CN117399000A - Sulfur poisoning resistant oxidation catalyst and preparation method and application thereof - Google Patents
Sulfur poisoning resistant oxidation catalyst and preparation method and application thereof Download PDFInfo
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- CN117399000A CN117399000A CN202311487487.6A CN202311487487A CN117399000A CN 117399000 A CN117399000 A CN 117399000A CN 202311487487 A CN202311487487 A CN 202311487487A CN 117399000 A CN117399000 A CN 117399000A
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- noble metal
- sulfur poisoning
- oxidation catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 56
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 41
- 239000011593 sulfur Substances 0.000 title claims abstract description 41
- 231100000572 poisoning Toxicity 0.000 title claims abstract description 39
- 230000000607 poisoning effect Effects 0.000 title claims abstract description 39
- 230000003647 oxidation Effects 0.000 title claims abstract description 29
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000002131 composite material Substances 0.000 claims abstract description 59
- 239000000463 material Substances 0.000 claims abstract description 45
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 40
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 27
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 26
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000001035 drying Methods 0.000 claims abstract description 19
- 230000003197 catalytic effect Effects 0.000 claims abstract description 17
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000010936 titanium Substances 0.000 claims abstract description 14
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 14
- 238000007598 dipping method Methods 0.000 claims abstract description 5
- 150000003839 salts Chemical class 0.000 claims description 12
- 239000012855 volatile organic compound Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000005470 impregnation Methods 0.000 claims description 8
- 229910052723 transition metal Inorganic materials 0.000 claims description 8
- 150000003624 transition metals Chemical class 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000000746 purification Methods 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- 239000010955 niobium Substances 0.000 claims description 5
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- 238000007084 catalytic combustion reaction Methods 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 150000003863 ammonium salts Chemical class 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- 231100000331 toxic Toxicity 0.000 claims description 3
- 230000002588 toxic effect Effects 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 150000001555 benzenes Chemical class 0.000 claims 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 239000000243 solution Substances 0.000 description 8
- 239000002912 waste gas Substances 0.000 description 6
- KMWBBMXGHHLDKL-UHFFFAOYSA-N [AlH3].[Si] Chemical class [AlH3].[Si] KMWBBMXGHHLDKL-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 4
- 239000010970 precious metal Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000033116 oxidation-reduction process Effects 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- KUJRRRAEVBRSIW-UHFFFAOYSA-N niobium(5+) pentanitrate Chemical compound [Nb+5].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O KUJRRRAEVBRSIW-UHFFFAOYSA-N 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/652—Chromium, molybdenum or tungsten
- B01J23/6525—Molybdenum
-
- 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
- B01J23/648—Vanadium, niobium or tantalum or polonium
- B01J23/6484—Niobium
-
- 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
- B01J23/652—Chromium, molybdenum or tungsten
- B01J23/6527—Tungsten
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
- F23G7/06—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
- F23G7/07—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases in which combustion takes place in the presence of catalytic material
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G2202/00—Combustion
- F23G2202/60—Combustion in a catalytic combustion chamber
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G2209/00—Specific waste
- F23G2209/14—Gaseous waste or fumes
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
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- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Catalysts (AREA)
Abstract
The invention provides a sulfur poisoning resistant oxidation catalyst, a preparation method and application thereof. Belongs to the technical field of catalyst preparation. The preparation method comprises the following steps: (1) Titanium is soaked on the surface of the silicon-aluminum composite oxide material to form yTiO 2 /SiO 2 ‑Al 2 O 3 A composite oxide; (2) Dipping non-noble metal M and noble metal Pt into yTiO prepared in the step (1) 2 /SiO 2 ‑Al 2 O 3 On the composite oxide material, a bimetallic active catalytic material impregnated with non-noble metal M and noble metal is obtained; (3) And (3) drying and roasting the composite oxide material prepared in the step (2) to obtain the sulfur poisoning resistant oxidation catalyst. By passing throughThe catalyst prepared by the method has the characteristics of excellent catalytic performance, strong applicability and excellent sulfur poisoning resistance.
Description
Technical Field
The invention relates to the technical field of catalyst preparation, in particular to a sulfur poisoning resistant oxidation catalyst, a preparation method and application thereof.
Background
The problems of haze, VOCs and other atmospheric environmental pollution seriously threaten the life, health and safety of human beings. Volatile Organic Compounds (VOCs) are one of the causes of the above pollution problems.
