CN106824175B - A kind of hud typed platinum based catalyst and its preparation and application with controllable acidity - Google Patents
A kind of hud typed platinum based catalyst and its preparation and application with controllable acidity Download PDFInfo
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- CN106824175B CN106824175B CN201611114425.0A CN201611114425A CN106824175B CN 106824175 B CN106824175 B CN 106824175B CN 201611114425 A CN201611114425 A CN 201611114425A CN 106824175 B CN106824175 B CN 106824175B
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 117
- 239000003054 catalyst Substances 0.000 title claims abstract description 44
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 18
- 230000003647 oxidation Effects 0.000 claims abstract description 17
- 239000002253 acid Substances 0.000 claims abstract description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 16
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 16
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 7
- 239000002131 composite material Substances 0.000 claims abstract description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910020442 SiO2—TiO2 Inorganic materials 0.000 claims abstract description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 60
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 42
- 238000003756 stirring Methods 0.000 claims description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 19
- 229910052681 coesite Inorganic materials 0.000 claims description 18
- 229910052906 cristobalite Inorganic materials 0.000 claims description 18
- 229910052682 stishovite Inorganic materials 0.000 claims description 18
- 229910052905 tridymite Inorganic materials 0.000 claims description 18
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 16
- 239000013049 sediment Substances 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 230000001376 precipitating effect Effects 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 13
- 239000006228 supernatant Substances 0.000 claims description 13
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 12
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 12
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- 238000010792 warming Methods 0.000 claims description 12
- 235000019441 ethanol Nutrition 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 11
- 229960004756 ethanol Drugs 0.000 claims description 10
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 239000012452 mother liquor Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 230000003197 catalytic effect Effects 0.000 claims description 6
- 239000001307 helium Substances 0.000 claims description 6
- 229910052734 helium Inorganic materials 0.000 claims description 6
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 6
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 5
- 230000002378 acidificating effect Effects 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 239000013618 particulate matter Substances 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- 239000000470 constituent Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- WWHFPJVBJUJTEA-UHFFFAOYSA-N n'-[3-chloro-4,5-bis(prop-2-ynoxy)phenyl]-n-methoxymethanimidamide Chemical compound CONC=NC1=CC(Cl)=C(OCC#C)C(OCC#C)=C1 WWHFPJVBJUJTEA-UHFFFAOYSA-N 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 2
- 230000008929 regeneration Effects 0.000 claims description 2
- 238000011069 regeneration method Methods 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 claims description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims 1
- GEIAQOFPUVMAGM-UHFFFAOYSA-N Oxozirconium Chemical compound [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 claims 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims 1
- 229910017604 nitric acid Inorganic materials 0.000 claims 1
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 abstract description 17
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 230000032683 aging Effects 0.000 abstract description 8
- 238000003483 aging Methods 0.000 abstract description 7
- 239000001294 propane Substances 0.000 abstract description 7
- 230000010718 Oxidation Activity Effects 0.000 abstract description 4
- 239000002245 particle Substances 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract 1
- 230000005540 biological transmission Effects 0.000 description 14
- 238000005119 centrifugation Methods 0.000 description 8
- 239000011258 core-shell material Substances 0.000 description 8
- 238000012545 processing Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- JKGITWJSGDFJKO-UHFFFAOYSA-N ethoxy(trihydroxy)silane Chemical class CCO[Si](O)(O)O JKGITWJSGDFJKO-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 3
- 238000000746 purification Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- -1 2vol.%O2 Chemical compound 0.000 description 1
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical class [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000005446 dissolved organic matter Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/10—Capture or disposal of greenhouse gases of nitrous oxide (N2O)
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Environmental & Geological Engineering (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Combustion & Propulsion (AREA)
- Catalysts (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
Abstract
The invention discloses the technical fields for belonging to tail-gas catalyst, in particular to one kind for exhaust gas from diesel vehicle catalysis oxidation (DOC) has controllable acid hud typed platinum based catalyst and preparation method thereof.The catalyst is using nano-platinum particle as kernel, SiO2‑Al2O3、SiO2‑TiO2、SiO2‑ZrO2It is shell composition Deng acid composite oxides.In the presence of the catalyst, to simulate exhaust gas from diesel vehicle atmosphere, propane (HC) conversion can be reached to 50% temperature (T50) 250 DEG C are reduced to hereinafter, and can be realized 200 DEG C or less 85% or more NO is oxidized to NO2.In addition, handling even across 800 DEG C of long-time high temperature hydrothermal agings, this kind of material still is able to keep original structure, and embodies excellent oxidation activity, can meet the use demand of advanced diesel vehicle DOC catalyst.
