CN108906044A - A kind of manganese cerium ruthenium composite oxide catalysts and its preparation method and application - Google Patents
A kind of manganese cerium ruthenium composite oxide catalysts and its preparation method and application Download PDFInfo
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- CN108906044A CN108906044A CN201810620896.1A CN201810620896A CN108906044A CN 108906044 A CN108906044 A CN 108906044A CN 201810620896 A CN201810620896 A CN 201810620896A CN 108906044 A CN108906044 A CN 108906044A
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- manganese
- ruthenium
- cerium
- oxide
- cerium oxide
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- 239000003054 catalyst Substances 0.000 title claims abstract description 108
- 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 33
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 86
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 86
- LQWKWJWJCDXKLK-UHFFFAOYSA-N cerium(3+) manganese(2+) oxygen(2-) Chemical compound [O--].[Mn++].[Ce+3] LQWKWJWJCDXKLK-UHFFFAOYSA-N 0.000 claims abstract description 79
- 238000000034 method Methods 0.000 claims abstract description 42
- 230000003647 oxidation Effects 0.000 claims abstract description 30
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 30
- 239000002105 nanoparticle Substances 0.000 claims abstract description 24
- 239000007788 liquid Substances 0.000 claims abstract description 21
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 17
- 238000000975 co-precipitation Methods 0.000 claims abstract description 12
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 10
- 229910003023 Mg-Al Inorganic materials 0.000 claims abstract description 9
- 239000006185 dispersion Substances 0.000 claims abstract description 9
- 230000007062 hydrolysis Effects 0.000 claims abstract description 9
- 238000004062 sedimentation Methods 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 61
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 45
- 239000011572 manganese Substances 0.000 claims description 41
- 229910052748 manganese Inorganic materials 0.000 claims description 30
- 239000012286 potassium permanganate Substances 0.000 claims description 30
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 29
- 239000011259 mixed solution Substances 0.000 claims description 27
- 229910052684 Cerium Inorganic materials 0.000 claims description 22
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 22
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 13
- 239000003638 chemical reducing agent Substances 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 11
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 9
- 239000012279 sodium borohydride Substances 0.000 claims description 8
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 8
- 238000010790 dilution Methods 0.000 claims description 5
- 239000012895 dilution Substances 0.000 claims description 5
- 229910019891 RuCl3 Inorganic materials 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- WYCDUUBJSAUXFS-UHFFFAOYSA-N [Mn].[Ce] Chemical compound [Mn].[Ce] WYCDUUBJSAUXFS-UHFFFAOYSA-N 0.000 claims description 3
- 239000005416 organic matter Substances 0.000 claims description 3
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 2
- -1 manganese-cerium oxide Manganese Chemical compound 0.000 claims 1
- 239000012855 volatile organic compound Substances 0.000 abstract description 23
- 229910000420 cerium oxide Inorganic materials 0.000 abstract description 20
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 11
- 239000000460 chlorine Substances 0.000 abstract description 9
- 229910052801 chlorine Inorganic materials 0.000 abstract description 8
- 231100000572 poisoning Toxicity 0.000 abstract description 7
- 230000000607 poisoning effect Effects 0.000 abstract description 7
- 239000012752 auxiliary agent Substances 0.000 description 23
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 18
- 238000011156 evaluation Methods 0.000 description 17
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 15
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 14
- 230000003197 catalytic effect Effects 0.000 description 12
- 238000001035 drying Methods 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052763 palladium Inorganic materials 0.000 description 7
- 229910052697 platinum Inorganic materials 0.000 description 7
- 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
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 4
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000005352 clarification Methods 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-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
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- ROZSPJBPUVWBHW-UHFFFAOYSA-N [Ru]=O Chemical group [Ru]=O ROZSPJBPUVWBHW-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003426 co-catalyst 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
- 150000001875 compounds Chemical class 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000001802 infusion Methods 0.000 description 2
- 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 2
- 238000002156 mixing Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 239000002699 waste material Substances 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 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- ROLJWXCAVGNMAK-UHFFFAOYSA-N [Ce]=O Chemical compound [Ce]=O ROLJWXCAVGNMAK-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000003708 ampul Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- ZRICEPGNZRJYMQ-UHFFFAOYSA-N cerium ruthenium Chemical compound [Ru].[Ce].[Ce].[Ce] ZRICEPGNZRJYMQ-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 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
- 230000002153 concerted effect Effects 0.000 description 1
- 238000006298 dechlorination reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 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
- 230000006872 improvement Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 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 1
- 210000000653 nervous system Anatomy 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001902 propagating effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000002633 protecting effect Effects 0.000 description 1
- 230000001681 protective effect Effects 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
- 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
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 239000002912 waste gas Substances 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
- B01J23/002—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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—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
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
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- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
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Abstract
The present invention provides a kind of manganese cerium ruthenium composite oxide catalysts and its preparation method and application.The manganese cerium ruthenium composite oxide catalysts include manganese-cerium oxide and are dispersed in the manganese-cerium oxide surface ru oxide.The preparation method includes：(1) manganese-cerium oxide is prepared using redox-Mg-Al hydrolysis and coprecipitation method；(2) dispersion liquid of ruthenium nano-particle is prepared using colloidal sol-sedimentation, the ruthenium nano-particle is dispersed in step (1) manganese-cerium oxide surface, obtained manganese-cerium oxide containing ruthenium, manganese-the cerium oxide containing ruthenium is roasted, the manganese cerium ruthenium composite oxide catalysts are obtained.Cost is relatively low for manganese cerium ruthenium composite oxide catalysts catalyst provided by the invention, lower to common VOCs complete oxidation temperature, and anti-chlorine poisoning performance is excellent, activity stabilized during catalysis oxidation CVOCs in lower temperature section.
Description
Technical field
The invention belongs to resource and environment technical fields, and in particular to a kind of manganese cerium ruthenium composite oxide catalysts and its system
Preparation Method and purposes.
Background technique
Volatile organic matter (volatile organic compounds, abbreviation VOCs) is PM2.5And O3Important forerunner
Body, can trigger the atmospheric environments problem such as haze, photochemical fog, and human body is chronically in the exceeded environment of VOCs, will cause
Liver, kidney and nervous system go to bits.By catalytic oxidation, VOCs is decomposed into CO at 150-500 DEG C2And H2O etc.
Small-molecule substance can thoroughly eliminate VOCs pollution, be suitably applied the VOCs mix waste gas without recovery value.