Because VOCs waste gas relates to the kind many, and the emission requirement difference is big, and the treatment degree of difficulty is different big, consequently to different VOCs types, can select corresponding high-efficient technique, through including condensation adsorption method, plasma purification method, direct combustion method, catalytic oxidation method etc.. Various treatment techniques have corresponding advantages and disadvantages. The method aims at the direct catalytic combustion method which is widely applied at present. The catalyst technology is used as a core, and VOCs waste gas is directly catalyzed and oxidized into CO at a certain temperature 2 And H 2 O is mainly characterized by low energy consumption and high purification efficiency, has remarkable characteristics of energy conservation and consumption reduction, and is especially suitable for large-air-volume low-concentration waste gas emission.
With the increasing strictness of emission regulations, catalysts used for purifying industrial VOCs exhaust gas by catalytic combustion are required to have higher catalyst purification efficiency, better use stability and long service life, and in the purification of part of VOCs exhaust gas, the catalysts are required to have good sulfur poisoning resistance.
Disclosure of Invention
In view of the above, the invention provides a preparation method of an oxidation catalyst with sulfur poisoning resistance, and the catalyst prepared by the method has the characteristics of excellent catalytic performance, strong applicability and excellent sulfur poisoning resistance. Preparation of yTiO by designing the catalytic Material formulation 2 /SiO 2 -Al 2 O 3 The composite oxide combines noble metal and non-noble metal M thereof with composite catalytic oxide material, and the noble metal Pt and oxide MO thereof by regulating and controlling the surface acidity of the material x The interface acting force is further used for improving the Pt active center structure and the oxidation-reduction state of the Pt active center structure, so that the beneficial effects of high catalytic activity, strong sulfur poisoning resistance and the like are realized.
The preparation method of the sulfur poisoning resistant oxidation catalyst provided by the invention comprises the following steps:
(1) Titanium is soaked on the surface of the silicon-aluminum composite oxide material to form yTiO 2 /SiO 2 -Al 2 O 3 A composite oxide;
(2) Dipping non-noble metal M and noble metal Pt into yTiO prepared in the step (1) 2 /SiO 2 -Al 2 O 3 On the composite oxide material, a bimetallic active catalytic material impregnated with non-noble metal M and noble metal Pt is obtained;
(3) And (3) drying and roasting the bimetallic active catalytic material prepared in the step (2) to obtain the sulfur poisoning resistant oxidation catalyst.
Preferably, the deposition method in step (1) is as follows: the titanium sol is directly immersed on the silicon-aluminum composite oxide material, and the required material is obtained through roasting treatment.
Preferably, the impregnation method in the step (1) is as follows: directly adding the silicon-aluminum composite oxide material into the titanium sol, and continuously stirring to complete the impregnation process; drying and roasting to obtain the required material; the stirring speed is 200 r/min-500 r/min, and the stirring time is 2-5 h; the drying temperature is 60-90 ℃ and the drying time is 1-10 h; the roasting temperature is 450-550 ℃ and the roasting time is 3-10 h.
Preferably, the silicon oxide in the silicon-aluminum composite oxide in the step (1) accounts for 10 to 30 weight percent; the yTiO 2 /SiO 2 -Al 2 O 3 Y is titanium oxide in the composite oxide and occupies the yTiO 2 /SiO 2 -Al 2 O 3 The mass percent of the composite oxide is y=10wt% -30wt%.
Preferably, the step (1) further comprises a step of impregnating and modifying the silicon-aluminum composite oxide by adopting a soluble salt solution of a transition metal, wherein the transition metal is any one or more of iron, manganese, niobium, zirconium, tin, antimony, bismuth, indium, lanthanum, cerium, praseodymium and neodymium; the transition metal is added according to the mass ratio of the transition metal oxide to the silicon-aluminum composite oxide of 0-10wt%, and the soluble salt comprises but is not limited to nitrate, acetate and ammonium salt.
Preferably, the non-noble metal M in the step (2) is any one or more of molybdenum, tungsten, niobium, cobalt and vanadium.
