CN108906044B - Manganese-cerium-ruthenium composite oxide catalyst and preparation method and application thereof - Google Patents
Manganese-cerium-ruthenium composite oxide catalyst and preparation method and application thereof Download PDFInfo
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- CN108906044B CN108906044B CN201810620896.1A CN201810620896A CN108906044B CN 108906044 B CN108906044 B CN 108906044B CN 201810620896 A CN201810620896 A CN 201810620896A CN 108906044 B CN108906044 B CN 108906044B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 109
- ALYYYDHBRHGFLF-UHFFFAOYSA-N [Ru].[Ce].[Mn] Chemical compound [Ru].[Ce].[Mn] ALYYYDHBRHGFLF-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 239000002131 composite material Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- LQWKWJWJCDXKLK-UHFFFAOYSA-N cerium(3+) manganese(2+) oxygen(2-) Chemical compound [O--].[Mn++].[Ce+3] LQWKWJWJCDXKLK-UHFFFAOYSA-N 0.000 claims abstract description 115
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 99
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 98
- 238000000034 method Methods 0.000 claims abstract description 86
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims abstract description 55
- 229910001925 ruthenium oxide Inorganic materials 0.000 claims abstract description 54
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 31
- 239000002105 nanoparticle Substances 0.000 claims abstract description 30
- 230000003647 oxidation Effects 0.000 claims abstract description 30
- 239000012855 volatile organic compound Substances 0.000 claims abstract description 28
- 230000003197 catalytic effect Effects 0.000 claims abstract description 27
- 239000007788 liquid Substances 0.000 claims abstract description 22
- 238000000975 co-precipitation Methods 0.000 claims abstract description 15
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 13
- 239000006185 dispersion Substances 0.000 claims abstract description 10
- 238000000151 deposition Methods 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 57
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 45
- 239000011572 manganese Substances 0.000 claims description 42
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 35
- 229910052748 manganese Inorganic materials 0.000 claims description 34
- 239000011259 mixed solution Substances 0.000 claims description 32
- 239000000203 mixture Substances 0.000 claims description 27
- 229910052684 Cerium Inorganic materials 0.000 claims description 26
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 26
- 239000012286 potassium permanganate Substances 0.000 claims description 25
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 20
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 18
- 239000002243 precursor Substances 0.000 claims description 17
- 238000000926 separation method Methods 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 16
- 239000003638 chemical reducing agent Substances 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- 238000001556 precipitation Methods 0.000 claims description 13
- 238000001354 calcination Methods 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 10
- 229910019891 RuCl3 Inorganic materials 0.000 claims description 9
- 239000012279 sodium borohydride Substances 0.000 claims description 6
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 4
- 238000010304 firing Methods 0.000 claims description 3
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical group [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 4
- 230000000694 effects Effects 0.000 abstract description 12
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 10
- 239000000460 chlorine Substances 0.000 abstract description 10
- 229910052801 chlorine Inorganic materials 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 9
- 231100000572 poisoning Toxicity 0.000 abstract description 7
- 230000000607 poisoning effect Effects 0.000 abstract description 7
- 239000012752 auxiliary agent Substances 0.000 description 19
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 19
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 18
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 14
- 229910000420 cerium oxide Inorganic materials 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 229910052763 palladium Inorganic materials 0.000 description 7
- 229910052697 platinum Inorganic materials 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000004408 titanium dioxide Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 229910000314 transition metal oxide Inorganic materials 0.000 description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 2
- VEUMANXWQDHAJV-UHFFFAOYSA-N 2-[2-[(2-hydroxyphenyl)methylideneamino]ethyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCN=CC1=CC=CC=C1O VEUMANXWQDHAJV-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- 230000010718 Oxidation Activity Effects 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- WYCDUUBJSAUXFS-UHFFFAOYSA-N [Mn].[Ce] Chemical compound [Mn].[Ce] WYCDUUBJSAUXFS-UHFFFAOYSA-N 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 241000264877 Hippospongia communis Species 0.000 description 1
- ROZSPJBPUVWBHW-UHFFFAOYSA-N [Ru]=O Chemical class [Ru]=O ROZSPJBPUVWBHW-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000006298 dechlorination reaction Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000010812 mixed waste Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 210000000653 nervous system Anatomy 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- -1 platinum group metals Chemical class 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/656—Manganese, technetium or rhenium
- B01J23/6562—Manganese
-
- B01J35/40—
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Abstract
The invention provides a manganese-cerium-ruthenium composite oxide catalyst and a preparation method and application thereof. The manganese-cerium-ruthenium composite oxide catalyst comprises manganese-cerium oxide and ruthenium oxide dispersed on the surface of the manganese-cerium oxide. The preparation method comprises the following steps: (1) preparing manganese-cerium oxide by adopting an oxidation reduction-hydrolysis coprecipitation method; (2) preparing a dispersion liquid of ruthenium nano particles by adopting a sol-deposition method, dispersing the ruthenium nano particles on the surface of the manganese-cerium oxide obtained in the step (1) to obtain a ruthenium-containing manganese-cerium oxide, and roasting the ruthenium-containing manganese-cerium oxide to obtain the manganese-cerium-ruthenium composite oxide catalyst. The manganese-cerium-ruthenium composite oxide catalyst provided by the invention is low in cost, low in complete oxidation temperature of common VOCs, excellent in chlorine poisoning resistance and stable in activity in the process of catalytic oxidation of CVOCs in a lower temperature range.
Description
Technical Field
The invention belongs to the technical field of resources and environment, and particularly relates to a manganese-cerium-ruthenium composite oxide catalyst, and a preparation method and application thereof.
Background
Volatile Organic Compounds (VOCs) are PM2.5And O3The important precursor can cause atmospheric environment problems such as haze, photochemical smog and the like, and the health of the liver, the kidney and the nervous system can be damaged when a human body is in an environment with excessive VOCs for a long time. Decomposing VOCs into CO at 150-500 deg.C by catalytic oxidation2And H2And small molecular substances such as O and the like can thoroughly eliminate the pollution of the VOCs and are suitable for being applied to VOCs mixed waste gas without recovery value.
