CN108067227A - A kind of high dispersive is in platinum based catalyst of carrier alundum and its preparation method and application - Google Patents
A kind of high dispersive is in platinum based catalyst of carrier alundum and its preparation method and application Download PDFInfo
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- CN108067227A CN108067227A CN201710197705.0A CN201710197705A CN108067227A CN 108067227 A CN108067227 A CN 108067227A CN 201710197705 A CN201710197705 A CN 201710197705A CN 108067227 A CN108067227 A CN 108067227A
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- carrier
- catalyst
- high dispersive
- mass percentage
- base catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 61
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229910052697 platinum Inorganic materials 0.000 title abstract description 13
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title description 48
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 47
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 47
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 239000001294 propane Substances 0.000 claims abstract description 20
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims abstract description 17
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- 230000009467 reduction Effects 0.000 claims abstract description 5
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 21
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 238000010792 warming Methods 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 239000012298 atmosphere Substances 0.000 claims description 8
- 239000012018 catalyst precursor Substances 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000007598 dipping method Methods 0.000 claims description 4
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000008139 complexing agent Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- 239000012495 reaction gas Substances 0.000 claims description 2
- 238000011084 recovery Methods 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims 1
- 229910017604 nitric acid Inorganic materials 0.000 claims 1
- 238000012216 screening Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 11
- 239000002245 particle Substances 0.000 abstract description 7
- 229910052738 indium Inorganic materials 0.000 abstract description 4
- 229910003437 indium oxide Inorganic materials 0.000 abstract description 4
- 230000004888 barrier function Effects 0.000 abstract description 2
- 230000008901 benefit Effects 0.000 abstract description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 20
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 20
- 239000000047 product Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000003915 liquefied petroleum gas Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 239000011865 Pt-based catalyst Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000004231 fluid catalytic cracking Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical class O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 150000003057 platinum Chemical class 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 235000007686 potassium Nutrition 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 239000002699 waste material 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
- B01J23/63—Platinum group metals with rare earths or actinides
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/394—Metal dispersion value, e.g. percentage or fraction
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0205—Impregnation in several steps
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
- C07C5/3335—Catalytic processes with metals
- C07C5/3337—Catalytic processes with metals of the platinum group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
- C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
- C07C2523/42—Platinum
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
- C07C2523/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/56—Platinum group metals
- C07C2523/63—Platinum group metals with rare earths or actinides
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of high dispersive in carrier Al2O3Pt base catalyst and its preparation method and application, a kind of high dispersive is in carrier Al2O3Pt base catalyst, with Al2O3For carrier, with In2O3、La2O3For auxiliary agent, using Pt metal as active component；On the basis of catalyst gross mass, the mass percentage of the Pt metal is 0.2~2%, the In2O3Mass percentage for 7~9%, the La2O3Mass percentage for 10~12%, the Al2O3Mass percentage is 75~85%, and the catalyst can be applied in dehydrogenating propane.It is an advantage of the present invention that the catalyst mixes Pt, In in perovskite B site, Pt, In is made to be homogeneously dispersed in atomic level in perovskite structure, make the Pt particles after reduction and indium oxide that can be distributed in the state of high dispersive on alumina catalyst support；The grain size of Pt is small and particle between play the role of indium oxide, lanthana particles play barrier, and Pt is made to be not easy to reunite at high temperature, active site is more exposed, so as to improve the activity of reaction and stability.
Description
Technical field
The invention belongs to the technical fields of metallic catalyst, and in particular to a kind of high dispersive is in the platinum of carrier alundum
Base catalyst and its preparation method and application.
Background technology
Propylene is very important industrial chemicals, is the base stock of three big synthetic materials, mainly for the production of polypropylene,
Acrylonitrile, isopropanol, acetone and propylene oxide etc..It is corresponding with flourishing for economy and propylene downstream industry, to third
The demand of alkene is consequently increased.Propylene is essentially from naphtha steam cracking and the by-product of fluid catalytic cracking at present.But with
The continuous shortage and rise in price of oil, the propylene yield of both techniques far can not meet the domestic need to propylene
It asks.So accelerating other production technologies of research propylene, the notch for filling up propylene demand is current urgent problem to be solved.
