CN111686754A - Non-noble metal catalyst for catalytic combustion of volatile organic compounds and preparation method thereof - Google Patents
Non-noble metal catalyst for catalytic combustion of volatile organic compounds and preparation method thereof Download PDFInfo
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- CN111686754A CN111686754A CN202010644265.0A CN202010644265A CN111686754A CN 111686754 A CN111686754 A CN 111686754A CN 202010644265 A CN202010644265 A CN 202010644265A CN 111686754 A CN111686754 A CN 111686754A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 91
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 64
- 239000012855 volatile organic compound Substances 0.000 title claims abstract description 28
- 238000007084 catalytic combustion reaction Methods 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000010949 copper Substances 0.000 claims abstract description 24
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 19
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 19
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052802 copper Inorganic materials 0.000 claims abstract description 11
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 10
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 109
- 239000012286 potassium permanganate Substances 0.000 claims description 37
- 239000000243 solution Substances 0.000 claims description 30
- 239000012266 salt solution Substances 0.000 claims description 24
- 239000011572 manganese Substances 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 238000002441 X-ray diffraction Methods 0.000 claims description 10
- 239000013078 crystal Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 150000002696 manganese Chemical class 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 238000001179 sorption measurement Methods 0.000 claims description 6
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229940099596 manganese sulfate Drugs 0.000 claims description 4
- 239000011702 manganese sulphate Substances 0.000 claims description 4
- 235000007079 manganese sulphate Nutrition 0.000 claims description 4
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 229940071125 manganese acetate Drugs 0.000 claims description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 abstract description 75
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 54
- 230000003197 catalytic effect Effects 0.000 abstract description 24
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 238000012360 testing method Methods 0.000 abstract description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 2
- 239000001301 oxygen Substances 0.000 abstract description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 42
- 239000012153 distilled water Substances 0.000 description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 33
- 239000002244 precipitate Substances 0.000 description 27
- 238000005303 weighing Methods 0.000 description 20
- 239000011148 porous material Substances 0.000 description 11
- CESXSDZNZGSWSP-UHFFFAOYSA-L manganese(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].CC([O-])=O.CC([O-])=O CESXSDZNZGSWSP-UHFFFAOYSA-L 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 229940082328 manganese acetate tetrahydrate Drugs 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000003344 environmental pollutant Substances 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 231100000719 pollutant Toxicity 0.000 description 5
- 230000010718 Oxidation Activity Effects 0.000 description 4
- 238000002159 adsorption--desorption isotherm Methods 0.000 description 4
- 239000000356 contaminant Substances 0.000 description 4
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 4
- XGOFWPBOVBWOOR-UHFFFAOYSA-N O.O.O.[Sr++].[O-][N+]([O-])=O.[O-][N+]([O-])=O Chemical compound O.O.O.[Sr++].[O-][N+]([O-])=O.[O-][N+]([O-])=O XGOFWPBOVBWOOR-UHFFFAOYSA-N 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000012795 verification Methods 0.000 description 2
- 230000010849 Ion Exchange Activity Effects 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000005564 crystal structure determination Methods 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000013101 initial test Methods 0.000 description 1
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical group [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
Images
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
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- B01J35/613—
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- B01J35/633—
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- B01J35/647—
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
- F23G7/06—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
- F23G7/07—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases in which combustion takes place in the presence of catalytic material
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- 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 discloses a non-noble metal catalyst for catalytic combustion of volatile organic compounds and a preparation method thereof. The non-noble metal catalyst comprises layered manganese dioxide and a doped metal oxide. According to the invention, the non-noble metal catalyst for catalytic combustion of volatile organic compounds is obtained by introducing the metal oxide between the layers of the layered manganese oxide, so that the structural stability, the specific surface area and the number of surface active oxygen species of the layered manganese oxide are improved. Verified by a contrast testThe non-noble metal catalyst has high stability, and the toluene complete conversion temperature (T) of the undoped modified lamellar manganese oxide is high under the same test condition90) 230 ℃ and the toluene complete conversion temperature (T) of the copper, strontium and nickel doped modified layered manganese oxide catalyst90) Can be reduced to 196 ℃. The results show that the copper, strontium and nickel doped modified layered manganese oxide catalyst has superior catalytic performance, and the performance of the catalyst is superior to that of the traditional commercial noble metal catalyst (T of the catalyst)90Typically above 220 c).
