CN117861683A - Metal catalyst for degrading sulfur-containing VOCs, preparation method and application - Google Patents
Metal catalyst for degrading sulfur-containing VOCs, preparation method and application Download PDFInfo
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- CN117861683A CN117861683A CN202311729368.7A CN202311729368A CN117861683A CN 117861683 A CN117861683 A CN 117861683A CN 202311729368 A CN202311729368 A CN 202311729368A CN 117861683 A CN117861683 A CN 117861683A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 84
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 45
- 239000011593 sulfur Substances 0.000 title claims abstract description 45
- 239000012855 volatile organic compound Substances 0.000 title claims abstract description 42
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 26
- 230000000593 degrading effect Effects 0.000 title claims abstract description 24
- 239000002184 metal Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 48
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 34
- 150000003624 transition metals Chemical group 0.000 claims abstract description 34
- 239000010949 copper Substances 0.000 claims abstract description 32
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 26
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 26
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052802 copper Inorganic materials 0.000 claims abstract description 25
- 239000002253 acid Substances 0.000 claims abstract description 12
- 229910001092 metal group alloy Inorganic materials 0.000 claims abstract description 10
- 239000000725 suspension Substances 0.000 claims description 40
- 238000011068 loading method Methods 0.000 claims description 35
- 230000003197 catalytic effect Effects 0.000 claims description 22
- 238000006731 degradation reaction Methods 0.000 claims description 22
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 20
- 238000001354 calcination Methods 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 20
- 230000015556 catabolic process Effects 0.000 claims description 19
- 239000002243 precursor Substances 0.000 claims description 19
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 9
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 9
- 229910052763 palladium Inorganic materials 0.000 claims description 9
- 229910052707 ruthenium Inorganic materials 0.000 claims description 9
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 8
- 239000012691 Cu precursor Substances 0.000 claims description 8
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- FSJSYDFBTIVUFD-SUKNRPLKSA-N (z)-4-hydroxypent-3-en-2-one;oxovanadium Chemical compound [V]=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FSJSYDFBTIVUFD-SUKNRPLKSA-N 0.000 claims description 5
- 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
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- 229910021536 Zeolite Inorganic materials 0.000 claims description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 4
- 239000002808 molecular sieve Substances 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 4
- 239000010457 zeolite Substances 0.000 claims description 4
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 3
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims description 3
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 235000002867 manganese chloride Nutrition 0.000 claims description 3
- 239000011565 manganese chloride Substances 0.000 claims description 3
- 229940099607 manganese chloride Drugs 0.000 claims description 3
- 229940099596 manganese sulfate Drugs 0.000 claims description 3
- 235000007079 manganese sulphate Nutrition 0.000 claims description 3
- 239000011702 manganese sulphate Substances 0.000 claims description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 3
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 3
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 claims description 3
- 229940041260 vanadyl sulfate Drugs 0.000 claims description 3
- 229910000352 vanadyl sulfate Inorganic materials 0.000 claims description 3
- 230000007613 environmental effect Effects 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 18
- 229910052760 oxygen Inorganic materials 0.000 abstract description 18
- 239000001301 oxygen Substances 0.000 abstract description 18
- 125000001741 organic sulfur group Chemical group 0.000 abstract description 10
- 230000003993 interaction Effects 0.000 abstract description 5
- 230000004913 activation Effects 0.000 abstract description 4
- 229910045601 alloy Inorganic materials 0.000 abstract description 4
- 239000000956 alloy Substances 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 239000001257 hydrogen Substances 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- 150000002739 metals Chemical class 0.000 abstract description 3
- 230000002269 spontaneous effect Effects 0.000 abstract description 3
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 40
- 239000000243 solution Substances 0.000 description 14
- 229910021642 ultra pure water Inorganic materials 0.000 description 14
- 239000012498 ultrapure water Substances 0.000 description 14
- 238000001291 vacuum drying Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000002245 particle Substances 0.000 description 6
- 238000009210 therapy by ultrasound Methods 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 231100000572 poisoning Toxicity 0.000 description 4
- 230000000607 poisoning effect Effects 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 3
- 239000013067 intermediate product Substances 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
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- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
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- 238000001132 ultrasonic dispersion Methods 0.000 description 2
- 229910016551 CuPt Inorganic materials 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
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- 229910001385 heavy metal Inorganic materials 0.000 description 1
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- 150000002484 inorganic compounds Chemical class 0.000 description 1
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Abstract
The invention discloses a catalyst for degrading sulfur-containing VOCs (volatile organic compounds) metals, a preparation method and application thereof, wherein the catalyst comprises an active component metal alloy and a modified carrier; the active component metal alloy comprises copper and noble metal, and the modified carrier is transition metal modified metal oxide. The active sites of metal oxide on organic sulfur VOCs can be increased by adding metal elements, the metal oxide provides more active sites, energy is provided for decomposing hydrogen bonds in organic sulfur, active oxygen is promoted to be generated, oxygen vacancies on the surface of metal generate more active oxygen, the spontaneous formation of asymmetric oxygen vacancies in the catalyst is promoted by strong interaction caused by doping copper and noble metal, and the asymmetric oxygen vacancies promote H 2 Activation of O and generation of dissociated active oxygen; the catalyst with Cu and noble metal alloy loaded on the transition metal modified carrier is selected, so that more acid sites are provided, the sulfur resistance of the catalyst is improved, and the loss of the catalyst is reduced.