Preferably, the impregnation method in the step (2) is as follows:
the yTiO is first impregnated with a soluble salt of a non-noble metal M 2 /SiO 2 -Al 2 O 3 A composite oxide material, then the material is impregnated with a soluble salt of noble metal Pt;
or preparing a mixed solution of a soluble salt of a non-noble metal M and a soluble salt of a noble metal Pt, and then impregnating the yTiO with the mixed solution 2 /SiO 2 -Al 2 O 3 A composite oxide material; soluble salts include, but are not limited to, nitrate, acetate, ammonium salts; the impregnation method is to impregnate the yTiO 2 /SiO 2 -Al 2 O 3 The composite oxide material is directly added into the water solution of the soluble salt, and the dipping time is 1 to 5 hours.
The molar ratio of the non-noble metal M to the noble metal in the step (2) is 10:1-1:30.
Preferably, the drying temperature in the step (3) is 60-90 ℃ and the drying time is 3-5 h; the roasting temperature is 450-550 ℃ and the roasting time is 1-10 h.
It is another object of the present invention to provide a sulfur poisoning resistant oxidation catalyst prepared by the above method, wherein the content of the noble metal Pt in the catalyst is 0.5-5 wt%.
The invention also provides application of the sulfur poisoning resistant oxidation catalyst, and the catalyst is used for catalytic combustion purification of toxic and harmful VOCs waste gas such as carbon monoxide, formaldehyde, styrene, aromatic hydrocarbon, alkane, ethers, alcohols, esters, benzene and oxygen-containing derivatives thereof.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a sulfur poisoning resistant oxidation catalyst, a preparation method and application thereof, which comprises the steps of mixing SiO 2 -Al 2 O 3 Composite oxide and TiO 2 The catalyst is compounded to be used as a catalyst carrier, then noble metal Pt and non-noble metal M are combined with the catalyst carrier, the noble metal Pt is used as an active component, the non-noble metal M is used as an auxiliary agent, the high-temperature structural stability and the surface acidity of the material are enhanced, the interface acting force between the noble metal Pt and the non-noble metal M oxide is regulated and controlled, the active center structure of Pt and the oxidation-reduction state of the Pt are further improved, the physical or chemical adsorption of sulfur-containing waste gas on the surface of the Pt is inhibited, the beneficial effects of high catalytic activity, strong sulfur poisoning resistance and the like are realized, and a foundation is laid for the long service life of the catalyst.
Drawings
FIG. 1 shows the results of the catalytic performance test of the catalysts of examples 1 to 3 and comparative examples of the present invention;
FIG. 2 shows the sulfur poisoning resistance test results of the catalysts of examples 1 to 3 and comparative examples of the present invention.
Detailed Description
The invention provides a preparation method of a sulfur poisoning oxidation catalyst, and in the specific embodiment of the invention, the concentration of the titanium sol and the concentration of the soluble salt solution are not particularly limited.
The invention is further illustrated below with reference to examples.
Example 1
A preparation method of a sulfur poisoning resistant oxidation catalyst comprises the following steps:
(1) According to the mass ratio of 30% of titanium dioxide, directly adding an unmodified silicon-aluminum composite oxide (the mass percentage of silicon oxide in the silicon-aluminum composite oxide is 30%) material into a titanium sol solution, stirring at 300r/min, drying at 80 ℃ for 3h, and roasting at 500 ℃ for 2h to form 30TiO 2 /SiO 2 -Al 2 O 3 Composite oxidationA material;
(2) According to the mol ratio of Pt to Mo of 1:5, firstly, 30TiO prepared in the step (1) is prepared 2 /SiO 2 -Al 2 O 3 Adding the composite oxide material into an ammonium molybdate solution to obtain a Mo-impregnated composite oxide material, and then impregnating the Mo-impregnated composite oxide material with a platinum nitrate solution for 2 hours respectively to finish an impregnation process;
(3) Drying the composite oxide material impregnated in the step (2) at 80 ℃ for 5 hours, and then roasting at 550 ℃ for 5 hours to obtain Pt-5Mo/30TiO 2 /SiO 2 -Al 2 O 3 The sulfur poisoning resistant oxidation catalyst has a theoretical content of noble metal Pt of 1.0wt%.