Efficiently, stable catalyst is the key that catalytic oxidation application.Currently, catalysis oxidation VOCs mainly uses valuableness
Platinum, palladium catalyst, the method that generalling use in reduces active component content reduces primary investment, practical catalysis oxidation fortune
Trip temperature is high, while platinum, palladium catalyst are in VOCs containing chlorine (chlorinated volatile organic compounds, letter
Claim CVOCs) catalytic oxidation process in activity it is lower and more chloro by-products are more.Studies have shown that the mistake by system optimization
The catalytic activity for crossing metal oxide catalyst can greatly improve, even more than platinum, palladium catalyst.However, transiting metal oxidation
Object catalyst is easy to fluorine poisoning inactivation in the catalytic oxidation process of CVOCs, this phenomenon is at lower temperature section (150-300 DEG C)
It is more obvious.
CN105289651A discloses the bimetallic catalyst and its preparation method and application of catalysis oxidation VOCs a kind of.It should
Catalyst using titanium dioxide as carrier, activating agent be ruthenium, in palladium or platinum any one element simple substance and/or its oxide, help
Catalyst is any one in cobaltosic oxide, manganese oxide, copper oxide or nickel oxide.Salen is utilized by nanometer control measures
, there is therebetween stronger concerted catalysis effect in the agent of ligand synthesizing activity and the uniform compound nano particle of co-catalyst, can
Improve the catalysis oxidation efficiency to VOCs.
CN107362800A discloses a kind of VOCs and eliminates catalyst and preparation method thereof, by hydrothermal method, by adding
Enter reducing agent, promotor, and adjust the molar ratio of Co and Mn, regulates and controls the pattern and nano-particles size of catalyst.The catalyst
Higher benzene catalytic oxidation activity is showed in wider temperature range.Catalyst reaches in 207 DEG C of benzene catalytic conversion
90%.The clean-up effect that the present invention provides catalyst is better than traditional benzene catalyst for catalytic oxidation.
CN107983365A provide it is a kind of using titanium foam as the preparation method of the VOCs catalyst of carrier, using titanium foam as base
Body generates TiO 2 precursor in its surface and duct after pre-processing titanium foam, and then high-temperature calcination obtains titanium foam-
Titanium dioxide, using titanium foam-titanium dioxide as carrier, by self- propagating calcination method load active component copper oxide, manganese oxide, with
And co-catalyst neodymia, cobalt oxide, obtain the catalyst for catalysis oxidation VOCs.
But there is higher cost, use scope relative narrower, preparation flow length etc. for the catalyst of above scheme offer
Problem.
Therefore, cost is relatively low, the research and development of catalyst of transition metal oxide applied widely and application are catalysis oxidations
Method is in the important channel of VOCs control field widespread adoption.
Summary of the invention
In view of the deficiencies of the prior art, the present invention intends to provide a kind of manganese cerium ruthenium composite oxide catalysts
And its preparation method and application.Manganese cerium ruthenium composite oxide catalysts provided by the invention have it is cheap, efficiently, universality it is strong
Advantage.
For this purpose, the present invention uses following technical scheme：
In a first aspect, the present invention provides a kind of manganese cerium ruthenium composite oxide catalysts, the manganese cerium ruthenium composite oxides are urged
Agent includes manganese-cerium oxide and is dispersed in the manganese-cerium oxide surface ru oxide.
In manganese cerium ruthenium composite oxide catalysts provided by the invention, active component is manganese-cerium oxide, and auxiliary agent is ruthenium oxygen
Compound.
Mn oxide hydro carbons VOCs common to ethane, propane, n-hexane, benzene, toluene etc. in active component manganese-cerium oxide
Preferable oxidability is all had, reaction process follows M-K mechanism, the process comprising providing Lattice Oxygen.And Mn oxide passes through
After cerium oxide doping, the Lattice Oxygen of cerium oxide can pass to the Mn oxide for losing Lattice Oxygen.In addition cerium oxide from
The ability that gas phase oxygen supplements Lattice Oxygen is stronger, thus manganese-cerium has synergistic effect in VOCs catalytic oxidation process, is catalyzed oxygen
Change the more single manganese of activity or cerium oxide significantly improves.
Manganese-cerium oxide is in the catalytic oxidation process of CVOCs, and catalyst surface is easy accumulation chlorine species, even if in height
Temperature roasting is also difficult to remove, and leading to active component, there are a degree of chlorinations to inactivate.RuO2It is that Deacon reacts Cl processed2Master
Active component is wanted, manganese-cerium oxide surface chlorine species can be in RuO2Under the action of effectively remove.
Compared with platinum, palladium catalyst, cost is relatively low, applied widely for manganese cerium ruthenium composite oxide catalysts, has good
Application prospect.
Manganese cerium ruthenium composite oxide catalysts provided by the invention are solid powdery, can be made according to actual needs various
Planform, such as catalyst can be made to the spherical of different sizes, graininess and honeycomb etc..
It is used as currently preferred technical solution below, but not as the limitation to technical solution provided by the invention, leads to
Following preferred technical solution is crossed, can preferably reach and realize technical purpose and beneficial effect of the invention.
As currently preferred technical solution, manganese and cerium molar ratio are 1 in the manganese-cerium oxide:4-9:1, such as
1:4,1:3,1:2,1:1,3:1,5:1,7:1 or 9:1 etc., it is not limited to cited numerical value, in the numberical range other
Unlisted numerical value is equally applicable.
Preferably, in the manganese cerium ruthenium composite oxide catalysts, the mass fraction of ru oxide is calculated as 0.1- with ruthenium
5wt%, such as 0.1wt%, 0.5wt%, 1wt%, 2wt%, 3wt%, 4wt% or 5wt% etc., it is not limited to cited
Numerical value, other unlisted numerical value are equally applicable in the numberical range.
Preferably, in the manganese cerium ruthenium composite oxide catalysts, the partial size of ru oxide is 3-10nm, such as 3nm,
4nm, 6nm, 8nm or 10nm etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are same
It is applicable in.Ru oxide has Particle size effect, the ruthenium atom of its surface unsaturation of various sizes of ru oxide particle coordination
Dechlorination is different, the control of ru oxide particle size may be implemented by preparation condition regulation, and then improve the anti-of catalyst
Fluorine poisoning ability.
Second aspect, the present invention provide a kind of preparation side of manganese cerium ruthenium composite oxide catalysts as described in relation to the first aspect
Method the described method comprises the following steps：
(1) manganese-cerium oxide is prepared using redox-Mg-Al hydrolysis and coprecipitation method；
(2) dispersion liquid that ruthenium nano-particle is prepared using colloidal sol-sedimentation, is dispersed in step for the ruthenium nano-particle
(1) manganese-cerium oxide surface, obtained manganese-cerium oxide containing ruthenium roast the manganese-cerium oxide containing ruthenium, obtain
The manganese cerium ruthenium composite oxide catalysts.
