noble metals Pt, Pd and Au is loaded on an integral catalyst of any two of composite metals Co, Zn, Cu, Ce, Ni and Mn, the catalyst makes a breakthrough in ethylene oxide combustion, and the conversion rate of 90 percent still needs about 150 ℃. Patent CN110075887A provides a preparation method and application of a Pd-supported catalyst for methanol catalytic combustion, the catalyst utilizes the characteristic of high specific surface area of alumina, Pd and P-doped manganese oxide are highly dispersed on the surface of the alumina, more surface active sites are constructed, and excellent methanol catalytic combustion performance is shown.
However, the Pt and Pd noble metal catalysts belong to strategic resources, have low earth abundance and high cost, and whether high-efficiency combustion catalysts with low cost and low noble metal content can be developed is a hot spot of research of scientific workers. Ruthenium (Ru) is a noble metal that is less expensive than platinum and palladium, and exhibits superior performance in some hydrogenation and partial oxidation reactions. Patent CN106391001A discloses an activated carbon supported ruthenium-platinum bimetallic composite catalyst, which shows excellent activity in the synthesis of L-aminopropanol. The patent CN113578316A provides a supported porous nano platinum ruthenium alloy catalyst, which shows good hydrogenation activity in the o- (m, p) -chloronitrobenzene hydrogenation reaction. Patent CN113198465A provides a ruthenium-platinum alloy catalyst and a preparation method thereof, and is successfully applied to catalytic degradation of aromatic hydrocarbon compounds. In view of the similar oxidation characteristics of Ru and Pt and Pd catalysts, when Ru partially replaces Pt and Pd, the catalyst forming Pt-Ru and Pd-Ru alloy has more advantages in catalytic combustion of low-carbon oxygen-containing organic waste gas, and an innovative idea is provided for finding a novel low-cost catalyst.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention aims to provide a high-efficiency and stable low-carbon oxygen-containing organic waste gas ruthenium-based noble metal combustion catalyst, and a preparation method and application thereof.
The invention is realized by the following technical scheme:
the low-carbon oxygen-containing organic waste gas ruthenium-based noble metal combustion catalyst is characterized in that the catalyst is a copper-cerium composite oxide CuCeO x Loading Ru and Pt active components on carrier as carrier, and labeling it as Pt-Ru/CuCeO x A catalyst; wherein, CuCeO x The molar weight of Ce element in the carrier is 90-99%, preferably 97-99% of the sum of the molar weights of Cu and Ce; the supported amount of Pt in the catalyst is 0.01-0.2 wt%, preferably 0.05-0.1 wt%, and the supported amount of Ru is 0.1-1.0 wt%, preferably 0.5-1.0 wt%.
The preparation method of the low-carbon oxygen-containing organic waste gas ruthenium-based noble metal combustion catalyst is characterized by comprising the following specific preparation steps of:
1) dissolving cerium salt and copper salt in water according to the molar ratio of Cu to Ce, adjusting the pH to 9.0-11.0 by using ammonia water or NaOH solution, stirring the mixture for 2-4 hours, standing and aging at room temperature for 10-12 hours, filtering and removingWashing the washed seed crystals for multiple times until the filtrate is neutral, drying, calcining for 2-4 hours at 450-600 ℃ in air atmosphere to obtain CuCeO x A composite oxide powder;
2) mixing CuCeO x Dispersing the composite oxide powder in an Ru salt aqueous solution, stirring the obtained mixture in a water bath at 65-85 ℃ for 1-3 hours, filtering, drying, calcining at 350-450 ℃ for 3-5 hours in an air atmosphere to obtain the CuCeO loaded with the Ru element x Composite powder, labeled as Ru/CuCeO x A composite powder;
3) mixing Ru/CuCeO x Dispersing the composite powder in a Pt precursor aqueous solution, stirring the obtained mixture in a water bath at 65-85 ℃ for 1-3 hours, filtering, dispersing the obtained solid in deionized water, adding an excessive hydrazine hydrate solution, reacting the mixture at 65-85 ℃ for 1-3 hours, completely reducing Pt element into a metal simple substance, filtering, drying, calcining at 350-450 ℃ for 2-4 hours in an air atmosphere to obtain Pt-Ru/CuCeO x A catalyst.
