CN116272980A - Anti-poisoning catalyst and preparation method and application thereof - Google Patents
Anti-poisoning catalyst and preparation method and application thereof Download PDFInfo
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- CN116272980A CN116272980A CN202310317178.8A CN202310317178A CN116272980A CN 116272980 A CN116272980 A CN 116272980A CN 202310317178 A CN202310317178 A CN 202310317178A CN 116272980 A CN116272980 A CN 116272980A
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- roasting
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- 239000003054 catalyst Substances 0.000 title claims abstract description 142
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 230000000607 poisoning effect Effects 0.000 claims abstract description 68
- 231100000572 poisoning Toxicity 0.000 claims abstract description 67
- 239000002131 composite material Substances 0.000 claims abstract description 44
- 239000011148 porous material Substances 0.000 claims abstract description 13
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 10
- 239000010936 titanium Substances 0.000 claims description 139
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 60
- 239000000243 solution Substances 0.000 claims description 52
- 238000001556 precipitation Methods 0.000 claims description 46
- 239000000463 material Substances 0.000 claims description 42
- 238000002156 mixing Methods 0.000 claims description 42
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 30
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 30
- 239000007864 aqueous solution Substances 0.000 claims description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 27
- 230000032683 aging Effects 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 27
- 239000002243 precursor Substances 0.000 claims description 27
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 26
- -1 cerium oxide-titanium dioxide-silicon dioxide Chemical group 0.000 claims description 22
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims description 22
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 20
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 18
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 16
- 238000004321 preservation Methods 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 12
- 230000008021 deposition Effects 0.000 claims description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 11
- 229910052684 Cerium Inorganic materials 0.000 claims description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 10
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 10
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 claims description 10
- 229910003446 platinum oxide Inorganic materials 0.000 claims description 10
- 229910052710 silicon Inorganic materials 0.000 claims description 10
- 239000010703 silicon Substances 0.000 claims description 10
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- 239000004408 titanium dioxide Substances 0.000 claims description 10
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 9
- 239000001099 ammonium carbonate Substances 0.000 claims description 9
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 9
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical group [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 8
- 239000012716 precipitator Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 8
- 239000007853 buffer solution Substances 0.000 claims description 7
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 7
- 235000019441 ethanol Nutrition 0.000 claims description 7
- 239000004202 carbamide Substances 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical group CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- 230000007062 hydrolysis Effects 0.000 claims description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 4
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 4
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 33
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 abstract description 24
- 230000003197 catalytic effect Effects 0.000 abstract description 20
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 14
- 229910052717 sulfur Inorganic materials 0.000 abstract description 14
- 239000011593 sulfur Substances 0.000 abstract description 14
- 239000000460 chlorine Substances 0.000 abstract description 13
- 229910052801 chlorine Inorganic materials 0.000 abstract description 13
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 12
- 230000001988 toxicity Effects 0.000 abstract description 12
- 231100000419 toxicity Toxicity 0.000 abstract description 12
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 abstract description 6
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- 229910000510 noble metal Inorganic materials 0.000 abstract description 5
- 239000000843 powder Substances 0.000 description 67
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 61
- 239000008367 deionised water Substances 0.000 description 39
- 229910021641 deionized water Inorganic materials 0.000 description 39
- 239000002244 precipitate Substances 0.000 description 38
- 239000011259 mixed solution Substances 0.000 description 37
- 238000001035 drying Methods 0.000 description 35
- 239000002245 particle Substances 0.000 description 35
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 35
- 238000000227 grinding Methods 0.000 description 32
- 238000003756 stirring Methods 0.000 description 32
- 238000005406 washing Methods 0.000 description 23
- 238000000967 suction filtration Methods 0.000 description 21
- 239000000203 mixture Substances 0.000 description 15
- 239000011363 dried mixture Substances 0.000 description 7
- 238000007084 catalytic combustion reaction Methods 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000010304 firing Methods 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 3
- 230000003301 hydrolyzing effect Effects 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- 239000006226 wash reagent Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000002912 waste gas Substances 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
- B01J23/56—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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8678—Removing components of undefined structure
- B01D53/8687—Organic components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/708—Volatile organic compounds V.O.C.'s
-
- 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)
- Environmental & Geological Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the technical field of organic pollutant control, and particularly relates to an anti-poisoning catalyst, a preparation method and application thereof. The poisoning-resistant catalyst provided by the invention consists of the composite oxide carrier, the noble metal active component and the cocatalyst, wherein the composite oxide carrier has an obvious macroporous structure, the multicomponent noble metal active component is deposited in and on the surface of a macroporous pore canal, the content of the active component is low, and the cost is reduced while the catalytic activity is ensured. The results of the examples show that the chlorobenzene achieves 100% conversion at 232 ℃ under the catalysis of the catalyst provided by the invention, and toluene achieves 100% conversion at 211 ℃ in the presence of sulfur dioxide, so that the catalyst has excellent low-temperature catalytic activity and good sulfur toxicity resistance and chlorine toxicity resistance. The invention also provides a preparation method of the poisoning-resistant catalyst. The preparation method provided by the invention has the advantages of simple steps, convenient operation and low cost.
Description
Technical Field
The invention belongs to the technical field of organic pollutant control, and particularly relates to an anti-poisoning catalyst, a preparation method and application thereof.
Background
Volatile organic pollutants (VOCs) are one of the main components of atmospheric pollutants, causing great damage to the environment, plants and human body. At present, the domestic treatment of organic waste gas of VOCs, catalytic combustion is a main VOCs waste gas treatment method with more mature technology and lower cost. In the field of catalytic combustion of VOCs, catalysts are used as a core technology of a catalytic combustion process, which generally consist of a carrier and an active component, wherein the active component is a component that actually plays a catalytic role.
In the actual industrial application process, due to the existence of complex feeding and reaction products in the reaction environment, the phenomena of carbon deposition, coking, poisoning and the like of the VOCs catalytic oxidation catalyst are easy to occur, so that the VOCs catalytic oxidation catalyst loses the original good performances of catalytic activity, selectivity, stability and the like. For example, chlorides such as chlorine-containing volatile organic compounds in industrial waste gas and sulfides such as hydrogen sulfide and sulfur dioxide are extremely liable to cause chlorine poisoning phenomenon by chlorination of metal substances in the catalyst by the chlorides or sulfur poisoning phenomenon by vulcanization by the sulfides, so that the activity of the catalyst is lowered.
At present, various anti-toxicity VOCs catalytic oxidation catalysts are disclosed in various patents at home and abroad. Chinese patent CN110404534A discloses a catalyst for catalytic oxidation of volatile organic compounds with high activity against chlorine poisoning and its preparation method, wherein the catalyst comprises ruthenium dioxide as active component and Sn as active component y Ti 1-y O 2 Or MO (metal oxide semiconductor) x- Sn y Ti 1-y O 2 The mixed metal oxide is used as a carrier. The doping of Sn to titanium dioxide realizes the regulation and control of the crystal form of the carrier oxide so as to improve the catalytic activity and the anti-chlorine poisoning property of the catalyst, but the noble metal loading amount is higher, and the preparation cost is high.
Chinese patent CN108176397a discloses a catalytic combustion catalyst with sulfur poisoning resistance and its preparation methodThe method comprises the steps of preparing a catalyst comprising an active component and a titanium dioxide carrier, wherein the active component is Ce x Sb y A z O 2 Wherein A is at least one of Cu, co and Mn, but the catalyst has low catalytic activity.
Disclosure of Invention
The invention aims to provide an anti-poisoning catalyst, a preparation method and application thereof, and the anti-poisoning catalyst provided by the invention has the advantages of less active component loading, low cost and high catalytic activity, especially low-temperature catalytic activity.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides an anti-poisoning catalyst, which comprises 70-89.9 wt% of a carrier, 0.1-7 wt% of an active component loaded in a pore canal of the carrier and on the surface of the carrier, and 10-25 wt% of a cocatalyst loaded on the surface of the carrier;
the carrier is cerium oxide-titanium dioxide-silicon dioxide composite oxide macroporous material;
The active component comprises one or more of platinum oxide, ruthenium dioxide and vanadium pentoxide;
the promoter includes titanium dioxide and tungsten oxide.
Preferably, the ceria-titania-silica composite oxide macroporous material contains 10 to 30wt% of ceria, 40 to 60wt% of titania and 30 to 50wt% of silica.
Preferably, when the active component comprises platinum oxide, the content of the platinum oxide is 0.1 to 1wt%;
when the active component comprises ruthenium dioxide, the content of the ruthenium dioxide is 0.1-1wt%;
when the active component comprises vanadium pentoxide, the content of the vanadium pentoxide is 0.5-5 wt%.