Preparing propylene by dehydrogenating propane obtains very big concern when having cheap cost.Propane is essentially from liquefied petroleum gas
With the low-carbon alkanes in associated gas.Liquefied petroleum gas is mainly used as domestic fuel and burns, and causes great waste.Institute
Propane utilization rate on the one hand can be improved so that dehydrogenating propane is made propylene, secondly change of the propylene as raw material production more value
Chemical product can generate the economic benefit of bigger.Industrialized dehydrogenating propane technique have Uop Inc. Oleflex techniques,
The Catofin techniques of Lummus Technology companies, the STAR techniques of KruppUhde companies, Snamprogetti-
The FBD techniques of Yarsintez companies and the Linde techniques of Linde/BASF companies.Catofin techniques, FBD techniques, Linde works
The catalyst that skill uses is chromium-based catalysts, and chromium has certain toxicity, unfriendly to environment.Oleflex techniques, STAR techniques
The catalyst platinum series catalysts used, excellent catalytic effect is environmental-friendly, but platinum is expensive, the easy carbon distribution inactivation of catalyst, unstable
It is fixed.Therefore exploitation activity is high, stability is good, high selectivity catalyst is the key that solve preparing propylene by dehydrogenating propane technology institute
.
The content of the invention
For the present invention for the problem that the easy agglomeration of Pt based catalyst systems, carbon distribution is seriously and selectivity is low proposes one kind
High dispersive is in carrier Al2O3Pt bases method for preparing catalyst and its preparing propylene by dehydrogenating propane reaction in application.The catalyst
The problem of catalyst easy-sintering, carbon distribution seriously decline activity is effectively improved, there is good dehydrogenating propane activity, propylene choosing
Selecting property and reaction stability.
The present invention is realized by following technical method：
A kind of high dispersive is in carrier Al2O3Pt base catalyst, with Al2O3For carrier, with In2O3、La2O3For auxiliary agent, with gold
Category Pt is active component；On the basis of catalyst gross mass, the mass percentage of the Pt metal is 0.2~2%, described
In2O3Mass percentage for 7~9%, the La2O3Mass percentage for 10~12%, the Al2O3Matter
It is 75~85% to measure percentage composition.
It is further preferred that on the basis of catalyst gross mass, the mass percentage of the Pt metal for 0.2~
1.5%, the In2O3Mass percentage for 7.4~9.0%, the La2O3Mass percentage for 10.4~
10.8%, the Al2O3Mass percentage is 78~82%.
A kind of high dispersive is in carrier Al2O3Pt base catalyst preparation method, step is as follows：
Lanthanum nitrate, indium nitrate, chloroplatinic acid are dissolved in deionized water, add in complexing agent citric acid and ethylene glycol, nitre by step 1
Sour lanthanum, indium nitrate, chloroplatinic acid, the molar ratio of citric acid and ethylene glycol are 1：(0.8~1.0)：(0.01~0.18):(0.4~
3.5)：(0.1~6.0)；
Step 2, by Al2O35~6h of high-temperature roasting at 600~650 DEG C, heating rate are 5 DEG C/min, will be in step 1
The mixed solution Al that is added drop-wise to that treated dropwise2O3On, carry out incipient impregnation；
Step 3, by the Al after dipping2O3It is dry, then under Muffle furnace air atmosphere, 350 are warming up to from 20~25 DEG C
~400 DEG C, 2~3h is roasted, heating rate is 1~5 DEG C/min；Again 700~800 DEG C are warming up to 1~5 DEG C/min heating rates
5~6h is roasted, obtains LaIn1-yPtyO3/Al2O3Catalyst precursor；After naturally cooling to 500~550 DEG C, in H2-N2Atmosphere
In fully reduce LaIn1-yPtyO3/Al2O3Catalyst precursor obtains high dispersive in carrier Al2O3Pt base catalyst, i.e. Pt-
La2O3-In2O3/Al2O3Catalyst.