Description
Technical field
The invention belongs to exhaust gas from diesel vehicle catalyst technical field, in particular to a kind of hud typed platinum with controllable acidity
Base catalyst and its preparation and application.
Background technique
Since diesel vehicle has good fuel economy, excellent dynamic property and lower CO2 emissions,
So currently widely being promoted in the world.However, since diesel engine is run under lean-burn condition, in tail gas
O2Concentration it is relatively high, therefore three-effect catalysis technology can not effectively purification of diesel vehicle discharge CO, HC, SO2And NOxDeng pollution
Object.In general, diesel engine post-processing system uses a variety of purification techniques integrated systems, wherein diesel vehicle oxidation catalysis (DOC)
Technology is a kind of important component part.
DOC is the diesel exhaust aftertreatment technology being applied earliest, the technology mainly for the treatment of in exhaust HC,
Dissolved organic matter in CO and particulate matter, and the NO in tail gas is oxidized to NO2To meet needed for SCR or the DPF use of downstream.
The core of DOC technology is oxidation catalyst.As current mainstream commercial catalyst, platinum based catalyst has remote super other materials
Oxidability.In general, platinum based catalyst is considered as a kind of catalyst of better heat stability.However, sudden and violent for a long time
Being exposed at a temperature of motor-vehicle tail-gas also, which can make Pt particle that irreversible reunion occur, grows up, and then influences its catalytic performance.
In order to improve the thermal stability of platinum based catalyst, a kind of ideal technique be its outer surface wrap up one layer have enrich it is mesoporous
Oxide shell layer is migrated in a high temperauture environment, reunites and is sintered to limit Pt particle.Furtherly, if this layer aoxidizes
Object itself can keep its porous core-shell structure to stablize under motor-vehicle tail-gas high temperature, moist environment, then such hud typed platinum
Base catalyst will have extremely strong application potential.
Summary of the invention
In order to overcome the disadvantages of the above prior art, the purpose of the present invention is to provide a kind of nucleocapsids with controllable acidity
Type platinum based catalyst and its preparation and application, the general formula of catalyst are Pt@SiO2-MOx, wherein SiO2-MOxIt is with SiO2Based on
, with heterogeneity and acidity multicomponent composite oxide shell, the shell component of selection includes SiO2-Al2O3、SiO2-
TiO2、SiO2-ZrO2And its multiplexed combination, the catalyst have good result for exhaust gas from diesel vehicle oxidation catalysis.
To achieve the goals above, the technical solution adopted by the present invention is that:
A kind of hud typed platinum based catalyst with controllable acidity, general formula are Pt@SiO2-MOx, wherein SiO2-MOxBe with
SiO2Based on, polynary acid composite oxides shell with heterogeneity and acidity.
The group of the shell is divided into SiO2-Al2O3、SiO2-TiO2、SiO2-ZrO2Or its multiplexed combination.
The present invention also provides the preparation methods with controllable acid hud typed platinum based catalyst, including walk as follows
It is rapid:
1) appropriate platinum nitrate solution and polyvinylpyrrolidone mixing are weighed, make Pt and PVP molar ratio (1:20)~
(1:80), is added ethylene glycol later, and being vigorously stirred dissolves it sufficiently, and clear solution is obtained after standing；
2) clarified solution obtained by step 1) is heated up under inert atmosphere protection, still room is down in stirring under an inert atmosphere later
Temperature；
3) acetone is added in step 2) acquired solution, separates platinum grain with ethylene glycol with centrifuge after stirring, goes
Supernatant leaves brownish black precipitating；
4) dehydrated alcohol is added in step 3) gained sediment, n-hexane is added after stirring, centrifugal treating is gone
Clear liquid leaves brownish black precipitating, dehydrated alcohol is added in last gained sediment, is made into the mother liquor containing Pt；
5) ethanol solution dissolved with appropriate ethyl orthosilicate will be added after the mother liquid obtained ultrasonic treatment of step 4), room temperature is stirred
It mixes, and is dried under the conditions of 40-60 DEG C, is i.e. acquisition Pt@PVP-SiO2Powder, is calcined later and cooling obtains hud typed Pt
SiO2Powder；
6) by Pt@PVP-SiO obtained by step 5)2Or Pt@SiO2Powder is finely ground, and the soluble-salt of the M containing metal in right amount is added,
So that M:Si molar ratio is maintained at 1:5~1:20, deionized water is added after mixing, be ultrasonically treated, drying is calcined, and furnace is cold to obtain the final product
To two kinds of hud typed Pt@SiO with different acid constituents distribution2-MOxPowder, by Pt@PVP-SiO2Obtained powder acidic site
Distance Pt is put farther out, by Pt@SiO2Obtained powder acidic site and Pt is in close contact.