Preferably, the promoter comprises 30 to 60wt% tungsten oxide and 40 to 70wt% titanium dioxide.
The invention also provides a preparation method of the poisoning-resistant catalyst, which comprises the following steps:
(1) Mixing a titanium source, a silicon source, a cerium source, a template agent and an alcohol solvent, and performing first roasting after hydrolysis and precipitation in an aqueous nitrogen atmosphere to obtain a cerium oxide-titanium dioxide-silicon dioxide composite oxide macroporous material;
(2) Mixing the cerium oxide-titanium dioxide-silicon dioxide composite oxide macroporous material, an active component precursor and a precipitator for first deposition, aging and second roasting to obtain a supported active component catalyst;
Or mixing the active component precursor solution and the cerium oxide-titanium dioxide-silicon dioxide composite oxide macroporous material, and then sequentially standing, heating and mixing A, heating and mixing B and roasting A to obtain a supported active component catalyst;
(3) And mixing the supported active component catalyst, the promoter precursor and the precipitator, and then sequentially carrying out second deposition and third roasting to obtain the anti-poisoning catalyst.
Preferably, the aging temperature is 80-90 ℃, and the heat preservation time is 5-7 hours;
the temperature of the first roasting is 350-500 ℃, and the heat preservation time is 3-4 hours;
the temperature of the second roasting is 350-500 ℃, and the heat preservation time is 3-4 hours;
the roasting temperature of the first step is 350-500 ℃ and the heat preservation time is 3-4 h;
the temperature of the third roasting is 350-500 ℃ and the heat preservation time is 3-4 h.
Preferably, the active component precursor comprises one or more of ruthenium chloride, chloroplatinic acid and ammonium metavanadate;
the promoter precursor comprises ammonium meta-tungstate and tetrabutyl titanate.
Preferably, the titanium source is tetrabutyl titanate; the silicon source is tetraethoxysilane; the cerium source is cerium nitrate; the template agent is polymethyl methacrylate; the alcohol solvent is absolute ethyl alcohol.
Preferably, the first deposited precipitant is urea or a first sodium bicarbonate aqueous solution, and the concentration of the first sodium bicarbonate aqueous solution is 1.2-3.6 mol/L; the first deposited buffer solution is an ammonium carbonate aqueous solution with the concentration of 0.8-1.2 mol/L; the ratio of the mole number of the precipitant to the total mole number of the titanium source, the silicon source and the cerium source is 1-3:1;
the second deposited precipitant is urea or second sodium bicarbonate aqueous solution, and the concentration of the second sodium bicarbonate aqueous solution is 1.2-3.6 mol/L; the second deposited buffer solution is an ammonium carbonate aqueous solution with the concentration of 0.8-1.2 mol/L; the mol ratio of the precipitant to the promoter precursor is 1-3:1.
The invention also provides an application of the poisoning-resistant catalyst in treating volatile organic pollutants at 200-450 ℃.
The invention provides an anti-poisoning catalyst. The poisoning-resistant catalyst provided by the invention consists of the composite oxide carrier, the noble metal active component and the cocatalyst, wherein the composite oxide carrier has an obvious macroporous structure, the multicomponent noble metal active component is deposited in and on the macroporous pore canal of the composite oxide carrier, the deposition amount of the active component is lower, but the macroporous structure of the composite oxide carrier has a larger specific surface area, more dispersing sites can be provided for the active component, the dispersion degree of the active component is improved, and more active sites are provided for catalytic reaction, so that the catalytic activity of the catalyst is improved, and the cost is reduced while the catalytic activity is ensured. The results of the examples show that the chlorobenzene achieves 100% conversion at 232 ℃ under the catalysis of the catalyst provided by the invention, and toluene achieves 100% conversion at 211 ℃ in the presence of sulfur dioxide, so that the catalyst has excellent low-temperature catalytic activity and good sulfur toxicity resistance and chlorine toxicity resistance.
The invention also provides a preparation method of the poisoning-resistant catalyst. The invention takes cerium oxide-titanium dioxide-silicon dioxide composite oxide macroporous material as a carrier, then carries active components in and on the macroporous pore canal of the composite oxide macroporous material by an immersion method or a deposition precipitation method, and then deposits titanium dioxide and tungsten oxide on the surface of the obtained catalyst carrying the active components by the deposition precipitation method so as to encapsulate the active components in the macroporous pore canal, thereby avoiding poisoning of active sites in the pore canal, improving the poisoning resistance of the catalyst, and playing the role of promoting catalysis. Meanwhile, the composite oxide macroporous material can protect active components loaded on the surface of the composite oxide macroporous material, lighten the poisoning degree of active sites and ensure the catalytic activity of the catalyst. The preparation method provided by the invention has the advantages of simple steps, convenient operation and low cost.
The invention also provides an application of the poisoning-resistant catalyst in treating volatile organic pollutants at 200-450 ℃. The poisoning-resistant catalyst provided by the invention has good sulfur toxicity resistance, chlorine toxicity resistance, and good activity and stability in catalytic oxidation reaction. The results of the examples show that at a space velocity of 20000mL g -1 ·h -1 、SO 2 At a concentration of 50ppm, the toluene complete conversion temperature is 211 ℃; at a space velocity of 20000mL g -1 ·h -1 At a chlorobenzene concentration of 800ppm, the chlorobenzene complete conversion temperature was 232 ℃.
Detailed Description
The invention provides an anti-poisoning catalyst, which comprises 70-89.9 wt% of a carrier, 0.1-7 wt% of an active component loaded in a pore canal of the carrier and on the surface of the carrier, and 10-25 wt% of a cocatalyst loaded on the surface of the carrier;
the carrier is cerium oxide-titanium dioxide-silicon dioxide composite oxide macroporous material;
the active component comprises one or more of platinum oxide, ruthenium dioxide and vanadium pentoxide;
the promoter includes titanium dioxide and tungsten oxide.
The poisoning-resistant catalyst provided by the invention comprises 70-89.9 wt% of a carrier, preferably 75-88 wt%, and more preferably 79-86 wt%; the carrier is cerium oxide-titanium dioxide-silicon dioxide composite oxide macroporous material.
In the present invention, the ceria-titania-silica composite macroporous material preferably contains 10 to 30wt% of ceria, more preferably 15 to 25wt%, still more preferably 18 to 22wt%.
In the present invention, the ceria-titania-silica composite macroporous material preferably contains titania 40 to 60wt%, more preferably 45 to 55wt%, still more preferably 48 to 52wt%.
In the present invention, the ceria-titania-silica composite oxide macroporous material preferably contains 30 to 50wt% of silica, more preferably 35 to 45wt%, still more preferably 38 to 42wt%.
The poisoning-resistant catalyst provided by the invention comprises 0.1-7wt%, preferably 0.5-5wt%, more preferably 1-3wt% of active components loaded in and on the pore channels of the carrier; the active component comprises one or more of platinum oxide, ruthenium dioxide and vanadium pentoxide.
In the present invention, when the active component preferably includes platinum oxide, the content of the platinum oxide is preferably 0.1 to 1wt%, more preferably 0.3 to 0.8wt%, and still more preferably 0.5 to 0.7wt%.
In the present invention, when the active component preferably includes ruthenium dioxide, the content of ruthenium dioxide is preferably 0.1 to 1wt%, more preferably 0.3 to 0.8wt%, and still more preferably 0.5 to 0.7wt%.
In the present invention, when the active component preferably includes vanadium pentoxide, the content of the vanadium pentoxide is preferably 0.5 to 5wt%, more preferably 1 to 4wt%, and still more preferably 2 to 3wt%.
The poisoning-resistant catalyst provided by the invention comprises 10-25 wt%, preferably 12-22 wt%, more preferably 15-20 wt% of cocatalyst supported on the surface of the carrier; the promoter includes titanium dioxide and tungsten oxide.
In the present invention, the promoter preferably contains 30 to 60wt%, more preferably 35 to 55wt%, still more preferably 40 to 50wt% of tungsten oxide.
In the present invention, the cocatalyst preferably contains 40 to 70wt%, more preferably 50 to 65wt%, still more preferably 55 to 60wt% of titanium dioxide. According to the invention, by adding the cocatalyst, on one hand, active site poisoning is avoided, the poisoning resistance of the catalyst is improved, and on the other hand, the catalyst plays a role in promoting catalysis.
In the present invention, the particle diameter of the poisoning resistant catalyst is preferably 10 to 50. Mu.m, more preferably 20 to 45. Mu.m, still more preferably 30 to 40. Mu.m.