In preparation method provided by the invention, the manganese-cerium oxide prepared using redox-Mg-Al hydrolysis and coprecipitation method, with
The conventional obtained manganese-cerium oxide of coprecipitation is compared, and more preferable in the uniformity coefficient of micro-scale mixing, catalyst activity is more
It is high.Metal ruthenium nano-particle is prepared using colloidal sol-sedimentation and is dispersed in manganese-cerium oxide surface, is fired to obtain ruthenium oxidation
Object (predominantly RuO2), traditional infusion process defect unevenly distributed is avoided, while ruthenium can control by preparation condition regulation
The partial size of oxide is between 3-10nm.
As currently preferred technical solution, in step (1), the redox-Mg-Al hydrolysis and coprecipitation method prepares manganese-cerium
Oxide includes the following steps：Manganese source and cerium source are mixed to get mixed solution in a solvent, are added into the mixed solution
H2O2And adjust pH and precipitated, it is separated by solid-liquid separation later, solid is roasted, obtain the manganese-cerium oxide.Here, it is added
H2O2And the operation that adjusting pH is precipitated is so that the substance containing manganese in solution and species precipitate containing cerium are complete.
As technical solution of the present invention, the manganese source is KMnO4。
Preferably, in the mixed solution, the concentration of manganese source is 10-50, for example, 10g/L, 20g/L, 30g/L, 40g/L or
50g/L etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally applicable such as excellent
It is selected as 20g/L.
Preferably, the cerium source includes Ce (NO3)3·6H2O。
Preferably, in the mixed solution, the molar ratio in manganese source and cerium source is 2:1-4:1, such as 2:1,2.5:1,3:1,
3.5:1 or 4:1 etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally applicable, excellent
It is selected as 3:1.
Preferably, the solvent is water.
Preferably, the H2O2Adding manner be added dropwise.To guarantee fully reacting, excessive H can be added2O2。
Preferably, H is added2O2While with stirring.
Preferably, the H2O2For the H after dilution2O2。
Preferably, the H after the dilution2O2In, H2O2Mass concentration be 0.5-10%, such as 0.5%, 1%, 2%,
4%, 6% or 10% etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally suitable
With preferably 2%.
Preferably, the H2O2Molar ratio with manganese source is 3:1-6:1, such as 3:1,4:1,5:1 or 6:1 etc., but not
It is only limitted to cited numerical value, other unlisted numerical value are equally applicable in the numberical range, and preferably 4.5:1.
Preferably, pH is adjusted with the NaOH solution of 0.1mol/L.
In the present invention, in H2O2To KMnO4With Ce (NO3)3It is chemically reacted during mixed solution and dripping, 6MnO4 -
+2Ce3++9H2O2=6MnO2+2Ce(OH)3+6H2O+9O2, manganese, cerium precipitating are then generated simultaneously.KMnO in mixed solution4And Ce
(NO3)3Or the H after dilution2O2Concentration it is too low will cause water resource waste, and excessive concentration causes redox reaction excessively
Strongly, it will lead to manganese, cerium is deposited in micro-scale mixing unevenly.Excessive H is added2O2It can guarantee KMnO4Fully reacting, when
Ce3+It can guarantee Ce by adjusting pH when excessive3+Precipitating is complete.
Preferably, described to be separated by solid-liquid separation to be separated by filtration.
Preferably, it further includes obtaining to separation of solid and liquid that the redox-Mg-Al hydrolysis and coprecipitation method, which prepares manganese-cerium oxide,
Solid is washed and is dried.
Preferably, the roasting carries out in air atmosphere.
Preferably, the temperature of the roasting is 400-600 DEG C, such as 400 DEG C, 450 DEG C, 500 DEG C, 550 DEG C or 600 DEG C
Deng, it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally applicable, preferably 500 DEG C；
Preferably, the time of the roasting is 2-10h, such as 2h, 4h, 6h, 8h or 10h etc., it is not limited to listed
The numerical value of act, other interior unlisted numerical value of the numberical range are equally applicable, preferably 6h.
During preparing manganese-cerium oxide using redox-Mg-Al hydrolysis and coprecipitation method, maturing temperature is too low, the time
The too short catalyst microstructure that will cause is not sufficiently stable, and maturing temperature is excessively high, overlong time will lead to manganese-cerium oxide and burn
Knot, specific surface area degradation influence catalyst activity.
As currently preferred technical solution, in step (2), the colloidal sol-sedimentation prepares point of ruthenium nano-particle
The method of dispersion liquid includes the following steps：Polyvinyl alcohol is added into ruthenium precursor solution, adds reducing agent, obtains ruthenium nanometer
The dispersion liquid of grain.
Preferably, the ruthenium presoma is RuCl3And/or Ru (NO) (NO3)3, preferably RuCl3。
Preferably, the concentration of the ruthenium precursor solution be 25-100mg/L, such as 25mg/L, 35mg/L, 40mg/L,
50mg/L, 65mg/L, 75mg/L, 95mg/L or 100mg/L etc., it is not limited to cited numerical value, in the numberical range
Other unlisted numerical value are equally applicable, preferably 40mg/L.
Preferably, the weight average molecular weight of the polyvinyl alcohol is 8000-10000g/mol.
Preferably, the mass ratio of the polyvinyl alcohol and the ruthenium element in ruthenium precursor solution is 1:1-5:1, such as 1:1,
2:1,3:1,4:1 or 5:1 etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are same
It is applicable in, preferably 2:1.
Preferably, with stirring while reducing agent is added.
In the present invention, it is preferably rapidly added reducing agent.
Polyvinyl alcohol plays a protective role during the presoma of reducing agent reduction ruthenium obtains metal ruthenium nano-particle,
Polyvinyl alcohol ratio is too low to will cause that protecting effect is bad, and obtained metal Ru nanoparticle size is excessive or even forms precipitating,
And the excessively high metal ruthenium nano-particle that will lead to generation of polyvinyl alcohol ratio is too small.
Preferably, the reducing agent is NaBH4Solution.
Preferably, the NaBH4The concentration of solution be 0.01-0.5mol/L, such as 0.01mol/L, 0.05mol/L,
0.1mol/L, 0.2mol/L, 0.3mol/L, 0.4mol/L or 0.5mol/L etc., it is not limited to cited numerical value, the number
It is equally applicable to be worth other unlisted numerical value in range, preferably 0.1mol/L.
Preferably, the molar ratio of the reducing agent and ruthenium element in ruthenium precursor solution is 3:1-10:1, such as 3:1,5:
1,7:1,9:1 or 10:1 etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally suitable
With preferably 5:1.
NaBH4As the reducing agent of ruthenium, the too low ruthenium that will cause of ratio can not be restored all, and ratio is excessively excessively high to lead
Cause forms larger-size metal ruthenium nano-particle or even metal Ru precipitating.NaBH4The concentration of solution is too low to will cause water resource
Waste, and excessive concentration will lead to local reduction and react excessively strong, obtained metal ruthenium nano-particle homogeneity is poor.