The key to the application of catalytic oxidation is the high-efficiency and stable catalyst. At present, expensive platinum and palladium catalysts are mainly used for catalytic oxidation of VOCs, one-time investment is usually reduced by adopting a method for reducing the content of active components in application, the actual catalytic oxidation operating temperature is high, and meanwhile, the platinum and palladium catalysts have lower activity and more polychlorinated byproducts in the catalytic oxidation process of chlorine-containing VOCs (chlorinated volatile organic compounds, CVOCs for short). Researches show that the catalytic activity of the transition metal oxide catalyst optimized by the system can be greatly improved and even exceeds that of platinum and palladium catalysts. However, transition metal oxide catalysts are prone to deactivation by chlorine poisoning during the catalytic oxidation of CVOCs, which is significant at lower temperature ranges (150-300 ℃).
CN105289651A discloses a bimetallic catalyst for catalytic oxidation of VOCs and a preparation method and application thereof. The catalyst takes titanium dioxide as a carrier, an activator is a simple substance of any element of ruthenium, palladium or platinum and/or an oxide thereof, and a cocatalyst is any one of cobaltosic oxide, manganese oxide, copper oxide or nickel oxide. The Salen ligand is used for synthesizing the nano-particles with the uniform composition of the activator and the cocatalyst by a nano regulation and control means, and the Salen ligand and the cocatalyst have stronger synergistic catalysis effect, so that the catalytic oxidation efficiency of the VOCs can be improved.
CN107362800A discloses a catalyst for eliminating VOCs and a preparation method thereof, wherein the morphology and the size of nano particles of the catalyst are regulated and controlled by adding a reducing agent and an accelerating agent and regulating the molar ratio of Co to Mn through a hydrothermal method. The catalyst has high catalytic oxidation activity of benzene in a wide temperature range. The catalytic conversion rate of the catalyst to benzene at 207 ℃ reaches 90 percent. The purification effect of the catalyst provided by the invention is superior to that of the traditional benzene catalytic oxidation catalyst.
CN107983365A provides a preparation method of a VOCs catalyst with titanium foam as a carrier, which comprises the steps of taking titanium foam as a substrate, pretreating the titanium foam, generating a titanium dioxide precursor on the surface and in a pore channel, calcining at high temperature to obtain titanium foam-titanium dioxide, taking the titanium foam-titanium dioxide as the carrier, and loading active components of copper oxide and manganese oxide, and a cocatalyst of neodymium oxide and cobalt oxide by a self-propagating calcination method to obtain the catalyst for catalytically oxidizing VOCs.
However, the catalyst provided by the scheme has the problems of high cost, relatively narrow application range, long preparation process and the like.
Therefore, the research and development and application of the transition metal oxide catalyst with low cost and wide application range are important ways for the catalytic oxidation method to be applied in the field of VOCs control in a large range.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a manganese-cerium-ruthenium composite oxide catalyst and a preparation method and application thereof. The manganese-cerium-ruthenium composite oxide catalyst provided by the invention has the advantages of low cost, high efficiency and strong universality.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a manganese-cerium-ruthenium composite oxide catalyst comprising a manganese-cerium oxide and a ruthenium oxide dispersed on the surface of the manganese-cerium oxide.
In the manganese-cerium-ruthenium composite oxide catalyst provided by the invention, the active component is manganese-cerium oxide, and the auxiliary agent is ruthenium oxide.
The manganese oxide in the active component manganese-cerium oxide has better oxidizing capability on common hydrocarbon VOCs such as ethane, propane, normal hexane, benzene, toluene and the like, and the reaction process follows an M-K mechanism and comprises a process of giving lattice oxygen. And after the manganese oxide is doped by the cerium oxide, the lattice oxygen of the cerium oxide can be transferred to the manganese oxide losing the lattice oxygen. In addition, the cerium oxide has stronger capability of supplementing lattice oxygen from gas-phase oxygen, so that the manganese-cerium has a synergistic effect in the catalytic oxidation process of VOCs, and the catalytic oxidation activity of the cerium oxide is obviously improved compared with that of single manganese or cerium oxide.
During the catalytic oxidation process of the manganese-cerium oxide in CVOCs, chlorine species are easy to accumulate on the surface of the catalyst and are difficult to remove even if the catalyst is roasted at high temperature, so that the active components are subjected to chlorination inactivation to a certain extent. RuO2Is prepared by Deacon reaction2Manganese-cerium as the main active componentThe chlorine species on the surface of the oxide can be in RuO2Effectively removed under the action of (1).
Compared with platinum and palladium catalysts, the manganese-cerium-ruthenium composite oxide catalyst has the advantages of low cost, wide application range and good application prospect.
The manganese-cerium-ruthenium composite oxide catalyst provided by the invention is solid powder, and can be made into various structural shapes according to actual requirements, for example, the catalyst can be made into spheres, granules, honeycombs and the like with different sizes.
The following is a preferred technical solution of the present invention, but not a limitation to the technical solution provided by the present invention, and the technical objects and advantageous effects of the present invention can be better achieved and achieved by the following preferred technical solution.
In a preferred embodiment of the present invention, the molar ratio of manganese to cerium in the manganese-cerium oxide is 1:4 to 9:1, for example, 1:4, 1:3, 1:2, 1:1, 3:1, 5:1, 7:1 or 9:1, but the present invention is not limited to the recited values, and other values not recited in the above range of values are also applicable.
Preferably, the mass fraction of the ruthenium oxide in the manganese-cerium-ruthenium composite oxide catalyst is 0.1 to 5 wt%, such as 0.1 wt%, 0.5 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%, or 5 wt%, etc., in terms of ruthenium, but is not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, in the manganese-cerium-ruthenium composite oxide catalyst, the particle size of the ruthenium oxide is 3 to 10nm, for example, 3nm, 4nm, 6nm, 8nm, 10nm, etc., but is not limited to the recited values, and other values not recited in the range of the values are also applicable. The ruthenium oxide has a particle size effect, the surface unsaturated coordination ruthenium atoms of ruthenium oxide particles with different sizes have different dechlorination performance, and the particle size control of the ruthenium oxide can be realized by regulating and controlling the preparation conditions, so that the chlorine poisoning resistance of the catalyst is improved.
