CN115532257B - VOCs combustion catalyst used in sulfur-containing atmosphere and preparation method thereof - Google Patents
VOCs combustion catalyst used in sulfur-containing atmosphere and preparation method thereof Download PDFInfo
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- CN115532257B CN115532257B CN202211368736.5A CN202211368736A CN115532257B CN 115532257 B CN115532257 B CN 115532257B CN 202211368736 A CN202211368736 A CN 202211368736A CN 115532257 B CN115532257 B CN 115532257B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 139
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 239000011593 sulfur Substances 0.000 title claims abstract description 54
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 54
- 239000012855 volatile organic compound Substances 0.000 title claims abstract description 29
- 238000002485 combustion reaction Methods 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000011259 mixed solution Substances 0.000 claims abstract description 35
- 239000002243 precursor Substances 0.000 claims abstract description 33
- 239000010936 titanium Substances 0.000 claims abstract description 29
- 238000001035 drying Methods 0.000 claims abstract description 22
- 229910052709 silver Inorganic materials 0.000 claims abstract description 21
- DEJJSDCGHQNYBS-UHFFFAOYSA-N [Mn].[Ag].[Ti] Chemical compound [Mn].[Ag].[Ti] DEJJSDCGHQNYBS-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 15
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002131 composite material Substances 0.000 claims abstract description 6
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims abstract description 5
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 5
- 238000002791 soaking Methods 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 65
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 37
- 239000000243 solution Substances 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 239000008367 deionised water Substances 0.000 claims description 24
- 229910021641 deionized water Inorganic materials 0.000 claims description 24
- 239000011572 manganese Substances 0.000 claims description 24
- 229910052748 manganese Inorganic materials 0.000 claims description 22
- 229910052719 titanium Inorganic materials 0.000 claims description 20
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 19
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 16
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 14
- 239000004332 silver Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- 238000004090 dissolution Methods 0.000 claims description 11
- 229910052697 platinum Inorganic materials 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 2
- 239000012670 alkaline solution Substances 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical group [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical group [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 2
- -1 polytetrafluoroethylene Polymers 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 22
- MECMQNITHCOSAF-UHFFFAOYSA-N manganese titanium Chemical compound [Ti].[Mn] MECMQNITHCOSAF-UHFFFAOYSA-N 0.000 abstract description 18
- 238000000746 purification Methods 0.000 abstract description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 57
- 239000007789 gas Substances 0.000 description 36
- 229910052760 oxygen Inorganic materials 0.000 description 21
- 238000012360 testing method Methods 0.000 description 20
- 238000006555 catalytic reaction Methods 0.000 description 18
- 239000000203 mixture Substances 0.000 description 18
- 239000010453 quartz Substances 0.000 description 18
- 239000012495 reaction gas Substances 0.000 description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 18
- 238000007084 catalytic combustion reaction Methods 0.000 description 15
- 229910052799 carbon Inorganic materials 0.000 description 13
- 238000011156 evaluation Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 11
- 238000004817 gas chromatography Methods 0.000 description 9
- 238000001514 detection method Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 238000009210 therapy by ultrasound Methods 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 239000002202 Polyethylene glycol Substances 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 230000003993 interaction Effects 0.000 description 5
- 229920001223 polyethylene glycol Polymers 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 150000001555 benzenes Chemical class 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-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
- 230000009471 action Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000006255 coating slurry Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 229910003446 platinum oxide Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- KZJPVUDYAMEDRM-UHFFFAOYSA-M silver;2,2,2-trifluoroacetate Chemical compound [Ag+].[O-]C(=O)C(F)(F)F KZJPVUDYAMEDRM-UHFFFAOYSA-M 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/688—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with manganese, technetium or rhenium
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/656—Manganese, technetium or rhenium
- B01J23/6562—Manganese
-
- 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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Catalysts (AREA)
Abstract
The invention provides a VOCs combustion catalyst used in a sulfur-containing atmosphere and a preparation method thereof, belonging to the field of VOCs purification. The catalyst comprises a carrier and an active component, wherein the carrier comprises Mn-Ti composite oxide or Mn-Ag-Ti composite oxide, and the active component comprises one or more of Pd, pt or Ag. The preparation method of the catalyst comprises the following steps: firstly preparing a manganese-titanium precursor or a manganese-titanium-silver precursor; and fully soaking the manganese-titanium precursor or the manganese-titanium-silver precursor in a mixed solution containing one or more of palladium nitrate, silver nitrate or platinum nitrate, and drying and roasting to obtain the catalyst. The catalyst has the advantages of excellent activity, good sulfur resistance, good hydrothermal stability and the like.
Description
Technical Field
The invention relates to the field of VOCs purification, in particular to a VOCs combustion catalyst used in a sulfur-containing atmosphere and a preparation method thereof.
Background
Volatile organic Compounds (Volatile organic compound)s, VOCs) refers to organic compounds with a boiling point of less than or equal to 250 ℃ at normal temperature and pressure, and VOCs include alkanes, aromatic hydrocarbons, olefins, halocarbons, esters, aldehydes, ketones and the like. At present, the atmospheric pollution problem in China is complex, the characteristics of high pollution load, multi-pollutant superposition and the like are presented, and the traditional soot type pollution is gradually changed into O type pollution 3 And PM 2.5 Is the characteristic composite pollution. O in six monitoring indexes of 2016 national air quality 3 Is the only contaminant that does not drop and rise. Therefore, the propulsion O must be accelerated 3 And PM 2.5 Is used as O 3 And PM 2.5 Common key precursors, strengthening comprehensive management of VOCs is an urgent issue.