As currently preferred technical solution, in step (2), it is described that the ruthenium nano-particle is dispersed in step (1)
Manganese-cerium oxide surface method includes the following steps：It is described that step (1) is added into the dispersion liquid of the ruthenium nano-particle
Manganese-cerium oxide is stood, and is separated by solid-liquid separation, and obtained solid is manganese-cerium oxide containing ruthenium.
Preferably, the mass ratio for stating ruthenium element in manganese-cerium oxide and ruthenium nano-particle is 49:1-199:1, such as
49:1,99:1,149:1 or 199:1 etc., it is not limited to cited numerical value, other interior unlisted numbers of the numberical range
Be worth it is equally applicable, preferably 99:1.
Preferably, described to be separated by solid-liquid separation to be separated by filtration.
Preferably, the ruthenium nano-particle is dispersed in step (1) manganese-cerium oxide surface method further includes：
The solid obtained to separation of solid and liquid is washed and is dried.
As currently preferred technical solution, in step (2), the roasting carries out in air atmosphere.
In step (2), the temperature of the roasting is 100-400 DEG C, such as 100 DEG C, 150 DEG C, 200 DEG C, 250 DEG C, 300
DEG C, 350 DEG C or 400 DEG C etc., it is not limited to cited numerical value, other unlisted numerical value are equally suitable in the numberical range
With preferably 250 DEG C.
Preferably, in step (2), time of the roasting is 0.5-2h, such as 0.5h, 1h, 1.5h or 2h etc., preferably
1h。
Although the price of ruthenium is far below platinum, palladium, for ruthenium as a member in platinum group metal, price is still higher, therefore
The dosage of ruthenium should be reduced while improving catalyst anti-chlorine poisoning capability to the greatest extent.
The further preferred technical solution of preparation method as negative electrode material of the present invention, the method includes following
Step：
(1) by KMnO4With Ce (NO3)3·6H2O is dissolved in water and forms mixed solution, under stiring to mixed solution and dripping
The H that mass concentration is 2%2O2, pH is adjusted using the NaOH solution of 0.1mol/L later and is precipitated, mixture is filtered, washed
500 DEG C of roasting 6h obtain manganese-cerium oxide in air after washing, drying；
Wherein, KMnO in the mixed solution4Concentration is 20g/L, KMnO4With Ce (NO3)3Molar ratio be 3:1；H2O2With
KMnO4Molar ratio is 4.5:1；
(2) to the RuCl of 40mg/L3Polyvinyl alcohol is added in solution, after it is completely dissolved, is rapidly added under stiring
The NaBH of 0.1mol/L4Manganese-cerium oxide is added later and stands to solution and clarifies for solution, and mixture is filtered, washed, is done
250 DEG C of roasting 1h obtain manganese cerium ruthenium composite oxide catalysts in air after dry；
Wherein, the weight average molecular weight of the polyvinyl alcohol is 8000-10000g/mol, the polyvinyl alcohol and ruthenium element
Mass ratio is 2:1, NaBH4Molar ratio with ruthenium element is 5:1, manganese-cerium oxide and ruthenium element mass ratio are 99:1.
The third aspect, the present invention provide a kind of purposes of manganese cerium ruthenium composite oxide catalysts as described in relation to the first aspect, institute
Manganese cerium ruthenium composite oxide catalysts are stated for catalysis oxidation volatile organic matter.
Compared with prior art, the invention has the advantages that：
(1) in manganese cerium ruthenium composite oxide catalysts provided by the invention, manganese-cerium oxide is uniformly mixed in micro-scale
It closes, there are stronger synergistic effect between manganese-cerium, catalyst activity is significantly improved, and is dispersed in manganese-cerium oxide surface ruthenium oxygen
Compound enhances the anti-chlorine poisoning capability of catalyst, and compared with platinum, palladium catalyst, cost is relatively low for catalyst of the invention, to normal
See that VOCs complete oxidation temperature is 210-420 DEG C, and anti-chlorine poisoning performance is excellent, at lower temperature section (150-300 DEG C)
It is activity stabilized during catalysis oxidation CVOCs.
(2) preparation method process provided by the invention is short, and easy to operate, preparation cost is low, is appropriate for extensive industry
Metaplasia produces.
Specific embodiment
Below by specific embodiment to further illustrate the technical scheme of the present invention.Those skilled in the art should be bright
, the described embodiments are merely helpful in understanding the present invention, should not be regarded as a specific limitation of the invention.
Embodiment 1
A kind of preparation method of manganese cerium ruthenium composite oxide catalysts, specific method are：
(1) by KMnO4With Ce (NO3)3·6H2O is dissolved in water and forms mixed solution (KMnO4Concentration is 20g/L, KMnO4And Ce
(NO3)3Molar ratio be 3:1) H for being under stiring, 2% to mixed solution and dripping mass concentration2O2(with KMnO4Molar ratio
It is 4.5:1) it, adjusts pH using the NaOH solution of 0.1mol/L later to be precipitated, mixture exists after filtration, washing and drying
500 DEG C of roasting 6h obtain manganese-cerium oxide in air.
(2) to the RuCl of 40mg/L3PVA (weight average molecular weight 8000-10000g/mol, with ruthenium element is added in solution
Mass ratio is 2:1), after it is completely dissolved, it is rapidly added the NaBH of 0.1mol/L under stiring4Solution is (with rubbing for ruthenium element
You are than being 5:1) it (is 99 with ruthenium element mass ratio that manganese-cerium oxide, is added later:1) it and stands to solution clarification, mixture warp
250 DEG C of roasting 1h obtain manganese cerium ruthenium composite oxide catalysts in air after being filtered, washed, drying.
The manganese cerium ruthenium composite oxide catalysts that the present embodiment is prepared are by manganese-cerium oxide and are dispersed in the manganese-
The ru oxide on cerium oxide surface forms, and active component is manganese-cerium oxide, and auxiliary agent is ru oxide, manganese in active component,
Cerium molar ratio is 3:1, auxiliary agent ru oxide (in terms of ruthenium) mass fraction is about 1%, and the partial size of ru oxide is 3-10nm.
Performance evaluation is carried out to the manganese cerium ruthenium composite oxide catalysts that the present embodiment is prepared, what is obtained the results are shown in Table
1。
Embodiment 2
The present embodiment removes manganese in active component manganese-cerium oxide, cerium molar ratio is 1:Except 4, remaining and 1 phase of embodiment
Together.