In a second aspect, the present invention provides a method for preparing the manganese-cerium-ruthenium composite oxide catalyst according to the first aspect, the method comprising the steps of:
(1) preparing manganese-cerium oxide by adopting an oxidation reduction-hydrolysis coprecipitation method;
(2) preparing a dispersion liquid of ruthenium nano particles by adopting a sol-deposition method, dispersing the ruthenium nano particles on the surface of the manganese-cerium oxide obtained in the step (1) to obtain a ruthenium-containing manganese-cerium oxide, and roasting the ruthenium-containing manganese-cerium oxide to obtain the manganese-cerium-ruthenium composite oxide catalyst.
In the preparation method provided by the invention, the manganese-cerium oxide prepared by adopting the oxidation reduction-hydrolysis coprecipitation method has better uniform degree of mixing in a microscale and higher catalyst activity compared with the manganese-cerium oxide obtained by the conventional coprecipitation method. Preparing ruthenium nanoparticles by sol-deposition method, dispersing the nanoparticles on the surface of manganese-cerium oxide, and calcining to obtain ruthenium oxide (mainly RuO)2) The defect of uneven distribution of the traditional dipping method is avoided, and the grain diameter of the ruthenium oxide can be controlled between 3nm and 10nm by regulating and controlling the preparation conditions.
As a preferred embodiment of the present invention, in the step (1), the preparation of the manganese-cerium oxide by the redox-hydrolysis coprecipitation method comprises the following steps: mixing a manganese source and a cerium source in a solvent to obtain a mixed solution, and adding H into the mixed solution2O2And adjusting the pH value to precipitate, then carrying out solid-liquid separation, and roasting the solid to obtain the manganese-cerium oxide. Here, H is added2O2And adjusting the pH value to perform precipitation so as to completely precipitate the manganese-containing substance and the cerium-containing substance in the solution.
As the technical scheme of the invention, the manganese source is KMnO4。
Preferably, the concentration of the manganese source in the mixed solution is 10-50, such as 10g/L, 20g/L, 30g/L, 40g/L or 50g/L, but not limited to the recited values, and other values within the range are equally applicable, such as 20 g/L.
Preferably, the cerium source comprises Ce (NO)3)3·6H2O。
Preferably, the molar ratio of the manganese source to the cerium source in the mixed solution is 2:1 to 4:1, such as 2:1, 2.5:1, 3:1, 3.5:1 or 4:1, but not limited to the recited values, and other values not recited within this range are equally applicable, preferably 3: 1.
Preferably, the solvent is water.
Preferably, said H2O2The addition mode of (A) is dropwise addition. To ensure the reaction is complete, an excess of H may be added2O2。
Preferably, H is added2O2While stirring.
Preferably, said H2O2Is diluted H2O2。
Preferably, the diluted H2O2In (H)2O2The mass concentration of (b) is 0.5 to 10%, for example, 0.5%, 1%, 2%, 4%, 6%, or 10%, but is not limited to the recited values, and other values not recited in the numerical range are also applicable, preferably 2%.
Preferably, said H2O2The molar ratio to the manganese source is 3:1 to 6:1, for example 3:1, 4:1, 5:1, or 6:1, but is not limited to the recited values, and other values not recited within the numerical range are equally applicable, preferably 4.5: 1.
Preferably, the pH is adjusted with a 0.1mol/L NaOH solution.
In the present invention, in H2O2To KMnO4And Ce (NO)3)36MnO chemical reaction during the dropping process in the mixed solution4 -+2Ce3++9H2O2＝6MnO2+2Ce(OH)3+6H2O+9O2Then, manganese and cerium precipitates are generated simultaneously. KMnO in the mixed solution4And Ce (NO)3)3Or after dilution H2O2Too low concentration of (2) can cause water resource waste, while too high concentration can cause too strong redox reaction, and can cause uneven mixing of manganese and cerium precipitates on a micro scale. Adding excess H2O2Can guarantee KMnO4Reaction is complete when Ce3+When excessive, the Ce can be ensured by adjusting the pH3+The precipitation was complete.
Preferably, the solid-liquid separation is a filtration separation.
Preferably, the preparation of the manganese-cerium oxide by the redox-hydrolysis coprecipitation method further comprises washing and drying the solid obtained by solid-liquid separation.
Preferably, the firing is performed under an air atmosphere.
Preferably, the temperature of the calcination is 400-600 ℃, such as 400 ℃, 450 ℃, 500 ℃, 550 ℃ or 600 ℃, but not limited to the recited values, and other unrecited values within the range of values are equally applicable, preferably 500 ℃;
preferably, the calcination time is 2-10h, such as 2h, 4h, 6h, 8h or 10h, but not limited to the recited values, and other values not recited within this range are equally applicable, preferably 6 h.
In the process of preparing the manganese-cerium oxide by adopting an oxidation reduction-hydrolysis coprecipitation method, the microstructure of the catalyst is not stable enough due to the excessively low roasting temperature and the excessively short roasting time, and the manganese-cerium oxide is sintered due to the excessively high roasting temperature and the excessively long roasting time, so that the specific surface area is seriously reduced, and the activity of the catalyst is influenced.
As a preferred embodiment of the present invention, in the step (2), the method for preparing the ruthenium nanoparticle dispersion by the sol-deposition method comprises the following steps: and adding polyvinyl alcohol into the ruthenium precursor solution, and then adding a reducing agent to obtain the dispersion liquid of the ruthenium nano-particles.
Preferably, the ruthenium precursor is RuCl3And/or Ru (NO)3)3Preferably RuCl3。
Preferably, the concentration of the ruthenium precursor solution is 25-100mg/L, such as 25mg/L, 35mg/L, 40mg/L, 50mg/L, 65mg/L, 75mg/L, 95mg/L, or 100mg/L, but is not limited to the recited values, and other values within this range are equally applicable, preferably 40 mg/L.
Preferably, the polyvinyl alcohol has a weight average molecular weight of 8000 to 10000 g/mol.
Preferably, the mass ratio of the polyvinyl alcohol to the ruthenium element in the ruthenium precursor solution is 1:1 to 5:1, for example, 1:1, 2:1, 3:1, 4:1, or 5:1, but not limited to the recited values, and other values not recited in the range of the values are also applicable, preferably 2: 1.
Preferably, the reducing agent is added with stirring.
In the present invention, it is preferable to add the reducing agent rapidly.