The preparation method of the low-carbon oxygen-containing organic waste gas ruthenium-based noble metal combustion catalyst is characterized in that cerium salt is cerium nitrate hexahydrate, copper salt is copper nitrate trihydrate, Ru salt is ruthenium trichloride hydrate, and a Pt precursor is chloroplatinic acid hexahydrate.
The preparation method of the low-carbon oxygen-containing organic waste gas ruthenium-based noble metal combustion catalyst is characterized in that in the step 1), the concentration of ammonia water or NaOH solution is 0.5-2M, and 1M is preferred.
The low-carbon oxygen-containing organic waste gas ruthenium-based noble metal combustion catalyst is applied to low-temperature catalytic combustion of low-carbon oxygen-containing organic waste gas, the catalyst is filled in a tubular reactor, and the low-carbon oxygen-containing organic waste gas and air are introduced into the tubular reactor together for catalytic combustion reaction.
The low-carbon oxygen-containing organic waste gas ruthenium-based noble metal combustion catalyst is applied to low-temperature catalytic combustion of the low-carbon oxygen-containing organic waste gas, the low-carbon oxygen-containing organic waste gas is ethylene oxide, the concentration of the ethylene oxide is less than 10000ppm, the ethylene oxide feed gas passes through an ice water bath at 0 ℃, is mixed with air and is introduced into a tubular reactor for catalytic combustion reaction, and the catalytic combustion reaction temperature is 120 ℃.
The beneficial effects obtained by the invention are as follows:
adopts chloroplatinic acid hexahydrate (H) 2 PtCl 6 ·6H 2 O), ruthenium trichloride hydrate (RuCl) 3 ) Cerium nitrate hexahydrate (Ce (NO) 3 ) 3 ·6H 2 O), copper nitrate trihydrate (Cu (NO) 3 ) 2 ·3H 2 O) as main material and adopting precipitation method to prepare CuCeO x The composite oxide carrier is prepared by loading Ru and Pt step by adopting a co-impregnation method to prepare Pt-Ru/CuCeO x Catalyst, catalyst of CuO 2 /CeO 2 The molar ratio of (A) to (B) is 1-10: 99-90, simple preparation process and low catalyst cost, and is a high-efficiency and stable low-carbon oxygen-containing organic waste gas combustion catalyst. The catalyst prepared by the method is particularly suitable for low-temperature catalytic combustion of ethylene oxide, the complete oxidation temperature of the catalyst is only about 120 ℃, the catalyst has good catalytic activity on various low-carbon oxygen-containing organic waste gases, and the catalyst has great industrial application potential and value.
Drawings
FIG. 1 is a graph showing the relationship between the amount of Cu ion doped and the conversion rate of ethylene oxide.
FIG. 2 is a graph of Pt-Ru loading versus ethylene oxide conversion.
Detailed Description
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.
Example 1
The first step is as follows: 42.9878g of cerium nitrate hexahydrate and 0.2416g of copper nitrate trihydrate were dissolved in 100mL of deionized water, and the pH was adjusted to 10.0 by dropwise addition of an aqueous ammonia solution having a concentration of 1mol/L with vigorous stirring. Stirring the mixture for 3 hours, standing and aging for 12 hours at room temperature, then filtering, washing for multiple times by deionized water until the filtrate is neutral, drying for 12 hours at 110 ℃, calcining for 4 hours at 550 ℃ to prepare Cu 1 Ce 99 O x Composite oxide, the molar ratio of Cu/Ce is 1: 99;
the second step is that: 2.0mL of ruthenium chloride solution (Ru concentration in solution is 2.5g/L) was dissolved in 20mL of deionized water, and 1g of step-CuCeO x Dispersing the composite oxide powder in ruthenium chloride solution, stirring the obtained mixture in 75 ℃ water bath for 1 hour, filtering, drying at 100 ℃ for 1 hour, calcining at 400 ℃ for 4 hours to obtain CuCeO loaded with Ru element x Composite powder, with a loading of 0.5 wt.% of Ru element, labeled as 0.5 wt.% Ru/Cu 1 Ce 99 O x Composite (same as in the examples below);
the third step: 0.4mL of chloroplatinic acid solution (Pt concentration in solution is 2.5g/L) was dissolved in 20mL of deionized water, and the 0.5 wt.% Ru/CuCeO obtained in step two was added x The complex powder was dispersed in a chloroplatinic acid solution, the resulting mixture was stirred in a water bath at 75 ℃ for 1 hour and then filtered, and the resulting solid was dissolved in an additional 20mL of deionized water together with 140. mu.L of 85% hydrazine hydrate solution. Reacting the mixture at 75 deg.C for 1 hr, drying at 100 deg.C for 1 hr, calcining at 400 deg.C for 4 hr to obtain 0.1wt% Pt-0.5 wt.% Ru/Cu 1 Ce 99 O x A catalyst.