In the step 1), polyvinylpyrrolidonemolecules molecules amount is 36000-63000, and ethylene glycol additional amount is Pt mole
3000-4000 times.
In the step 2), inert atmosphere is nitrogen or helium atmosphere, is warming up to 140-200 DEG C, continues 20 points of stirring
Clock, room temperature is down in stirring later.
In the step 3), acetone is pressed to be added with the amount of the volume ratio 10:3 of ethylene glycol in step 1)；
In the step 4), the amount that dehydrated alcohol is added into step 3) gained sediment is ethylene glycol in step 1)
0.8-1.2 times, the amount that n-hexane is added is 3-5 times of dehydrated alcohol, and centrifugal treating, removes supernatant later, leaves brownish black
Precipitating repeats the link 2 times, and the anhydrous second of 0.4-0.6 times of ethylene glycol volume in step 1) is added in last gained sediment
Alcohol is made into the mother liquor containing Pt.
In the step 5), dissolved in the additional amount of the ethanol solution of ethyl orthosilicate, the additional amount of ethyl orthosilicate is
2-4 times of Pt mole, the additive amount of ethyl alcohol are 5-15 times of ethyl orthosilicate volume, 500-600 DEG C of calcination temperature, time 1-
3h, calcining heating rate control is in 2 DEG C/min or less.
In the step 6), metal M is Al, Zr, Ti or its multiplexed combination, and the soluble-salt of the M containing metal is aluminum nitrate, sulphur
Any one in sour aluminium, zirconyl nitrate, zirconium sulfate and titanium sulfate or combination.
In the step 6), 500-600 DEG C of calcination temperature, time 1-3h, calcining heating rate control 2 DEG C/min with
Under.
There is the present invention controllable acid hud typed platinum based catalyst can be used for exhaust gas from diesel vehicle oxidation catalysis,.Specifically
Ground can be used for removing the low-temperature oxidation catalyst of HC, or for catalytic oxidation NO to which the nitrous oxides selectivity to postposition is urged
Change reduction (SCR) catalyst or catalytic type particulate matter trap (CDPF) regeneration provides NO2。
Compared with prior art, the beneficial effects of the present invention are: using hud typed Pt@SiO made from the technique2-MOxIt urges
Agent has high hydrothermal stability, controllable acid and excellent oxidability, can by exhaust gas from diesel vehicle NO and
HC is fully oxidized in lower temperature range, while itself keeps good stability.In the presence of the catalyst, with mould
Propane (HC) conversion can be reached 50% temperature (T by quasi- exhaust gas from diesel vehicle atmosphere50) 250 DEG C are reduced to hereinafter, and can be real
85% or more NO is oxidized to NO by existing 200 DEG C or less2.In addition, handled even across 800 DEG C of long-time high temperature hydrothermal agings,
This kind of material still is able to keep original structure, and embodies excellent oxidation activity, can meet advanced diesel vehicle DOC catalyst
Use demand.
Detailed description of the invention
Fig. 1 is the hud typed Pt@SiO that the embodiment of the present invention 1 synthesizes2-Al2O3The transmission electron microscope of sample (Si:Al=10:1)
Figure.
Fig. 2 is the hud typed Pt@SiO that the embodiment of the present invention 2 synthesizes2@Al2O3The transmission electron microscope of sample (Si:Al=10:1)
Figure.
Fig. 3 is the hud typed Pt@SiO that the embodiment of the present invention 3 synthesizes2-Al2O3The transmission electron microscope of sample (Si:Al=5:1)
Figure.
Fig. 4 is the hud typed Pt@SiO that the embodiment of the present invention 4 synthesizes2The transmission electron microscope picture of sample.