Moreover, in step 1, it is preferable that lanthanum nitrate, indium nitrate, chloroplatinic acid, the molar ratio of citric acid and ethylene glycol are 1：
(0.85~0.95)：(0.02~0.15):(0.5~2.5)：(1.5~4.5).
Moreover, in step 2, the time of dipping is for 24 hours, temperature is room temperature.
Moreover, in step 3, dry condition is first at 80~90 DEG C then dry 6~7h is done at 120~130 DEG C
Dry 12~13h.
Moreover, in step 3, it is preferable that under Muffle furnace air atmosphere, 360~380 DEG C are warming up to from 22~25 DEG C, roasting
2.5~3h is burnt, heating rate is 1~5 DEG C/min；750~770 DEG C of roastings 5.5 are warming up to 1~5 DEG C/min heating rates again
~6h.
Moreover, in step 3,500~520 DEG C are naturally cooled to.
Moreover, in step 3, in H2-N2The time reduced in atmosphere is 2~3h, H2The volume ratio of hydrogen is 5%.
A kind of high dispersive is in carrier Al2O3Application of the Pt base catalyst in dehydrogenating propane.
When carrying out dehydrogenating propane, step is as follows：
Step 1, by Pt-La2O3-In2O3/Al2O3Catalyst carries out compressing tablet process and sieves to obtain the particle of 40~60 mesh
Shape catalyst is simultaneously packed into fixed bed reactors, is passed through hydrogen nitrogen mixed gas, and 500~520 are warming up to the heating rate of 10 DEG C/min
DEG C catalyst is reduced, the recovery time is 2~2.5h, H in hydrogen nitrogen mixed gas2Volume ratio is 5~6%；
Step 2, after the completion of reduction, under conditions of normal pressure and reaction bed temperature is 600 DEG C, into reactor with
1500h-1Mass space velocity be passed through C3H8、H2And N2Reaction gas reacted, C3H8：H2：N2Volume ratio be (8~8.5)：(7
~7.5)：(35~35.5), the reaction time is 10~240 minutes.
Beneficial effects of the present invention are：
The catalyst mixes Pt, In in perovskite B site, and Pt, In is made to be homogeneously dispersed in perovskite knot in atomic level
In structure, Pt particles and indium oxide after so reducing can be in that the state of high dispersive is distributed on alumina catalyst support.The grain size of Pt is small
And play the role of indium oxide between particle, lanthana particles play barrier, Pt is made to be not easy to reunite at high temperature, more exposure live
Property site, so as to improve the activity of reaction and stability.
Description of the drawings
Fig. 1 is the LaIn of x%wt Pt load capacity1-yPtyO3/Al2O3XRD spectra.Wherein ◆ be perovskite diffraction maximum.
a：Al2O3, b：X=0.2, c：X=0.5, d：X=1.0, e：X=1.5, f：X=2.0.(y is atomicities of the Pt in perovskite)
Fig. 2 is the Pt-La that the Pt contents after reduction are 0.5%2O3-In2O3/Al2O3Catalyst TEM schemes.
Specific embodiment
The present invention will be described in detail with reference to the accompanying drawings and examples.
Embodiment 1
(1) Al is taken2O3White powder is placed in Muffle furnace in 200mL crucibles.600 are risen to the heating rate of 5 DEG C/min
DEG C roasting 5h.Take 1.6g SiO2In 25mL small beakers.
(2) 0.569g lanthanum nitrate hexahydrates, six nitric hydrate indiums of 0.403g are taken, 0.01g platinum is added in 25mL small beakers
0.6mL deionized water dissolvings.