Example 2
A preparation method of a sulfur poisoning resistant oxidation catalyst comprises the following steps:
(1) Firstly, impregnating a silicon-aluminum composite oxide (the mass percentage of silicon oxide in the silicon-aluminum composite oxide is 30 wt%) with a zirconium nitrate solution, carrying out stable modification on the silicon-aluminum composite oxide for 2 hours to obtain a zirconium-modified silicon-aluminum composite oxide (the zirconium content accounts for 5wt% of the mass ratio of the silicon-aluminum composite oxide according to zirconium oxide), then directly adding a zirconium-modified silicon-aluminum composite oxide material into titanium sol according to the mass ratio of titanium dioxide of 30%, stirring for 300r/min, drying for 3 hours at 80 ℃, and roasting for 2 hours at 500 ℃ to form 30TiO 2 -5ZrO 2 /SiO 2 -Al 2 O 3 A composite oxide;
(2) According to the mol ratio of Pt to W of 1:5, firstly, 30TiO prepared in the step (1) is prepared 2 -5ZrO 2 /SiO 2 -Al 2 O 3 Immersing the composite oxide material into an ammonium metatungstate solution to obtain a composite oxide material immersed in W, and then immersing the composite oxide material immersed with W into a platinum nitrate solution for 2 hours respectively to finish an immersing process;
(3) Drying the composite oxide material impregnated in the step (2) at 80 ℃ for 5 hours, and then roasting at 550 ℃ for 5 hours to obtain Pt-5W/30TiO 2 -5ZrO 2 /SiO 2 -Al 2 O 3 Sulfur resistance mediumAnd the toxic oxidation catalyst contains 1.0wt% of noble metal Pt.
Example 3
A preparation method of a sulfur poisoning resistant oxidation catalyst comprises the following steps:
(1) Firstly, dipping an aluminum silicon composite oxide (silicon oxide in the aluminum silicon composite oxide is 30 weight percent) into an ammonium metavanadate solution, stabilizing and modifying the silicon composite oxide for 2 hours to obtain a vanadium-modified aluminum silicon composite oxide (wherein the vanadium content accounts for 5 weight percent of the aluminum silicon composite oxide according to vanadium pentoxide), directly adding the vanadium-modified aluminum silicon composite oxide material into titanium sol according to 10 weight percent of titanium dioxide, stirring the titanium sol at 300r/min, drying the titanium sol at 80 ℃ for 3 hours, and roasting the titanium sol at 500 ℃ for 2 hours to form 10TiO 2 -5V 2 O 5 /SiO 2 -Al 2 O 3 A composite oxide;
(2) Mixing niobium nitrate and platinum nitrate according to the mol ratio of Pt to Nb of 1:5 to prepare a mixed solution of niobium nitrate and platinum nitrate, and then mixing the 10TiO prepared in the step (1) 2 -5V 2 O 5 /SiO 2 -Al 2 O 3 Adding the composite oxide material into the mixed solution for soaking for 2 hours;
(3) Drying the composite oxide material impregnated in the step (2) at 80 ℃ for 5 hours, and roasting at 550 ℃ for 5 hours to obtain Pt-5Nb/10TiO 2 -5V 2 O 5 /SiO 2 -Al 2 O 3 The sulfur poisoning resistant oxidation catalyst has a theoretical content of noble metal Pt of 1.0wt%.
Catalyst Pt-SiO purchased in market 2 /Al 2 O 3 (silica content 10%, pt content 1.0 wt%) as a comparative example, the catalysts prepared in examples 1 to 3 and the catalysts of the comparative examples were tested for catalytic performance and sulfur poisoning resistance thereof by the following test methods:
the catalyst was coated on the inner channel surface of a honeycomb ceramic support (400 cpsi) and the toluene concentration at the catalyst inlet and outlet was measured by chromatograph and the toluene concentration and test boundary test conditions were as shown in table 1:
TABLE 1
| Test object | Toluene (toluene) |
| Test atmosphere | O 2 :10%, balance gas: n (N) 2 1000ppm of toluene, H 2 O：5vol％； |
| Test airspeed/h -1 | 25000 |
| Test temperature/. Degree.C | 120，160，180，190，200，210，230，240，250，260 |
| Test status | Steady state |
Sulfur poisoning resistance exhaust gas concentration and test boundaries are shown in table 2:
TABLE 2
The catalytic performance results are shown in FIG. 1, and the sulfur poisoning resistance results are shown in FIG. 2. As can be seen from fig. 1 and 2, the results of the test of the performance of the catalysts prepared in examples 1 to 3 against sulfur poisoning are superior to those of the comparative examples, and the catalysts exhibit good poisoning resistance and catalytic activity. The method is mainly characterized in that the precious metal Pt and the non-precious metal M cooperate to regulate and control the acting force between the precious metal Pt and the non-precious metal M oxide MOx, improve the structure of the Pt active center and the oxidation-reduction state of the Pt active center, help to promote the activity of the catalyst, further modify transition metal and deposit titanium on the surface of the silicon-aluminum composite oxide, enhance the high-temperature structural stability and the surface acidity of the material, inhibit the physical or chemical adsorption of sulfur-containing waste gas on the surface of the material, realize the beneficial effects of high catalytic activity, strong sulfur poisoning resistance and the like, and lay a foundation for the long service life of the catalyst.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (9)
1. The preparation method of the sulfur poisoning resistant oxidation catalyst is characterized by comprising the following steps of:
(1) Titanium is soaked on the surface of the silicon-aluminum composite oxide material to form yTiO 2 /SiO 2 -Al 2 O 3 A composite oxide;
(2) Dipping non-noble metal M and noble metal Pt into yTiO prepared in the step (1) 2 /SiO 2 -Al 2 O 3 On the composite oxide material, a bimetallic active catalytic material impregnated with non-noble metal M and noble metal Pt is obtained;
(3) And (3) drying and roasting the bimetallic active catalytic material prepared in the step (2) to obtain the sulfur poisoning resistant oxidation catalyst.