What Fig. 5 obtained for the embodiment of the present invention 5, Pt@SiO2-Al2O3Sample (Si:Al=10:1) passes through 800 DEG C of high-temperature water
The transmission electron microscope picture of sample after heat ageing processing.
What Fig. 6 obtained for the embodiment of the present invention 6, Pt@SiO2@Al2O3Sample (Si:Al=10:1) passes through 800 DEG C of high-temperature water
The transmission electron microscope picture of sample after heat ageing processing.
What Fig. 7 obtained for the embodiment of the present invention 7, Pt@SiO2Sample sample after 800 DEG C of high temperature hydrothermal agings are handled
Transmission electron microscope picture.
Fig. 8 is various embodiments of the present invention oxidation of propane activity and NO oxidation activity contrast schematic diagram.
Specific embodiment
In order to illustrate more clearly of the present invention, following embodiment is enumerated, but should not be accordingly to practical range of the invention
Constitute any restriction.The present invention can have other embodiments and can be practiced or be carried out in various ways.
Embodiment 1:
1) claim platinum nitrate solution 0.325g and 0.7g polyvinylpyrrolidone (PVP, M=containing platinum nitrate 18%
58000) 60mL ethylene glycol, is added jointly, being vigorously stirred dissolves it sufficiently, after stewing process 1 minute, obtains clear solution；
2) clarified solution obtained by step 1) is warming up to 180 DEG C under inert atmosphere (such as nitrogen, helium) protection, continues to stir
20 minutes, still room temperature was down in stirring under an inert atmosphere later；
3) about 200mL acetone is added in step 2) acquired solution, stirring is after five minutes, fast using the centrifugation of 8000r/min
Degree centrifugation 10 minutes, separates platinum grain with ethylene glycol.Supernatant is removed, brownish black precipitating is left；
4) 50mL dehydrated alcohol is added in step 3) gained sediment, stirring after five minutes, adds 200mL n-hexane,
It is centrifuged 10 minutes using the centrifugal speed of 8000r/min later, removes supernatant, leave brownish black precipitating.Repeat the step 2
It is secondary, 30mL dehydrated alcohol is finally added in gained sediment, is made into the mother liquor containing Pt；
5) by step 4) mother liquid obtained ultrasonic 15 minutes, addition is molten dissolved with the 2mL ethyl alcohol of 200 μ L ethyl orthosilicates (TEOS)
Liquid.It is stirred at room temperature 12 hours, and is dried under the conditions of 50 DEG C.Sample is warming up to 500 DEG C in 2 DEG C/min later, keeps the temperature 3h；
6) sample obtained by step 5) is finely ground, 0.034g aluminum nitrate is added.5mL deionized water is added after mixing, surpasses
Sound 15 minutes.Sample is warming up to 500 DEG C in 2 DEG C/min after drying, furnace is cold to obtain hud typed Pt SiO2-Al2O3Sample
(Si:Al=10:1).Fig. 1 is the transmission electron microscope photo of the sample, it can be seen that the sample is uniform core-shell structure.
Embodiment 2:
1) claim platinum nitrate solution 0.325g and 0.7g polyvinylpyrrolidone (PVP, M=containing platinum nitrate 18%
58000) 60mL ethylene glycol, is added jointly, being vigorously stirred dissolves it sufficiently, after stewing process 1 minute, obtains clear solution；
2) clarified solution obtained by step 1) is warming up to 180 DEG C under inert atmosphere (such as nitrogen, helium) protection, continues to stir
20 minutes, still room temperature was down in stirring under an inert atmosphere later；
3) about 200mL acetone is added in step 2) acquired solution, stirring is after five minutes, fast using the centrifugation of 8000r/min
Degree centrifugation 10 minutes, separates platinum grain with ethylene glycol.Supernatant is removed, brownish black precipitating is left；
4) 50mL dehydrated alcohol is added in step 3) gained sediment, stirring after five minutes, adds 200mL n-hexane,
It is centrifuged 10 minutes using the centrifugal speed of 8000r/min later, removes supernatant, leave brownish black precipitating.Repeat the step 2
It is secondary, 30mL dehydrated alcohol is finally added in gained sediment, is made into the mother liquor containing Pt；
5) by step 4) mother liquid obtained ultrasonic 15 minutes, addition is molten dissolved with the 2mL ethyl alcohol of 200 μ L ethyl orthosilicates (TEOS)
Liquid.It is stirred at room temperature 12 hours, and is dried under the conditions of 50 DEG C；
6) sample obtained by step 5) is finely ground, 0.034g aluminum nitrate is added.5mL deionized water is added after mixing, surpasses
Sound 15 minutes.Sample is warming up to 500 DEG C in 2 DEG C/min after drying, furnace is cold to obtain hud typed Pt SiO2-Al2O3Sample
(Si:Al=10:1).Fig. 2 is the transmission electron microscope photo of the sample, it can be seen that the sample is uniform core-shell structure.