The polyvinyl alcohol plays a role in protecting the precursor of ruthenium through a reducing agent to obtain the metal ruthenium nano-particles, the protection effect is poor due to the fact that the proportion of the polyvinyl alcohol is too low, the obtained metal ruthenium nano-particles are too large in size and even form precipitates, and the generated metal ruthenium nano-particles are too small due to the fact that the proportion of the polyvinyl alcohol is too high.
Preferably, the reducing agent is NaBH4And (3) solution.
Preferably, the NaBH4The concentration of the solution is 0.01 to 0.5mol/L, for example, 0.01mol/L, 0.05mol/L, 0.1mol/L, 0.2mol/L, 0.3mol/L, 0.4mol/L, or 0.5mol/L, etc., but is not limited to the values listed, and other values not listed in the numerical range are also applicable, and 0.1mol/L is preferable.
Preferably, the molar ratio of the reducing agent to the ruthenium element in the ruthenium precursor solution is 3:1 to 10:1, such as 3:1, 5:1, 7:1, 9:1, or 10:1, but not limited to the recited values, and other values within this range are equally applicable, preferably 5: 1.
NaBH4As a reducing agent for ruthenium, too low a ratio may result in incomplete reduction of ruthenium, while too high a ratio may result in formation of metallic ruthenium nanoparticles of larger size, and even precipitation of metallic ruthenium. NaBH4Too low concentration of the solution can cause water resource waste, while too high concentration can cause too strong local reduction reaction, and the obtained metallic ruthenium nano-particles have poor uniformity.
As a preferred embodiment of the present invention, the method of dispersing the ruthenium nanoparticles on the surface of the manganese-cerium oxide in the step (1) in the step (2) comprises the steps of: adding the manganese-cerium oxide obtained in the step (1) into the dispersion liquid of the ruthenium nano particles, standing, and carrying out solid-liquid separation to obtain a solid which is the manganese-cerium oxide containing ruthenium.
Preferably, the mass ratio of the manganese-cerium oxide to the ruthenium element in the ruthenium nanoparticles is 49:1 to 199:1, for example 49:1, 99:1, 149:1 or 199:1, but not limited to the recited values, and other values not recited in the range of the values are also applicable, preferably 99: 1.
Preferably, the solid-liquid separation is a filtration separation.
Preferably, the method of dispersing the ruthenium nanoparticles on the surface of the manganese-cerium oxide of step (1) further comprises: and washing and drying the solid obtained by solid-liquid separation.
In the preferred embodiment of the present invention, in the step (2), the calcination is performed in an air atmosphere.
In step (2), the temperature of the calcination is 100 to 400 ℃, for example, 100 ℃, 150 ℃, 200 ℃, 250 ℃, 300 ℃, 350 ℃ or 400 ℃, but is not limited to the recited values, and other values not recited in the range of the values are also applicable, preferably 250 ℃.
Preferably, in step (2), the calcination time is 0.5-2h, such as 0.5h, 1h, 1.5h or 2h, etc., preferably 1 h.
Although the price of ruthenium is far lower than that of platinum and palladium, ruthenium is still high as one of platinum group metals, so that the dosage of ruthenium is reduced as much as possible while the chlorine poisoning resistance of the catalyst is improved.
As a further preferable technical scheme of the preparation method of the anode material, the method comprises the following steps:
(1) mixing KMnO4And Ce (NO)3)3·6H2Dissolving O in water to form a mixed solution, and dropwise adding H with the mass concentration of 2% into the mixed solution under stirring2O2Then, adjusting the pH value by adopting 0.1mol/L NaOH solution to carry out precipitation, filtering, washing and drying the mixture, and roasting the mixture in the air at 500 ℃ for 6 hours to obtain manganese-cerium oxide;
wherein KMnO in the mixed solution4The concentration is 20g/L, KMnO4And Ce (NO)3)3In a molar ratio of 3:1；H2O2And KMnO4The molar ratio is 4.5: 1;
(2) to 40mg/L of RuCl3Adding polyvinyl alcohol into the solution, and after the polyvinyl alcohol is completely dissolved, rapidly adding 0.1mol/L NaBH under stirring4Adding manganese-cerium oxide into the solution, standing until the solution is clear, filtering, washing and drying the mixture, and roasting the mixture in the air at 250 ℃ for 1h to obtain the manganese-cerium-ruthenium composite oxide catalyst;
wherein the weight average molecular weight of the polyvinyl alcohol is 8000-10000g/mol, the mass ratio of the polyvinyl alcohol to the ruthenium element is 2:1, and NaBH is added4The molar ratio of the manganese-cerium oxide to the ruthenium element is 5:1, and the mass ratio of the manganese-cerium oxide to the ruthenium element is 99: 1.
In a third aspect, the present invention provides a use of the manganese-cerium-ruthenium composite oxide catalyst according to the first aspect, for catalytic oxidation of volatile organic compounds.
Compared with the prior art, the invention has the following beneficial effects:
(1) in the manganese-cerium-ruthenium composite oxide catalyst provided by the invention, manganese-cerium oxides are uniformly mixed on a microscale, a strong synergistic effect exists between manganese and cerium, the activity of the catalyst is obviously improved, the ruthenium oxides dispersed on the surface of the manganese-cerium oxides enhance the chlorine poisoning resistance of the catalyst, and compared with platinum and palladium catalysts, the catalyst provided by the invention has the advantages of low cost, complete oxidation temperature of common VOCs (volatile organic compounds) of 210-420 ℃, excellent chlorine poisoning resistance and stable activity in the process of catalytic oxidation of CVOCs at a lower temperature range (150-300 ℃).
(2) The preparation method provided by the invention has the advantages of short flow, simple operation and low preparation cost, and is suitable for large-scale industrial production.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
A preparation method of a manganese-cerium-ruthenium composite oxide catalyst comprises the following specific steps:
(1) mixing KMnO4And Ce (NO)3)3·6H2Dissolving O in water to form a mixed solution (KMnO)4The concentration is 20g/L, KMnO4And Ce (NO)3)3At a molar ratio of 3:1), adding H with a mass concentration of 2% dropwise to the mixed solution while stirring2O2(with KMnO4The molar ratio is 4.5:1), then the pH is adjusted by 0.1mol/L NaOH solution for precipitation, and the mixture is filtered, washed and dried and then roasted for 6h at 500 ℃ in the air to obtain the manganese-cerium oxide.