(3) 0.646g monohydrate potassiums are taken, 0.039mL ethylene glycol adds in above-mentioned solution, and stirring and dissolving is simultaneously uniformly mixed.
(4) solution obtained in (3) is instilled to the Al in (1) dropwise2O3On carrier, it is stored at room temperature and is allowed to be sufficiently impregnated
For 24 hours, gelatinous solid is obtained.
(5) by dry 6h at above-mentioned 80 DEG C of gelatinous solid, 120 DEG C of dry 12h, dry product is 350 in Muffle furnace
DEG C roasting 2h, 700 DEG C roasting 5h, obtain LaIn1-yPtyO3/Al2O3Catalyst precursor.
(6) by the LaIn of 0.5%Pt contents1-yPtyO3/Al2O3Catalyst precursor carries out compressing tablet process and sieves to obtain
The pellet type catalyst of 40~60 mesh.
(7) by the LaIn of the granular 0.5%Pt contents of 0.4g1-yPtyO3/Al2O3Catalyst precursor is packed into fixed bed
Reactor is passed through hydrogen nitrogen mixed gas, and being warming up to 500 DEG C with the heating rate of 10 DEG C/min reduces catalyst, during reduction
Between for 2h, H in hydrogen nitrogen mixed gas2Volume ratio is 5%；
(8) after the completion of to be restored, under conditions of normal pressure and reaction bed temperature is 600 DEG C, into reactor with
1500h-1Mass space velocity be passed through C3H8：H2：N2=8：7：35 synthesis gas is reacted.
Above-mentioned steps obtain LaIn in (5)1-yPtyO3/Al2O3After catalyst precursor, LaIn is made1-yPtyO3/Al2O3Catalysis
Agent presoma is in H2-N2Reductase 12 h under atmosphere obtains the Pt-In of 0.5%Pt load capacity2O3-La2O3/Al2O3Catalyst, gained
Pt-In2O3-La2O3/Al2O3(XRD is in German Brooker AXS Co., Ltds D8-Focus as shown in Figure 1 for the XRD spectra of catalyst
It is carried out on type X-ray diffractometer.Before test, catalyst is ground to powder, and powdered samples are laid in sample cell simultaneously
It flattens.CuK α (λ=0.15406nm) rays are as radiation source, tube voltage 40kV, tube current 200mA, 2 θ measurable angle ranges
10-75 ° of sweep speed is 8 °/min).The Pt-In of gained 0.5%Pt contents after reduction2O3-La2O3/Al2O3The TEM of catalyst
(the Flied emission transmission electron microscope photo of sample is in the electricity of Japan Electronics Corporation model JEOLJEM-2100F as shown in Figure 2
It is obtained on sub- microscope.Test sample is scattered in after grinding, ultrasound in ethyl alcohol, and obtained suspension is placed in copper mesh
On, treat to be tested after sample drying).
The reaction product of gained is analyzed using gas chromatograph after above-mentioned steps (8), conversion of propane, propylene
Selectivity is as shown in table 1 with the relation of time, and conversion of propane, each selectivity of product calculation formula are as follows：
C3H8In conversion ratio %=tail gas in product total carbon atom number/tail gas (including unreacted reactant) total carbon atom number
× 100%
Product total carbon atom number × 100% in carbon number/tail gas of a certain component in selectivity of product %=tail gas
The conversion of propane of 1 differential responses time of table, Propylene Selectivity
| Reaction time (min) | Conversion of propane (%) | Propylene Selectivity (%) |
| 0 | 34.04 | 50.25 |
| 60 | 9.7 | 84.36 |
| 120 | 9.2 | 84.95 |
| 180 | 9.12 | 85.77 |
| 240 | 9.08 | 86.12 |
By table 1 as it can be seen that as the time carries out, reaction has been initially just unstable, and conversion of propane is very high but propylene selects
Property it is relatively low, with the progress of reaction, activity and conversion ratio tend towards stability substantially, and reaction 4h activity does not decline substantially, illustrate that this is urged
Agent stability is good.