The existing VOCs treatment technology mainly comprises a condensation method, an absorption method, an adsorption method, a membrane separation method, a catalytic combustion method, a photocatalysis method, biodegradation and the like. The catalytic combustion method converts VOCs into harmless components such as water, carbon dioxide and the like through a redox reaction mode. The catalytic combustion has the advantages of wide application range, low ignition temperature, high purification efficiency, no secondary pollution and the like, and is a mainstream technology for treating VOCs. The core of the catalytic technology is a catalyst, VOCs are catalytically oxidized in a sulfur-containing and water-containing atmosphere, the catalyst is easy to be poisoned by sulfur, and the hydrothermal stability is poor. CN114367287a discloses a catalytic oxidation catalyst suitable for treating high sulfur tail gas and a preparation method thereof, the catalyst uses titanium dioxide, molybdenum and magnesium modified alumina as carriers, noble metals palladium and platinum as active components, the component ratio of molybdenum to alumina is 1:99-1:9, the component ratio of magnesium to alumina is 1:99-1:9, wherein the proportion of molybdenum to magnesium is 1:1, and the weight of noble metals accounts for 0.5% -2.5% of the weight of coating slurry. The catalyst can completely convert maleic acid under the temperature of 300 ℃ after being subjected to the atmosphere condition of sulfur dioxide and water vapor for 100 hours, but T 50 Increasing the temperature by 10 to 20 ℃ and T 100 The temperature is increased by 15-20 ℃. CN113680352A discloses a low-load Pt-Mn bimetallic catalyst for CO oxidation, and a preparation method and application thereof, wherein the catalyst takes titanium dioxide as a carrier, platinum simple substance or platinum oxide as a first active component, manganese oxide as a second active component, and platinumThe content of the elements is 0.02-0.2%, and the content of the manganese element is 0.1-0.8%. Pt-Mn bimetallic catalyst with flue gas flow of 1000Nm at 240 DEG C 3 ·h -1 CO concentration is 70000 ppm, O 2 The concentration is 16%, H 2 O concentration is 10%, SO 2 Catalytic oxidation is carried out in the atmosphere with the concentration of 0-500 ppm, and the CO conversion rate is 78-99%. The above sulfur-containing exhaust gas catalytic combustion catalyst was not evaluated for the corresponding sulfur resistance stability.
Therefore, it is a practical need for current industrial applications to design a catalyst with excellent activity, sulfur resistance and good hydrothermal stability.
Disclosure of Invention
The purpose of the present application is to provide a catalyst for burning VOCs in a sulfur-containing atmosphere and a preparation method thereof, so as to solve the above problems.
In order to achieve the above purpose, the present application adopts the following technical scheme:
a VOCs combustion catalyst used in a sulfur-containing atmosphere comprises a carrier and an active component, wherein the carrier comprises Mn-Ti composite oxide or Mn-Ag-Ti composite oxide, and the active component comprises one or more of Pd, pt or Ag.
Further, the catalyst comprises 70 parts of carrier and 1 (0.5-4) of Mn-Ti-Ag in a molar ratio of 0.05-1; the active component Pd is 0-0.5 part, pt is 0-0.7 part, and Ag is 0-1 part; preferably, pd is 0.01-0.5 parts, pt is 0.01-0.7 parts, and Ag is 0.1-1 parts.
The titanium dioxide surface has acidity and electron transfer characteristics, and the titanium-based carrier can enhance the acidity of the catalyst surface, reduce the adsorption of sulfides and improve the activity of the catalyst. Meanwhile, strong interaction exists between the active components of the catalyst and the carrier, and the components of the catalyst are not easy to sulfate, so that the catalyst has better sulfur resistance and hydrothermal stability. Particularly when silver exists in the carrier and the active component at the same time, the strong interaction between the carrier and the active component is enhanced.
The invention also provides a preparation method of the VOCs combustion catalyst under the sulfur-containing atmosphere, firstly, preparing a manganese-titanium precursor or a manganese-titanium-silver precursor; and secondly, fully soaking the manganese-titanium precursor or the manganese-titanium-silver precursor in a mixed solution containing one or more of palladium nitrate, silver nitrate or platinum nitrate, and drying and roasting to obtain the catalyst.
Further, the preparation of the manganese-titanium precursor or the manganese-titanium-silver precursor comprises the following steps:
s11, adding a manganese source, a titanium source and a surfactant into deionized water, stirring and dissolving at room temperature to obtain a manganese-titanium mixed solution A1; or alternatively, the first and second heat exchangers may be,
manganese source, titanium source and AgCF 3 And adding the ethanol solution of COO into deionized water, stirring and dissolving at room temperature to obtain a manganese titanium silver mixed solution A2.
Wherein the manganese source is preferably manganese nitrate, the titanium source is preferably titanium sulfate, and the surfactant is preferably polyethylene glycol.
When preparing the manganese-titanium precursor, the molar ratio of the manganese source to the titanium source is preferably 1 (0.5-4) according to Mn and Ti, and the addition amount of polyethylene glycol is 15% of the total mass of the manganese source and the titanium source; when preparing the manganese titanium silver precursor, the manganese source, the titanium source and AgCF 3 COO is 1 (0.5-4) in terms of mole ratio of Mn, ti and Ag (0.05-0.1).