Description
Technical Field
The invention relates to the technical field of catalytic combustion of volatile organic compounds, in particular to a non-noble metal catalyst for catalytic combustion of volatile organic compounds and a preparation method thereof.
Background
The large amount of Volatile Organic Compounds (VOCs) emitted by industrial processes is PM2.5And O3The main precursor of pollution is an important reason for regional atmospheric problems in China. The catalytic combustion technology is a mainstream technology for controlling VOCs pollution, and has the advantages of low energy consumption, no secondary pollution, convenient operation and the like. The traditional noble metal catalyst has high activity, but has the problems of high price, easy poisoning, easy inactivation and the like. Therefore, the manganese oxide catalyst has wide industrial application prospect due to low price and good activity of catalyzing and oxidizing volatile organic compounds such as toluene and the like.
The manganese oxide includes manganese oxide (MnO), manganese dioxide (MnO)2) Manganese oxide (Mn)2O3) Manganomanganic oxide (Mn)3O4) And the like, wherein the catalytic activity of manganese dioxide is the best. The structure and performance of the catalyst are strongly related. MnO2The layered manganese oxide can be divided into three major structures, namely birnessite with a (1 × ∞) configuration, birnessite or birnessite with a (2 × ∞) configuration and bushel with a (3 × ∞) configuration, wherein the interlayer charge density and the interlayer spacing (d ═ 0.7nm) of the birnessite or birnessite type layered manganese oxide are moderate, and the layered structure has strong ion exchange activity.
Disclosure of Invention
The invention mainly aims to further improve the catalytic activity of birnessite or birnessite type layered manganese oxide in catalytic combustion of volatile organic compounds, and provides a non-noble metal catalyst for catalytic combustion of volatile organic compounds, a preparation method and application thereof by carrying out metal doping modification on the birnessite or birnessite type layered manganese oxide, so as to solve the technical problems of unstable structure, smaller specific surface area and lower catalytic reaction activity of the layered manganese oxide catalyst in the prior art.
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
a non-noble metal catalyst for catalytic combustion of volatile organic compounds comprises layered manganese dioxide and doped metal oxide.
Further, the doped metal in the doped metal oxide is one or more of copper, strontium and nickel.
Further, the doped metal in the doped metal oxide is copper/strontium.
Further, in the non-noble metal catalyst, the molar ratio of the doping metal in the doping metal oxide to manganese is 0.05-0.3, preferably 0.1-0.2.
Further, birnessite or birnessite type MnO was detected at 12.4 ° and 25.1 ° 2 θ in an X-ray diffraction pattern2Characteristic diffraction peaks of the '001' and '002' crystal faces, and the average grain size of the non-noble metal catalyst is 5-30 nanometers.
Furthermore, the catalyst has a mesoporous structure, an adsorption loop can be observed in a low-temperature nitrogen adsorption curve, and the specific surface area of the non-noble metal catalyst is 20-150 m2/g。
The preparation method of the non-noble metal catalyst for catalytic combustion of volatile organic compounds comprises the following steps:
(1) preparing a potassium hydroxide solution; preparing a potassium permanganate solution; preparing a mixed salt solution containing manganese salt and a salt of a doped metal in a doped metal oxide;
(2) firstly, dropwise adding a mixed salt solution into a potassium hydroxide solution, then dropwise adding a potassium permanganate solution, and stirring for a period of time after dropwise adding is finished;
(3) and collecting, washing and precipitating, drying and then carrying out heat treatment to obtain the non-noble metal catalyst.
Further, the manganese salt is selected from one or more of manganese acetate, manganese nitrate and manganese sulfate.
Further, the heat treatment is roasting at 300-500 ℃ for 2-8 h.
The method for catalytic combustion of volatile organic compounds adopts the non-noble metal catalyst or the non-noble metal catalyst prepared by the preparation method.