(2) To 40mg/L of RuCl3Adding PVA (weight average molecular weight of 8000-10000g/mol, and ruthenium mass ratio of 2:1) into the solution, dissolving completely, and rapidly adding 0.1mol/L NaBH under stirring4Adding manganese-cerium oxide (the mass ratio of the manganese-cerium oxide to the ruthenium element is 99:1) into the solution (the molar ratio of the manganese-cerium oxide to the ruthenium element is 5:1), standing until the solution is clear, filtering, washing and drying the mixture, and roasting the mixture in the air at 250 ℃ for 1h to obtain the manganese-cerium-ruthenium composite oxide catalyst.
The manganese-cerium-ruthenium composite oxide catalyst prepared in the embodiment comprises manganese-cerium oxide and ruthenium oxide dispersed on the surface of the manganese-cerium oxide, wherein an active component is the manganese-cerium oxide, an auxiliary agent is the ruthenium oxide, the molar ratio of manganese to cerium in the active component is 3:1, the mass fraction of the auxiliary agent ruthenium oxide (calculated by ruthenium) is about 1%, and the particle size of the ruthenium oxide is 3-10 nm.
The performance of the manganese-cerium-ruthenium composite oxide catalyst prepared in this example was evaluated, and the results are shown in table 1.
Example 2
This example was the same as example 1 except that the molar ratio of manganese to cerium in the manganese-cerium oxide as an active component was 1: 4.
The manganese-cerium-ruthenium composite oxide catalyst prepared in the embodiment comprises manganese-cerium oxide and ruthenium oxide dispersed on the surface of the manganese-cerium oxide, wherein an active component is the manganese-cerium oxide, an auxiliary agent is the ruthenium oxide, the molar ratio of manganese to cerium in the active component is 1:4, the mass fraction of the auxiliary agent ruthenium oxide (calculated by ruthenium) is about 1%, and the particle size of the ruthenium oxide is 3-10 nm.
The performance of the manganese-cerium-ruthenium composite oxide catalyst prepared in this example was evaluated, and the results are shown in table 1.
Example 3
This example was the same as example 1 except that the molar ratio of manganese to cerium in the manganese-cerium oxide as an active component was 9: 1.
The manganese-cerium-ruthenium composite oxide catalyst prepared in the embodiment comprises manganese-cerium oxide and ruthenium oxide dispersed on the surface of the manganese-cerium oxide, wherein an active component is the manganese-cerium oxide, an auxiliary agent is the ruthenium oxide, the molar ratio of manganese to cerium in the active component is 9:1, the mass fraction of the auxiliary agent ruthenium oxide (calculated by ruthenium) is 1%, and the particle size of the ruthenium oxide is 3-10 nm.
The performance of the manganese-cerium-ruthenium composite oxide catalyst prepared in this example was evaluated, and the results are shown in table 1.
Example 4
This example was conducted in the same manner as example 1 except that the assistant ruthenium oxide (in terms of ruthenium) was contained in an amount of 0.1% by mass.
The manganese-cerium-ruthenium composite oxide catalyst prepared in the embodiment comprises manganese-cerium oxide and ruthenium oxide dispersed on the surface of the manganese-cerium oxide, wherein the active component is the manganese-cerium oxide, the auxiliary agent is the ruthenium oxide, the molar ratio of manganese to cerium in the active component is 3:1, the mass fraction of the auxiliary agent ruthenium oxide (calculated by ruthenium) is 0.1%, and the particle size of the ruthenium oxide is 3-10 nm.
The performance of the manganese-cerium-ruthenium composite oxide catalyst prepared in this example was evaluated, and the results are shown in table 1.
Example 5
This example was conducted in the same manner as example 1 except that the assistant ruthenium oxide (in terms of ruthenium) was contained in an amount of 5.0% by mass.
The manganese-cerium-ruthenium composite oxide catalyst prepared in the embodiment comprises manganese-cerium oxide and ruthenium oxide dispersed on the surface of the manganese-cerium oxide, wherein the active component is the manganese-cerium oxide, the auxiliary agent is the ruthenium oxide, the molar ratio of manganese to cerium in the active component is 3:1, the mass fraction of the auxiliary agent ruthenium oxide (calculated by ruthenium) is 5.0%, and the particle size of the ruthenium oxide is 3-10 nm.
The performance of the manganese-cerium-ruthenium composite oxide catalyst prepared in this example was evaluated, and the results are shown in table 1.
Example 6
This example was the same as example 1 except that the average particle diameter of the ruthenium oxide as the assistant was less than 2 nm.
The manganese-cerium-ruthenium composite oxide catalyst prepared in the embodiment comprises manganese-cerium oxide and ruthenium oxide dispersed on the surface of the manganese-cerium oxide, an active component is the manganese-cerium oxide, an auxiliary agent is the ruthenium oxide, the molar ratio of manganese to cerium in the active component is 3:1, the mass fraction of the auxiliary agent ruthenium oxide (calculated by ruthenium) is 1%, and the average particle size of the ruthenium oxide is less than 2 nm.
The performance of the manganese-cerium-ruthenium composite oxide catalyst prepared in this example was evaluated, and the results are shown in table 1.
Example 7
This example was the same as example 1 except that the particle diameter of the ruthenium oxide as the assistant was 10 to 15 nm.
The manganese-cerium-ruthenium composite oxide catalyst prepared in the embodiment comprises manganese-cerium oxide and ruthenium oxide dispersed on the surface of the manganese-cerium oxide, wherein an active component is the manganese-cerium oxide, an auxiliary agent is the ruthenium oxide, the molar ratio of manganese to cerium in the active component is 3:1, the mass fraction of the auxiliary agent ruthenium oxide (calculated by ruthenium) is 1%, and the particle size of the ruthenium oxide is 10-15 nm.
The performance of the manganese-cerium-ruthenium composite oxide catalyst prepared in this example was evaluated, and the results are shown in table 1.
Example 8
A preparation method of a manganese-cerium-ruthenium composite oxide catalyst comprises the following specific steps:
(1) mixing KMnO4And Ce (NO)3)3·6H2Dissolving O in water to form a mixed solution (KMnO)4The concentration is 10g/L, KMnO4And Ce (NO)3)3At a molar ratio of 2:1), and a mass concentration of 0 was added dropwise to the mixed solution under stirring.5% of H2O2(with KMnO4The molar ratio is 4:1), then the pH value is adjusted by 0.1mol/L NaOH solution for precipitation, the mixture is filtered, washed and dried, and then the mixture is roasted for 10 hours at the temperature of 400 ℃ in the air to obtain the manganese-cerium oxide.