Embodiment 2：
It is reacted using 1 method of embodiment, differs only in Pt and account for the mass percentage of catalyst gross mass and be
0.2%.
Embodiment 3：
It is reacted using 1 method of embodiment, differs only in Pt and account for the mass percentage of catalyst gross mass and be
1%.
Embodiment 4：
It is reacted using 1 method of embodiment, differs only in Pt and account for the mass percentage of catalyst gross mass and be
1.5%.
Embodiment 5：
It is reacted using 1 method of embodiment, differs only in Pt and account for the mass percentage of catalyst gross mass and be
2%.
It on above-described embodiment result and data, is compared using the activity data of 240min after reaction, to investigate not
With influence of the Pt contents to catalyst reaction performance.
Influence of the Pt mass percentages to catalyst reaction activity, referring to table 2.Reaction condition with embodiment 1,2,3,4,
5。
Influence of the table 2Pt mass percentages to catalyst reaction activity and Propylene Selectivity
| Pt mass percentages (%) | Conversion of propane (%) | Propylene Selectivity (%) |
| 0.2 | 2.41 | 54.1 |
| 0.5 | 9.08 | 86.12 |
| 1 | 12.06 | 89.26 |
| 1.5 | 24.88 | 94.34 |
| 2 | 33.7 | 96.14 |
Result can be seen that from table, and with the increase of Pt contents, conversion of propane gradually increases, when Pt load capacity reaches
When 2%, conversion ratio has reached 33.7%, and Propylene Selectivity has also reached 96%, and stability is fine, and reaction 4h activity is without appointing
What declines.
Process conditions are recorded according to present invention to be prepared, and can prepare heretofore described high dispersive in carrier
Al2O3Pt bases catalyst and show the performance basically identical with embodiment.Example has been done to technical scheme above
Property description, it should explanation, in the case where not departing from the core of the technical program, it is any it is simple deformation, modification or
Person other skilled in the art can not spend the equivalent substitution of creative work to each fall within the protection domain of this patent.
Claims (10)
1. a kind of high dispersive is in carrier Al2O3Pt base catalyst, it is characterised in that：With Al2O3For carrier, with In2O3、La2O3For
Auxiliary agent, using Pt metal as active component；On the basis of catalyst gross mass, the mass percentage of the Pt metal is 0.2
~2%, the In2O3Mass percentage for 7~9%, the La2O3Mass percentage for 10~12%, institute
The Al stated2O3Mass percentage is 75~85%.
2. a kind of high dispersive according to claim 1 is in carrier Al2O3Pt base catalyst, it is characterised in that：With catalyst
On the basis of gross mass, the mass percentage of the Pt metal is 0.2~1.5%, the In2O3Mass percentage
For 7.4~9.0%, the La2O3Mass percentage for 10.4~10.8%, the Al2O3Mass percentage is
78~82%.
3. a kind of high dispersive is in carrier Al2O3Pt base catalyst preparation method, it is characterised in that step is as follows：
Lanthanum nitrate, indium nitrate, chloroplatinic acid are dissolved in deionized water, add in complexing agent citric acid and ethylene glycol, nitric acid by step 1
Lanthanum, indium nitrate, chloroplatinic acid, the molar ratio of citric acid and ethylene glycol are 1：(0.8~1.0)：(0.01~0.18):(0.4~
3.5)：(0.1~6.0)；
Step 2, by Al2O35~6h of high-temperature roasting at 600~650 DEG C, heating rate are 5 DEG C/min, will be mixed in step 1
Close the solution Al that is added drop-wise to that treated dropwise2O3On, carry out incipient impregnation；
Step 3, by the Al after dipping2O3It is dry, then under Muffle furnace air atmosphere, 350~400 are warming up to from 20~25 DEG C
DEG C, 2~3h is roasted, heating rate is 1~5 DEG C/min；700~800 DEG C of roastings 5 are warming up to 1~5 DEG C/min heating rates again
~6h, obtains LaIn1-yPtyO3/Al2O3Catalyst precursor；After naturally cooling to 500~550 DEG C, in H2-N2In atmosphere fully
Reduce LaIn1-yPtyO3/Al2O3Catalyst precursor obtains high dispersive in carrier Al2O3Pt base catalyst, i.e. Pt-La2O3-
In2O3/Al2O3Catalyst.