S12, adding the solution A1 or the solution A2 obtained in the step S11 into an alkali solution, and stirring for 4-8 hours at room temperature to obtain a mixed solution B1 or B2.
Wherein the alkali solution is preferably an ammonia solution; more preferably, the alkaline solution has a pH of 9 to 12.
Preferably, the deionized water is added dropwise; more preferably, the dropwise addition rate is 4 to 8 mL-min -1 。
S13, reacting the solution B1 or B2 obtained in the step S12 at 80-120 ℃ for 20-28 h to obtain a mixed solution C1 or C2.
Preferably, the solution B1 or B2 is filled into a polytetrafluoroethylene lining and put into a stainless steel reaction kettle for reaction; the reaction is typically an aging reaction;
s14, cooling, washing and drying the solution C1 or C2 obtained in the step S13 to obtain a manganese-titanium precursor or a manganese-titanium-silver precursor.
Preferably, the drying temperature is 90-140 ℃ and the drying time is 10-15 h.
Further, the preparation of the manganese-titanium precursor or manganese-titanium-silver precursor into the catalyst comprises the following steps:
s21, adding one or more of a palladium source, a silver source or a platinum source into deionized water for ultrasonic dissolution to obtain a mixed solution D. Preferably, the palladium source, the silver source or the platinum source are sequentially added into deionized water for ultrasonic dissolution.
Preferably, the palladium source is palladium nitrate, the silver source is silver nitrate, and the platinum source is platinum nitrate;
preferably, the palladium source, silver source or platinum source is (0.1-0.5): (0.1-0.7): (0.1-1), more preferably (0.1-0.5): (0.1-0.6): (0.1-0.7) according to the mass ratio.
S22, adding manganese-titanium precursor or manganese-titanium-silver precursor particles into the solution D obtained in the step S21, carrying out ultrasonic impregnation, drying and roasting to obtain the catalyst.
Preferably, the drying temperature is 90-140 ℃ and the drying time is 10-15 h;
preferably, the roasting temperature is 450-650 ℃, the roasting time is 4-6 h, and the roasting atmosphere is air.
The catalyst for catalyzing and burning benzene series has excellent activity, and the preparation method is simple, is easy and convenient to operate, and has good industrial application prospect.
Meanwhile, the catalyst can be used as a catalyst for catalyzing and burning benzene series in a sulfur-containing and water-containing atmosphere, and has good sulfur resistance and hydrothermal stability.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate certain embodiments of the present application and therefore should not be considered as limiting the scope of the present application.
FIG. 1 is a graph showing the evaluation of the catalytic combustion of benzene by the catalysts prepared in examples 1 to 6;
FIG. 2 is a graph showing the evaluation of the catalytic combustion of benzene by the catalysts prepared in comparative examples 1 to 3;
FIG. 3 is a graph showing the benzene conversion with time (h) and temperature change in the sulfur resistance test of the catalyst prepared in example 4;
FIG. 4 is a graph showing the benzene conversion versus time (h) for the catalyst prepared in example 5 when tested for sulfur resistance at various temperatures;
FIG. 5 is a graph showing the change of benzene conversion with time (h) at 260℃in sulfur resistance test of the catalyst prepared in example 5;
FIG. 6 is a graph showing the change of benzene conversion with time (h) when sulfur resistance of the catalysts prepared in comparative examples 1 to 3 were measured.
Detailed Description
Embodiments of the present application will be described in detail below with reference to specific examples, but it will be understood by those skilled in the art that the following examples are only for illustration of the present application and should not be construed as limiting the scope of the present application. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
A preparation method of a VOCs combustion catalyst under a sulfur-containing atmosphere comprises the following steps:
(1) 20mL of deionized water and 2.7g of 50 wt% Mn (NO) were measured with a measuring cylinder and a pipette, respectively 3 ) 2 The solution was placed in a 50mL beaker and 5.4g of Ti (SO 4 ) 2 And 1.22g of polyethylene glycol, stirred for 2h, labeled as solution A1;
(2) Taking 10mL of deionized water in a 100mL beaker, taking a certain amount of 25% concentrated ammonia water by a pipetting gun, adding the concentrated ammonia water into the deionized water, and marking the diluted ammonia water solution;
(3) Dropwise adding an ammonia water solution into the solution A1 to ensure that the final pH value of the mixed solution is=10;
(4) Stirring the mixed solution at room temperature for 6 hours, then loading the mixed solution into a reaction kettle, putting the reaction kettle into a baking oven, and aging for 20 hours at 100 ℃;
(5) And cooling the aged mixed solution to room temperature, washing and filtering the mixed solution with deionized water for multiple times, and putting the obtained solid into an oven to be dried for 15 hours at 100 ℃.
(6) Pressing the solid obtained in the step (5) for 2min under 8MPa, and granulating to obtain 40-60-mesh MnTiO x A precursor.
(7) According to mass ratio Pd: pt: ag: mnTiO x =0.1: 0.5:0.2:70 Pd (NO) 3 ) 2 、Pt(NO 3 ) 2 And Ag (NO) 3 ) 2 Sequentially adding 2mL of deionized water for ultrasonic dissolution to obtain a mixed solution D, and adding MnTiO into the mixed solution D x Ultrasonic treatment of the precursor particles for 40min, drying at 120 deg.c for 14 hr, and roasting at 550 deg.c in air atmosphere for 6 hr to obtain 40-60 mesh Pd-Pt-Ag/MnTiO x A catalyst.