(2) To 25mg/L of RuCl3Adding PVA (weight average molecular weight of 8000-10000g/mol, and mass ratio of PVA to ruthenium element of 5:1) into the solution, dissolving completely, and rapidly adding 0.01mol/L NaBH under stirring4Adding manganese-cerium oxide (the mass ratio of the manganese-cerium oxide to the ruthenium element is 49:1) into the solution (the molar ratio of the manganese-cerium oxide to the ruthenium element is 3:1), standing until the solution is clear, filtering, washing and drying the mixture, and roasting the mixture in the air at 100 ℃ for 2 hours to obtain the manganese-cerium-ruthenium composite oxide catalyst.
The manganese-cerium-ruthenium composite oxide catalyst prepared in the embodiment comprises manganese-cerium oxide and ruthenium oxide dispersed on the surface of the manganese-cerium oxide, wherein the active component is the manganese-cerium oxide, the auxiliary agent is the ruthenium oxide, the molar ratio of manganese to cerium in the active component is 2:1, the mass fraction of the auxiliary agent ruthenium oxide (calculated by ruthenium) is about 2%, and the particle size of the ruthenium oxide is 4-12 nm.
The performance of the manganese-cerium-ruthenium composite oxide catalyst prepared in this example was evaluated, and the results are shown in table 1.
Example 9
A preparation method of a manganese-cerium-ruthenium composite oxide catalyst comprises the following specific steps:
(1) mixing KMnO4And Ce (NO)3)3·6H2Dissolving O in water to form a mixed solution (KMnO)4The concentration is 50g/L, KMnO4And Ce (NO)3)3At a molar ratio of 4:1), adding H with a mass concentration of 10% dropwise to the mixed solution under stirring2O2(with KMnO4The molar ratio is 5:1), then the pH value is adjusted by 0.1mol/L NaOH solution for precipitation, and the mixture is filtered, washed and dried and then is roasted in the air at 600 ℃ for 2h to obtain the manganese-cerium oxide.
(2) To 100mg/L of RuCl3Adding PVA (weight average molecular weight of 8000-10000g/mol, and mass ratio of PVA to ruthenium element of 1:1) into the solution, stirring after completely dissolvingRapidly adding 0.5mol/L NaBH4Adding manganese-cerium oxide (the mass ratio of the manganese-cerium oxide to the ruthenium element is 199:1) into the solution (the molar ratio of the manganese-cerium oxide to the ruthenium element is 10:1), standing until the solution is clear, filtering, washing and drying the mixture, and roasting the mixture in the air at 400 ℃ for 0.5h to obtain the manganese-cerium-ruthenium composite oxide catalyst.
The manganese-cerium-ruthenium composite oxide catalyst prepared in the embodiment comprises manganese-cerium oxide and ruthenium oxide dispersed on the surface of the manganese-cerium oxide, wherein the active component is the manganese-cerium oxide, the auxiliary agent is the ruthenium oxide, the molar ratio of manganese to cerium in the active component is 4:1, the mass fraction of the auxiliary agent ruthenium oxide (calculated as ruthenium) is about 0.5%, and the particle size of the ruthenium oxide is 3-8 nm.
The performance of the manganese-cerium-ruthenium composite oxide catalyst prepared in this example was evaluated, and the results are shown in table 1.
Comparative example 1
A manganese oxide catalyst for catalytic oxidation of VOCs, the preparation method of the catalyst is a precipitation method, and the catalyst comprises the following steps:
with a (CH) configuration of 20g/L3COO)2Mn solution and 8g/L NaOH solution, the same volume of (CH)3COO)2And dropwise adding the Mn solution into the NaOH solution, filtering, washing and drying the mixture, and roasting the mixture in the air at 500 ℃ for 6 hours to obtain the manganese oxide.
The performance of the manganese oxide catalyst obtained in this comparative example was evaluated, and the results are shown in table 1.
Comparative example 2
A cerium oxide catalyst for catalytic oxidation of VOCs, the preparation method of the catalyst is a precipitation method, and the catalyst comprises the following steps:
configuration of 20g/L Ce (NO)3)3·6H2O solution and 8g/L NaOH solution, the same volume of Ce (NO) is added with stirring3)3The solution is dripped into NaOH solution, and the mixture is filtered, washed and dried and then is roasted for 6 hours at 500 ℃ in the air to obtain cerium oxide.
The cerium oxide catalyst obtained in this comparative example was evaluated for its performance, and the results are shown in table 1.
Comparative example 3
A manganese-cerium oxide catalyst for catalyzing and oxidizing VOCs is prepared by a coprecipitation method and comprises the following steps:
mixing Mn (CH)3COO)2·4H2O and Ce (NO)3)3·6H2O is dissolved in water to form a mixed solution (Mn (CH)3COO)2Mn (CH) at a concentration of 15g/L3COO)2And Ce (NO)3)3At a molar ratio of 3:1), preparing a NaOH solution of 8g/L, and adding Mn (CH) under stirring3COO)2And Ce (NO)3)3The mixed solution is dripped into NaOH solution with the same volume, and the mixture is filtered, washed and dried and then is roasted for 6 hours at 500 ℃ in the air to obtain manganese oxide.
The performance of the manganese-cerium oxide catalyst obtained in this comparative example was evaluated, and the results obtained are shown in table 1.
Comparative example 4
A manganese-cerium oxide catalyst for catalytic oxidation of VOCs, the preparation method of the catalyst is an oxidation reduction-hydrolysis coprecipitation method, and the catalyst comprises the following steps:
mixing KMnO4And Ce (NO)3)3·6H2Dissolving O in water to form a mixed solution (KMnO)4The concentration is 20g/L, KMnO4And Ce (NO)3)3At a molar ratio of 3:1), adding H with a mass concentration of 2% dropwise to the mixed solution while stirring2O2(with KMnO4The molar ratio is 4.5:1), then the pH is adjusted by 0.1mol/L NaOH solution for precipitation, and the mixture is filtered, washed and dried and then roasted for 6h at 500 ℃ in the air to obtain the manganese-cerium oxide.