Embodiment 3:
1) claim platinum nitrate solution 0.325g and 1.4g polyvinylpyrrolidone (PVP, M=containing platinum nitrate 18%
58000) 60mL ethylene glycol, is added jointly, being vigorously stirred dissolves it sufficiently, after stewing process 1 minute, obtains clear solution；
2) clarified solution obtained by step 1) is warming up to 180 DEG C under inert atmosphere (such as nitrogen, helium) protection, continues to stir
20 minutes, still room temperature was down in stirring under an inert atmosphere later；
3) about 200mL acetone is added in step 2) acquired solution, stirring is after five minutes, fast using the centrifugation of 8000r/min
Degree centrifugation 10 minutes, separates platinum grain with ethylene glycol.Supernatant is removed, brownish black precipitating is left；
4) 50mL dehydrated alcohol is added in step 3) gained sediment, stirring after five minutes, adds 200mL n-hexane,
It is centrifuged 10 minutes using the centrifugal speed of 8000r/min later, removes supernatant, leave brownish black precipitating.Repeat the step 2
It is secondary, 30mL dehydrated alcohol is finally added in gained sediment, is made into the mother liquor containing Pt；
5) by step 4) mother liquid obtained ultrasonic 15 minutes, addition is molten dissolved with the 2mL ethyl alcohol of 200 μ L ethyl orthosilicates (TEOS)
Liquid.It is stirred at room temperature 12 hours, and is dried under the conditions of 50 DEG C.Sample is warming up to 500 DEG C in 2 DEG C/min later, keeps the temperature 3h；
6) sample obtained by step 5) is finely ground, 0.068g aluminum nitrate is added.5mL deionized water is added after mixing, surpasses
Sound 15 minutes.Sample is warming up to 500 DEG C in 2 DEG C/min after drying, furnace is cold to obtain hud typed Pt SiO2-Al2O3Sample
(Si:Al=5:1).Fig. 3 is the transmission electron microscope photo of the sample, it can be seen that the sample is uniform core-shell structure.
Embodiment 4 (comparative example):
1) claim platinum nitrate solution 0.325g and 0.7g polyvinylpyrrolidone (PVP, M=containing platinum nitrate 18%
58000) 60mL ethylene glycol, is added jointly, being vigorously stirred dissolves it sufficiently, after stewing process 1 minute, obtains clear solution；
2) clarified solution obtained by step 1) is warming up to 180 DEG C under inert atmosphere (such as nitrogen, helium) protection, continues to stir
20 minutes, still room temperature was down in stirring under an inert atmosphere later；
3) about 200mL acetone is added in step 2) acquired solution, stirring is after five minutes, fast using the centrifugation of 8000r/min
Degree centrifugation 10 minutes, separates platinum grain with ethylene glycol.Supernatant is removed, brownish black precipitating is left；
4) 50mL dehydrated alcohol is added in step 3) gained sediment, stirring after five minutes, adds 200mL n-hexane,
It is centrifuged 10 minutes using the centrifugal speed of 8000r/min later, removes supernatant, leave brownish black precipitating.Repeat the step 2
It is secondary, 30mL dehydrated alcohol is finally added in gained sediment, is made into the mother liquor containing Pt；
5) by step 4) mother liquid obtained ultrasonic 15 minutes, addition is molten dissolved with the 2mL ethyl alcohol of 200 μ L ethyl orthosilicates (TEOS)
Liquid.It is stirred at room temperature 12 hours, and is dried under the conditions of 50 DEG C.Sample is warming up to 500 DEG C in 2 DEG C/min later, keeps the temperature 3h, furnace
It is cold to obtain hud typed Pt SiO2Sample.Fig. 4 is the transmission electron microscope photo of the sample, it can be seen that the sample is uniform core
Shell structure.