The catalyst comprises 70 parts of carrier, manganese-titanium molar ratio of 1:3, 0.1 part of Pd, 0.5 part of Pt and 0.2 part of Ag in parts by mass.
Experimental results of the catalytic combustion of benzene by the catalyst:
catalyst activity evaluation: 0.2g of Pd-Pt-Ag/MnTiO with 40-60 meshes x The catalyst is filled into a quartz tube of a fixed bed catalytic reaction device, and the total gas flow is 200 mL.min -1 Space velocity of 60000 mL.g -1 ·min -1 The reaction gas composition was 1000ppm C 6 H 6 ，4％O 2 ，N 2 For balancing the gas, the test temperature is 100-260 ℃. The reaction temperature is C at 100, 160, 180, 200, 220, 240 and 260 ℃ by gas chromatography detection 6 H 6 The conversion rates were 0, 2.6%, 5.4%, 14.1%, 93.6%, 99.8%, 99.9%, respectively.
Test of sulfur and water resistance of the catalyst: 0.2g of Pd-Pt-Ag/MnTiO with 40-60 meshes x The catalyst is filled into a quartz tube of a fixed bed catalytic reaction device, and the total gas flow is 200 mL.min -1 Space velocity of 60000 mL.g -1 ·min -1 The reaction gas composition was 1000ppm C 6 H 6 ，4％O 2 ，100ppm SO 2 ，5％H 2 O，N 2 To balance the gas, the reaction temperature is 300 ℃ and C is within 72 hours 6 H 6 The conversion rate is stabilized at 95%The above.
Example 2
A process for preparing a catalyst for the combustion of VOCs in a sulfur-containing atmosphere, which differs from example 1 in the following steps:
(1) 20mL of deionized water and 2.7g of 50 wt% Mn (NO) were measured with a measuring cylinder and a pipette, respectively 3 ) 2 The solution was placed in a 50mL beaker and, after the solution was stirred well, 1.8g of Ti (SO 4 ) 2 And 0.67g of polyethylene glycol, stirred for 2h, labeled as solution A1;
(7) According to mass ratio Pd: pt: ag: mnTiO x =0.1: 0.5:0.2:70 Pd (NO) 3 ) 2 、Pt(NO 3 ) 2 And Ag (NO) 3 ) 2 Sequentially adding 2mL of deionized water for ultrasonic dissolution to obtain a mixed solution D, and adding 0.63g of MnTiO into the mixed solution D x Ultrasonic treatment of the precursor particles for 40min, drying at 120 deg.c for 14 hr, and roasting at 450 deg.c in air atmosphere for 6 hr to obtain 40-60 mesh Pd-Pt-Ag/MnTiO x A catalyst.
The catalyst comprises 70 parts of carrier, manganese-titanium molar ratio of 1:1, 0.1 part of Pd, 0.5 part of Pt and 0.2 part of Ag in parts by mass.
Experimental results of the catalytic combustion of benzene by the catalyst:
catalyst activity evaluation: 0.2g of Pd-Pt-Ag/MnTiO with 40-60 meshes x The catalyst is filled into a quartz tube of a fixed bed catalytic reaction device, and the total gas flow is 200 mL.min -1 Space velocity of 60000 mL.g -1 ·min -1 The reaction gas composition was 1000ppm C 6 H 6 ，4％O 2 ，N 2 For balancing the gas, the test temperature is 100-260 ℃. The reaction temperature is C at 100, 160, 180, 200, 220, 230, 240 and 260 ℃ by gas chromatography detection 6 H 6 The conversion was 0, 1.3%, 3.6%, 10.7%, 15.6%, 90.6%, 99.5%, 99.7%, respectively.
Test of sulfur and water resistance of the catalyst: 0.2g of Pd-Pt-Ag/MnTiO with 40-60 meshes x The catalyst is filled into a quartz tube of a fixed bed catalytic reaction device, and the total gas flow is 200 mL.min -1 Space velocity of 60000 mL.g -1 ·min -1 The reaction gas composition was 1000ppm C 6 H 6 ，4％O 2 ，100ppm SO 2 ，5％H 2 O，N 2 To balance the gas, the reaction temperature is 320 ℃ and C is within 72 hours 6 H 6 The conversion rate is stabilized to be more than 95%.
Example 3
A process for preparing a catalyst for the combustion of VOCs in a sulfur-containing atmosphere, which differs from example 1 in the following steps:
(1) 20mL of deionized water and 2.7g of 50 wt% Mn (NO) were measured with a measuring cylinder and a pipette, respectively 3 ) 2 The solution was placed in a 50mL beaker, and after the solution was stirred well, 5.4g of Ti (SO 4 ) 2 And 0.88g of 30wt% silver trifluoroacetate in ethanol, stirred for 2h, labeled as solution A1;
(6) Pressing the solid obtained in the step (5) for 2min under 8MPa, and granulating to obtain 40-60-mesh MnAgTiO x A precursor.
(7) According to mass ratio Pd: pt: ag: mnAgTiO x =0.1: 0.5:0.2:70 Pd (NO) 3 ) 2 、Pt(NO 3 ) 2 And Ag (NO) 3 ) 2 Sequentially adding 2mL of deionized water for ultrasonic dissolution to obtain a mixed solution D, and adding MnAgTiO into the mixed solution D x Ultrasonic treatment of the precursor particles for 40min, drying at 120 deg.c for 14 hr, and roasting at 550 deg.c in air atmosphere for 6 hr to obtain 40-60 mesh Pd-Pt-Ag/MnAgTiO x A catalyst.