The invention also provides a preparation method of the poisoning-resistant catalyst, which comprises the following steps:
(1) Mixing a titanium source, a silicon source, a cerium source, a template agent and an alcohol solvent, and performing first roasting after hydrolysis and precipitation in an aqueous nitrogen atmosphere to obtain a cerium oxide-titanium dioxide-silicon dioxide composite oxide macroporous material;
(2) Mixing the cerium oxide-titanium dioxide-silicon dioxide composite oxide macroporous material, an active component precursor and a precipitator, and sequentially carrying out first deposition, aging and second roasting to obtain a supported active component catalyst;
Or mixing the active component precursor solution and the cerium oxide-titanium dioxide-silicon dioxide composite oxide macroporous material, and then sequentially standing, heating and mixing A, heating and mixing B and roasting A to obtain a supported active component catalyst;
(3) And mixing the supported active component catalyst, the promoter precursor and the precipitator, and then sequentially carrying out second deposition and third roasting to obtain the anti-poisoning catalyst.
The invention mixes titanium source, silicon source, cerium source, template agent and alcohol solvent, and the porous material of cerium oxide-titanium dioxide-silicon dioxide composite oxide is obtained by first roasting after hydrolytic precipitation in the atmosphere of water-containing nitrogen. In the present invention, the titanium source is preferably tetrabutyl titanate; the silicon source is preferably tetraethoxysilane; the cerium source is preferably cerium nitrate; the template agent is preferably polymethyl methacrylate; the alcohol solvent is preferably absolute ethanol.
In the present invention, the first mixing is preferably stirring; the rotation speed of the stirring is preferably 180 to 300r/min, more preferably 200 to 280r/min, and still more preferably 230 to 250r/min.
In the present invention, the water vapor content of the aqueous nitrogen gas is preferably 10 to 20vol%, more preferably 13 to 17vol%; the pH value of the hydrolytic precipitation is preferably 9.5-10.5, more preferably 10, the temperature is preferably 70-90 ℃, more preferably 80 ℃, and the heat preservation time is preferably 5-7 h, more preferably 6h; the pH regulator used for the hydrolytic precipitation is preferably ammonia water.
In the present invention, the product obtained after the hydrolysis and precipitation is preferably subjected to filtration, washing and drying in sequence; the filtration is preferably suction filtration; the wash reagent is preferably deionized water; the number of times of the washing is preferably 2 or more, more preferably 3 or more; the drying temperature is preferably 80-90 ℃, more preferably 84-88 ℃, and the heat preservation time is preferably 10-15 h, more preferably 12h.
In the present invention, the temperature of the first firing is preferably 350 to 500 ℃, more preferably 370 to 470 ℃, still more preferably 400 to 450 ℃, and the holding time is preferably 3 to 4 hours, more preferably 3.2 to 3.7 hours, still more preferably 3.5 hours.
In the present invention, the resultant product is preferably ground after the first firing; the target particle diameter of the ceria-titania-silica composite oxide macroporous material is preferably 10 to 50 μm, more preferably 15 to 45 μm, and even more preferably 20 to 40 μm.
In the present invention, the pore diameter of the ceria-titania-silica composite oxide macroporous material is preferably 40 to 200nm, more preferably 50 to 150nm, still more preferably 60 to 90nm; the pore type of the cerium oxide-titanium dioxide-silicon dioxide composite oxide macroporous material is preferably macroporous. The cerium oxide-titanium dioxide-silicon dioxide composite oxide macroporous material prepared by the invention is a multicomponent carrier and has poisoning resistance.
In the invention, the macroporous material of the cerium oxide-titanium dioxide-silicon dioxide composite oxide is preferably Ce 0.2 Ti 0.6 Si 0.2 O 2 Macroporous material of composite oxide, ce 0.3 Ti 0.5 Si 0.2 O 2 Macroporous material of composite oxide, ce 0.3 Ti 0.4 Si 0.3 O 2 Macroporous material of composite oxide, ce 0.2 Ti 0.5 Si 0.3 O 2 Composite oxide macroporous material or Ce 0.1 Ti 0.6 Si 0.3 O 2 Composite oxide macroporous materials.
After the cerium oxide-titanium dioxide-silicon dioxide composite oxide macroporous material is obtained, the cerium oxide-titanium dioxide-silicon dioxide composite oxide macroporous material, an active component precursor and a precipitator are mixed and then sequentially subjected to first deposition, aging and second roasting to obtain the supported active component catalyst. In the present invention, the active component precursor preferably includes one or more of ruthenium chloride, chloroplatinic acid, and ammonium metavanadate.
In the present invention, the first deposited precipitant is preferably urea or a first aqueous sodium bicarbonate solution; the concentration of the first aqueous sodium bicarbonate solution is preferably 1.2 to 3.6mol/L, more preferably 1.5 to 3.0mol/L, and still more preferably 2.0 to 2.7mol/L; the ratio of the number of moles of the precipitant to the total number of moles of the titanium source, the silicon source and the cerium source is preferably 1 to 3:1, more preferably 1.2 to 2:1; the first deposited buffer solution is preferably an aqueous ammonium carbonate solution; the concentration of the aqueous ammonium carbonate solution is preferably 0.8 to 1.2mol/L, more preferably 1.0 to 1.1mol/L, and still more preferably 1.05mol/L.
In the present invention, the first deposited precipitant is preferably added dropwise (noted as first dropwise) to the active ingredient precursor and the ceria-titania-silica composite oxide macroporous material; the first dropping rate is preferably 20 to 90 drops/min, more preferably 30 to 80 drops/min, and still more preferably 60 drops/min.
In the present invention, the aging temperature is preferably 80 to 90 ℃, more preferably 82 to 88 ℃, still more preferably 84 to 86 ℃, and the holding time is preferably 5 to 7 hours, more preferably 5 to 6 hours, still more preferably 6 hours;
in the present invention, the obtained product is preferably subjected to filtration, washing and drying in this order after the aging; the filtration is preferably suction filtration; the wash reagent is preferably deionized water; the number of times of the washing is preferably 2 or more, more preferably 3 or more; the drying temperature is preferably 80 to 90 ℃, more preferably 83 to 87 ℃, and the heat preservation time is preferably 10 to 15 hours, more preferably 12 to 14 hours.
In the present invention, the temperature of the second firing is preferably 350 to 500 ℃, more preferably 370 to 470 ℃, still more preferably 400 to 450 ℃, and the holding time is preferably 3 to 4 hours, more preferably 3.2 to 3.7 hours, still more preferably 3.5 hours.
The invention can also mix the active component precursor solution with the cerium oxide-titanium dioxide-silicon dioxide composite oxide macroporous material (marked as A mixture), and then sequentially stand, A heat and mix, B heat and mix and A bake to obtain the supported active component catalyst. In the present invention, the active component precursor in the active component precursor solution preferably includes one or more of ruthenium chloride, chloroplatinic acid, and ammonium metavanadate; the concentration of the active component precursor solution is preferably 10 to 50mg/mL, more preferably 15 to 40mg/mL, and even more preferably 20 to 30mg/mL; the mass ratio of the active component precursor solution to the cerium oxide-titanium dioxide-silicon dioxide composite oxide macroporous material is preferably 0.001-0.050:0.950-0.999, more preferably 0.002-0.050:0.995-0.998.
In the present invention, the mode of the A-th mixing is preferably stirring, the rotation speed of the stirring is preferably 60-180 r/min, more preferably 90-120 r/min, the temperature is preferably room temperature, and the time is preferably 1.5-3 h, more preferably 2-2.5 h.
In the present invention, the temperature of the standing is preferably room temperature, and the time is preferably 0.5 to 2 hours, more preferably 1 to 1.5 hours.
In the present invention, the mode of the A-th heating and mixing is preferably heating and stirring, the temperature of the heating and stirring is preferably 40-80 ℃, more preferably 50-60 ℃, the stirring speed is preferably 60-180 r/min, more preferably 90-120 r/min, and the stirring time is preferably 2-5 h, more preferably 3-4 h.
In the present invention, the mode of the heating and mixing of the B-th is preferably heating and stirring, the temperature of the heating and stirring is preferably 50 to 80 ℃, more preferably 60 to 70 ℃, the stirring speed is preferably 60 to 180r/min, more preferably 90 to 120r/min, and the stirring time is preferably 0.5 to 2 hours, more preferably 1 to 1.5 hours. The active component and the carrier powder are fully mixed by stirring in the heating process; the invention can slowly evaporate the water by heating in sections and slowly heating up, thereby avoiding the rapid dehydration in the subsequent roasting process and bringing out the active components from the pore channels.