Example 2
The same procedure as in the first step of example 1 was followed, except that: the dosage of cerous nitrate hexahydrate is changed to 43.422g, the dosage of copper nitrate trihydrate is changed to 0g, and the molar ratio of Cu/Ce in the catalyst is 0: 100. finally preparing the catalyst Cu 0 Ce 100 O x 。
Example 3
The same procedure as in the first step of example 1 was followed, except that: the dosage of cerous nitrate hexahydrate is changed to 42.5536g, the dosage of copper nitrate trihydrate is changed to 0.4832g, and the molar ratio of Cu/Ce in the catalyst is 2: 98. finally preparing the catalyst Cu 2 Ce 98 O x 。
Example 4
The same procedure as in the first step of example 1 was followed, except that: the dosage of cerous nitrate hexahydrate is changed to 42.1193g, the dosage of copper nitrate trihydrate is changed to 0.7248g, and the molar ratio of Cu/Ce in the catalyst is 3: 97. most preferablyFinal catalyst Cu 3 Ce 97 O x 。
Example 5
The same procedure as in the first step of example 1 was followed, except that: the dosage of cerous nitrate hexahydrate is changed to 41.6851g, the dosage of copper nitrate trihydrate is changed to 0.9664g, and the molar ratio of Cu/Ce in the catalyst is 4: 96. finally preparing the catalyst Cu 4 Ce 96 O x 。
Example 6
The same procedure as in the first step of example 1 was followed, except that: the dosage of cerous nitrate hexahydrate is changed to 41.2509g, the dosage of copper nitrate trihydrate is changed to 1.2080g, and the molar ratio of Cu/Ce in the catalyst is 5: 95. finally preparing the catalyst Cu 5 Ce 95 O x 。
Example 7
The same procedure as in the first step of example 1 was followed, except that: the dosage of cerous nitrate hexahydrate is changed to 39.0798g, the dosage of copper nitrate trihydrate is changed to 2.4160g, and the molar ratio of Cu/Ce in the catalyst is 10: 90. finally preparing the catalyst Cu 10 Ce 90 O x 。
Example 8
The same operation as in example 1 was carried out except that: the amount of ruthenium chloride solution was changed to 0.4mL and the final catalyst was expressed as 0.1wt% Pt to 0.1 wt.% Ru/Cu 1 Ce 99 O x 。
Example 9
The same operation as in example 1 was carried out except that: the amount of ruthenium chloride solution was changed to 0.8mL and the final catalyst was expressed as 0.1wt% Pt to 0.2 wt.% Ru/Cu 1 Ce 99 O x 。
Example 10
The same operation as in example 1 was carried out except that: the amount of ruthenium chloride solution was changed to 4.0mL and the final catalyst was expressed as 0.1wt% Pt-1.0 wt.% Ru/Cu 1 Ce 99 O x 。
Example 11
The same operation as in example 1 was carried out except that: mixing ruthenium chloride solutionThe amount of (B) was changed to 0mL and the final catalyst was expressed as 0.1wt% Pt/Cu 1 Ce 99 O x 。
Application example 1:
the catalytic degradation experiment of the catalyst in the embodiment 1-10 on the low-carbon oxygen-containing organic waste gas is as follows: the catalyst and the quartz sand are filled in a tubular reactor according to the mass ratio of 1:1 (the quartz sand is filled to disperse the catalyst), and the low-carbon oxygen-containing organic waste gas and air are introduced into the tubular reactor together for catalytic combustion reaction. The experimental conditions were: the carbon oxygen-containing organic waste gas is ethylene oxide, the ethylene oxide is diluted to the concentration of 10000ppm by using air as diluent gas of the ethylene oxide to obtain ethylene oxide feed gas, and the ethylene oxide feed gas is mixed with another path of air according to the ratio of 1.004: 65.662 are mixed and are introduced into the tubular reactor together for catalytic combustion reaction at different reaction temperatures, and the reaction space velocity of the total mixed gas is WHSV 40000mL g -1 ·h -1 . The catalytic degradation activity of the catalyst in examples 1-10 on low-carbon oxygen-containing organic waste gas is shown in table 1:
TABLE 1
Table 1 above lists 0.1wt% Pt-Ru/Cu at different Cu/Ce molar ratios and different Ru loadings 1 Ce 99 O x Catalytic Oxidation Activity of the catalysts (examples 1-10) on ethylene oxide, complete conversion of ethylene oxide (conversion)>90%) of temperature (T) 90 ) Lower means higher oxidation activity of the catalyst; the optimal molar ratio of Cu/Ce is 1: 99, the complete conversion temperature of the catalyst to ethylene oxide at a Ru loading of 0.5 wt.% was around 120 ℃.