Embodiment 5 (comparative example):
By 1 gained Pt@SiO of embodiment2-Al2O3Sample (Si:Al=10:1) is placed in (water content under 800 DEG C of moving airs
10%, flow velocity 500mL/min), continuous processing 10 hours to get the Pt@SiO handled to hydrothermal aging2-Al2O3Sample.Fig. 5 is
The transmission electron microscope photo of the sample, it can be seen that the sample is maintained as uniform core-shell structure, only a small amount of Pt sintering group
It is poly-.
Embodiment 6 (comparative example):
By 2 gained Pt@SiO of embodiment2@Al2O3Sample (Si:Al=10:1) is placed in (water content under 800 DEG C of moving airs
10%, flow velocity 500mL/min), continuous processing 10 hours to get the Pt@SiO handled to hydrothermal aging2@Al2O3Sample.Fig. 6 is
The transmission electron microscope photo of the sample, it can be seen that the sample is maintained as uniform core-shell structure, only a small amount of Pt sintering group
It is poly-.
Embodiment 7 (comparative example):
By 4 gained Pt@SiO of embodiment2Sample is placed under 800 DEG C of moving airs (water content 10%, flow velocity 500mL/
Min), continuous processing 10 hours is to get to the Pt@SiO of hydrothermal aging processing2Sample.Fig. 7 is that the transmission electron microscope of the sample shines
Piece, it can be seen that the sample core-shell structure has collapsed, most of Pt particle agglomeration due to heat ageing.
The catalyst performance evaluation of above-described embodiment:
Catalyst sample is subjected to laboratory simulation distribution evaluation, uses sample by catalyst and quartz sand in evaluation procedure
It is mixed by weight 50mg:300mg.Sample after mixing is put into the crystal reaction tube that diameter is 10mm.NO oxidation
Test reaction atmosphere is 500ppm NO, 5vol.%O2, nitrogen balance；C3H8Oxidation test reaction atmosphere is 800ppm C3H8、
2vol.%O2, nitrogen balance.Total gas flow rate is 500ml/min, air speed 100000h in all reactions-1.Active testing
Temperature range be 30 DEG C~600 DEG C, 10 DEG C/min of heating rate.1%H is used before test every time2/N2(500mL/min) is to various kinds
Product carry out 30 minutes reduction pretreatments at 250 DEG C.In reaction process, electric furnace temperature programming is controlled by temperature controller, by infrared
Spectroanalysis instrument measures NO in reaction process2、CO2Concentration is generated, obtains what sample under different temperatures reacted NO and oxidation of propane
Conversion ratio, and thus obtain the oxidation of propane T of sample50(temperature when conversion ratio is 50%).
Table 1 is embodiment 1, embodiment 2, embodiment 4,7 catalyst DOC oxidisability of embodiment 5, embodiment 6 and embodiment
It can compare, Fig. 8 is corresponding histogram.With conventionally produced, no acidic Pt@SiO2Catalyst (embodiment 4) is compared,
Sample of several classes using composite oxides as shell shows the huge advantage in performance, oxidation of propane T50Reduce by 100 DEG C
More than；At 180 DEG C, the NO high conversion rate of embodiment 1 is up to 89.4%.After 800 DEG C of hydrothermal agings, Pt@SiO2Aging sample
The NO and oxidation of propane ability of (embodiment 7) lose substantially.And the sample using composite oxides as shell (implemented by embodiment 5
Example 6) it still is able to show excellent oxidation activity.In conclusion the hud typed platinum based catalyst of acidity of technique synthesis has both
Excellent NO, HC catalytic activity and extremely strong hydrothermal stability.