In the present invention, the obtained product is preferably dried after the heating and mixing of the B-th; the drying temperature is preferably 80 to 90 ℃, more preferably 83 to 87 ℃, and the heat preservation time is preferably 10 to 15 hours, more preferably 12 to 14 hours.
In the present invention, the temperature of the A-th firing is preferably 350 to 500 ℃, more preferably 450 to 500 ℃, and the holding time is preferably 3 to 4 hours, more preferably 3.3 to 3.6 hours.
After the supported active component catalyst is obtained, the supported active component catalyst, the promoter precursor and the precipitator are mixed and then subjected to second deposition and third roasting in sequence, so that the poisoning-resistant catalyst is obtained. In the present invention, the promoter precursor preferably includes ammonium metatungstate and tetrabutyl titanate.
In the present invention, the second deposited precipitant is preferably urea or a second aqueous sodium bicarbonate solution; the concentration of the second aqueous sodium bicarbonate solution is preferably 1.2 to 3.6mol/L, more preferably 1.8 to 3.0mol/L, and still more preferably 2.0 to 2.5mol/L; the molar ratio of the precipitant to the promoter precursor is preferably 1-3:1, more preferably 1.2-2:1; the second deposited buffer solution is preferably an aqueous ammonium carbonate solution; the concentration of the aqueous ammonium carbonate solution is preferably 0.8 to 1.2mol/L, more preferably 0.9 to 1.1mol/L, and still more preferably 1.0mol/L.
In the present invention, the second deposited precipitant is preferably added dropwise (noted as a second dropwise addition) to the promoter precursor; the second dropping rate is preferably 20 to 90 drops/min, more preferably 30 to 80 drops/min, and still more preferably 60 drops/min.
In the present invention, the particle diameter of the active component-supported catalyst is preferably 10 to 50. Mu.m, more preferably 20 to 45. Mu.m, still more preferably 30 to 40. Mu.m.
In the present invention, the temperature of the third firing is preferably 350 to 500 ℃, more preferably 370 to 470 ℃, still more preferably 400 to 450 ℃, and the holding time is preferably 3 to 4 hours, more preferably 3.3 to 3.7 hours, still more preferably 3.5 hours.
The invention also provides an application of the poisoning-resistant catalyst in treating volatile organic pollutants at 200-450 ℃.
The poisoning resistant catalyst provided by the invention can be used for treating volatile organic pollutants, and is suitable for treating chlorine-containing organic pollutants and sulfur-containing organic pollutants, such as chlorobenzene, toluene or sulfur-containing toluene. At a space velocity of 20000mL g -1 ·h -1 、SO 2 At a concentration of 50ppm, the toluene complete conversion temperature is 211 ℃; at a space velocity of 20000mL g -1 ·h -1 At a chlorobenzene concentration of 800ppm, the chlorobenzene complete conversion temperature was 232 ℃. Therefore, the poisoning-resistant catalyst provided by the invention has good chlorine toxicity resistance and sulfur toxicity resistance.
The following describes the invention in detail with reference to examples for further illustration of the invention, but they should not be construed as limiting the scope of the invention.
Example 1
Carrier Ce of poisoning-resistant catalyst 0.2 Ti 0.6 Si 0.2 O 2 Is prepared from the following steps:
taking absolute ethyl alcohol as a solvent, weighing 0.1g of cerium nitrate, 2.6g of TEOS (tetraethyl orthosilicate) and 1.8mL of tetrabutyl titanate, mixing the materials with 100mL of absolute ethyl alcohol, and adding 0.2g of template agent PMMA to obtain a mixed solution;
slowly dripping 140mL of ammonium carbonate solution serving as a buffer solution into the mixed solution, dripping 35mL of ammonia water until precipitation is complete, keeping the pH at 10 in the precipitation process, aging the mixed solution in water bath at 80 ℃ for 6 hours after precipitation is completed, and performing suction filtration, and washing with deionized water for 3 times to obtain a precipitate;
drying the precipitate, roasting at 400 ℃ for 3 hours, and fully grinding to obtain the carrier Ce with the particle size of 10-50 mu m 0.2 Ti 0.6 Si 0.2 O 2 And (3) powder.
Example 2
Supported active component catalyst Pt 0.001 -Ce 0.2 Ti 0.6 Si 0.2 O 2 Is prepared from the following steps:
ce prepared by the method of example 1 0.2 Ti 0.6 Si 0.2 O 2 The powder was mixed with 100mL of deionized water, 0.1mL of a chloroplatinic acid solution (0.002 g of chloroplatinic acid) having a concentration of 20mg/mL was added to the mixture, and then 30mL of an aqueous sodium hydrogencarbonate solution (1.2 mol/L in concentration) was added dropwise to the resulting mixture at a rate of 60 drops/min to precipitate;
after the precipitation is completed, stirring and aging the obtained mixed solution in a water bath at 80 ℃ for 6 hours, and then carrying out suction filtration, washing with deionized water for 3 times to obtain a precipitate;
Drying the precipitate, roasting at 400 ℃ for 3 hours, and fully grinding to obtain the anti-poisoning catalyst Pt with the particle size of 10-50 mu m 0.001 -Ce 0.2 Ti 0.6 Si 0.2 O 2 And (3) powder.
Example 3
Supported active component catalyst Ru 0.001 -Ce 0.2 Ti 0.6 Si 0.2 O 2 Is prepared from the following steps:
ce prepared by the method of example 1 0.2 Ti 0.6 Si 0.2 O 2 The powder was mixed with 100mL of deionized water, 0.1mL of a ruthenium chloride solution (containing 0.002g of ruthenium chloride) having a concentration of 20mg/mL was added to the mixture, and then 30mL of an aqueous sodium hydrogencarbonate solution (having a concentration of 1.2 mol/L) was added dropwise to the resulting mixture at a rate of 60 drops/min to precipitate;
after the precipitation is completed, stirring and aging the obtained mixed solution in a water bath at 80 ℃ for 6 hours, and then carrying out suction filtration, washing with deionized water for 3 times to obtain a precipitate;
drying the precipitate, roasting at 400 ℃ for 3 hours, and fully grinding to obtain the anti-poisoning catalyst Ru with the particle size of 10-50 mu m 0.001 -Ce 0.2 Ti 0.6 Si 0.2 O 2 And (3) powder.
Example 4
Supported active component catalyst V 0.005 -Ce 0.2 Ti 0.6 Si 0.2 O 2 Is prepared from the following steps:
ce prepared by the method of example 1 0.2 Ti 0.6 Si 0.2 O 2 Mixing the powder with 100mL of deionized water, adding 0.25mL of ammonium metavanadate solution (containing 0.01g of ammonium metavanadate) with the concentration of 40mg/mL into the mixed solution, and then dropwise adding 30mL of sodium bicarbonate aqueous solution (with the concentration of 1.2 mol/L) into the obtained mixed solution at the rate of 60 drops/min for precipitation;
After the precipitation is completed, stirring and aging the obtained mixed solution in a water bath at 80 ℃ for 6 hours, and then carrying out suction filtration, washing with deionized water for 3 times to obtain a precipitate;
drying the precipitate, roasting at 400 ℃ for 3 hours, and fully grinding to obtain the anti-poisoning catalyst V with the particle size of 10-50 mu m 0.005 -Ce 0.2 Ti 0.6 Si 0.2 O 2 And (3) powder.
Example 5
Supported active component catalyst Pt 0.001 /Ce 0.2 Ti 0.6 Si 0.2 O 2 Is prepared from the following steps:
the support Ce prepared according to the procedure of example 1 was weighed 0.2 Ti 0.6 Si 0.2 O 2 1.99g of powder, 0.1mL of chloroplatinic acid solution (0.002 g of chloroplatinic acid) with the concentration of 20mg/mL, stirring at room temperature for 2h, standing for 1h to fully impregnate the powder, stirring at 60 ℃ for 3h, stirring at 70 ℃ for 1h, and drying at 80 ℃ overnight;
drying the mixture, roasting at 400 ℃ for 4 hours, and fully grinding to obtain the supported active component catalyst Pt with the particle size of 10-50 mu m 0.001 /Ce 0.2 Ti 0.6 Si 0.2 O 2 And (3) powder.