In addition, the above procedure of catalytic combustion reaction was repeated except that the ethylene oxide feed gas was replaced with methanol, formaldehyde, methyl ethyl ketone or ethyl acetate of the same concentration, and it was determined that 0.1wt% Pt-0.5 wt.% Ru/Cu of example 1 was used 1 Ce 99 O x The catalyst and the experimental results are shown in table 2.
TABLE 2
The catalyst prepared in example 1 is taken as a representative, and the oxidation activity of the catalyst on other low-carbon oxygen-containing organic waste gases (methanol, formaldehyde, butanone and ethyl acetate) is evaluated, and the catalyst can be completely oxidized and converted at the temperature of below 200 ℃, so that the catalyst shows good catalytic activity on a plurality of low-carbon oxygen-containing organic waste gases, and has great industrial application potential and value.
Application example 2:
CuCeO prepared as in examples 1-7 x Composite oxide, commercially available CeO 2 And CuO is used as a catalyst, and the catalytic degradation experiment on low-carbon oxygen-containing organic waste gas comprises the following steps: filling a catalyst and quartz sand into a tubular reactor according to the mass ratio of 1:1, and introducing low-carbon oxygen-containing organic waste gas and air into the tubular reactor together for catalytic combustion reaction. The experimental conditions were: the low-carbon oxygen-containing organic waste gas is ethylene oxide, the ethylene oxide is diluted to the concentration of 10000ppm by using air as diluent gas of the ethylene oxide to obtain ethylene oxide feed gas, and the ethylene oxide feed gas and another path of air are mixed according to the ratio of 1.004: 65.662, and introducing the mixture into a tubular reactor for catalytic combustion reaction at different reaction temperatures, wherein the reaction space velocity of the total mixed gas is WHSV 40000mL g -1 ·h -1 。
A graph of the ethylene oxide conversion versus reaction temperature for different Cu doping levels of the catalyst is shown in figure 1. As can be seen from fig. 1, the doping amounts of Cu ions of 1% and 2% both allow to achieve a complete catalytic oxidation of ethylene oxide at 180 ℃, preferably a doping of 1%.
Application example 3:
with Cu of example 1 1 Ce 99 O x The catalytic degradation of the composite oxide and the catalysts with different Pt-Ru loadings in the examples 1 and 8 to 11 on the low-carbon oxygen-containing organic waste gas is realizedTesting: filling a catalyst and quartz sand into a tubular reactor according to the mass ratio of 1:1, and introducing low-carbon oxygen-containing organic waste gas and air into the tubular reactor together for catalytic combustion reaction. The experimental conditions were: the carbon oxygen-containing organic waste gas is ethylene oxide, the ethylene oxide is diluted to the concentration of 10000ppm by using air as diluent gas of the ethylene oxide to obtain ethylene oxide feed gas, and the ethylene oxide feed gas and another path of air are mixed according to the ratio of 1.004: 65.662 are mixed and are introduced into the tubular reactor together for catalytic combustion reaction at different reaction temperatures, and the reaction space velocity of the total mixed gas is WHSV 40000mL g -1 ·h -1 。
A comparison of the ethylene oxide conversion versus reaction temperature for different Pt-Ru loading catalysts is shown in FIG. 2. As can be seen from fig. 2: the noble metal Ru loading of 0.5% and 1% shows the best catalytic activity, can achieve 90% of ethylene oxide conversion at 158 ℃, and the loading of 0.5% is selected, so that the cost performance is highest.