1 different catalysts DOC oxidation susceptibility of table compares
Claims (8)
1. a kind of preparation method of the hud typed platinum based catalyst with controllable acidity, the general formula of the hud typed platinum based catalyst are
Pt@SiO2-MOx, wherein SiO2-MOxIt is with SiO2Based on, polynary acid composite oxides with heterogeneity and acidity
Shell, which is characterized in that preparation includes the following steps:
1) appropriate platinum nitrate solution and polyvinylpyrrolidone mixing are weighed, make Pt and PVP molar ratio (1:20)~(1:
80) ethylene glycol, is added later, being vigorously stirred dissolves it sufficiently, and clear solution is obtained after standing；
2) clarified solution obtained by step 1) is heated up under inert atmosphere protection, still room temperature is down in stirring under an inert atmosphere later；
3) acetone is added in step 2) acquired solution, separates platinum grain with ethylene glycol with centrifuge after stirring, removes supernatant
Liquid leaves brownish black precipitating；
4) dehydrated alcohol is added in step 3) gained sediment, n-hexane is added after stirring, centrifugal treating removes supernatant
Liquid leaves brownish black precipitating, dehydrated alcohol is added in last gained sediment, is made into the mother liquor containing Pt；
5) ethanol solution dissolved with appropriate ethyl orthosilicate will be added after the mother liquid obtained ultrasonic treatment of step 4), is stirred at room temperature, and
It is dried under the conditions of 40-60 DEG C, i.e. acquisition Pt@PVP-SiO2Powder, is calcined later and cooling obtains hud typed Pt SiO2Powder
End；
6) by Pt@PVP-SiO obtained by step 5)2Or Pt@SiO2Powder is finely ground, and the soluble-salt of the M containing metal in right amount is added, makes M:
Si molar ratio is maintained at 1:5~1:20, and deionized water is added after mixing, ultrasonic treatment, drying calcining, and furnace is cold to obtain two
Kind has the hud typed Pt@SiO of different acid constituents distribution2-MOxPowder, by Pt@PVP-SiO2Obtained powder acidic site away from
Farther out from Pt, by Pt@SiO2Obtained powder acidic site and Pt is in close contact.
2. having the preparation method of controllable acid hud typed platinum based catalyst according to claim 1, which is characterized in that institute
It states in step 1), polyvinylpyrrolidonemolecules molecules amount is 36000-63000, and ethylene glycol additional amount is the 3000- of Pt mole
4000 times；
In the step 2), inert atmosphere is nitrogen or helium atmosphere, is warming up to 140-200 DEG C, continues stirring 20 minutes, it
Room temperature is down in stirring afterwards.
3. having the preparation method of controllable acid hud typed platinum based catalyst according to claim 1, which is characterized in that institute
It states in step 3), acetone is pressed to be added with the amount of the volume ratio 10:3 of ethylene glycol in step 1)；
In the step 4), the amount that dehydrated alcohol is added into step 3) gained sediment is the 0.8- of ethylene glycol in step 1)
1.2 times, the amount that n-hexane is added is 3-5 times of dehydrated alcohol, and centrifugal treating, removes supernatant later, leaves brownish black precipitating,
It repeats the link 2 times, the dehydrated alcohol of 0.4-0.6 times of ethylene glycol volume in step 1) is added in last gained sediment, matches
At the mother liquor containing Pt.
4. having the preparation method of controllable acid hud typed platinum based catalyst according to claim 1, which is characterized in that institute
It states in step 5), dissolved in the additional amount of the ethanol solution of ethyl orthosilicate, the additional amount of ethyl orthosilicate is Pt mole
2-4 times, the additive amount of ethyl alcohol is 5-15 times of ethyl orthosilicate volume, and 500-600 DEG C of calcination temperature, time 1-3h, calcining rises
Warm rate control is in 2 DEG C/min or less.
5. having the preparation method of controllable acid hud typed platinum based catalyst according to claim 1, which is characterized in that institute
It states in step 6), metal M is Al, Zr, Ti or its multiplexed combination, and the soluble-salt of the M containing metal is aluminum nitrate, aluminum sulfate, nitric acid
Any one in oxygen zirconium, zirconium sulfate and titanium sulfate or combination.
6. having the preparation method of controllable acid hud typed platinum based catalyst according to claim 1, which is characterized in that institute
It states in step 6), 500-600 DEG C of calcination temperature, time 1-3h, calcining heating rate control is in 2 DEG C/min or less.
7. having the preparation method of controllable acid hud typed platinum based catalyst according to claim 1, which is characterized in that institute
The group for stating shell is divided into SiO2-Al2O3、SiO2-TiO2、SiO2-ZrO2Or its multiplexed combination.
8. there is claim 1 preparation gained controllable acid hud typed platinum based catalyst to be used for exhaust gas from diesel vehicle oxidation catalysis,
It is characterized by: the low-temperature oxidation catalyst for removing HC, or for catalytic oxidation NO to be selected to the nitrogen oxides of postposition
Selecting property catalysis reduction (SCR) catalyst or catalytic type particulate matter trap (CDPF) regeneration provide NO2。
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