The performance of the manganese-cerium oxide catalyst obtained in this comparative example was evaluated, and the results obtained are shown in table 1.
Comparative example 5
A manganese-cerium-ruthenium mixed oxide catalyst for catalytic oxidation of VOCs is prepared by an oxidation-reduction-hydrolysis coprecipitation method and an impregnation method, and comprises the following steps:
(1) mixing KMnO4And Ce (NO)3)3·6H2Dissolving O in water to form a mixed solution (KMnO)4The concentration is 20g/L, KMnO4And Ce (NO)3)3At a molar ratio of 3:1), adding H with a mass concentration of 2% dropwise to the mixed solution while stirring2O2(with KMnO4The molar ratio is 4.5:1), then the pH is adjusted by 0.1mol/L NaOH solution for precipitation, and the mixture is filtered, washed and dried and then roasted for 6h at 500 ℃ in the air to obtain the manganese-cerium oxide.
(2) Configuration of 1g/L of Ru (NO)3)3Adding manganese-cerium oxide (the mass ratio of the manganese-cerium oxide to the ruthenium element is 99:1) into the solution, evaporating and drying the mixture, and roasting the mixture in the air at 250 ℃ for 1h to obtain the manganese-cerium-ruthenium composite oxide catalyst.
The performance of the mixed oxide catalyst of manganese, cerium and ruthenium obtained in the comparative example was evaluated, and the results are shown in table 1.
In the examples and comparative examples given, the conditions for the performance evaluation of the catalysts are as follows:
a reactor: the fixed bed microreactor is a quartz tube with the inner diameter of 4 mm;
reaction temperature range: 100-450 ℃;
system pressure: 1-1.05 atm;
the mass of the catalyst is as follows: 100 mg;
the reaction space velocity: 60000mL g-1·h-1；
Concentration of organic matter: 1000 ppm;
oxygen content: 20 vol.%.
The results of the catalytic evaluation of benzene and dichloroethane with the different example and comparative catalysts are shown in table 1.
TABLE 1 catalytic evaluation results of catalysts for benzene and dichloroethane
It can be known from the above examples and comparative examples that the manganese-cerium-ruthenium composite oxide catalyst provided by the invention has a low complete oxidation temperature for common VOCs, is excellent in chlorine poisoning resistance, and has stable activity in the process of catalytic oxidation of CVOCs at a low temperature range. The comparative example did not adopt the scheme of the present invention, and thus the effects of the present invention could not be obtained.
The applicant states that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e. it is not meant that the present invention must rely on the above detailed methods for its implementation. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (49)
1. A manganese-cerium-ruthenium composite oxide catalyst, characterized in that the manganese-cerium-ruthenium composite oxide catalyst comprises a manganese-cerium oxide and a ruthenium oxide dispersed on the surface of the manganese-cerium oxide;
in the manganese-cerium-ruthenium composite oxide catalyst, the particle size of ruthenium oxide is 3-10 nm;
the manganese-cerium-ruthenium composite oxide catalyst is prepared according to the following method, and the method comprises the following steps:
(1) preparing manganese-cerium oxide by adopting an oxidation reduction-hydrolysis coprecipitation method;
(2) preparing a dispersion liquid of ruthenium nanoparticles by adopting a sol-deposition method, dispersing the ruthenium nanoparticles on the surface of the manganese-cerium oxide obtained in the step (1) to obtain a ruthenium-containing manganese-cerium oxide, and roasting the ruthenium-containing manganese-cerium oxide to obtain the manganese-cerium-ruthenium composite oxide catalyst;
in the step (1), the preparation of the manganese-cerium oxide by the redox-hydrolysis coprecipitation method comprises the following steps: mixing a manganese source and a cerium source in a solvent to obtain a mixed solution, and adding H into the mixed solution2O2And adjusting the pH value for precipitation, then carrying out solid-liquid separation,roasting the solid to obtain the manganese-cerium oxide;
said H2O2The molar ratio of the manganese source to the manganese source is 3:1-6: 1;
in the method for preparing the manganese-cerium oxide, the roasting temperature is 400-600 ℃, and the roasting time is 2-10 h.
2. The manganese-cerium-ruthenium composite oxide catalyst according to claim 1, wherein the manganese-cerium oxide has a manganese to cerium molar ratio of 1:4 to 9: 1.
3. The manganese-cerium-ruthenium composite oxide catalyst according to claim 1, wherein the mass fraction of the ruthenium oxide in the manganese-cerium-ruthenium composite oxide catalyst is 0.1 to 5 wt% in terms of ruthenium.
4. The method for preparing a manganese-cerium-ruthenium composite oxide catalyst according to any one of claims 1 to 3, comprising the steps of:
(1) preparing manganese-cerium oxide by adopting an oxidation reduction-hydrolysis coprecipitation method;
(2) preparing a dispersion liquid of ruthenium nanoparticles by adopting a sol-deposition method, dispersing the ruthenium nanoparticles on the surface of the manganese-cerium oxide obtained in the step (1) to obtain a ruthenium-containing manganese-cerium oxide, and roasting the ruthenium-containing manganese-cerium oxide to obtain the manganese-cerium-ruthenium composite oxide catalyst;
in the step (1), the preparation of the manganese-cerium oxide by the redox-hydrolysis coprecipitation method comprises the following steps: mixing a manganese source and a cerium source in a solvent to obtain a mixed solution, and adding H into the mixed solution2O2Adjusting the pH value to precipitate, then carrying out solid-liquid separation, and roasting the solid to obtain the manganese-cerium oxide;
said H2O2The molar ratio of the manganese source to the manganese source is 3:1-6: 1;
in the method for preparing the manganese-cerium oxide, the roasting temperature is 400-600 ℃, and the roasting time is 2-10 h.
5. The method of claim 4, wherein the manganese source is KMnO4。
6. The method according to claim 4, wherein the concentration of the manganese source in the mixed solution is 10 to 50 g/L.
7. The method according to claim 6, wherein the concentration of the manganese source in the mixed solution is 20 g/L.
8. The method of claim 4, wherein the cerium source comprises Ce (NO)3)3·6H2O。
9. The method according to claim 4, wherein the molar ratio of the manganese source to the cerium source in the mixed solution is 2:1 to 4: 1.
10. The method according to claim 9, wherein the molar ratio of the manganese source to the cerium source in the mixed solution is 3: 1.