According to the invention, the non-noble metal catalyst for catalytic combustion of volatile organic compounds is obtained by introducing the metal oxide between the layers of the layered manganese oxide, so that the structural stability, the specific surface area and the number of surface active oxygen species of the layered manganese oxide are improved. The non-noble metal catalyst has high stability and the toluene complete conversion temperature (T) of the non-doped modified layered manganese oxide is proved by a control test under the same test condition90) 230 ℃ and the toluene complete conversion temperature (T) of the copper, strontium and nickel doped modified layered manganese oxide catalyst90) Can be reduced to 196 ℃. The results show that the copper, strontium and nickel doped modified layered manganese oxide catalyst has superior catalytic performance, and the performance of the catalyst is superior to that of the traditional commercial noble metal catalyst (T of the catalyst)90Generally above 220 ℃); in conclusion, the catalytic activity of the layered manganese oxide for catalytic oxidation of volatile organic compounds can be remarkably improved by introducing metal oxides such as copper, strontium, nickel and the like into the layered manganese oxide layer.
The invention is further described with reference to the following figures and detailed description. Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to assist in understanding the invention, and are included to explain the invention and their equivalents and not limit it unduly. In the drawings:
fig. 1 is a schematic view of a miniature fixed bed apparatus for evaluating the catalytic activity of a non-noble metal catalyst.
FIG. 2 shows the removal efficiency of L-MnO, L-CuMnO, L-SrMnO and L-NiMnO for toluene at different temperatures.
FIG. 3 shows the removal efficiency of ethyl acetate at different temperatures for L-MnO, L-CuMnO, L-SrMnO, and L-NiMnO.
FIG. 4 is an X-ray diffraction pattern of L-MnO, L-CuMnO, L-SrMnO, L-NiMnO.
FIG. 5 shows N in L-MnO, L-CuMnO, L-SrMnO and L-NiMnO2Adsorption-desorption isotherms (a) and pore size profiles (B).
FIG. 6 shows the removal efficiency of L-CuSrMnO, L-NiSrMnO and L-CuNiMnO for toluene at different temperatures.
FIG. 7 shows the removal efficiency of L-CuSrMnO, L-NiSrMnO and L-CuNiMnO for ethyl acetate at different temperatures.
FIG. 8 is an X-ray diffraction pattern for L-CuSrMnO, L-NiSrMnO and L-CuNiMnO.
Detailed Description
The invention will be described more fully hereinafter with reference to the accompanying drawings. Those skilled in the art will be able to implement the invention based on these teachings. Before the present invention is described in detail with reference to the accompanying drawings, it is to be noted that:
the technical solutions and features provided in the present invention in the respective sections including the following description may be combined with each other without conflict.
Moreover, the embodiments of the present invention described in the following description are generally only some embodiments of the present invention, and not all embodiments. Therefore, all other embodiments obtained by a person of ordinary skill in the art based on the embodiments of the present invention without any creative effort shall fall within the protection scope of the present invention.
With respect to terms and units in the present invention. The terms "comprising," "having," and any variations thereof in the description and claims of this invention and the related sections are intended to cover non-exclusive inclusions.
The preparation method of the non-noble metal catalyst for catalytic combustion of volatile organic compounds comprises the following steps:
(1) preparing a solution:
preparing a potassium hydroxide solution: dissolving 250mmol of potassium hydroxide in 20-200 mL of distilled water;
preparing a potassium permanganate solution: dissolving 6mmol of potassium permanganate in 50-500 mL of distilled water;
preparing a mixed salt solution: dissolving 16mmol of manganese salt and a certain amount of metal-doped salt in 10-100 mL of distilled water; the usage amount of the doped metal salt is determined according to the theoretical calculation molar ratio of the doped metal/Mn in the target product; the resulting layered manganese oxide catalyst was used as a control to illustrate the effect of the doped metal oxide on the catalytic activity of the non-noble metal catalyst when no salt of the doped metal was added.
(2) Firstly, dropwise adding the mixed salt solution into a potassium hydroxide solution, then dropwise adding a potassium permanganate solution, and stirring for 2-24 hours at 20-60 ℃ after dropwise adding.
(3) And collecting, washing and precipitating, drying and roasting for 2-8 hours at the temperature of 300-500 ℃ to obtain the non-noble metal catalyst.
The manganese salt is any one or more of manganese acetate, manganese nitrate and manganese sulfate.
The metal-doped salt is any one or more of metal-doped chloride salt, nitrate and sulfate.