The manganese cerium ruthenium composite oxide catalysts that the present embodiment is prepared are by manganese-cerium oxide and are dispersed in the manganese-
The ru oxide on cerium oxide surface forms, and active component is manganese-cerium oxide, and auxiliary agent is ru oxide, manganese in active component,
Cerium molar ratio is 1:4, auxiliary agent ru oxide (in terms of ruthenium) mass fraction is about 1%, and the partial size of ru oxide is 3-10nm.
Performance evaluation is carried out to the manganese cerium ruthenium composite oxide catalysts that the present embodiment is prepared, what is obtained the results are shown in Table
1。
Embodiment 3
The present embodiment removes manganese in active component manganese-cerium oxide, cerium molar ratio is 9:Except 1, remaining and 1 phase of embodiment
Together.
The manganese cerium ruthenium composite oxide catalysts that the present embodiment is prepared are by manganese-cerium oxide and are dispersed in the manganese-
The ru oxide on cerium oxide surface forms, and active component is manganese-cerium oxide, and auxiliary agent is ru oxide, manganese in active component,
Cerium molar ratio is 9:1, auxiliary agent ru oxide (in terms of ruthenium) mass fraction is 1%, and the partial size of ru oxide is 3-10nm.
Performance evaluation is carried out to the manganese cerium ruthenium composite oxide catalysts that the present embodiment is prepared, what is obtained the results are shown in Table
1。
Embodiment 4
For the present embodiment in addition to auxiliary agent ru oxide (in terms of ruthenium) mass fraction is 0.1%, remaining is same as Example 1.
The manganese cerium ruthenium composite oxide catalysts that the present embodiment is prepared are by manganese-cerium oxide and are dispersed in the manganese-
The ru oxide on cerium oxide surface forms, and active component is manganese-cerium oxide, and auxiliary agent is ru oxide, manganese in active component,
Cerium molar ratio is 3:1, auxiliary agent ru oxide (in terms of ruthenium) mass fraction is 0.1%, and the partial size of ru oxide is 3-10nm.
Performance evaluation is carried out to the manganese cerium ruthenium composite oxide catalysts that the present embodiment is prepared, what is obtained the results are shown in Table
1。
Embodiment 5
For the present embodiment in addition to auxiliary agent ru oxide (in terms of ruthenium) mass fraction is 5.0%, remaining is same as Example 1.
The manganese cerium ruthenium composite oxide catalysts that the present embodiment is prepared are by manganese-cerium oxide and are dispersed in the manganese-
The ru oxide on cerium oxide surface forms, and active component is manganese-cerium oxide, and auxiliary agent is ru oxide, manganese in active component,
Cerium molar ratio is 3:1, auxiliary agent ru oxide (in terms of ruthenium) mass fraction is 5.0%, and the partial size of ru oxide is 3-10nm.
Performance evaluation is carried out to the manganese cerium ruthenium composite oxide catalysts that the present embodiment is prepared, what is obtained the results are shown in Table
1。
Embodiment 6
For the present embodiment in addition to the average grain diameter of auxiliary agent ru oxide is less than 2nm, remaining is same as Example 1.
The manganese cerium ruthenium composite oxide catalysts that the present embodiment is prepared are by manganese-cerium oxide and are dispersed in the manganese-
The ru oxide on cerium oxide surface forms, and active component is manganese-cerium oxide, and auxiliary agent is ru oxide, manganese in active component,
Cerium molar ratio is 3:1, auxiliary agent ru oxide (in terms of ruthenium) mass fraction is 1%, and the average grain diameter of ru oxide is less than 2nm.
Performance evaluation is carried out to the manganese cerium ruthenium composite oxide catalysts that the present embodiment is prepared, what is obtained the results are shown in Table
1。
Embodiment 7
For the present embodiment in addition to the partial size of auxiliary agent ru oxide is 10-15nm, remaining is same as Example 1.
The manganese cerium ruthenium composite oxide catalysts that the present embodiment is prepared are by manganese-cerium oxide and are dispersed in the manganese-
The ru oxide on cerium oxide surface forms, and active component is manganese-cerium oxide, and auxiliary agent is ru oxide, manganese in active component,
Cerium molar ratio is 3:1, auxiliary agent ru oxide (in terms of ruthenium) mass fraction is 1%, and the partial size of ru oxide is 10-15nm.
Performance evaluation is carried out to the manganese cerium ruthenium composite oxide catalysts that the present embodiment is prepared, what is obtained the results are shown in Table
1。
Embodiment 8
A kind of preparation method of manganese cerium ruthenium composite oxide catalysts, specific method are：
(1) by KMnO4With Ce (NO3)3·6H2O is dissolved in water and forms mixed solution (KMnO4Concentration is 10g/L, KMnO4And Ce
(NO3)3Molar ratio be 2:1) H for being under stiring, 0.5% to mixed solution and dripping mass concentration2O2(with KMnO4Mole
Than being 4:1) it, adjusts pH using the NaOH solution of 0.1mol/L later to be precipitated, mixture exists after filtration, washing and drying
400 DEG C of roasting 10h obtain manganese-cerium oxide in air.
(2) to the RuCl of 25mg/L3PVA (weight average molecular weight 8000-10000g/mol, with ruthenium element is added in solution
Mass ratio is 5:1), after it is completely dissolved, it is rapidly added the NaBH of 0.01mol/L under stiring4Solution is (with rubbing for ruthenium element
You are than being 3:1) it (is 49 with ruthenium element mass ratio that manganese-cerium oxide, is added later:1) it and stands to solution clarification, mixture warp
100 DEG C of roasting 2h obtain manganese cerium ruthenium composite oxide catalysts in air after being filtered, washed, drying.
The manganese cerium ruthenium composite oxide catalysts that the present embodiment is prepared are by manganese-cerium oxide and are dispersed in the manganese-
The ru oxide on cerium oxide surface forms, and active component is manganese-cerium oxide, and auxiliary agent is ru oxide, manganese in active component,
Cerium molar ratio is 2:1, auxiliary agent ru oxide (in terms of ruthenium) mass fraction is about 2%, and the partial size of ru oxide is 4-12nm.
Performance evaluation is carried out to the manganese cerium ruthenium composite oxide catalysts that the present embodiment is prepared, what is obtained the results are shown in Table
1。
Embodiment 9
A kind of preparation method of manganese cerium ruthenium composite oxide catalysts, specific method are：
(1) by KMnO4With Ce (NO3)3·6H2O is dissolved in water and forms mixed solution (KMnO4Concentration is 50g/L, KMnO4And Ce
(NO3)3Molar ratio be 4:1) H for being under stiring, 10% to mixed solution and dripping mass concentration2O2(with KMnO4Molar ratio
It is 5:1) it, adjusts pH using the NaOH solution of 0.1mol/L later to be precipitated, mixture is after filtration, washing and drying in sky
600 DEG C of roasting 2h obtain manganese-cerium oxide in gas.
(2) to the RuCl of 100mg/L3PVA (weight average molecular weight 8000-10000g/mol, with ruthenium element is added in solution
Mass ratio is 1:1), after it is completely dissolved, it is rapidly added the NaBH of 0.5mol/L under stiring4Solution is (with rubbing for ruthenium element
You are than being 10:1) it (is 199 with ruthenium element mass ratio that manganese-cerium oxide, is added later:1) it and stands to solution clarification, mixture
400 DEG C of roasting 0.5h obtain manganese cerium ruthenium composite oxide catalysts in air after filtration, washing and drying.