Description
Technical Field
The invention relates to the technical field of environmental catalysis, in particular to a metal catalyst for degrading sulfur-containing VOCs, a preparation method and application thereof.
Background
VOCs (Volatile Organic Compounds) volatile organic compounds can have negative effects on air quality and environment, and organic sulfur VOCs are used as volatile organic compounds commonly found in garbage landfill and petroleum industry, have very low olfactory threshold and obvious toxicity, and seriously harm ecological environment and human health.
At present, the method for removing the organic sulfur mainly comprises a photocatalysis method, a thermocatalytic combustion method, an adsorption method and the like, wherein the thermocatalytic combustion technology has the advantages of mature technology, simple operation and the like, is widely applied to the treatment of high-medium-low concentration organic waste gas in the typical chemical industry, and still has the following technical problems: (1) The active site of the catalyst has strong interaction with sulfur, so that the catalyst is easy to poison, poor in stability and poor in catalytic effect; (2) The degradation process has more intermediate products and is easy to produce more toxic intermediate products. (3) the noble metal is used in large amount and the cost is high; therefore, the method has the advantages of low noble metal consumption, good sulfur poisoning resistance, high stability, few byproducts and capability of thoroughly converting organic sulfur into SO 2 、CO 2 And H 2 The catalyst of O has very important significance.
Disclosure of Invention
The invention mainly aims to provide a catalyst for degrading sulfur-containing VOCs metals, a preparation method and application thereof, and aims to solve the technical problem that the existing catalyst is poor in sulfur resistance.
In order to achieve the above object, a first aspect of the present invention proposes a catalyst for degrading sulfur-containing VOCs metal, the catalyst comprising an active component metal alloy and a modified support; the active component metal alloy comprises copper and noble metal, and the modified carrier is transition metal modified metal oxide.
Further, the copper loading is 0.1-20wt% and the noble metal loading is 0.1-20wt%.
Further, the mass percentage of copper and noble metal is 1:0.01 to 20:1.
further, the metal oxide is Al 2 O 3 、SiO 2 Any one of zeolite molecular sieves.
Further, the transition metal is at least one of cerium, manganese and vanadium; the noble metal is at least one of platinum, palladium, ruthenium and gold.
Further, the transition metal loading is 0.1 to 50wt%.
The second aspect of the present invention proposes a method for preparing the catalyst for degrading sulfur-containing VOCs metal according to any one of the above, the method comprising the steps of:
s1: dispersing the metal oxide in water to obtain a first suspension;
s2: adding a transition metal precursor into the first suspension, and sequentially stirring, centrifuging, washing, drying and calcining to obtain the modified carrier;
s3: dispersing the modified carrier in water to obtain a second suspension;
s4: and adding an aqueous solution of a copper precursor and a noble metal precursor into the second suspension, and sequentially stirring, centrifuging, washing, drying and calcining to obtain the catalyst.
Further, the transition metal precursor is at least one of cerium nitrate, cerium sulfate, cerium oxide, manganese nitrate, manganese sulfate, manganese chloride, vanadyl acetylacetonate and vanadyl sulfate.