The phase analysis and the crystal structure determination of the non-noble metal catalyst are characterized by powder X-ray diffraction (XRD) by using a PANalyticalX' PertPRO diffractometer and adopting Cu target Ka radiation (lambda is 0.1540598nm), the voltage is 40kV, the current is 30mA, the scanning range 2 theta is 5-80 degrees, and the scanning step is 0.03 degrees. The XRD results were indexed to determine the phase according to the reference data from the international diffraction data centre.
The pore structure of the obtained non-noble metal catalyst adopts an AUTONORB-IQ automatic adsorption instrument to measure N2And analyzing an absorption and desorption curve. All non-noble metal catalysts were degassed for 6h at 180 ℃ under vacuum before each analysis. Adsorption isotherm number from non-noble metal catalyst using Brunauer-Emmett-teller (bet) equationThe specific surface area and the total pore volume were calculated. The pore size distribution was calculated using the Barrett-Joyner-Halenda (BJH) formula.
The catalytic activity of the obtained non-noble metal catalyst was evaluated using a miniature fixed bed apparatus as shown in fig. 1, and the tests were all performed under normal pressure. In fig. 1, the heating parts outside the reactor are a tubular resistance furnace and an electric heating box, a thermocouple is arranged on the catalyst bed layer inside the reactor and used for measuring the actual temperature of the catalyst bed layer, and the thermocouple, the heating parts and a temperature controller are interlocked with each other to accurately control the temperature of the reactor; toluene or ethyl acetate is used as a target pollutant in the experiment, and dry air is used as an air source. The gas volume space velocity (GHSV) is 30000h-1The filling volume of the non-noble metal catalyst is 1mL, and the reactor is a quartz tube with the inner diameter of 8 mm. And (3) measuring the concentration of the target pollutant before and after the reaction by using a gas chromatograph. The conversion of the target pollutant was calculated using the following formula:
wherein η is the conversion of the target contaminant, CinAnd CoutFeed and outlet concentrations of the target contaminant, respectively.
The following describes advantageous effects of the present invention by using specific embodiments and with reference to the drawings.
Example 1:
weighing 250mmol of potassium hydroxide, and dissolving the potassium hydroxide in 30mL of distilled water to obtain potassium hydroxide; weighing 6mmol of potassium permanganate and dissolving in 100mL of distilled water to obtain a potassium permanganate solution; 16mmol of manganese acetate tetrahydrate and a proper amount of copper nitrate trihydrate (the molar ratio of Cu to Mn is 0.1) are weighed and dissolved in 30mL of distilled water to obtain a mixed salt solution.
Firstly, dropwise adding a mixed salt solution into a potassium hydroxide solution, then dropwise adding a potassium permanganate solution, and stirring the obtained mixed solution at 40 ℃ for 12 hours; and collecting the precipitate, washing and drying the precipitate, and finally roasting the precipitate for 2 hours at 300 ℃ in the air atmosphere to obtain the copper-doped layered manganese oxide catalyst which is marked as L-CuMnO or L-CuMnO-0.1.
Example 2:
weighing 250mmol of potassium hydroxide, and dissolving the potassium hydroxide in 30mL of distilled water to obtain potassium hydroxide; weighing 6mmol of potassium permanganate and dissolving in 100mL of distilled water to obtain a potassium permanganate solution; 16mmol of manganese acetate tetrahydrate and a proper amount of strontium nitrate trihydrate (the molar ratio of Sr to Mn is 0.1) are weighed and dissolved in 30mL of distilled water to obtain a mixed salt solution.
Firstly, dropwise adding a mixed salt solution into a potassium hydroxide solution, then dropwise adding a potassium permanganate solution, and stirring the obtained mixture at 40 ℃ for 12 hours; and collecting the precipitate, washing and drying the precipitate, and finally roasting the precipitate for 2 hours at 300 ℃ in the air atmosphere to obtain the strontium-doped layered manganese oxide catalyst which is marked as L-SrMnO.
Example 3:
weighing 250mmol of potassium hydroxide, and dissolving the potassium hydroxide in 30mL of distilled water to obtain potassium hydroxide; weighing 6mmol of potassium permanganate and dissolving in 100mL of distilled water to obtain a potassium permanganate solution; 16mmol of manganese acetate tetrahydrate and a proper amount of nickel nitrate hexahydrate (the molar ratio of Ni to Mn is 0.1) are weighed and dissolved in 30mL of distilled water to obtain a mixed salt solution.