Example 6
Supported active component catalyst Ru 0.001 /Ce 0.2 Ti 0.6 Si 0.2 O 2 Is prepared from the following steps:
the support Ce prepared according to the procedure of example 1 was weighed 0.2 Ti 0.6 Si 0.2 O 2 1.99g of powder was thoroughly mixed with 0.1mL of a 20mg/mL ruthenium chloride solution (containing 0.002g of ruthenium chloride), stirred at room temperature for 2 hours and then allowed to stand1h to fully impregnate the material, stirring the material at 60 ℃ for 3h, stirring the material at 70 ℃ for 1h, and drying the material at 80 ℃ for overnight;
drying the mixture, roasting at 400 ℃ for 3 hours, and fully grinding to obtain the active component-loaded catalyst Ru with the particle size of 10-50 mu m 0.001 /Ce 0.2 Ti 0.6 Si 0.2 O 2 And (3) powder.
Example 7
Supported active component catalyst Pt 0.001 Ru 0.001 /Ce 0.2 Ti 0.6 Si 0.2 O 2 Is prepared from the following steps:
the support Ce prepared according to the procedure of example 1 was weighed 0.2 Ti 0.6 Si 0.2 O 2 1.99g of powder, which was mixed with 0.1mL of a chloroplatinic acid solution having a concentration of 20mg/mL (0.002 g of chloroplatinic acid) and 0.1mL of a ruthenium chloride solution having a concentration of 20mg/mL (0.002 g of ruthenium chloride), stirred at room temperature for 2 hours, allowed to stand for 1 hour to allow sufficient impregnation, stirred at 60℃for 3 hours, stirred at 70℃for 1 hour, and dried at 80℃overnight;
roasting the dried mixture at 400 ℃ for 3 hours, and fully grinding to obtain the active component-loaded catalyst Pt with the particle size of 10-50 mu m 0.001 Ru 0.001 /Ce 0.2 Ti 0.6 Si 0.2 O 2 And (3) powder.
Example 8
Supported active component catalyst V 0.005 /Ce 0.2 Ti 0.6 Si 0.2 O 2 Is prepared from the following steps:
the support Ce prepared according to the procedure of example 1 was weighed 0.2 Ti 0.6 Si 0.2 O 2 1.99g of powder, and 0.25mL of ammonium metavanadate solution (containing ammonium metavanadate 0.01 g) with the concentration of 40mg/mL, stirring at room temperature for 2 hours, standing for 1 hour to fully impregnate the powder, stirring at 60 ℃ for 3 hours, stirring at 70 ℃ for 1 hour, and drying at 80 ℃ overnight;
roasting the dried mixture at 400 ℃ for 3 hours, and fully grinding to obtain the supported active component catalyst V with the particle size of 10-50 mu m 0.005 /Ce 0.2 Ti 0.6 Si 0.2 O 2 And (3) powder.
Example 9
Supported active component catalyst Pt 0.002 /Ce 0.2 Ti 0.6 Si 0.2 O 2 Is prepared from the following steps:
the support Ce prepared according to the procedure of example 1 was weighed 0.2 Ti 0.6 Si 0.2 O 2 1.99g of powder, and 0.2mL of chloroplatinic acid solution (0.004 g of chloroplatinic acid) with the concentration of 20mg/mL are fully mixed, stirred at room temperature for 2 hours, then kept stand for 1 hour to fully impregnate the powder, stirred at 60 ℃ for 3 hours, stirred at 70 ℃ for 1 hour and then dried at 80 ℃ for overnight;
roasting the dried mixture at 400 ℃ for 3 hours, and fully grinding to obtain the active component-loaded catalyst Pt with the particle size of 10-50 mu m 0.002 /Ce 0.2 Ti 0.6 Si 0.2 O 2 And (3) powder.
Example 10
Supported active component catalyst Ru 0.002 /Ce 0.2 Ti 0.6 Si 0.2 O 2 Is prepared from the following steps:
the support Ce prepared according to the procedure of example 1 was weighed 0.2 Ti 0.6 Si 0.2 O 2 1.99g of powder, and 0.2mL of ruthenium chloride solution (containing ruthenium chloride 0.004 g) with the concentration of 20mg/mL are fully mixed, stirred at room temperature for 2 hours, then kept stand for 1 hour to fully impregnate, stirred at 60 ℃ for 3 hours, stirred at 70 ℃ for 1 hour and then dried at 80 ℃ for overnight;
roasting the mixture obtained by drying at 400 ℃ for 3 hours, and fully grinding to obtain the active component-loaded catalyst Ru with the particle size of 10-50 mu m 0.002 /Ce 0.2 Ti 0.6 Si 0.2 O 2 And (3) powder.
Example 11
Supported active component catalyst Pt 0.002 Ru 0.002 /Ce 0.2 Ti 0.6 Si 0.2 O 2 Is prepared from the following steps:
the support Ce prepared according to the procedure of example 1 was weighed 0.2 Ti 0.6 Si 0.2 O 2 1.99g of powder, and 0.2mL of a chloroplatinic acid solution having a concentration of 20mg/mL (chloroplatinic acid 0.004 g) and 0.2mL of a ruthenium chloride solution having a concentration of 20mg/mL (ruthenium chloride 0.004 g)) After mixing, stirring for 2 hours at room temperature, standing for 1 hour to fully impregnate the mixture, stirring for 3 hours at 60 ℃, stirring for 1 hour at 70 ℃ and drying at 80 ℃ overnight;
Roasting the dried mixture at 400 ℃ for 3 hours, and fully grinding to obtain the active component-loaded catalyst Pt with the particle size of 10-50 mu m 0.002 Ru 0.002 /Ce 0.2 Ti 0.6 Si 0.2 O 2 And (3) powder.
Example 12
Supported active component catalyst V 0.02 /Ce 0.2 Ti 0.6 Si 0.2 O 2 Is prepared from the following steps:
the support Ce prepared according to the procedure of example 1 was weighed 0.2 Ti 0.6 Si 0.2 O 2 1.99g of powder, fully mixing with 1mL of ammonium metavanadate solution (containing 0.04g of ammonium metavanadate) with the concentration of 40mg/mL, stirring at room temperature for 2h, standing for 1h to fully impregnate the powder, stirring at 60 ℃ for 3h, stirring at 70 ℃ for 1h, and drying at 80 ℃ overnight;
roasting the dried mixture at 400 ℃ for 3 hours, and fully grinding to obtain the supported active component catalyst V with the particle size of 10-50 mu m 0.02 /Ce 0.2 Ti 0.6 Si 0.2 O 2 And (3) powder.
Example 13
Supported active component catalyst Pt 0.005 /Ce 0.2 Ti 0.6 Si 0.2 O 2 Is prepared from the following steps:
the support Ce prepared according to the procedure of example 1 was weighed 0.2 Ti 0.6 Si 0.2 O 2 1.99g of powder, and 0.5mL of chloroplatinic acid solution (0.01 g of chloroplatinic acid) with the concentration of 20mg/mL are fully mixed, stirred at room temperature for 2 hours, then kept stand for 1 hour to fully impregnate the powder, stirred at 60 ℃ for 3 hours, stirred at 70 ℃ for 1 hour and then dried at 80 ℃ for overnight;
roasting the dried mixture at 400 ℃ for 3 hours, and fully grinding to obtain the active component-loaded catalyst Pt with the particle size of 10-50 mu m 0.005 /Ce 0.2 Ti 0.6 Si 0.2 O 2 And (3) powder.
Example 14
Supported active component catalyst Ru 0.005 /Ce 0.2 Ti 0.6 Si 0.2 O 2 Is prepared from the following steps:
the support Ce prepared according to the procedure of example 1 was weighed 0.2 Ti 0.6 Si 0.2 O 2 1.99g of powder, and 0.5mL of ruthenium chloride solution (containing ruthenium chloride 0.01 g) with the concentration of 20mg/mL are fully mixed, stirred at room temperature for 2 hours, then kept stand for 1 hour to fully impregnate, stirred at 60 ℃ for 3 hours, stirred at 70 ℃ for 1 hour and then dried at 80 ℃ for overnight;
roasting the mixture obtained by drying at 400 ℃ for 3 hours, and fully grinding to obtain the active component-loaded catalyst Ru with the particle size of 10-50 mu m 0.005 /Ce 0.2 Ti 0.6 Si 0.2 O 2 And (3) powder.
Example 15
Supported active component catalyst Pt 0.005 Ru 0.005 /Ce 0.2 Ti 0.6 Si 0.2 O 2 Is prepared from the following steps:
the support Ce prepared according to the procedure of example 1 was weighed 0.2 Ti 0.6 Si 0.2 O 2 1.98g of powder, which was thoroughly mixed with 0.5mL of a chloroplatinic acid solution having a concentration of 20mg/mL (0.01 g of chloroplatinic acid) and 0.5mL of a ruthenium chloride solution having a concentration of 20mg/mL (0.01 g of ruthenium chloride), and then stirred at room temperature for 2 hours and allowed to stand for 1 hour to allow sufficient impregnation, and stirred at 60℃for 3 hours and then stirred at 70℃for 1 hour and dried at 80℃overnight;
roasting the mixture obtained by drying at 400 ℃ for 3 hours, and fully grinding to obtain the active component-supported catalyst Pt with the particle size of 10-50 mu m 0.005 Ru 0.005 /Ce 0.2 Ti 0.6 Si 0.2 O 2 And (3) powder.