Further, the copper precursor is at least one of copper nitrate, copper sulfate and copper chloride, and the noble metal precursor is at least one of chloroplatinic acid, palladium nitrate, palladium sulfate and ruthenium nitrosylnitrate.
The third aspect of the invention provides application of a catalyst for degrading sulfur-containing VOCs in the environment-friendly field of catalytic degradation of sulfur-containing VOCs in catalytic oxidation atmosphere.
The beneficial effects are that:
the invention relates to a metal catalyst for degrading sulfur-containing VOCs, which comprises an active component metal alloy and a modified carrier; the active component metal alloy comprises copper and noble metal, and the modified carrier is transition metal modified metal oxide. The active sites of the metal oxide on the organic sulfur VOCs can be increased by adding the metal element, more active sites are provided for the metal oxide, energy is provided for decomposing hydrogen bonds in the organic sulfur, the generation of active oxygen is promoted, more active oxygen is generated by oxygen vacancies on the surface of the metal, the spontaneous formation of asymmetric oxygen vacancies in the catalyst is promoted by strong interaction caused by doping of copper and noble metal, and the asymmetric oxygen vacancies promote H 2 Activation of O and generation of dissociated active oxygen; according to the catalyst, the Cu and noble metal alloy are used for loading the catalyst on the transition metal modified carrier, so that the bond energy of sulfur species adsorbed on an active site is weakened, sulfur poisoning of the catalyst is prevented, the sulfur resistance and the catalytic performance of the catalyst are improved, and the loss of the catalyst is reduced.
Drawings
FIG. 1 shows the performance of catalytic degradation of methyl mercaptan at 50-350℃and atmospheric pressure for examples 1-3 and comparative examples 1-3 and the blank;
FIG. 2 is a graph showing the catalytic degradation performance of catalysts with different loadings of copper and noble metals supported on metal oxides at 50-350 ℃ under normal pressure;
FIG. 3 is a graph showing the catalytic degradation of different noble metal supported metal oxide catalysts at 50-400℃and atmospheric pressure;
FIG. 4 SO at 50-350℃under normal pressure for examples 1-3 and comparative examples 1-3 and blank pair methyl mercaptan 2 A plot of yield versus temperature;
FIG. 5 is a graph showing the stability of the catalyst of examples 1-3 to catalyze the degradation of methyl mercaptan.
The achievement of the objects, functional features and advantages of the present invention will be further described with reference to the accompanying drawings, in conjunction with the embodiments.
Detailed Description
It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
In the description of the present invention, it should be understood that the terms "center", "longitudinal", "lateral", "length", "width", "thickness", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", "clockwise", "counterclockwise", etc. indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings are merely for convenience in describing the present invention and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, be configured and operated in a specific orientation, and thus should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more of the described features. In the description of the present invention, the meaning of "a plurality" is two or more, unless specifically defined otherwise.
In the description of the present invention, it should be noted that, unless explicitly specified and limited otherwise, the terms "mounted," "connected," and "connected" are to be construed broadly, and may be either fixedly connected, detachably connected, or integrally connected, for example; the connection may be mechanical connection, direct connection or indirect connection through an intermediate medium, and may be internal connection of two elements or interaction relationship of two elements. The specific meaning of the above terms in the present invention can be understood by those of ordinary skill in the art according to the specific circumstances.
In the present invention, unless expressly stated or limited otherwise, a first feature "above" or "below" a second feature may include both the first and second features being in direct contact, as well as the first and second features not being in direct contact but being in contact with each other through additional features therebetween. Moreover, a first feature being "above," "over" and "on" a second feature includes the first feature being directly above and obliquely above the second feature, or simply indicating that the first feature is higher in level than the second feature. The first feature being "under", "below" and "beneath" the second feature includes the first feature being directly under and obliquely below the second feature, or simply means that the first feature is less level than the second feature.