2. The method for preparing sulfur poisoning resistant oxidation catalyst according to claim 1, wherein the impregnation method of step (1) is as follows: directly adding the silicon-aluminum composite oxide material into the titanium sol, and continuously stirring to complete the impregnation process; drying and roasting to obtain the required material; the stirring speed is 200 r/min-500 r/min, and the stirring time is 2-5 h; the drying temperature is 60-90 ℃ and the drying time is 1-10 h; the roasting temperature is 450-550 ℃ and the roasting time is 3-10 h.
3. The method for preparing a sulfur poisoning resistant oxidation catalyst according to claim 1, wherein the mass percentage of silicon oxide in the silicon-aluminum composite oxide in the step (1) is 10wt% -30 wt%; the yTiO 2 /SiO 2 -Al 2 O 3 Y is titanium oxide in the composite oxide and occupies the yTiO 2 /SiO 2 -Al 2 O 3 The mass percent of the composite oxide is y=10wt% -30wt%.
4. The method for preparing the sulfur poisoning resistant oxidation catalyst according to claim 1, wherein the step (1) further comprises a step of impregnating and modifying the silicon-aluminum composite oxide with a soluble salt solution of a transition metal, wherein the transition metal is any one or more of iron, manganese, niobium, zirconium, tin, antimony, bismuth, indium, lanthanum, cerium, praseodymium, and neodymium; the transition metal is added according to the mass ratio of the transition metal oxide to the silicon-aluminum composite oxide of 0-10wt%; the soluble salts of transition metals include, but are not limited to, nitrate, acetate, ammonium salts.
5. The method for preparing sulfur poisoning resistant oxidation catalyst according to claim 1, wherein the non-noble metal M in step (2) is any one or more of molybdenum, tungsten, niobium, cobalt and vanadium.
6. The method for preparing sulfur poisoning resistant oxidation catalyst according to claim 1, wherein the impregnation method of step (2) is as follows:
the yTiO is first impregnated with a soluble salt of a non-noble metal M 2 /SiO 2 -Al 2 O 3 A composite oxide material, then the material is impregnated with a soluble salt of noble metal Pt;
or preparing a mixed solution of a soluble salt of a non-noble metal M and a soluble salt of a noble metal Pt, and then impregnating the yTiO with the mixed solution 2 /SiO 2 -Al 2 O 3 Composite materialAn oxide material;
the soaking time is 1-5 h;
the molar ratio of the non-noble metal M to the noble metal in the step (2) is 10:1-1:30.
7. The method for preparing sulfur poisoning resistant oxidation catalyst according to claim 1, wherein the drying temperature in step (3) is 60-90 ℃ and the drying time is 3-5 hours; the roasting temperature is 450-550 ℃ and the roasting time is 1-10 h.
8. An oxidation catalyst resistant to sulfur poisoning, characterized in that the catalyst is prepared by the method according to any one of claims 1 to 7, and the noble metal Pt content in the catalyst is 0.5 to 5wt%.
9. The use of the sulfur poisoning resistant oxidation catalyst according to claim 8, wherein the catalyst is used for catalytic combustion purification of toxic and harmful VOCs exhaust gas such as carbon monoxide, formaldehyde, styrene, aromatic hydrocarbons, alkanes, ethers, alcohols, esters, benzenes and oxygen-containing derivatives thereof.
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