Example 16
Supported active component catalyst V 0.05 /Ce 0.2 Ti 0.6 Si 0.2 O 2 Is prepared from the following steps:
the support Ce prepared according to the procedure of example 1 was weighed 0.2 Ti 0.6 Si 0.2 O 2 1.99g of powder was thoroughly mixed with 2.5mL of an ammonium metavanadate solution (containing 0.1g of ammonium metavanadate) having a concentration of 40mg/mL, and the mixture was then stirred under a stirringStirring at room temperature for 2h, standing for 1h to fully impregnate, stirring at 60 ℃ for 3h, stirring at 70 ℃ for 1h, and drying at 80 ℃ overnight;
roasting the dried mixture at 400 ℃ for 3 hours, and fully grinding to obtain the supported active component catalyst V with the particle size of 10-50 mu m 0.05 /Ce 0.2 Ti 0.6 Si 0.2 O 2 And (3) powder.
Example 17
Poisoning-resistant catalyst Ti 0.3 Si 0.7 -Pt 0.001 -Ce 0.2 Ti 0.6 Si 0.2 O 2 Is prepared from the following steps:
0.21g of ammonium metatungstate was dissolved in 20mL of deionized water, 0.85g of tetra-n-butyl titanate was dissolved in 20mL of absolute ethanol, and the two solutions were mixed and then reacted with 1.6g of Pt prepared as in example 2 0.001 -Ce 0.2 Ti 0.6 Si 0.2 O 2 Mixing the powder, and then dropwise adding 30mL of sodium bicarbonate aqueous solution (with the concentration of 1.2 mol/L) into the obtained mixed solution at the rate of 60 drops/min for precipitation;
after the precipitation is completed, aging the obtained mixed solution in a water bath at 80 ℃ for 6 hours, and performing suction filtration, washing with deionized water for 3 times to obtain a precipitate;
drying the precipitate, roasting at 400 ℃ for 3 hours, and fully grinding to obtain the anti-poisoning catalyst Ti with the particle size of 10-50 mu m 0.3 Si 0.7 -Pt 0.001 -Ce 0.2 Ti 0.6 Si 0.2 O 2 And (3) powder.
Example 18
Poisoning-resistant catalyst Ti 0.3 Si 0.7 -Ru 0.001 -Ce 0.2 Ti 0.6 Si 0.2 O 2 Is prepared from the following steps:
0.21g of ammonium metatungstate was dissolved in 20mL of deionized water, 0.85g of tetra-n-butyl titanate was dissolved in 20mL of absolute ethanol, and the two solutions were mixed and then reacted with 1.6g of Ru prepared as in example 3 0.001 -Ce 0.2 Ti 0.6 Si 0.2 O 2 Mixing the powder, and then dropwise adding 30mL of sodium bicarbonate aqueous solution (with the concentration of 1.2 mol/L) into the obtained mixed solution at the rate of 60 drops/min for precipitation;
after the precipitation is completed, aging the obtained mixed solution in a water bath at 80 ℃ for 6 hours, and performing suction filtration, washing with deionized water for 3 times to obtain a precipitate;
drying the precipitate, roasting at 400 ℃ for 3 hours, and fully grinding to obtain the poisoning-resistant catalyst Ti with the particle size of 10-50 mu m 0.3 Si 0.7 -Ru 0.001 -Ce 0.2 Ti 0.6 Si 0.2 O 2 And (3) powder.
Example 19
Poisoning-resistant catalyst Ti 0.3 Si 0.7 -V 0.005 -Ce 0.2 Ti 0.6 Si 0.2 O 2 Is prepared from the following steps:
0.21g of ammonium metatungstate was dissolved in 20mL of deionized water, 0.85g of tetra-n-butyl titanate was dissolved in 20mL of absolute ethanol, and the two solutions were mixed and then reacted with 1.6g of V prepared as in example 4 0.005 -Ce 0.2 Ti 0.6 Si 0.2 O 2 Mixing the powder, and then dropwise adding 30mL of sodium bicarbonate aqueous solution (with the concentration of 1.2 mol/L) into the obtained mixed solution at the rate of 60 drops/min for precipitation;
after the precipitation is completed, aging the obtained mixed solution in a water bath at 80 ℃ for 6 hours, and performing suction filtration, washing with deionized water for 3 times to obtain a precipitate;
drying the precipitate, roasting at 400 ℃ for 3 hours, and fully grinding to obtain the poisoning-resistant catalyst Ti with the particle size of 10-50 mu m 0.3 Si 0.7 -V 0.005 -Ce 0.2 Ti 0.6 Si 0.2 O 2 And (3) powder.
Example 20
Poisoning-resistant catalyst Ti 0.3 Si 0.7 -Pt 0.001 /Ce 0.2 Ti 0.6 Si 0.2 O 2 Is prepared from the following steps:
0.21g of ammonium metatungstate was dissolved in 20mL of deionized water, 0.85g of tetra-n-butyl titanate was dissolved in 20mL of absolute ethanol, and the two solutions were mixed and then reacted with 1.6g of Pt prepared as in example 5 0.001 /Ce 0.2 Ti 0.6 Si 0.2 O 2 Mixing the powder, and adding 60% to the obtained mixture30mL of sodium bicarbonate aqueous solution (with the concentration of 1.2 mol/L) is added dropwise at the rate of dripping/min for precipitation;
after the precipitation is completed, aging the obtained mixed solution in a water bath at 80 ℃ for 6 hours, and performing suction filtration, washing with deionized water for 3 times to obtain a precipitate;
drying the precipitate, roasting at 400 ℃ for 3 hours, and fully grinding to obtain the anti-poisoning catalyst Ti with the particle size of 10-50 mu m 0.3 Si 0.7 -Pt 0.001 /Ce 0.2 Ti 0.6 Si 0.2 O 2 And (3) powder.
Example 21
Poisoning-resistant catalyst Ti 0.3 Si 0.7 -Ru 0.001 /Ce 0.2 Ti 0.6 Si 0.2 O 2 Is prepared from the following steps:
0.21g of ammonium metatungstate was dissolved in 20mL of deionized water, 0.85g of tetra-n-butyl titanate was dissolved in 20mL of absolute ethanol, and the two solutions were mixed and then reacted with 1.6g of Ru prepared as in example 6 0.001 /Ce 0.2 Ti 0.6 Si 0.2 O 2 Mixing the powder, and then dropwise adding 30mL of sodium bicarbonate aqueous solution (with the concentration of 1.2 mol/L) into the obtained mixed solution at the rate of 60 drops/min for precipitation;
after the precipitation is completed, aging the obtained mixed solution in a water bath at 80 ℃ for 6 hours, and performing suction filtration, washing with deionized water for 3 times to obtain a precipitate;
drying the precipitate, roasting at 400 ℃ for 3 hours, and fully grinding to obtain the poisoning-resistant catalyst Ti with the particle size of 10-50 mu m 0.3 Si 0.7 -Ru 0.001 /Ce 0.2 Ti 0.6 Si 0.2 O 2 And (3) powder.
Example 22
Poisoning-resistant catalyst Ti 0.3 Si 0.7 -Pt 0.001 Ru 0.001 /Ce 0.2 Ti 0.6 Si 0.2 O 2 Is prepared from the following steps:
0.21g of ammonium metatungstate was dissolved in 20mL of deionized water, 0.85g of tetra-n-butyl titanate was dissolved in 20mL of absolute ethanol, and the two solutions were mixed and then reacted with 1.6g of Pt prepared as in example 7 0.001 Ru 0.001 /Ce 0.2 Ti 0.6 Si 0.2 O 2 Mixing the powder, and then dropwise adding 30mL of sodium bicarbonate aqueous solution (with the concentration of 1.2 mol/L) into the obtained mixed solution at the rate of 60 drops/min for precipitation;
after the precipitation is completed, aging the obtained mixed solution in a water bath at 80 ℃ for 6 hours, and performing suction filtration, washing with deionized water for 3 times to obtain a precipitate;
drying the precipitate, roasting at 400 ℃ for 3 hours, and fully grinding to obtain the poisoning-resistant catalyst Ti with the particle size of 10-50 mu m 0.3 Si 0.7 -Pt 0.001 Ru 0.001 /Ce 0.2 Ti 0.6 Si 0.2 O 2 And (3) powder.