The catalyst comprises 70 parts of carrier, 0.16 part of Pd, 0.5 part of Pt and 0.2 part of Ag, wherein the molar ratio of manganese to titanium to silver is 1:3:0.16.
Catalyst activity evaluation: 0.2g of Pd-Pt-Ag/MnAgTiO with 40-60 meshes x The catalyst is filled into a quartz tube of a fixed bed catalytic reaction device, and the total gas flow is 200 mL.min -1 Space velocity of 60000 mL.g -1 ·min -1 The reaction gas composition was 1000ppm C 6 H 6 ，4％O 2 ，N 2 For balancing the gas, the test temperature is 100-240 ℃. The reaction temperature detected by gas chromatography is 100, 160, 180, 200, 210, 220, 240C at C 6 H 6 The conversion rates were 0, 3.4%, 7.8%, 14.7%, 90.6%, 98.9% and 99.9%, respectively.
Test of sulfur and water resistance of the catalyst: 0.2g of Pd-Pt-Ag/MnTiO with 40-60 meshes x The catalyst is filled into a quartz tube of a fixed bed catalytic reaction device, and the total gas flow is 200 mL.min -1 Space velocity of 60000 mL.g -1 ·min -1 The reaction gas composition was 1000ppm C 6 H 6 ，4％O 2 ，100ppm SO 2 ，5％H 2 O，N 2 To balance the gas, the reaction temperature is 260 ℃ and C is within 72 hours 6 H 6 The conversion rate is stabilized to be more than 99 percent.
Example 4
A process for preparing a catalyst for the combustion of VOCs in a sulfur-containing atmosphere, which differs from example 1 in the following steps:
(7) According to mass ratio Pd, mnTiO x =0.5:70 Pd (NO 3 ) 2 Adding 2mL of deionized water for ultrasonic dissolution to obtain a mixed solution D, and adding MnTiO into the mixed solution D x Ultrasonic treatment of the precursor particles for 40min, drying at 120 deg.c for 14 hr, and roasting at 550 deg.c in air atmosphere for 6 hr to obtain 40-60 mesh Pd/MnTiO x A catalyst.
The catalyst is prepared by using 70 parts of carrier, wherein the molar ratio of manganese to titanium is 1:3, and Pd is 0.5 part.
Experimental results of the catalytic combustion of benzene by the catalyst:
catalyst activity evaluation: 0.2g of Pd/MnTiO with 40-60 meshes x The catalyst is filled into a quartz tube of a fixed bed catalytic reaction device, and the total gas flow is 150 mL.min -1 Space velocity of 45000 mL.g -1 ·min -1 The reaction gas composition was 1000ppm C 6 H 6 ，4％O 2 ，N 2 For balancing the gas, the test temperature is 100-260 ℃. The reaction temperature is C at 100, 160, 180, 200, 220, 240, 260, 280 and 300 ℃ by gas chromatography detection 6 H 6 The conversion was 0, 12.7%, 15.5%, 21.1%, 36.3%, 66.1%, 93.9%, 97%, 99%, respectively.
Sulfur resistance of catalystAnd (3) testing: 0.2g of Pd/MnTiO with 40-60 meshes x The catalyst is filled into a quartz tube of a fixed bed catalytic reaction device, and the total gas flow is 200 mL.min -1 Space velocity of 60000 mL.g -1 ·min -1 The reaction gas composition was 1000ppm C 6 H 6 ，4％O 2 ，20ppm SO 2 ，N 2 Is the balance of qi. C at 320℃for 48h 6 H 6 The conversion rate is stabilized to be more than 98 percent, when the temperature is reduced to 280 ℃, the catalyst is reversibly deactivated, C is in 24 hours 6 H 6 The conversion rate is reduced to 30 percent, and the SO is stopped to be introduced 2 After that, the catalyst activity is slowly recovered, C 6 H 6 The conversion rate is stabilized at about 65%.
Example 5
A process for preparing a catalyst for the combustion of VOCs in a sulfur-containing atmosphere, which differs from example 1 in the following steps:
(4) Stirring the mixed solution at room temperature for 6 hours, then loading the mixed solution into a reaction kettle, putting the reaction kettle into a baking oven, and aging for 28 hours at 100 ℃;
(5) And cooling the aged mixed solution, washing and filtering the cooled mixed solution with deionized water for multiple times, and putting the obtained solid into an oven to be dried for 24 hours at 100 ℃.
(7) According to the mass ratio of Pt to MnTiO x =0.5:70 Pt (NO 3 ) 2 Adding 2mL of deionized water for ultrasonic dissolution to obtain a mixed solution D, and adding MnTiO into the mixed solution D x Ultrasonic treatment of the precursor particles for 40min, drying at 110 deg.c for 14 hr, and roasting at 500 deg.c in air atmosphere for 6 hr to obtain 40-60 mesh Pt/MnTiO powder x A catalyst.
The catalyst obtained was 70 parts by mass of a carrier, wherein the molar ratio of manganese to titanium was 1:3 and pt was 0.5 part.