Firstly, dropwise adding a mixed salt solution into a potassium hydroxide solution, then dropwise adding a potassium permanganate solution, and stirring the obtained mixture at 40 ℃ for 12 hours; and collecting the precipitate, washing and drying the precipitate, and finally roasting the precipitate for 2 hours at 300 ℃ in the air atmosphere to obtain the nickel-doped layered manganese oxide catalyst which is marked as L-NiMnO.
Comparative example:
weighing 250mmol of potassium hydroxide, and dissolving the potassium hydroxide in 30mL of distilled water to obtain potassium hydroxide; weighing 6mmol of potassium permanganate and dissolving in 100mL of distilled water to obtain a potassium permanganate solution; 16mmol of manganese acetate tetrahydrate is weighed and dissolved in 30mL of distilled water to obtain a manganese acetate tetrahydrate solution.
Firstly, dropwise adding a tetrahydrate manganese acetate solution into a potassium hydroxide solution, then dropwise adding a potassium permanganate solution, and stirring the obtained mixture at 40 ℃ for 12 hours; and collecting the precipitate, washing and drying the precipitate, and finally roasting the precipitate for 2 hours at 300 ℃ in the air atmosphere to obtain the pure layered manganese oxide catalyst which is marked as L-MnO.
Example 4:
weighing 250mmol of potassium hydroxide, and dissolving the potassium hydroxide in 30mL of distilled water to obtain potassium hydroxide; weighing 6mmol of potassium permanganate and dissolving in 100mL of distilled water to obtain a potassium permanganate solution; 16mmol of manganese acetate tetrahydrate, a proper amount of copper nitrate trihydrate and a proper amount of strontium nitrate trihydrate (the molar ratio of Cu to Sr is 1: 1, and the molar ratio of Cu + Sr)/Mn is 0.1) are weighed and dissolved in 30mL of distilled water to obtain a mixed salt solution.
Firstly, dropwise adding a mixed salt solution into a potassium hydroxide solution, then dropwise adding a potassium permanganate solution, and stirring the obtained mixture at 40 ℃ for 12 hours; and collecting the precipitate, washing and drying the precipitate, and finally roasting the precipitate for 2 hours at 300 ℃ in the air atmosphere to obtain the copper/strontium doped layered manganese oxide catalyst which is marked as L-CuSrMnO.
Example 5:
weighing 250mmol of potassium hydroxide, and dissolving the potassium hydroxide in 30mL of distilled water to obtain potassium hydroxide; weighing 6mmol of potassium permanganate and dissolving in 100mL of distilled water to obtain a potassium permanganate solution; 16mmol of manganese acetate tetrahydrate, a proper amount of nickel nitrate hexahydrate and strontium nitrate trihydrate (the molar ratio of Ni to Sr is 1: 1, and the molar ratio of Ni + Sr)/Mn is 0.1) are weighed and dissolved in 30mL of distilled water to obtain a mixed salt solution.
Firstly, dropwise adding a mixed salt solution into a potassium hydroxide solution, then dropwise adding a potassium permanganate solution, and stirring the obtained mixture at 40 ℃ for 12 hours; and collecting the precipitate, washing and drying the precipitate, and finally roasting the precipitate for 2 hours at 300 ℃ in the air atmosphere to obtain the nickel/strontium-doped layered manganese oxide catalyst which is marked as L-NiSrMnO.
Example 6:
weighing 250mmol of potassium hydroxide, and dissolving the potassium hydroxide in 30mL of distilled water to obtain potassium hydroxide; weighing 6mmol of potassium permanganate and dissolving in 100mL of distilled water to obtain a potassium permanganate solution; 16mmol of manganese acetate tetrahydrate, a proper amount of nickel nitrate hexahydrate and copper nitrate trihydrate (the molar ratio of Ni to Cu is 1: 1, and the molar ratio of Cu + Ni to Mn is 0.1) are weighed and dissolved in 30mL of distilled water to obtain a mixed salt solution.