The manganese cerium ruthenium composite oxide catalysts that the present embodiment is prepared are by manganese-cerium oxide and are dispersed in the manganese-
The ru oxide on cerium oxide surface forms, and active component is manganese-cerium oxide, and auxiliary agent is ru oxide, manganese in active component,
Cerium molar ratio is 4:1, auxiliary agent ru oxide (in terms of ruthenium) mass fraction is about 0.5%, and the partial size of ru oxide is 3-8nm.
Performance evaluation is carried out to the manganese cerium ruthenium composite oxide catalysts that the present embodiment is prepared, what is obtained the results are shown in Table
1。
Comparative example 1
A kind of manganese oxide catalyst of catalysis oxidation VOCs, the preparation method of the catalyst are the precipitation method, including with
Lower step：
Configure (the CH of 20g/L3COO)2The NaOH solution of Mn solution and 8g/L, under stiring by same volume
(CH3COO)2Mn solution is added dropwise in NaOH solution, and 500 DEG C of roasting 6h are obtained mixture in air after filtration, washing and drying
To Mn oxide.
Performance evaluation is carried out to the manganese oxide catalyst that this comparative example obtains, what is obtained the results are shown in Table 1.
Comparative example 2
A kind of cerium oxide catalyst of catalysis oxidation VOCs, the preparation method of the catalyst are the precipitation method, including with
Lower step：
Configure the Ce (NO of 20g/L3)3·6H2The NaOH solution of O solution and 8g/L, under stiring by the Ce of same volume
(NO3)3Solution is added dropwise in NaOH solution, and 500 DEG C of roasting 6h obtain cerium oxygen to mixture in air after filtration, washing and drying
Compound.
Performance evaluation is carried out to the cerium oxide catalyst that this comparative example obtains, what is obtained the results are shown in Table 1.
Comparative example 3
A kind of manganese of catalysis oxidation VOCs-cerium oxide catalyst, the preparation method of the catalyst are coprecipitation, packet
Include following steps：
By Mn (CH3COO)2·4H2O and Ce (NO3)3·6H2O is dissolved in water and forms mixed solution (Mn (CH3COO)2Concentration is
15g/L, Mn (CH3COO)2With Ce (NO3)3Molar ratio be 3:1) NaOH solution of 8g/L, is configured, under stiring by Mn
(CH3COO)2With Ce (NO3)3Mixed solution be added dropwise in the NaOH solution of same volume, mixture is filtered, washed, is dried
500 DEG C of roasting 6h obtain Mn oxide in air afterwards.
The manganese obtained to this comparative example-cerium oxide catalyst carries out performance evaluation, and what is obtained the results are shown in Table 1.
Comparative example 4
A kind of manganese of catalysis oxidation VOCs-cerium oxide catalyst, the preparation method of the catalyst are redox-water
Coprecipitation is solved, is included the following steps：
By KMnO4With Ce (NO3)3·6H2O is dissolved in water and forms mixed solution (KMnO4Concentration is 20g/L, KMnO4And Ce
(NO3)3Molar ratio be 3:1) H for being under stiring, 2% to mixed solution and dripping mass concentration2O2(with KMnO4Molar ratio
It is 4.5:1) it, adjusts pH using the NaOH solution of 0.1mol/L later to be precipitated, mixture exists after filtration, washing and drying
500 DEG C of roasting 6h obtain manganese-cerium oxide in air.
The manganese obtained to this comparative example-cerium oxide catalyst carries out performance evaluation, and what is obtained the results are shown in Table 1.
Comparative example 5
A kind of manganese cerium ruthenium mixed oxide catalyst of catalysis oxidation VOCs, the preparation method of the catalyst are that oxidation is gone back
Original-Mg-Al hydrolysis and coprecipitation method and infusion process, include the following steps：
(1) by KMnO4With Ce (NO3)3·6H2O is dissolved in water and forms mixed solution (KMnO4Concentration is 20g/L, KMnO4And Ce
(NO3)3Molar ratio be 3:1) H for being under stiring, 2% to mixed solution and dripping mass concentration2O2(with KMnO4Molar ratio
It is 4.5:1) it, adjusts pH using the NaOH solution of 0.1mol/L later to be precipitated, mixture exists after filtration, washing and drying
500 DEG C of roasting 6h obtain manganese-cerium oxide in air.
(2) Ru (NO) (NO of 1g/L is configured3)3Solution, it (is 99 with ruthenium element mass ratio that manganese-cerium oxide is added later:
1) 250 DEG C of roasting 1h obtain manganese cerium ruthenium composite oxide catalysts in air after, mixture is evaporated, dried.
Performance evaluation is carried out to the manganese cerium ruthenium mixed oxide catalyst that this comparative example obtains, what is obtained the results are shown in Table 1.
In the embodiment and comparative example provided, the condition for carrying out performance evaluation to catalyst is as follows：
Reactor：Fixed-bed micro-reactor is internal diameter 4mm quartz ampoule；
Range of reaction temperature：100~450 DEG C；
System pressure：1~1.05atm；
Catalyst quality：100mg；
Reaction velocity：60000mL·g-1·h-1；
Organic concentration：1000ppm；
Oxygen content：20vol.%.
Different embodiment and comparative example catalyst the results are shown in Table 1 to the catalytic evaluation of benzene and dichloroethanes.
Catalytic evaluation result of 1 catalyst of table to benzene and dichloroethanes
Based on the above embodiments with comparative example it is found that manganese cerium ruthenium composite oxide catalysts provided by the invention are to common
VOCs complete oxidation temperature is lower, and anti-chlorine poisoning performance is excellent, in the process of lower temperature section catalysis oxidation CVOCs
In it is activity stabilized.Comparative example does not use the solution of the present invention, thus can not obtain effect of the invention.
The Applicant declares that the present invention is explained by the above embodiments method detailed of the invention, but the present invention not office
Be limited to above-mentioned method detailed, that is, do not mean that the invention must rely on the above detailed methods to implement.Technical field
Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to each raw material of product of the present invention
Addition, selection of concrete mode etc., all of which fall within the scope of protection and disclosure of the present invention.