4. a kind of high dispersive according to claim 3 is in carrier Al2O3Pt base catalyst preparation method, feature exists
In：In step 1, it is preferable that lanthanum nitrate, indium nitrate, chloroplatinic acid, the molar ratio of citric acid and ethylene glycol are 1：(0.85~
0.95)：(0.02~0.15):(0.5~2.5)：(1.5~4.5).
5. a kind of high dispersive according to claim 3 is in carrier Al2O3Pt base catalyst preparation method, feature exists
In：In step 2, the time of dipping is for 24 hours, temperature is room temperature.
6. a kind of high dispersive according to claim 3 is in carrier Al2O3Pt base catalyst preparation method, feature exists
In：In step 3, dry condition is first dry 6~7h and then dry 12~13h at 120~130 DEG C at 80~90 DEG C.
7. a kind of high dispersive according to claim 3 is in carrier Al2O3Pt base catalyst preparation method, feature exists
In：In step 3, it is preferable that under Muffle furnace air atmosphere, 360~380 DEG C are warming up to from 22~25 DEG C, roasts 2.5~3h,
Heating rate is 1~5 DEG C/min；750~770 DEG C of 5.5~6h of roasting are warming up to 1~5 DEG C/min heating rates again.
8. a kind of high dispersive according to claim 3 is in carrier Al2O3Pt base catalyst preparation method, feature exists
In：In step 3,500~520 DEG C are naturally cooled to；In H2-N2The time reduced in atmosphere is 2~3h, H2The volume ratio of hydrogen
For 5%.
9. a kind of high dispersive as claimed in claim 1 or 2 is in carrier Al2O3Application of the Pt base catalyst in dehydrogenating propane.
10. a kind of high dispersive according to claim 9 is in carrier Al2O3Application of the Pt base catalyst in dehydrogenating propane,
It is characterized in that step is as follows：
Step 1, by Pt-La2O3-In2O3/Al2O3The graininess that catalyst progress compressing tablet process and screening obtain 40~60 mesh is urged
Agent is simultaneously packed into fixed bed reactors, is passed through hydrogen nitrogen mixed gas, with the heating rate of 10 DEG C/min be warming up to 500~520 DEG C it is right
Catalyst is reduced, and the recovery time is 2~2.5h, H in hydrogen nitrogen mixed gas2Volume ratio is 5~6%；
Step 2, after the completion of reduction, under conditions of normal pressure and reaction bed temperature is 600 DEG C, into reactor with 1500h-1Mass space velocity be passed through C3H8、H2And N2Reaction gas reacted, C3H8：H2：N2Volume ratio be (8~8.5)：(7~
7.5)：(35~35.5), the reaction time is 10~240 minutes.
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| CN110871077A (en) * | 2019-11-09 | 2020-03-10 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation of gamma-aluminum oxide In-loaded cobaltosic oxide material with high-temperature stability, product and application |
| CN110871077B (en) * | 2019-11-09 | 2022-11-01 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation of gamma-aluminum oxide In-loaded cobaltosic oxide material with high-temperature stability, product and application |
| CN112604685A (en) * | 2020-12-14 | 2021-04-06 | 厦门大学 | Supported catalyst and preparation method and application thereof |
| CN112604685B (en) * | 2020-12-14 | 2022-02-18 | 厦门大学 | Supported catalyst and preparation method and application thereof |
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