Firstly, dropwise adding a mixed salt solution into a potassium hydroxide solution, then dropwise adding a potassium permanganate solution, and stirring the obtained mixture at 40 ℃ for 12 hours; and collecting the precipitate, washing and drying the precipitate, and finally roasting the precipitate for 2 hours at 300 ℃ in the air atmosphere to obtain the copper/nickel doped layered manganese oxide catalyst which is marked as L-CuNiMnO.
Example 7:
weighing 250mmol of potassium hydroxide, and dissolving the potassium hydroxide in 30mL of distilled water to obtain potassium hydroxide; weighing 6mmol of potassium permanganate and dissolving in 100mL of distilled water to obtain a potassium permanganate solution; 16mmol of manganese nitrate and a proper amount of copper nitrate trihydrate (the Cu/Mn molar ratio is 0.05) are weighed and dissolved in 30mL of distilled water to obtain a mixed salt solution.
Firstly, dropwise adding a mixed salt solution into a potassium hydroxide solution, then dropwise adding a potassium permanganate solution, and stirring the obtained mixture at 40 ℃ for 12 hours; and collecting the precipitate, washing and drying the precipitate, and finally roasting for 2 hours at 300 ℃ in the air atmosphere to obtain the copper-doped layered manganese oxide catalyst which is marked as L-CuMnO-0.05.
Example 8:
weighing 250mmol of potassium hydroxide, and dissolving the potassium hydroxide in 30mL of distilled water to obtain potassium hydroxide; weighing 6mmol of potassium permanganate and dissolving in 100mL of distilled water to obtain a potassium permanganate solution; 16mmol of manganese nitrate and a proper amount of copper chloride (Cu/Mn molar ratio is 0.2) are weighed and dissolved in 30mL of distilled water to obtain a mixed salt solution.
Firstly, dropwise adding a mixed salt solution into a potassium hydroxide solution, then dropwise adding a potassium permanganate solution, and stirring the obtained mixture at 40 ℃ for 12 hours; and collecting the precipitate, washing and drying the precipitate, and finally roasting for 2 hours at 300 ℃ in the air atmosphere to obtain the copper-doped layered manganese oxide catalyst which is marked as L-CuMnO-0.2.
Example 9:
weighing 250mmol of potassium hydroxide, and dissolving the potassium hydroxide in 30mL of distilled water to obtain potassium hydroxide; weighing 6mmol of potassium permanganate and dissolving in 100mL of distilled water to obtain a potassium permanganate solution; 16mmol of manganese sulfate and a proper amount of copper sulfate (the Cu/Mn molar ratio is 0.3) are weighed and dissolved in 30mL of distilled water to obtain a mixed salt solution.
Firstly, dropwise adding a mixed salt solution into a potassium hydroxide solution, then dropwise adding a potassium permanganate solution, and stirring the obtained mixture at 40 ℃ for 12 hours; and collecting the precipitate, washing and drying the precipitate, and finally roasting for 2 hours at 300 ℃ in the air atmosphere to obtain the copper-doped layered manganese oxide catalyst which is marked as L-CuMnO-0.3.
The results of characterization and performance testing of the non-noble metal catalysts of examples 1-3 and comparative example are described below.
FIGS. 2 and 3 show the catalytic activities of the four non-noble metal catalysts of examples 1-3 and comparative example, respectively, for the catalytic oxidation of toluene and ethyl acetate at different temperatures, and Table 1 shows the minimum temperatures (T) at which the removal efficiencies of the target pollutants reach 90% (T) for the four non-noble metal catalysts90). Compared with non-noble metal catalysts (L-MnO) which are not subjected to doping modification, the three metal oxide doping modified non-noble metal catalysts show excellent toluene and ethyl acetate catalytic activity. Wherein, the L-CuMnO has the best catalytic activity for degrading ethyl acetate, the ethyl acetate can be completely converted at 162 ℃, and compared with the L-MnO, the T of the L-CuMnO is90The reduction of the temperature by 16 ℃; the L-NiMnO has the best catalytic activity on the degradation of toluene, can completely convert toluene at 196 ℃, and has T of L-NiMnO compared with that of L-MnO90The reduction is 34 ℃.