The embodiment of the invention provides a metal catalyst for degrading sulfur-containing VOCs, which comprises an active component metal alloy and a modified carrier; the active component metal alloy comprises copper and noble metal, and the modified carrier is transition metal modified metal oxide. The catalyst takes transition metal modified metal oxide as a carrier, precursors of copper and noble metal are further reduced on the modified carrier through a dipping-calcining method, active sites of the metal oxide on organic sulfur VOCs can be increased through adding metal elements, the metal oxide provides more active sites, energy is provided for decomposing hydrogen bonds in the organic sulfur, the generation of active oxygen is promoted, oxygen vacancies on the surface of the metal generate more active oxygen, the spontaneous formation of asymmetric oxygen vacancies in the catalyst is promoted by strong interaction caused by doping of the copper and the noble metal, and the asymmetric oxygen vacancies promote H 2 Activation of O and generation of dissociated active oxygen; according to the catalyst, the Cu and noble metal alloy are selected to be loaded on the transition metal modified carrier, so that the bond energy of sulfur species adsorbed on an active site is weakened, sulfur poisoning of the catalyst is prevented, the sulfur resistance of the catalyst is improved, and the loss of the catalyst is reduced.
In the embodiment, copper can be replaced by other metals with excellent quality and low cost, such as iron, magnesium and the like, but experiments prove that the selectivity of copper material loaded on the modified carrier is better when organic sulfur is converted into sulfur dioxide, and byproducts, such as dimethyl disulfide and the like, are relatively difficult to generate during degradation, and are more preferable; the sulfur-containing VOCs can be more than one of methyl mercaptan, ethyl mercaptan or phenyl mercaptan.
In the embodiment, the catalyst not only has high dispersity and stable active metal particles, but also effectively increases the content of acid sites on the surface of the catalyst, improves the sulfur resistance, promotes the activation of the catalyst to sulfur-containing VOCs, and cooperates with noble metal to catalyze and oxidize the sulfur-containing VOCs and improve the catalytic performance, and still shows good low-temperature catalytic degradation performance in the catalytic degradation process of the sulfur-containing VOCs under the loading of low noble metal content, and has the advantages of high mineralization rate of the sulfur-containing VOCs, less intermediate products, less accumulation of toxic and side substances and capability of solving the problems of easy sulfur poisoning and easy deactivation of the catalyst.
In one embodiment, the copper loading is 0.1 to 20wt% and the noble metal loading is 0.1 to 20wt%. When the noble metal loading is lower than 0.1wt%, the catalyst has poor catalytic effect, and when the noble metal loading is higher than 20wt%, the cost is higher.
In the above examples, the mass percentages of copper and noble metal are 1:0.01 to 20:1. preferably 5: with reference to fig. 1, copper and platinum loadings of 5wt% and 0.1wt%, respectively, were 0.1, at which time costs were low and performance could be guaranteed.
In one embodiment, the metal oxide is Al 2 O 3 、SiO 2 Any one of zeolite molecular sieves. Al (Al) 2 O 3 、SiO 2 The zeolite molecular sieve is an inorganic compound and has specific pore structure and chemical inertness, is favorable for catalytic reaction, and is preferably gamma-Al with larger specific surface area 2 O 3 More active sites can be provided.
In one embodiment, the transition metal is any one of cerium, manganese and vanadium; the noble metal is at least one of platinum, palladium, ruthenium and gold.
In one embodiment, the transition metal loading is from 0.1 to 50wt%, preferably from 5 to 20wt%, more preferably 10wt%.
The second aspect of the present invention proposes a method for preparing the catalyst for degrading sulfur-containing VOCs metal according to any one of the above, the method comprising the steps of:
s1: dispersing the metal oxide in water to obtain a first suspension;
s2: adding a transition metal precursor into the first suspension, and sequentially stirring, centrifuging, washing, drying and calcining to obtain the modified carrier;
s3: dispersing the modified carrier in water to obtain a second suspension;
s4: and adding an aqueous solution of a copper precursor and a noble metal precursor into the second suspension, and sequentially stirring, centrifuging, washing, drying and calcining to obtain the catalyst.