Experimental results of the catalytic combustion of benzene by the catalyst:
catalyst activity evaluation: 0.2g of Pt/MnTiO with 40-60 meshes x The catalyst is filled into a quartz tube of a fixed bed catalytic reaction device, and the total gas flow is 150 mL.min -1 Space velocity of 45000 mL.g -1 ·min -1 The reaction gas composition was 1000ppm C 6 H 6 ，5％O 2 ，N 2 To balance withThe testing temperature range is 100-260 ℃. C at 100, 160, 180, 200, 220 and 240 ℃ in gas chromatography detection reaction temperature 6 H 6 The conversion rates were 0, 0.4%, 3.9%, 8.2%, 99.2%, 99.8%, respectively.
Sulfur resistance test of catalyst: 0.2g of Pt/MnTiO with 40-60 meshes x The catalyst is filled into a quartz tube of a fixed bed catalytic reaction device, and the total gas flow is 150 mL.min -1 Space velocity of 45000 mL.g -1 ·min -1 The reaction gas composition was 1000ppm C 6 H 6 ，4％O 2 ，20/100ppm SO 2 ，N 2 To balance the gases, the reaction temperature was 240-320 ℃, the evaluation temperature was 320 ℃, and then the temperature was reduced to 260 ℃ and even to 240 ℃ for 31 days C 6 H 6 The conversion rate is still stabilized at 100%, but the catalyst is deactivated fast when the reaction is carried out directly under the condition of 260 ℃ and the benzene conversion rate after stabilization is only about 20%.
Example 6
A process for preparing a catalyst for the combustion of VOCs in a sulfur-containing atmosphere, which differs from example 1 in the following steps:
(7) According to mass ratio Pd, pt and MnTiO x =0.3:0.4:70 Pd (NO 3 ) 2 And Pt (NO) 3 ) 2 Sequentially adding 2mL of deionized water for ultrasonic dissolution to obtain a mixed solution D, and adding MnTiO into the mixed solution D x Ultrasonic treatment of the precursor particles for 40min, drying at 120 deg.c for 14 hr, and roasting at 550 deg.c in air atmosphere for 6 hr to obtain 40-60 mesh Pd-Pt/MnTiO x A catalyst.
The catalyst is prepared by 70 parts of carrier, wherein the molar ratio of manganese to titanium is 1:3, pd was 0.3 parts and Pt was 0.4 parts.
Experimental results of the catalytic combustion of benzene by the catalyst:
catalyst activity evaluation: 0.2g of Pd-Pt/MnTiO with 40-60 meshes x The catalyst is filled into a quartz tube of a fixed bed catalytic reaction device, and the total gas flow is 200 mL.min -1 Space velocity of 60000 mL.g -1 ·min -1 The reaction gas composition was 1000ppm C 6 H 6 ，4％O 2 ，N 2 For balancing the gas, the test temperature is 100-260 ℃. C at 100, 160, 180, 200, 220 and 240 ℃ in gas chromatography detection reaction temperature 6 H 6 The conversion rates were 0, 11.7%, 15.2%, 21.2%, 99.2%, 99.8%, respectively.
Sulfur resistance test of catalyst: 0.2g of Pd-Pt/MnTiO with 40-60 meshes x The catalyst is filled into a quartz tube of a fixed bed catalytic reaction device, and the total gas flow is 200 mL.min -1 Space velocity of 60000 mL.g -1 ·min -1 The reaction gas composition was 1000ppm C 6 H 6 ，4％O 2 ，100ppm SO 2 ，N 2 To balance the gas, the reaction temperature is 290 ℃ and C is within 36h 6 H 6 The conversion rate is stabilized to be more than 95%.
Comparative example 1
A process for preparing a catalyst for the combustion of VOCs in a sulfur-containing atmosphere, which differs from example 1 in the following steps:
(1) 20mL of deionized water and 2.7g of 50 wt% Mn (NO) were measured with a measuring cylinder and a pipette, respectively 3 ) 2 The solution was placed in a 50mL beaker and, after the solution was stirred well, 14.4g of Ti (SO 4 ) 2 And 2.56g of polyethylene glycol, stirred for 2h, labeled as solution A1.
The catalyst comprises 70 parts of carrier, manganese-titanium molar ratio of 1:8, 0.1 part of Pd, 0.5 part of Pt and 0.2 part of Ag in parts by mass.
Experimental results of the catalytic combustion of benzene by the catalyst:
catalyst activity evaluation: 0.2g of Pd-Pt-Ag/MnTiO with 40-60 meshes x The catalyst is filled into a quartz tube of a fixed bed catalytic reaction device, and the total gas flow is 200 mL.min -1 Space velocity of 60000 mL.g -1 ·min -1 The reaction gas composition was 1000ppm C 6 H 6 ，4％O 2 ，N 2 For balancing the gas, the test temperature is 100-260 ℃. The reaction temperature is C at 100, 160, 180, 200, 220, 230, 240 and 260 ℃ by gas chromatography detection 6 H 6 The conversion was 0, 1.8%, 3.7%, 14.1%, 9.6%, 80.7%, 91.2%, 99.6%, 99.9%, respectively.
Sulfur resistance test of catalyst: 0.2g of Pd-Pt-Ag/MnTiO with 40-60 meshes x The catalyst is filled into a quartz tube of a fixed bed catalytic reaction device, and the total gas flow is 200 mL.min -1 Space velocity of 60000 mL.g -1 ·min -1 The reaction gas composition was 1000ppm C 6 H 6 ，4％O 2 ，100ppm SO 2 ，N 2 To balance the gas, the reaction temperature is 300 ℃, C 6 H 6 The conversion rate slowly decreases, and the benzene conversion rate decreases to 80% after 36 hours.