TABLE 1
FIG. 4 is an XRD pattern of four non-noble metal catalysts of examples 1-3 and comparative example. As shown in FIG. 4, similarly to L-MnO, characteristic diffraction peaks of (001) and (002) crystal planes of layered manganese dioxide were detected at 2. theta. of 12.4 DEG and 25.1 DEG in X-ray diffraction patterns of L-CuMnO, L-NiMnO and L-SrMnO, and it was judged that it had a layered manganese oxide structure. No visible doped metal oxide phase was observed, indicating that the doped metal oxide was in the MnO2Interlayer or MnO2The surface of the layer. The grain sizes of L-MnO, L-CuMnO, L-NiMnO and L-SrMnO are respectively 11.9nm, 21.0nm, 6.9nm and 8.2nm which are obtained by calculation according to the prescription of the Sherle formula.
FIG. 5 is the N of the four non-noble metal catalysts of examples 1-3 and comparative example2Adsorption-desorption isotherms (a) and pore size profiles (B). Calculated specific surface area (S)BET) Pore volume (V)Total) And the results of the average pore diameter (D) are shown in Table 2. As shown in fig. 5, the four non-noble metal catalysts all showed typical type IV isotherms, indicating that they had mesoporous structures; as can be seen from Table 2, the specific surface areas and pores of L-CuMnO, L-SrMnO and L-NiMnOThe volume is larger than that of L-MnO, which is more beneficial to the diffusion of reactants and products.
TABLE 2
| Numbering | SBET(m2/g) | VTotal(cm3/g) | D(nm) |
| L-MnO | 44.7 | 0.23 | 23.5 |
| L-CuMnO | 55.4 | 0.37 | 24.9 |
| L-SrMnO | 52.7 | 0.45 | 3.8 |
| L-NiMnO | 57.8 | 0.45 | 9.6 |
The results of characterization and performance testing of the non-noble metal catalysts of examples 4-6 are described below.
FIGS. 6 and 7 show the catalytic activity of the non-noble metal catalysts of examples 4-6 for the catalytic oxidation of toluene and ethyl acetate at different temperatures, respectively, and Table 3 lists the minimum temperatures (T) at which the non-noble metal catalysts of examples 4-6 achieve 90% removal efficiency of the target contaminants90). From Table 3, it can be seen that L-CuSrMnO has the best ethyl acetate catalytic activity, and can completely convert ethyl acetate at 168 ℃, and the L-NiSrMnO with the worst activity can also realize the complete conversion of ethyl acetate at 180 ℃. For toluene, the catalytic oxidation activity of L-NiSrMnO is the worst, but the catalytic oxidation activity is still obviously improved compared with that of L-MnO; L-CuSrMnO also shows the best toluene catalytic activity compared with T of L-MnO90The decrease was 34 ℃. In conclusion, the activity of the layered manganese oxide for catalyzing and oxidizing the toluene and the ethyl acetate can be effectively improved by the bimetal doping, and particularly when the molar ratio of Cu/Sr is 1, the catalytic oxidation activity of the toluene and the ethyl acetate is the best.
TABLE 3
FIG. 8 is an XRD pattern of the non-noble metal catalysts of examples 4-6. As can be seen from FIG. 8, the main crystal phases of the three non-noble metal catalysts are all cryptomelane type MnO2The characteristic peaks at diffraction angles of 12.5 °, 25.1 °, 36.2 °, 65.5 ° were assigned to the (001), (002), (110), (-312) crystal planes, respectively, and no visible doped metal oxide phase was found. The grain sizes of the L-CuSrMnO, the L-NiSrMnO and the L-CuNiMnO are respectively 5.7nm, 6.2nm and 8.0nm through calculation.
N2The adsorption-desorption isotherms show that L-CuSrMnO, L-NiSrMnO and L-CuNiMnO all show typical IV-type isotherms, which show that the mesoporous structure is provided. The results of calculating the specific surface area, pore volume and average pore diameter are shown in Table 4, in which L-CuSrMnO possessed the highest specific surface area and pore volume.
TABLE 4
The results of characterization and performance testing of the non-noble metal catalysts of examples 1, 7-9 and comparative examples are described below.
Table 5 lists the minimum temperatures (T) at which the non-noble metal catalysts of examples 1, 7-9 and comparative examples achieve 90% removal efficiency for the target contaminants90). As can be seen from table 5, the addition of Cu has a beneficial effect on the catalytic oxidation activity of the catalyst. Wherein, both L-CuMnO-0.1 and L-CuMnO-0.2 show excellent activity, which indicates that the doping amount with the Cu/Mn molar ratio of 0.1 and 0.2 can obviously improve the catalytic activity of the layered manganese oxide.