In the above examples, the preparation of the modified support was first completed: dissolving metal oxide in 50-500 mL of ultrapure water, obtaining a first suspension by ultrasonic dispersion, adding a transition metal precursor into the first suspension, and stirring for 4-24 h, wherein the range of a metal salt solution of the transition metal precursor is 0.01-10mol/L, the solvent is ethanol or water, centrifuging and washing, vacuum drying for 4-24 h at 60-150 ℃, and calcining for 4h at 450-550 ℃ by a muffle furnace to obtain the metal oxide with a modified carrier modified by transition metal; and then copper and noble metal are loaded on the modified carrier: dissolving the modified carrier in 50-500 mL of ultrapure water, performing ultrasonic dispersion to obtain a second suspension, dissolving a Cu precursor and a noble metal precursor in water, adding a certain amount of Cu precursor solution and noble metal precursor solution into the second suspension, stirring for 4-24 hours at room temperature, centrifuging, washing, performing vacuum drying for 4-24 hours at 60-150 ℃, and calcining for 3 hours at 450-550 ℃ through a muffle furnace to obtain the catalyst for degrading sulfur-containing VOCs.
In the above embodiment, the transition metal precursor is at least one of cerium nitrate, cerium sulfate, cerium oxide, manganese nitrate, manganese sulfate, manganese chloride, vanadyl acetylacetonate, vanadyl sulfate; the copper precursor comprises copper nitrate, copper sulfate and copper chloride, the noble metal precursor comprises noble metal salts such as chloroplatinic acid, palladium nitrate, palladium sulfate, ruthenium subunit nitrite and the like, the dissolution concentration range is 0.1-20 mol/L, and the corresponding obtained transition metal is one or more of cerium, manganese and vanadium; the noble metal is one or more of platinum, palladium and ruthenium.
In order to more clearly illustrate the present invention, the following examples are set forth, but they do not limit the scope of the present invention in any way.
Example 1
S1: weighing a certain amount of gamma-Al with the particle size of 40nm 2 O 3 Dissolving in 50-500 mL of ultrapure water, and performing ultrasonic treatment at room temperature for 20min to obtain a first suspension;
s2: adding a certain amount of cerium nitrate into the first suspension, stirring for 4 hours at room temperature, sequentially centrifugally washing, vacuum drying for 24 hours at 80 ℃, and calcining for 4 hours at 550 ℃ by a muffle furnace to obtain the modified carrier 10Ce-AlO x The transition metal loading was 10wt%.
S3: a certain amount of the modified carrier was dissolved in 300mL of ultra pure water, and sonicated at room temperature for 20min to obtain a second suspension.
S4: adding a certain amount of copper nitrate solution and chloroplatinic acid solution into the second suspension, stirring for 4 hours at room temperature, centrifuging and washing, vacuum drying for 24 hours at 80 ℃, and calcining for 3 hours at 500 ℃ through a muffle furnace to obtain the metal catalyst for degrading sulfur-containing VOCs: 5Cu0.1PtO x 10Ce-Al, wherein the Ce loading is 10wt%, the Cu loading is 5wt% and the Pt loading is 0.1wt%.
Example 2
S1: weighing a certain amount of gamma-Al with the particle size of 40nm 2 O 3 Dissolving in 50-500 mL of ultrapure water, and performing ultrasonic treatment at room temperature for 20min to obtain a first suspension;
s2: adding a certain amount of manganese nitrate into the first suspension, stirring for 4 hours at room temperature, sequentially centrifugally washing, vacuum drying for 24 hours at 80 ℃, and calcining for 4 hours at 550 ℃ by a muffle furnace to obtain the modified carrier 10Mn-AlO x The transition metal loading was 10wt%.
S3: a certain amount of the modified carrier was dissolved in 300mL of ultra pure water, and sonicated at room temperature for 20min to obtain a second suspension.
S4: adding a certain amount of copper nitrate solution and chloroplatinic acid solution into the second suspension, stirring for 4 hours at room temperature, centrifuging and washing, vacuum drying for 24 hours at 80 ℃, and calcining for 3 hours at 500 ℃ through a muffle furnace to obtain the metal catalyst for degrading sulfur-containing VOCs: 5Cu0.1PtO x 10Mn-Al, mn loading of 10wt%, cu loading of 5wt%, pt loading of 0.1wt%.
Unlike example 1, the kind of transition metal precursor was manganese nitrate.