Claims (10)
1. a kind of manganese cerium ruthenium composite oxide catalysts, which is characterized in that the manganese cerium ruthenium composite oxide catalysts include manganese-
Cerium oxide and it is dispersed in the manganese-cerium oxide surface ru oxide.
2. manganese cerium ruthenium composite oxide catalysts according to claim 1, which is characterized in that in the manganese-cerium oxide
Manganese and cerium molar ratio are 1:4-9:1；
Preferably, in the manganese cerium ruthenium composite oxide catalysts, the mass fraction of ru oxide is calculated as 0.1-5wt% with ruthenium；
Preferably, in the manganese cerium ruthenium composite oxide catalysts, the partial size of ru oxide is 3-10nm.
3. the preparation method of manganese cerium ruthenium composite oxide catalysts according to claim 1 or 2, which is characterized in that described
Preparation method includes the following steps：
(1) manganese-cerium oxide is prepared using redox-Mg-Al hydrolysis and coprecipitation method；
(2) dispersion liquid that ruthenium nano-particle is prepared using colloidal sol-sedimentation, is dispersed in step (1) institute for the ruthenium nano-particle
Manganese-cerium oxide surface is stated, obtained manganese-cerium oxide containing ruthenium roasts the manganese-cerium oxide containing ruthenium, obtains described
Manganese cerium ruthenium composite oxide catalysts.
4. preparation method according to claim 3, which is characterized in that in step (1), the redox-hydrolysis is coprecipitated
Shallow lake method prepares manganese-cerium oxide and includes the following steps：Manganese source and cerium source are mixed to get mixed solution in a solvent, mixed to described
It closes in solution and H is added2O2And adjust pH and precipitated, it is separated by solid-liquid separation later, solid is roasted, obtain the manganese-cerium oxidation
Object.
5. the preparation method according to claim 4, which is characterized in that the manganese source is KMnO4；
Preferably, in the mixed solution, the concentration of manganese source is 10-50g/L, preferably 20g/L；
Preferably, the cerium source includes Ce (NO3)3·6H2O；
Preferably, in the mixed solution, the molar ratio in manganese source and cerium source is 2:1-4:1, preferably 3:1；
Preferably, the solvent is water；
Preferably, the H2O2Adding manner be added dropwise；
Preferably, H is added2O2While with stirring；
Preferably, the H2O2For the H after dilution2O2；
Preferably, the H after the dilution2O2In, H2O2Mass concentration be 0.5-10%, preferably 2%；
Preferably, the H2O2Molar ratio with manganese source is 3:1-6:1, preferably 4.5:1；
Preferably, pH is adjusted with the NaOH solution of 0.1mol/L；
Preferably, described to be separated by solid-liquid separation to be separated by filtration；
Preferably, it further includes the solid obtained to separation of solid and liquid that the redox-Mg-Al hydrolysis and coprecipitation method, which prepares manganese-cerium oxide,
It is washed and is dried；
Preferably, the roasting carries out in air atmosphere；
Preferably, the temperature of the roasting is 400-600 DEG C, preferably 500 DEG C；
Preferably, the time of the roasting is 2-10h, preferably 6h.
6. the preparation method according to any one of claim 3-5, which is characterized in that in step (2), the colloidal sol-is heavy
The method that area method prepares the dispersion liquid of ruthenium nano-particle includes the following steps：Polyvinyl alcohol is added into ruthenium precursor solution, then
Reducing agent is added, obtains the dispersion liquid of ruthenium nano-particle；
Preferably, the ruthenium presoma is RuCl3And/or Ru (NO) (NO3)3, preferably RuCl3；
Preferably, the concentration of the ruthenium precursor solution is 25-100mg/L, preferably 40mg/L；
Preferably, the weight average molecular weight of the polyvinyl alcohol is 8000-10000g/mol；
Preferably, the mass ratio of the polyvinyl alcohol and the ruthenium element in ruthenium precursor solution is 1:1-5:1, preferably 2:1；
Preferably, with stirring while reducing agent is added；
Preferably, the reducing agent is NaBH4Solution；
Preferably, the NaBH4The concentration of solution is 0.01-0.5mol/L, preferably 0.1mol/L；
Preferably, the molar ratio of the reducing agent and ruthenium element in ruthenium precursor solution is 3:1-10:1, preferably 5:1.
7. the preparation method according to any one of claim 3-6, which is characterized in that in step (2), by the ruthenium nanometer
Particle is dispersed in step (1) manganese-cerium oxide surface method and includes the following steps：Dispersion to the ruthenium nano-particle
Step (1) described manganese-cerium oxide is added in liquid, stands, is separated by solid-liquid separation, obtained solid is manganese-cerium oxide containing ruthenium；
Preferably, the mass ratio for stating ruthenium element in manganese-cerium oxide and ruthenium nano-particle is 49:1-199:1, preferably
99:1；
Preferably, described to be separated by solid-liquid separation to be separated by filtration；
Preferably, the ruthenium nano-particle is dispersed in step (1) manganese-cerium oxide surface method further includes：To solid
The isolated solid of liquid is washed and is dried.
8. the preparation method according to any one of claim 3-7, which is characterized in that in step (2), the roasting is in sky
It is carried out under gas atmosphere；
In step (2), the temperature of the roasting is 100-400 DEG C, preferably 250 DEG C；
Preferably, in step (2), the time of the roasting is 0.5-2h, preferably 1h.
9. the preparation method according to any one of claim 3-8, which is characterized in that the method includes steps once：
(1) by KMnO4With Ce (NO3)3·6H2O is dissolved in water and forms mixed solution, dense to mixed solution and dripping quality under stiring
The H that degree is 2%2O2, pH is adjusted using the NaOH solution of 0.1mol/L later and is precipitated, mixture is filtered, washed, is dried
500 DEG C of roasting 6h obtain manganese-cerium oxide in air afterwards；
Wherein, KMnO in the mixed solution4Concentration is 20g/L, KMnO4With Ce (NO3)3Molar ratio be 3:1；H2O2With KMnO4
Molar ratio is 4.5:1；
(2) to the RuCl of 40mg/L3Polyvinyl alcohol is added in solution, after it is completely dissolved, is rapidly added under stiring
The NaBH of 0.1mol/L4Manganese-cerium oxide is added later and stands to solution and clarifies for solution, and mixture is filtered, washed, is done
250 DEG C of roasting 1h obtain manganese cerium ruthenium composite oxide catalysts in air after dry；
Wherein, the weight average molecular weight of the polyvinyl alcohol is 8000-10000g/mol, the quality of the polyvinyl alcohol and ruthenium element
Than being 2:1, NaBH4Molar ratio with ruthenium element is 5:1, manganese-cerium oxide and ruthenium element mass ratio are 99:1.