TABLE 5
From the XRD spectrum, the main crystal phases of the non-noble metal catalysts of examples 7-9 are all cryptomelane type MnO2The grain sizes of L-CuMnO-0.05, L-CuMnO-0.2 and L-CuMnO-0.3 are calculated to be 16.6nm, 20.7nm and 11.6nm respectively. N is a radical of2The adsorption-desorption isotherms show that L-CuMnO-0.05, L-CuMnO-0.2 and L-CuMnO-0.3 all show typical IV-type isotherms, which show that the mesoporous structure is provided; proved by verification, the specific surface area of the obtained non-noble metal catalyst is remarkably increased along with the increase of the Cu content, wherein the specific surface area of L-CuMnO-0.3 is 150m2/g。
Further verification shows that the L-CuMnO-0.1 has very high stability, and the catalytic activity after three times of recycling tests is still basically consistent with that of the initial test.
Further investigating the change of the conversion rate of the target pollutant with the reaction time when L-CuMnO-0.1 was used, L-CuMnO-0.1 was kept in a continuous state during the test for 48 hours, and high treatment efficiency for toluene and ethyl acetate was exhibited.
The contents of the present invention have been explained above. Those skilled in the art will be able to implement the invention based on these teachings. All other embodiments, which can be derived by a person skilled in the art from the above description without inventive step, shall fall within the scope of protection of the present invention.
Claims (10)
1. A non-noble metal catalyst for catalytic combustion of volatile organic compounds, characterized in that: the non-noble metal catalyst comprises layered manganese dioxide and a doped metal oxide.
2. A non-noble metal catalyst for the catalytic combustion of volatile organic compounds according to claim 1, characterized in that: the doped metal in the doped metal oxide is any one or more of copper, strontium and nickel.
3. A non-noble metal catalyst for the catalytic combustion of volatile organic compounds according to claim 2, characterized in that: the doped metal in the doped metal oxide is copper/strontium.
4. A non-noble metal catalyst for the catalytic combustion of volatile organic compounds according to claim 1, characterized in that: in the non-noble metal catalyst, the molar ratio of the doping metal in the doping metal oxide to the manganese is 0.05-0.3, preferably 0.1-0.2.
5. A non-noble metal catalyst for the catalytic combustion of volatile organic compounds according to claim 1, characterized in that: birnessite or birnessite type MnO is detected at a 2 theta of 12.4 degrees and a 2.1 degree in an X-ray diffraction pattern2Characteristic diffraction peaks of the '001' and '002' crystal faces, and the average grain size of the non-noble metal catalyst is 5-30 nanometers.
6. A non-noble metal catalyst for the catalytic combustion of volatile organic compounds according to claim 1, characterized in that: the catalyst has a mesoporous structure, an adsorption loop can be observed in a low-temperature nitrogen adsorption curve, and the specific surface area of a non-noble metal catalyst is 20-150 m2/g。
7. The preparation method of the non-noble metal catalyst for catalytic combustion of volatile organic compounds comprises the following steps:
(1) preparing a potassium hydroxide solution; preparing a potassium permanganate solution; preparing a mixed salt solution containing manganese salt and a salt of a doped metal in a doped metal oxide;
(2) firstly, dropwise adding a mixed salt solution into a potassium hydroxide solution, then dropwise adding a potassium permanganate solution, and stirring for a period of time after dropwise adding is finished;
(3) and collecting, washing and precipitating, drying and then carrying out heat treatment to obtain the non-noble metal catalyst.
8. The method of claim 7 for preparing a non-noble metal catalyst for the catalytic combustion of volatile organic compounds, wherein: the manganese salt is selected from one or more of manganese acetate, manganese nitrate and manganese sulfate.
9. The method of claim 7 for preparing a non-noble metal catalyst for the catalytic combustion of volatile organic compounds, wherein: the heat treatment is roasting at 300-500 ℃ for 2-8 h.
10. A method of catalytically combusting volatile organic compounds, characterized by: non-noble metal catalyst prepared with the non-noble metal catalyst according to any one of claims 1 to 6 or with the preparation process according to any one of claims 7 to 9.
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