Example 3
S1: weighing a certain amount of gamma-Al with the particle size of 40nm 2 O 3 Dissolving in 50-500 mL of ultrapure water, and performing ultrasonic treatment at room temperature for 20min to obtain a first suspension;
s2: adding a certain amount of vanadyl acetylacetonate into the first suspension, stirring at room temperature for 4 hours, sequentially centrifugally washing, vacuum drying at 80 ℃ for 24 hours, and calcining at 550 ℃ for 4 hours by a muffle furnace to obtain the modified carrier 10V-AlO x The transition metal loading was 10wt%.
S3: a certain amount of the modified carrier was dissolved in 300mL of ultra pure water, and sonicated at room temperature for 20min to obtain a second suspension.
S4: adding a certain amount of copper nitrate solution and chloroplatinic acid solution into the second suspension, stirring for 4 hours at room temperature, centrifuging and washing, vacuum drying for 24 hours at 80 ℃, and calcining for 3 hours at 500 ℃ through a muffle furnace to obtain the metal catalyst for degrading sulfur-containing VOCs: 5Cu0.1PtO x and/10V-Al, wherein the V loading is 10wt%, the Cu loading is 5wt%, and the Pt loading is 0.1wt%.
Unlike example 1, the kind of transition metal precursor is vanadyl acetylacetonate.
Comparative example 1
S1: weighing a certain amount of gamma-Al with the particle size of 40nm 2 O 3 Dissolving in 50-500 mL of ultrapure water, and performing ultrasonic treatment at room temperature for 20min to obtain a first suspension;
s2: stirring the first suspension at room temperature for 4h, sequentially centrifugally washing, vacuum drying at 80 ℃ for 24h, and calcining at 550 ℃ for 4h by a muffle furnace to obtain an unmodified carrier AlO x 。
S3: a certain amount of unmodified carrier was dissolved in 300mL of ultrapure water and sonicated at room temperature for 20min to obtain a second suspension.
S4: adding a certain amount of copper nitrate solution and chloroplatinic acid solution into the second suspension, stirring for 4 hours at room temperature, centrifuging, washing, and then adding a certain amount of copper nitrate solution and chloroplatinic acid solution into the second suspensionVacuum drying at 80 ℃ for 24 hours, and calcining at 500 ℃ for 3 hours through a muffle furnace to obtain the catalyst: 5Cu0.1PtO x and/Al, wherein Cu loading is 5wt% and Pt loading is 0.1wt%.
Unlike example 1, the metal oxide was not modified with a transition metal.
Comparative example 2
S1: weighing a certain amount of gamma-Al with the particle size of 40nm 2 O 3 Dissolving in 50-500 mL of ultrapure water, and performing ultrasonic treatment at room temperature for 20min to obtain a first suspension;
s2: stirring the first suspension at room temperature for 4h, sequentially centrifugally washing, vacuum drying at 80 ℃ for 24h, and calcining at 550 ℃ for 4h by a muffle furnace to obtain an unmodified carrier AlO x 。
S3: a certain amount of unmodified carrier was dissolved in 300mL of ultrapure water and sonicated at room temperature for 20min to obtain a second suspension.
S4: adding a certain amount of copper nitrate solution into the second suspension, stirring for 4 hours at room temperature, centrifuging, washing, vacuum drying for 24 hours at 80 ℃, and calcining for 3 hours at 500 ℃ through a muffle furnace to obtain the catalyst: 5CuO x and/Al, wherein the Cu loading is 5wt%.
Unlike comparative example 1, no noble metal was incorporated.
Comparative example 3
S1: weighing a certain amount of gamma-Al with the particle size of 40nm 2 O 3 Dissolving in 50-500 mL of ultrapure water, and performing ultrasonic treatment at room temperature for 20min to obtain a first suspension;
s2: stirring the first suspension at room temperature for 4h, sequentially centrifugally washing, vacuum drying at 80 ℃ for 24h, and calcining at 550 ℃ for 4h by a muffle furnace to obtain an unmodified carrier AlO x 。
S3: a certain amount of unmodified carrier was dissolved in 300mL of ultrapure water and sonicated at room temperature for 20min to obtain a second suspension.
S4: adding a certain amount of chloroplatinic acid solution into the second suspension, stirring for 4 hours at room temperature, centrifuging, washing, vacuum drying at 80deg.C for 24 hours, and passing through a muffle furnace at 500deg.CCalcining for 3h to obtain the catalyst: 5PtO x and/Al, wherein the Pt loading is 5wt%.