The description is given for the sole purpose of illustrating the invention concept in its implementation form and the scope of the invention should not be considered as being limited to the particular form set forth in the examples.
Claims (7)
1. A ruthenium-based noble metal combustion catalyst for low-carbon oxygen-containing organic waste gas is characterized in that the catalyst is a copper-cerium composite oxide CuCeO x As carrier, loading active components Ru and Pt on the carrier, and marking the active components as Pt-Ru/CuCeO x A catalyst; wherein, CuCeO x The molar weight of Ce element in the carrier is 90-99% of the sum of the molar weight of Cu and Ce, preferably 97-99%; the supported amount of Pt in the catalyst is 0.01-0.2 wt%, preferably 0.05-0.1 wt%, and the supported amount of Ru is 0.1-1.0 wt%, preferably 0.5-1.0 wt%.
2. The preparation method of the low-carbon oxygen-containing organic exhaust gas ruthenium-based noble metal combustion catalyst as claimed in claim 1, which is characterized by comprising the following specific preparation steps:
1) dissolving cerium salt and copper salt in water according to the molar ratio of Cu and Ce, and adding ammonia waterOr adjusting the pH value of the mixture to 9.0-11.0 by using NaOH solution, stirring the mixture for 2-4 hours, standing and aging the mixture for 10-12 hours at room temperature, then filtering the mixture, washing the mixture for multiple times by using deionized water until the filtrate is neutral, drying the filtrate, and calcining the filtrate for 2-4 hours at the temperature of 450-600 ℃ in air atmosphere to obtain CuCeO x A composite oxide powder;
2) mixing CuCeO x Dispersing the composite oxide powder in an Ru salt aqueous solution, stirring the obtained mixture in a water bath at 65-85 ℃ for 1-3 hours, filtering, drying, calcining at 350-450 ℃ for 3-5 hours in an air atmosphere to obtain the CuCeO loaded with the Ru element x Composite powder, labeled as Ru/CuCeO x A composite powder;
3) mixing Ru/CuCeO x Dispersing the composite powder in a Pt precursor aqueous solution, stirring the obtained mixture in a water bath at 65-85 ℃ for 1-3 hours, filtering, dispersing the obtained solid in deionized water, adding an excessive hydrazine hydrate solution, reacting the mixture at 65-85 ℃ for 1-3 hours, completely reducing Pt element into a metal simple substance, filtering, drying, calcining at 350-450 ℃ for 2-4 hours in an air atmosphere to obtain Pt-Ru/CuCeO x A catalyst.
3. The method according to claim 2, wherein the cerium salt is cerium nitrate hexahydrate, the copper salt is copper nitrate trihydrate, the Ru salt is ruthenium trichloride hydrate, and the Pt precursor is chloroplatinic acid hexahydrate.
4. The method for preparing the ruthenium-based noble metal combustion catalyst as claimed in claim 2, wherein in the step 1), the concentration of ammonia water or NaOH solution is 0.5-2M, preferably 1M.
5. The use of the ruthenium-based noble metal combustion catalyst as claimed in claim 1 for the low-carbon oxygen-containing organic exhaust gas catalytic combustion at low temperature.
6. The method of claim 5, wherein the catalyst is filled in a tubular reactor, and the low-carbon oxygen-containing organic waste gas and air are introduced into the tubular reactor together for catalytic combustion reaction.
7. The application of claim 6, wherein the low-carbon oxygen-containing organic waste gas is ethylene oxide with a concentration of less than 10000ppm, the ethylene oxide feed gas passes through an ice-water bath at 0 ℃ and then is mixed with air and then is introduced into the tubular reactor for catalytic combustion reaction, and the catalytic combustion reaction temperature is 120 ℃.
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