11. The method according to claim 4, wherein the solvent is water.
12. The method of claim 4, wherein the H is2O2The addition mode of (A) is dropwise addition.
13. The method of claim 4, wherein H is added2O2While stirring.
14. The method of claim 4, wherein the H is2O2Is diluted H2O2。
15. The method of claim 14, wherein the diluted H is2O2In (H)2O2The mass concentration of (A) is 0.5-10%.
16. The method of claim 15, wherein the diluted H is2O2In (H)2O2The mass concentration of (2%).
17. The method of claim 4, wherein the H is2O2The molar ratio to the manganese source was 4.5: 1.
18. The method according to claim 4, wherein the pH is adjusted with 0.1mol/L NaOH solution.
19. The production method according to claim 4, wherein the solid-liquid separation is a filtration separation.
20. The method of claim 4, wherein the redox-hydrolysis coprecipitation method for preparing the manganese-cerium oxide further comprises washing and drying a solid obtained by solid-liquid separation.
21. The method according to claim 4, wherein the firing is performed in an air atmosphere in the method for preparing a manganese-cerium oxide.
22. The method according to claim 4, wherein the firing temperature is 500 ℃ in the method for preparing the manganese-cerium oxide.
23. The method of claim 4, wherein the calcination time is 6 hours in the method of preparing the manganese-cerium oxide.
24. The method according to claim 4, wherein the sol-deposition method for preparing the ruthenium nanoparticle dispersion liquid in the step (2) comprises the steps of: and adding polyvinyl alcohol into the ruthenium precursor solution, and then adding a reducing agent to obtain the dispersion liquid of the ruthenium nano-particles.
25. The method of claim 24, wherein the ruthenium precursor is RuCl3And/or Ru (NO)3)3。
26. The method of claim 25, wherein the ruthenium precursor is RuCl3。
27. The method according to claim 24, wherein the concentration of the ruthenium precursor solution is 25 to 100 mg/L.
28. The method according to claim 27, wherein the concentration of the ruthenium precursor solution is 40 mg/L.
29. The production method according to claim 24, wherein the polyvinyl alcohol has a weight average molecular weight of 8000 to 10000 g/mol.
30. The method according to claim 24, wherein the mass ratio of the polyvinyl alcohol to the ruthenium element in the ruthenium precursor solution is 1:1 to 5: 1.
31. The method according to claim 30, wherein the mass ratio of the polyvinyl alcohol to the ruthenium element in the ruthenium precursor solution is 2: 1.
32. The method according to claim 24, wherein the reducing agent is added with stirring.
33. According to the rightThe method of claim 24, wherein the reducing agent is NaBH4And (3) solution.
34. The method of claim 33, wherein the NaBH is introduced into the sample4The concentration of the solution is 0.01-0.5 mol/L.
35. The method of claim 34, wherein the NaBH is introduced into the sample4The concentration of the solution was 0.1 mol/L.
36. The method according to claim 24, wherein the molar ratio of the reducing agent to the ruthenium element in the ruthenium precursor solution is from 3:1 to 10: 1.
37. The method of claim 36, wherein the molar ratio of the reducing agent to the ruthenium element in the ruthenium precursor solution is 5: 1.
38. The method of claim 4, wherein the step (2) of dispersing the ruthenium nanoparticles on the surface of the manganese-cerium oxide in the step (1) comprises the steps of: adding the manganese-cerium oxide obtained in the step (1) into the dispersion liquid of the ruthenium nano particles, standing, and carrying out solid-liquid separation to obtain a solid which is the manganese-cerium oxide containing ruthenium.
39. The method of claim 38, wherein the mass ratio of the manganese-cerium oxide to the ruthenium element in the ruthenium nanoparticles is 49:1 to 199: 1.
40. The method of claim 39, wherein the mass ratio of the manganese-cerium oxide to the ruthenium element in the ruthenium nanoparticles is 99: 1.
41. The production method according to claim 38, wherein the solid-liquid separation is a filtration separation.
42. The method of claim 38, wherein the step of dispersing the ruthenium nanoparticles on the surface of the manganese-cerium oxide in step (1) further comprises: and washing and drying the solid obtained by solid-liquid separation.
43. The production method according to claim 4, wherein in the step (2), the calcination is performed in an air atmosphere.
44. The method according to claim 4, wherein the temperature of the calcination in the step (2) is 100 to 400 ℃.
45. The method according to claim 44, wherein in the step (2), the temperature of the calcination is 250 ℃.
46. The method according to claim 4, wherein in the step (2), the roasting time is 0.5-2 h.
47. The method according to claim 46, wherein in the step (2), the roasting time is 1 h.
48. The method for preparing according to claim 4, characterized in that it comprises the following steps:
(1) mixing KMnO4And Ce (NO)3)3·6H2Dissolving O in water to form a mixed solution, and dropwise adding H with the mass concentration of 2% into the mixed solution under stirring2O2Then, adjusting the pH value by adopting 0.1mol/L NaOH solution to carry out precipitation, filtering, washing and drying the mixture, and roasting the mixture in the air at 500 ℃ for 6 hours to obtain manganese-cerium oxide;
wherein KMnO in the mixed solution4The concentration is 20g/L, KMnO4And Ce (NO)3)3In a molar ratio of 3: 1; h2O2And KMnO4The molar ratio is 4.5: 1;
(2) to 40mg/L of RuCl3Adding polyvinyl alcohol into the solution, and after the polyvinyl alcohol is completely dissolved, rapidly adding 0.1mol/L NaBH under stirring4Adding manganese-cerium oxide into the solution, standing until the solution is clear, filtering, washing and drying the mixture, and roasting the mixture in the air at 250 ℃ for 1h to obtain the manganese-cerium-ruthenium composite oxide catalyst;
wherein the weight average molecular weight of the polyvinyl alcohol is 8000-10000g/mol, the mass ratio of the polyvinyl alcohol to the ruthenium element is 2:1, and NaBH is added4The molar ratio of the manganese-cerium oxide to the ruthenium element is 5:1, and the mass ratio of the manganese-cerium oxide to the ruthenium element is 99: 1.
49. Use of the manganese cerium ruthenium composite oxide catalyst according to any one of claims 1 to 3 for the catalytic oxidation of volatile organic compounds.
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