Unlike example 1, copper was not incorporated.
Methyl mercaptan is used as catalytic oxidation target, its initial concentration is 39+ -1 ppm, gas flow rate is 12000mL/h, and gamma-Al with grain size of 40nm 2 O 3 As a blank, methyl mercaptan was catalyzed by the catalysts synthesized in examples 1-3 and comparative examples 1-3, respectively, and the blank was used in an amount of 50mg, and the reaction conditions were 50 to 300℃and normal pressure.
FIG. 1 shows 5CuO x /Al、5PtO x /Al、5Cu0.1PtO x /Al、5Cu0.1PtO x /10Ce-Al、5Cu0.1PtO x /10Mn-Al、5Cu0.1PtO x 10V-Al catalyst and 40nm gamma-Al 2 O 3 As can be seen from the performance graph of catalytic degradation of methyl mercaptan at 50-350 ℃ and normal pressure, the degradation performance of methyl mercaptan in the whole reaction process of the unmodified carrier catalyst is 5CuO x /Al>5PtO x /Al>γ-Al 2 O 3 ，γ-Al 2 O 3 And 5PtO x The T90 of/Al is greater than 350℃which means that the temperature at 90% conversion is up to 350℃and 5Cu0.1PtO x The T90 of the/Al is 125 ℃, which is mainly because the CuPt alloy formed by the doping of the noble metal Pt has good affinity to methyl mercaptan, and the methyl mercaptan in the gas stream can be captured and then the next reaction can be carried out. While the modified supported catalyst 5Cu0.1PtO x /10Ce-Al、5Cu0.1PtO x /10Mn-Al、5Cu0.1PtO x In the degradation process of/10V-Al, T90 is between 110 and 120 ℃ due to transition metal and gamma-Al 2 O 3 The composite oxide can generate more surface acid sites, so that the sulfur resistance of the catalyst is improved, the loss of the catalyst is reduced, the adding cost of noble metal is reduced, and the degradation efficiency is improved.
Similar experiments are carried out on copper and noble metal loaded on metal oxides with different loading amounts to obtain 5Cu1.5PtO x /Al、5Cu1PtO x /Al、5Cu0.5PtO x /Al、5Cu0.1PtO x Al catalyst, p-methylthio catalyst at 50-350 deg.C and normal pressureThe performance test of the catalytic degradation of the alcohol gives the graph of FIG. 2, which shows that the noble metal loading of 0.1-1.5 wt% can reach 100% conversion before 150 ℃. It is understood that the same effect can be obtained by loading copper and noble metal at different loadings on the transition metal modified metal oxide.
Using different kinds of noble metals supported on metal oxides, e.g. ruthenium Ru, palladium Pd, silver Ag, to give 5RuO x /Al、5PdO x /Al、5AgO x The Al catalyst is used for carrying out the performance test of catalytic degradation on methyl mercaptan at the temperature of 50-400 ℃ and the normal pressure to obtain a degradation performance diagram shown in figure 3, and can be seen to be 5RuO x /Al、5PdO x /Al、5AgO x Al and 5PtO x The catalytic effect of the Al catalyst is similar, and it is understood that noble metals such as ruthenium Ru, palladium Pd and silver Ag can be doped in copper to play a role in having good affinity for methyl mercaptan.
The third aspect of the invention provides application of a catalyst for degrading sulfur-containing VOCs in the environment-friendly field of catalytic degradation of sulfur-containing VOCs in catalytic oxidation atmosphere.
Examples 1-3 and comparative examples 1-3 resulted in 5CuO x /Al、5PtO x /Al、5Cu0.1PtO x /Al、5Cu0.1PtO x /10Ce-Al、5Cu0.1PtO x /10Mn-Al、5Cu0.1PtO x The catalyst of/10V-Al and the blank group catalyst, the catalyst usage amount is 50mg, the methyl mercaptan concentration is 39+ -1 ppm, the gas flow is 12000mL/h, the methyl mercaptan is catalyzed and degraded at 50-300 ℃ under normal pressure, and the graph is 5CuO x /Al、5PtO x /Al、5Cu0.1PtO x /Al、5Cu0.1PtO x 10M-Al (m=ce, mn, V) catalyst and 40nm gamma-Al 2 O 3 SO of methyl mercaptan at 50-350 deg.c and normal pressure 2 The yield of (C) varies with temperature, and it can be seen that the transition metal modified gamma-Al is loaded with copper and heavy metal 2 O 3 Supported catalyst catalyzed by methyl mercaptan to form SO 2 The selectivity after the reaction reached stability was 100% and the products were all SO at 275 ℃ 2 Rather than dimethyl disulfide, hydrogen sulfide, or the likeOther byproducts, compared with other unmodified catalysts, the catalyst has the advantages of simple conditions, low technical requirements, lower investment cost and SO compared with other process reactions 2 High selectivity, low energy consumption and the like.