Comparative example 2
A process for preparing a catalyst for the combustion of VOCs in a sulfur-containing atmosphere, which differs from example 1 in the following steps:
(7) According to the mass ratio Ag to MnTiO x =0.7:70 Ag (NO 3 ) 2 Adding 2mL of deionized water for ultrasonic dissolution to obtain a mixed solution D, and adding MnTiO into the mixed solution D x Ultrasonic treatment of the precursor particles for 40min, drying at 120 deg.c for 14 hr, and roasting at 550 deg.c in air atmosphere for 6 hr to obtain 40-60 mesh Ag/MnTiO x A catalyst.
The catalyst obtained was 70 parts by mass of a carrier, wherein the molar ratio of manganese to titanium was 1:3 and Ag was 0.7 part.
Experimental results of the catalytic combustion of benzene by the catalyst:
catalyst activity evaluation: 0.2g of Ag/MnTiO with 40-60 meshes x The catalyst is filled into a quartz tube of a fixed bed catalytic reaction device, and the total gas flow is 200 mL.min -1 Space velocity of 60000 mL.g -1 ·min -1 The reaction gas composition was 1000ppm C 6 H 6 ，4％O 2 ，N 2 For balancing the gas, the test temperature is 150-260 ℃. The reaction temperature is C at 100, 160, 180, 200, 220, 240 and 260 ℃ by gas chromatography detection 6 H 6 The conversion rates were 0, 4.5%, 11.3%, 26.9%, 59.3%, 97.2%, 99.8%, respectively.
Sulfur resistance test of catalyst: 0.2g of Ag/MnTiO with 40-60 meshes x The catalyst is filled into a quartz tube of a fixed bed catalytic reaction device, and the total gas flow is 200 mL.min -1 Space velocity of 60000 mL.g -1 ·min -1 The reaction gas composition was 1000ppm C 6 H 6 ，4％O 2 ，20ppm SO 2 ，N 2 To balance the gas, the reaction temperature is 320 ℃, C 6 H 6 The conversion rate slowly decreases and C is after 28h 6 H 6 The conversion rate is reduced to 85 percent, and the SO is stopped to be introduced 2 After that, the catalyst activity was not recovered.
Comparative example 3
A process for preparing a catalyst for the combustion of VOCs in a sulfur-containing atmosphere, which differs from example 1 in the following steps:
(7) MnTiO is mixed with x The precursor is placed in a muffle furnace and roasted for 5 hours in an air atmosphere at 500 ℃ to obtain 40-60 mesh MnTiO x A catalyst.
Experimental results of the catalytic combustion of benzene by the catalyst:
catalyst activity evaluation: 0.2g of Ag/MnTiO with 40-60 meshes x The catalyst is filled into a quartz tube of a fixed bed catalytic reaction device, and the total gas flow is 200 mL.min -1 Space velocity of 60000 mL.g -1 ·min -1 The reaction gas composition was 1000ppm C 6 H 6 ，4％O 2 ，N 2 For balancing the gas, the test temperature is 100-260 ℃. The reaction temperature is C at 100, 160, 180, 200, 220, 240, 260, 280 and 300 ℃ by gas chromatography detection 6 H 6 The conversion was 0, 4.9%, 9.5%, 20%, 38%, 73.3%, 84%, 99%, 99.7%, respectively.
Sulfur resistance test of catalyst: 0.2g of Ag/MnTiO with 40-60 meshes x The catalyst is filled into a quartz tube of a fixed bed catalytic reaction device, and the total gas flow is 200 mL.min -1 Space velocity of 60000 mL.g -1 ·min -1 The reaction gas composition was 1000ppm C 6 H 6 ，4％O 2 ，20ppm SO 2 ，N 2 To balance the gas, the reaction temperature is 320 ℃, C 6 H 6 The conversion rate slowly decreases and C is after 16h 6 H 6 The conversion rate is reduced to 80 percent, and the SO is stopped to be introduced 2 After that, the catalyst activity was not recovered.
It can be seen from examples 1 to 3 that the catalyst has further improved sulfur resistance without a decrease in activity after the Ag component is added to the carrier. The strong interaction exists between the manganese, titanium and silver, so that the release and transfer of active oxygen on the surface of the catalyst are promoted, and the sulfur resistance of the catalyst is improved.
It can be seen from example 1 and comparative example 3 that the reason for the better sulfur and water resistance of the catalyst is the result of the combined action of the support manganese titanium and the active component.
As can also be seen from FIG. 1, in comparative examples 1-3, after Ag component is added to the carrier, benzene T is catalytically oxidized 90 At the lowest, the catalyst activity and the sulfur-resistant activity are further improved; the strong interaction exists between the manganese, titanium and silver, so that the release and transfer of active oxygen on the surface of the catalyst are promoted, and the sulfur resistance of the catalyst is improved. In comparative examples 1, 4, 5 and 6, one or more of Pd, pt and Ag are supported on a manganese-titanium carrier, so that the catalyst has better catalytic combustion benzene activity and sulfur resistance.
As can be seen from fig. 2, the manganese-titanium ratio in the carriers of comparative examples 1, 2 and comparative example 1 affects the activity and sulfur resistance of the catalyst. After optimized screening, when the manganese-titanium ratio is 0.25-2, noble metals Pd, pt and Ag are loaded on the manganese-titanium, and the catalyst has better sulfur resistance and water resistance.