Example 23
Poisoning-resistant catalyst Ti 0.3 Si 0.7 -V 0.005 /Ce 0.2 Ti 0.6 Si 0.2 O 2 Is prepared from the following steps:
0.21g of ammonium metatungstate was dissolved in 20mL of deionized water, 0.85g of tetra-n-butyl titanate was dissolved in 20mL of absolute ethanol, and the two solutions were mixed and then reacted with 1.6g of V prepared as in example 8 0.005 /Ce 0.2 Ti 0.6 Si 0.2 O 2 Mixing the powder, and then dropwise adding 30mL of sodium bicarbonate aqueous solution (with the concentration of 1.2 mol/L) into the obtained mixed solution at the rate of 60 drops/min for precipitation;
after the precipitation is completed, aging the obtained mixed solution in a water bath at 80 ℃ for 6 hours, and performing suction filtration, washing with deionized water for 3 times to obtain a precipitate;
Drying the precipitate, roasting at 400 ℃ for 3 hours, and fully grinding to obtain the poisoning-resistant catalyst Ti with the particle size of 10-50 mu m 0.3 Si 0.7 -V 0.005 /Ce 0.2 Ti 0.6 Si 0.2 O 2 And (3) powder.
Example 24
Poisoning-resistant catalyst Ti 0.3 Si 0.7 -Pt 0.002 /Ce 0.2 Ti 0.6 Si 0.2 O 2 Is prepared from the following steps:
0.21g of ammonium metatungstate was dissolved in 20mL of deionized water, and 0.85g of tetra-n-butyl titanate was addedThe ester was dissolved in 20mL of absolute ethanol, and the two solutions were mixed and then admixed with 1.6g of Pt prepared as in example 9 0.002 /Ce 0.2 Ti 0.6 Si 0.2 O 2 Mixing the powder, and then dropwise adding 30mL of sodium bicarbonate aqueous solution (with the concentration of 1.2 mol/L) into the obtained mixed solution at the rate of 60 drops/min for precipitation;
after the precipitation is completed, aging the obtained mixed solution in a water bath at 80 ℃ for 6 hours, and performing suction filtration, washing with deionized water for 3 times to obtain a precipitate;
drying the precipitate, roasting at 400 ℃ for 3 hours, and fully grinding to obtain the poisoning-resistant catalyst Ti with the particle size of 10-50 mu m 0.3 Si 0.7 -Pt 0.002 /Ce 0.2 Ti 0.6 Si 0.2 O 2 And (3) powder.
Example 25
Poisoning-resistant catalyst Ti 0.3 Si 0.7 -Ru 0.002 /Ce 0.2 Ti 0.6 Si 0.2 O 2 Is prepared from the following steps:
0.21g of ammonium metatungstate was dissolved in 20mL of deionized water, 0.85g of tetra-n-butyl titanate was dissolved in 20mL of absolute ethanol, and the two solutions were mixed and then reacted with 1.6g of Ru prepared according to the method of example 10 0.002 /Ce 0.2 Ti 0.6 Si 0.2 O 2 Mixing the powder, and then dripping 30mL of sodium bicarbonate aqueous solution (with the concentration of 1.2 mol/L) into the obtained mixed solution at the speed of 60 drops/min for precipitation;
After the precipitation is completed, aging the obtained mixed solution in a water bath at 80 ℃ for 6 hours, and performing suction filtration, washing with deionized water for 3 times to obtain a precipitate;
drying the precipitate, roasting at 400 ℃ for 3 hours, and fully grinding to obtain the poisoning-resistant catalyst Ti with the particle size of 10-50 mu m 0.3 Si 0.7 -Ru 0.002 /Ce 0.2 Ti 0.6 Si 0.2 O 2 And (3) powder.
Example 26
Poisoning-resistant catalyst Ti 0.3 Si 0.7 -Pt 0.002 Ru 0.002 /Ce 0.2 Ti 0.6 Si 0.2 O 2 Is prepared from the following steps:
0.21g of ammonium metatungstate was dissolved in 20mL of deionized water, 0.85g of tetra-n-butyl titanate was dissolved in 20mL of absolute ethanol, and the two solutions were mixed and then reacted with 1.6g of Pt prepared as in example 11 0.002 Ru 0.002 /Ce 0.2 Ti 0.6 Si 0.2 O 2 Mixing the powder, and dripping 30mL of sodium bicarbonate aqueous solution (with the concentration of 1.2 mol/L) into the mixed solution at the speed of 60 drops/min for precipitation;
after the precipitation is completed, aging the obtained mixed solution in a water bath at 80 ℃ for 6 hours, and performing suction filtration, washing with deionized water for 3 times to obtain a precipitate;
drying the precipitate, roasting at 400 ℃ for 3 hours, and fully grinding to obtain the poisoning-resistant catalyst Ti with the particle size of 10-50 mu m 0.3 Si 0.7 -Pt 0.002 Ru 0.002 /Ce 0.2 Ti 0.6 Si 0.2 O 2 And (3) powder.
Example 27
Poisoning-resistant catalyst Ti 0.3 Si 0.7 -V 0.02 /Ce 0.2 Ti 0.6 Si 0.2 O 2 Is prepared from the following steps:
0.21g of ammonium metatungstate was dissolved in 20mL of deionized water, 0.85g of tetra-n-butyl titanate was dissolved in 20mL of absolute ethanol, and the two solutions were mixed and then reacted with 1.6g of V prepared as in example 12 0.02 /Ce 0.2 Ti 0.6 Si 0.2 O 2 Mixing the powder, and then dripping 30mL of sodium bicarbonate aqueous solution (with the concentration of 1.2 mol/L) into the obtained mixed solution at the speed of 60 drops/min for precipitation;
after the precipitation is completed, aging the obtained mixed solution in a water bath at 80 ℃ for 6 hours, and performing suction filtration, washing with deionized water for 3 times to obtain a precipitate;
drying the precipitate, roasting at 400 ℃ for 3 hours, and fully grinding to obtain the poisoning-resistant catalyst Ti with the particle size of 10-50 mu m 0.3 Si 0.7 -V 0.02 /Ce 0.2 Ti 0.6 Si 0.2 O 2 And (3) powder.
Example 28
Poisoning-resistant catalyst Ti 0.3 Si 0.7 -Pt 0.005 /Ce 0.2 Ti 0.6 Si 0.2 O 2 Is prepared from the following steps:
0.21g of ammonium metatungstate was dissolved in 20mL of deionized water, 0.85g of tetra-n-butyl titanate was dissolved in 20mL of absolute ethanol, and the two solutions were mixed and then reacted with 1.6g of Pt prepared as in example 13 0.005 /Ce 0.2 Ti 0.6 Si 0.2 O 2 Mixing the powder, and then dripping 30mL of sodium bicarbonate aqueous solution (with the concentration of 1.2 mol/L) into the obtained mixed solution at the speed of 60 drops/min for precipitation;
after the precipitation is completed, aging the obtained mixed solution in a water bath at 80 ℃ for 6 hours, and performing suction filtration, washing with deionized water for 3 times to obtain a precipitate;
drying the precipitate, roasting at 400 ℃ for 3 hours, and fully grinding to obtain the poisoning-resistant catalyst Ti with the particle size of 10-50 mu m 0.3 Si 0.7 -Pt 0.005 /Ce 0.2 Ti 0.6 Si 0.2 O 2 And (3) powder.
Example 29
Poisoning-resistant catalyst Ti 0.3 Si 0.7 -Ru 0.005 /Ce 0.2 Ti 0.6 Si 0.2 O 2 Is prepared from the following steps:
0.21g of ammonium metatungstate was dissolved in 20mL of deionized water, 0.85g of tetra-n-butyl titanate was dissolved in 20mL of absolute ethanol, and the two solutions were mixed and then reacted with 1.6g of Ru prepared as in example 14 0.005 /Ce 0.2 Ti 0.6 Si 0.2 O 2 Mixing the powder, and dripping 30mL of sodium bicarbonate aqueous solution (with the concentration of 1.2 mol/L) into the mixed solution at the speed of 60 drops/min for precipitation;
after the precipitation is completed, aging the obtained mixed solution in a water bath at 80 ℃ for 6 hours, and performing suction filtration, washing with deionized water for 3 times to obtain a precipitate;
drying the precipitate, roasting at 400 ℃ for 3 hours, and fully grinding to obtain the poisoning-resistant catalyst Ti with the particle size of 10-50 mu m 0.3 Si 0.7 -Ru 0.005 /Ce 0.2 Ti 0.6 Si 0.2 O 2 And (3) powder.