For the 5Cu0.1PtO synthesized in examples 1-3 x /10Ce-Al、5Cu0.1PtO x /10Mn-Al、5Cu0.1PtO x The stability test was carried out on the 10V-Al catalyst, and the catalytic degradation performance of methyl mercaptan at 275 ℃ in 24 hours of the catalyst was tested to obtain FIG. 3. From the stability diagram of the catalyst catalytic degradation of methyl mercaptan in FIG. 5, it can be seen that various catalysts still have high stability to methyl mercaptan degradation at 24h and remain at 100%. Description of 5Cu0.1PtO x /10Ce-Al、5Cu0.1PtO x /10Mn-Al、5Cu0.1PtO x The 10V-Al catalyst has high stability to the degradation of methyl mercaptan at room temperature.
The foregoing is merely a preferred embodiment of the present invention and is not intended to limit the scope of the invention, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles of the present invention. All equivalent structures or equivalent flow changes made by the specification and the attached drawings of the invention or directly or indirectly applied to other related technical fields are included in the protection scope of the invention.
Claims (10)
1. A catalyst for degrading sulfur-containing VOCs (volatile organic compounds), which is characterized by comprising an active component metal alloy and a modified carrier; the active component metal alloy comprises copper and noble metal, and the modified carrier is transition metal modified metal oxide.
2. The sulfur-containing VOCs metal degrading catalyst according to claim 1, wherein the copper loading is 0.1-20 wt% and the noble metal loading is 0.1-20 wt%.
3. The catalyst for degrading sulfur-containing VOCs metal as set forth in claim 2, wherein the mass percentage of copper and noble metal is 1:0.01 to 20:1.
4. the sulfur-containing VOCs metal degrading catalyst of claim 1 wherein said metal oxide is Al 2 O 3 、SiO 2 Any one of zeolite molecular sieves.
5. The sulfur-containing VOCs metal degrading catalyst of claim 1 wherein said transition metal is at least one of cerium, manganese, vanadium; the noble metal is at least one of platinum, palladium, ruthenium and gold.
6. The sulfur-containing VOCs metal degrading catalyst according to claim 1, wherein the transition metal loading is 0.1 to 50wt%.
7. A method for preparing the catalyst according to any one of claims 1 to 6, characterized in that the method comprises the steps of:
s1: dispersing the metal oxide in water to obtain a first suspension;
s2: adding a transition metal precursor into the first suspension, and sequentially stirring, centrifuging, washing, drying and calcining to obtain the modified carrier;
s3: dispersing the modified carrier in water to obtain a second suspension;
s4: and adding an aqueous solution of a copper precursor and a noble metal precursor into the second suspension, and sequentially stirring, centrifuging, washing, drying and calcining to obtain the catalyst.
8. The method for preparing the catalyst for degrading sulfur-containing VOCs according to claim 7, wherein the transition metal precursor is at least one of cerium nitrate, cerium sulfate, cerium oxide, manganese nitrate, manganese sulfate, manganese chloride, vanadyl acetylacetonate, vanadyl sulfate.
9. The method for preparing the catalyst for degrading sulfur-containing VOCs according to claim 7, wherein the copper precursor is at least one of copper nitrate, copper sulfate and copper chloride, and the noble metal precursor is at least one of chloroplatinic acid, palladium nitrate, palladium sulfate and ruthenium nitrosylnitrate.
10. Use of the catalyst according to any one of claims 1-6 for the catalytic degradation of sulfur-containing VOCs in the catalytic oxidation atmosphere in the field of environmental protection.
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