As can be seen from FIG. 3, C is present within 48 hours at 320℃ 6 H 6 The conversion rate is stabilized to be more than 98 percent, when the temperature is reduced to 280 ℃, the catalyst is reversibly deactivated, C is in 24 hours 6 H 6 The conversion rate is reduced to 30 percent, and the SO is stopped to be introduced 2 After that, the catalyst activity is slowly recovered, C 6 H 6 The conversion rate is stabilized at about 65%. As can be seen in FIG. 5, pt/MnTiO x The catalyst has stronger sulfur resistance.
As can be seen from FIGS. 4 and 5, pt/MnTiO in example 5 x The catalyst is stable at 100% in 31 days when the evaluation temperature is 320 ℃, then the temperature is reduced to 260 ℃ and even to 240 ℃, but the catalyst is quickly deactivated when the catalyst is directly reacted under the condition of 260 ℃ containing sulfur, and the benzene conversion rate after the catalyst is stable is only about 20%. Example 3 after Ag component is added into the carrier, the sulfur resistance is further improvedThe reaction temperature is 260 ℃ and C is within 72 hours 6 H 6 The conversion rate is stabilized to be more than 99 percent. The strong interaction exists between the manganese, titanium and silver, so that the release and transfer of active oxygen on the surface of the catalyst are promoted, and the sulfur resistance of the catalyst is improved.
As can be seen in FIG. 6, the catalysts prepared in comparative examples 1-3 have less sulfur and water resistance than the catalysts of the examples.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present application, and not for limiting the same; although the present application has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the corresponding technical solutions from the scope of the technical solutions of the embodiments of the present application.
Furthermore, those skilled in the art will appreciate that while some embodiments herein include some features but not others included in other embodiments, combinations of features of different embodiments are meant to be within the scope of the present application and form different embodiments. For example, in the claims below, any of the claimed embodiments may be used in any combination. The information disclosed in this background section is only for enhancement of understanding of the general background of the application and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Claims (9)
1. A catalyst for the combustion of VOCs in a sulfur-containing atmosphere, characterized in that the catalyst comprises a support comprising a Mn-Ag-Ti composite oxide and an active component of Pd, pt and Ag.
2. The catalyst according to claim 1, wherein the carrier is 70 parts by mass, and the molar ratio of manganese to titanium to silver is 1 (0.5-4): 0.05-1; pd is 0-0.5 part and is not 0; pt is 0-0.7 part and is not 0; ag is 0 to 1 part and not 0.
3. A method for preparing a catalyst for the combustion of VOCs in a sulfur-containing atmosphere, comprising the steps of:
s1, preparing a manganese titanium silver precursor;
s2, fully soaking the manganese titanium silver precursor in a mixed solution containing palladium nitrate, silver nitrate and platinum nitrate, and drying and roasting to obtain the catalyst;
the step S1 comprises the following sub-steps:
s11, manganese source, titanium source and AgCF 3 Adding ethanol solution of COO into deionized water, stirring and dissolving at room temperature to obtain manganese-titanium-silver mixed solution A2;
s12, adding the solution A2 obtained in the step S11 into an alkali solution, and stirring at room temperature for 4-8 hours to obtain a mixed solution B2;
s13, reacting the solution B2 obtained in the step S12 at 80-120 ℃ for 20-28 hours to obtain a mixed solution C2;
and S14, cooling, washing and drying the solution C2 obtained in the step S13 to obtain the manganese titanium silver precursor.
4. A method of preparation according to claim 3, wherein step S11 fulfils one or more of the following conditions:
a. the manganese source is manganese nitrate, and the titanium source is titanium sulfate;
b. the manganese source, the titanium source and AgCF 3 COO is (0.5-4) in a molar ratio of Mn, ti and Ag of (0.05-0.1);
c. the deionized water is added dropwise;
the dropwise adding speed is 4-8 mL.min -1 。
5. The method according to claim 4, wherein the alkaline solution is an aqueous ammonia solution;
the pH value of the alkali solution is 9-12.
6. The preparation method according to claim 4, wherein in step S13, the solution B2 is filled into a polytetrafluoroethylene liner and placed into a stainless steel reaction kettle for reaction; the reaction is an aging reaction;
in step S14, the drying temperature is 90-140 ℃ and the drying time is 10-15 h.
7. The method according to any one of claims 3 to 6, wherein step S2 comprises the sub-steps of:
s21, adding a palladium source, a silver source and a platinum source into deionized water for ultrasonic dissolution to obtain a mixed solution D;
s22, adding particles of manganese titanium silver precursor into the solution D obtained in the step S21, carrying out ultrasonic impregnation, drying and roasting to obtain the catalyst.
8. The method of claim 7, wherein step S21 satisfies one or more of the following conditions:
d. sequentially adding the palladium source, the silver source and the platinum source into deionized water for ultrasonic dissolution;
e. the palladium source is palladium nitrate, the silver source is silver nitrate, and the platinum source is platinum nitrate;
f. the mass ratio of the palladium source to the silver source to the platinum source is (0.1-0.5) (0.1-0.7) (0.1-1).
9. The method of claim 7, wherein step S22 satisfies one or more of the following conditions:
g. the drying temperature is 90-140 ℃, and the drying time is 10-15 hours;
h. the roasting temperature is 450-650 ℃, the roasting time is 4-6 h, and the roasting atmosphere is air.
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