Example 30
Poisoning-resistant catalyst Ti 0.3 Si 0.7 -Pt 0.005 Ru 0.005 /Ce 0.2 Ti 0.6 Si 0.2 O 2 Is prepared from the following steps:
0.21g of ammonium metatungstate was dissolved in 20mL of deionized water, 0.85g of tetra-n-butyl titanate was dissolved in 20mL of absolute ethanol, and the two solutions were mixed and then reacted with 1.6g of Pt prepared as in example 15 0.005 Ru 0.005 /Ce 0.2 Ti 0.6 Si 0.2 O 2 Mixing the powder, and then dripping 30mL of sodium bicarbonate aqueous solution (with the concentration of 1.2 mol/L) into the obtained mixed solution at the speed of 60 drops/min for precipitation;
after the precipitation is completed, aging the obtained mixed solution in a water bath at 80 ℃ for 6 hours, and performing suction filtration, washing with deionized water for 3 times to obtain a precipitate;
drying the precipitate, roasting at 400 ℃ for 3 hours, and fully grinding to obtain the poisoning-resistant catalyst Ti with the particle size of 10-50 mu m 0.3 Si 0.7 -Pt 0.005 Ru 0.005 /Ce 0.2 Ti 0.6 Si 0.2 O 2 And (3) powder.
Example 31
Poisoning-resistant catalyst Ti 0.3 Si 0.7 -V 0.05 /Ce 0.2 Ti 0.6 Si 0.2 O 2 Is prepared from the following steps:
0.21g of ammonium metatungstate was dissolved in 20mL of deionized water, 0.85g of tetra-n-butyl titanate was dissolved in 20mL of absolute ethanol, and the two solutions were mixed and then reacted with 1.6g of V prepared as in example 16 0.05 /Ce 0.2 Ti 0.6 Si 0.2 O 2 Mixing the powder, and dripping 30mL of sodium bicarbonate aqueous solution (with the concentration of 1.2 mol/L) into the mixed solution at the speed of 60 drops/min for precipitation;
after the precipitation is completed, aging the obtained mixed solution in a water bath at 80 ℃ for 6 hours, and performing suction filtration, washing with deionized water for 3 times to obtain a precipitate;
drying the precipitate, roasting at 400 ℃ for 3 hours, and fully grinding to obtain the poisoning-resistant catalyst Ti with the particle size of 10-50 mu m 0.3 Si 0.7 -V 0.05 /Ce 0.2 Ti 0.6 Si 0.2 O 2 And (3) powder.
Weighing 0.3g of the poisoning resistant catalyst prepared in the embodiments 17-31, grinding and tabletting, screening catalyst particles with 40-60 meshes, testing, examining the catalytic combustion activity of the poisoning resistant catalyst on chlorobenzene, and respectively preparing the poisoning resistant catalyst in SO 2 Under the existence of chlorobenzene, the catalytic activity, sulfur-resistant toxicity and chlorine-resistant toxicity of the poisoning-resistant catalyst in toluene catalytic combustion reaction are examined, and the test conditions are as follows: nitrogen is used as balance gas, the total flow is 100mL/min, and the airspeed is 20000 mL.g -1 ·h -1 The concentration of chlorobenzene was 800ppm, SO 2 The concentration was 50ppm,20vol% air.
TABLE 1 VOCs removal test results for poisoning resistant catalysts prepared in examples 17-31 of the present invention
As can be seen from Table 1, the poisoning-resistant catalyst provided by the invention has good catalytic effects on chlorobenzene, toluene and sulfur-containing toluene, 90% of chlorobenzene can be removed at 224-315 ℃, 90% of toluene can be removed at 185-255 ℃, and 90% of sulfur-containing toluene can be removed at 200-272 ℃, so that the catalyst provided by the invention can still maintain good activity under chlorine-containing and sulfur-containing conditions.
As can be seen from the above examples, the poisoning-resistant catalyst provided by the invention has the advantages of low active component loading, good chlorine-resistant toxicity and sulfur-resistant toxicity, good catalytic activity and stability under chlorine-containing and sulfur-containing conditions, and low cost.
Although the foregoing embodiments have been described in some, but not all embodiments of the invention, other embodiments may be obtained according to the present embodiments without departing from the scope of the invention.
Claims (10)
1. An anti-poisoning catalyst is characterized by comprising 70-89.9 wt% of a carrier, 0.1-7 wt% of an active component loaded in a pore canal of the carrier and on the surface of the carrier, and 10-25 wt% of a cocatalyst loaded on the surface of the carrier;
the carrier is cerium oxide-titanium dioxide-silicon dioxide composite oxide macroporous material;
the active component comprises one or more of platinum oxide, ruthenium dioxide and vanadium pentoxide;
the promoter includes titanium dioxide and tungsten oxide.
2. The poisoning resistant catalyst according to claim 1, wherein the ceria-titania-silica composite oxide macroporous material contains 10 to 30wt% of ceria, 40 to 60wt% of titania, and 30 to 50wt% of silica.
3. The poisoning resistant catalyst according to claim 1, wherein when the active component includes platinum oxide, the content of the platinum oxide is 0.1 to 1wt%;
when the active component comprises ruthenium dioxide, the content of the ruthenium dioxide is 0.1-1wt%;
when the active component comprises vanadium pentoxide, the content of the vanadium pentoxide is 0.5-5 wt%.
4. The poisoning resistant catalyst of claim 1, wherein said promoter comprises 30-60 wt% tungsten oxide and 40-70 wt% titanium dioxide.
5. The method for preparing an anti-poisoning catalyst according to any one of claims 1 to 4, comprising the steps of:
(1) Mixing a titanium source, a silicon source, a cerium source, a template agent and an alcohol solvent, and performing first roasting after hydrolysis and precipitation in an aqueous nitrogen atmosphere to obtain a cerium oxide-titanium dioxide-silicon dioxide composite oxide macroporous material;
(2) Mixing the cerium oxide-titanium dioxide-silicon dioxide composite oxide macroporous material, an active component precursor and a precipitator for first deposition, aging and second roasting to obtain a supported active component catalyst;
or mixing the active component precursor solution and the cerium oxide-titanium dioxide-silicon dioxide composite oxide macroporous material, and then sequentially standing, heating and mixing A, heating and mixing B and roasting A to obtain a supported active component catalyst;
(3) And mixing the supported active component catalyst, the promoter precursor and the precipitator, and then sequentially carrying out second deposition and third roasting to obtain the anti-poisoning catalyst.
6. The preparation method according to claim 5, wherein the aging temperature is 80-90 ℃ and the heat preservation time is 5-7 h;
the temperature of the first roasting is 350-500 ℃, and the heat preservation time is 3-4 hours;
the temperature of the second roasting is 350-500 ℃, and the heat preservation time is 3-4 hours;
the roasting temperature of the first step is 350-500 ℃ and the heat preservation time is 3-4 h;
the temperature of the third roasting is 350-500 ℃ and the heat preservation time is 3-4 h.
7. The preparation method according to claim 5, wherein the active component precursor comprises one or more of ruthenium chloride, chloroplatinic acid and ammonium metavanadate;
the promoter precursor comprises ammonium meta-tungstate and tetrabutyl titanate.
8. The method of claim 5, wherein the titanium source is tetrabutyl titanate; the silicon source is tetraethoxysilane; the cerium source is cerium nitrate; the template agent is polymethyl methacrylate; the alcohol solvent is absolute ethyl alcohol.
9. The preparation method according to claim 5, wherein the first deposited precipitant is urea or a first sodium bicarbonate aqueous solution, and the concentration of the first sodium bicarbonate aqueous solution is 1.2-3.6 mol/L; the first deposited buffer solution is an ammonium carbonate aqueous solution with the concentration of 0.8-1.2 mol/L; the ratio of the mole number of the precipitant to the total mole number of the titanium source, the silicon source and the cerium source is 1-3:1;
The second deposited precipitant is urea or second sodium bicarbonate aqueous solution, and the concentration of the second sodium bicarbonate aqueous solution is 1.2-3.6 mol/L; the second deposited buffer solution is an ammonium carbonate aqueous solution with the concentration of 0.8-1.2 mol/L; the mol ratio of the precipitant to the promoter precursor is 1-3:1.
10. Use of an anti-poisoning catalyst according to any one of claims 1 to 4 or an anti-poisoning catalyst obtained by the preparation method according to any one of claims 5 to 9 for treating volatile organic pollutants at 200 to 450 ℃.
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