10. the purposes of manganese cerium ruthenium composite oxide catalysts according to claim 1 or 2, which is characterized in that the manganese cerium
Ruthenium composite oxide catalysts are used for catalysis oxidation volatile organic matter.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109569229A (en) * | 2018-12-29 | 2019-04-05 | 安徽工业大学 | Method for combined desulfurization and denitrification of iron ore sintering flue gas |
| CN113680383A (en) * | 2021-08-25 | 2021-11-23 | 江苏中科睿赛污染控制工程有限公司 | Composite material for purifying aldehydes and benzene series in air as well as preparation method and application thereof |
| CN113797935A (en) * | 2021-10-14 | 2021-12-17 | 常州汇清环保科技有限公司 | Catalyst for low-temperature efficient treatment of VOCs and preparation method thereof |
| CN114573450A (en) * | 2020-12-01 | 2022-06-03 | 中国科学院大连化学物理研究所 | Method for preparing acetic acid by catalyzing levulinic acid with MnCeOx |
| CN116212856A (en) * | 2023-03-07 | 2023-06-06 | 北京清新环境技术股份有限公司 | Method for preparing cerium-manganese catalyst for high-performance catalytic oxidation of toluene by hydrothermal method, obtained catalyst and application |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101245916A (en) * | 2008-03-25 | 2008-08-20 | 华东理工大学 | Method for eliminating chloro-aromatics low temperature catalytic combustion |
| CN101279253A (en) * | 2008-05-09 | 2008-10-08 | 华东理工大学 | Catalyst for eliminating chlorinated aromatic hydrocarbons by low-temperature catalytic combustion |
| CN102353064A (en) * | 2011-06-28 | 2012-02-15 | 华东理工大学 | Method for eliminating chlorinated aromatic hydrocarbons through low temperature catalytic combustion |
| CN102698751A (en) * | 2012-06-26 | 2012-10-03 | 华东理工大学 | Catalyst for eliminating chlorine-containing volatile organic compounds by low-temperature catalytic combustion |
| CN104353459A (en) * | 2014-11-11 | 2015-02-18 | 中国科学院过程工程研究所 | Supported bimetallic catalyst for catalytic oxidation of VOCs and preparation method and application thereof |
| CN105032409A (en) * | 2015-07-03 | 2015-11-11 | 中国科学院过程工程研究所 | Self-assembled nano ruthenium catalyst used for catalytic oxidation of VOCs, and preparation method and applications thereof |
| CN107519861A (en) * | 2017-08-10 | 2017-12-29 | 中国科学院生态环境研究中心 | A kind of cerium manganese composite oxides catalyst, preparation method and the usage |
| CN107961789A (en) * | 2016-10-19 | 2018-04-27 | 中国石油化工股份有限公司 | The preparation method of O composite metallic oxide catalyst and thus obtained catalyst and the method for application and O3 catalytic oxidation |
-
2018
- 2018-06-15 CN CN201810620896.1A patent/CN108906044B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101245916A (en) * | 2008-03-25 | 2008-08-20 | 华东理工大学 | Method for eliminating chloro-aromatics low temperature catalytic combustion |
| CN101279253A (en) * | 2008-05-09 | 2008-10-08 | 华东理工大学 | Catalyst for eliminating chlorinated aromatic hydrocarbons by low-temperature catalytic combustion |
| CN102353064A (en) * | 2011-06-28 | 2012-02-15 | 华东理工大学 | Method for eliminating chlorinated aromatic hydrocarbons through low temperature catalytic combustion |
| CN102698751A (en) * | 2012-06-26 | 2012-10-03 | 华东理工大学 | Catalyst for eliminating chlorine-containing volatile organic compounds by low-temperature catalytic combustion |
| CN104353459A (en) * | 2014-11-11 | 2015-02-18 | 中国科学院过程工程研究所 | Supported bimetallic catalyst for catalytic oxidation of VOCs and preparation method and application thereof |
| CN105032409A (en) * | 2015-07-03 | 2015-11-11 | 中国科学院过程工程研究所 | Self-assembled nano ruthenium catalyst used for catalytic oxidation of VOCs, and preparation method and applications thereof |
| CN107961789A (en) * | 2016-10-19 | 2018-04-27 | 中国石油化工股份有限公司 | The preparation method of O composite metallic oxide catalyst and thus obtained catalyst and the method for application and O3 catalytic oxidation |
| CN107519861A (en) * | 2017-08-10 | 2017-12-29 | 中国科学院生态环境研究中心 | A kind of cerium manganese composite oxides catalyst, preparation method and the usage |
Non-Patent Citations (3)
| Title |
|---|
| JIN CHEN，等: "Homogeneous introduction of CeOy into MnOx-based catalyst for oxidation of aromatic VOCs", 《APPLIED CATALYSIS B: ENVIRONMENTAL》 * |
| SEIICHIRO IMAMURA，等: "Wet-Oxidation of a Model Domestic Wastewater on a Ru/Mn/Ce Composite Catalyst", 《IND. ENG. CHEM. RES.》 * |
| ZHEN WANG，等: "Catalytic removal of benzene over CeO2–MnOx composite oxides with rod-like morphology supporting PdO", 《J NANOPART RES》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109569229A (en) * | 2018-12-29 | 2019-04-05 | 安徽工业大学 | Method for combined desulfurization and denitrification of iron ore sintering flue gas |
| CN109569229B (en) * | 2018-12-29 | 2021-11-05 | 安徽工业大学 | Method for combined desulfurization and denitrification of iron ore sintering flue gas |
| CN114573450A (en) * | 2020-12-01 | 2022-06-03 | 中国科学院大连化学物理研究所 | Method for preparing acetic acid by catalyzing levulinic acid with MnCeOx |
| CN114573450B (en) * | 2020-12-01 | 2023-05-30 | 中国科学院大连化学物理研究所 | Method for preparing acetic acid by catalyzing levulinic acid through MnCeOx |
| CN113680383A (en) * | 2021-08-25 | 2021-11-23 | 江苏中科睿赛污染控制工程有限公司 | Composite material for purifying aldehydes and benzene series in air as well as preparation method and application thereof |
| CN113797935A (en) * | 2021-10-14 | 2021-12-17 | 常州汇清环保科技有限公司 | Catalyst for low-temperature efficient treatment of VOCs and preparation method thereof |
| CN113797935B (en) * | 2021-10-14 | 2024-06-25 | 常州汇清环保科技有限公司 | Catalyst for low-temperature efficient treatment of VOCs and preparation method thereof |
| CN116212856A (en) * | 2023-03-07 | 2023-06-06 | 北京清新环境技术股份有限公司 | Method for preparing cerium-manganese catalyst for high-performance catalytic oxidation of toluene by hydrothermal method, obtained catalyst and application |
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