CN113559853A - Catalyst for preparing propylene by direct dehydrogenation of propane - Google Patents
Catalyst for preparing propylene by direct dehydrogenation of propane Download PDFInfo
- Publication number
- CN113559853A CN113559853A CN202110963865.8A CN202110963865A CN113559853A CN 113559853 A CN113559853 A CN 113559853A CN 202110963865 A CN202110963865 A CN 202110963865A CN 113559853 A CN113559853 A CN 113559853A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- solution
- percent
- propane
- maintaining
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 126
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 239000001294 propane Substances 0.000 title claims abstract description 51
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 31
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 18
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 46
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 23
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 68
- 229910052593 corundum Inorganic materials 0.000 claims description 66
- 238000003756 stirring Methods 0.000 claims description 66
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 66
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 41
- 238000000227 grinding Methods 0.000 claims description 33
- 239000000203 mixture Substances 0.000 claims description 33
- 229910003158 γ-Al2O3 Inorganic materials 0.000 claims description 32
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 20
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 20
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 229910009112 xH2O Inorganic materials 0.000 claims description 17
- 238000001354 calcination Methods 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 3
- 238000005253 cladding Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 claims 1
- 229910052697 platinum Inorganic materials 0.000 abstract description 17
- 229910052799 carbon Inorganic materials 0.000 abstract description 7
- 238000002360 preparation method Methods 0.000 abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 150000002739 metals Chemical class 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 118
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 65
- 238000006243 chemical reaction Methods 0.000 description 58
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 34
- 238000007789 sealing Methods 0.000 description 30
- 230000003197 catalytic effect Effects 0.000 description 22
- 235000012239 silicon dioxide Nutrition 0.000 description 22
- 238000005303 weighing Methods 0.000 description 19
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 17
- 229910052786 argon Inorganic materials 0.000 description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 16
- 239000006004 Quartz sand Substances 0.000 description 16
- 239000010453 quartz Substances 0.000 description 16
- 238000007605 air drying Methods 0.000 description 15
- 239000007864 aqueous solution Substances 0.000 description 15
- 239000003814 drug Substances 0.000 description 15
- 238000011156 evaluation Methods 0.000 description 15
- 239000011521 glass Substances 0.000 description 15
- 239000001257 hydrogen Substances 0.000 description 15
- 229910052739 hydrogen Inorganic materials 0.000 description 15
- 239000007788 liquid Substances 0.000 description 15
- 150000003839 salts Chemical class 0.000 description 15
- 239000000377 silicon dioxide Substances 0.000 description 15
- 238000012546 transfer Methods 0.000 description 15
- 230000002779 inactivation Effects 0.000 description 12
- 239000010410 layer Substances 0.000 description 10
- 230000009849 deactivation Effects 0.000 description 9
- 230000004075 alteration Effects 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 229910052681 coesite Inorganic materials 0.000 description 7
- 229910052906 cristobalite Inorganic materials 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 7
- 229910052682 stishovite Inorganic materials 0.000 description 7
- 229910052905 tridymite Inorganic materials 0.000 description 7
- 230000008021 deposition Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000000635 electron micrograph Methods 0.000 description 6
- 238000005245 sintering Methods 0.000 description 6
- 239000002105 nanoparticle Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- 238000004939 coking Methods 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 3
- 229910001195 gallium oxide Inorganic materials 0.000 description 3
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000011865 Pt-based catalyst Substances 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- FGQRHNWAVSBJHZ-UHFFFAOYSA-N CCCC[Zr] Chemical compound CCCC[Zr] FGQRHNWAVSBJHZ-UHFFFAOYSA-N 0.000 description 1
- CXRFDZFCGOPDTD-UHFFFAOYSA-M Cetrimide Chemical compound [Br-].CCCCCCCCCCCCCC[N+](C)(C)C CXRFDZFCGOPDTD-UHFFFAOYSA-M 0.000 description 1
- 229910019923 CrOx Inorganic materials 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-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
- 229910002847 PtSn Inorganic materials 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910021486 amorphous silicon dioxide Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000010506 ionic fission reaction Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000011807 nanoball Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229910001848 post-transition metal Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Substances [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Images
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
- 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
- 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
- B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
-
- 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
- B01J33/00—Protection of catalysts, e.g. by coating
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a catalyst for preparing propylene by direct dehydrogenation of propane and a preparation method thereof, belonging to the field of catalyst preparation. The catalyst consists of metals (or oxides) such as Pt, Ga, Al, Si and the like, and the weight percentage content is as follows: pt: 0.001 to 0.1%, Ga: 1% -10%, Al: 23.100% -51.635%, Si: 0.5-20%, O: 44.200-49.475%. The invention has the advantages of low preparation cost, high propylene selectivity, stable catalyst structure, less carbon deposit and the like, and has wide popularization and application prospect.
Description
Technical Field
The invention belongs to the field of catalyst preparation, and particularly relates to a catalyst for efficiently synthesizing propylene by directly dehydrogenating propane at low temperature, and a preparation method and application thereof.
Background
With the increasing shortage of petroleum resources and the rising price and day, the future world economic development faces the limitation of shortage of energy and resources, and simultaneously, the change of the world energy pattern is promoted. Shale gas is being developed as a novel unconventional natural gas resource in a large quantity and is known to have the advantages of large reserves, long mining life, long production cycle and the like. In recent years, means for effectively extracting shale gas by improving a hydraulic fracturing technology is continuously developed, a source of propane is effectively replaced, and the capacity increase and the operating rate of the traditional propylene production process are seriously compressed due to the influence of epidemic situations and the like. Therefore, how to convert the shale gas into high value-added chemicals in an effective way, and especially applying the shale gas to the aspect of propane dehydrogenation to prepare high-value propylene shows good economic benefits.
Propylene, as one of the most important production building blocks, can be used to produce a number of important organic chemicals, such as: polypropylene, acrylonitrile, butyl/octyl alcohol, propylene oxide, phenol/acetone, acrylic acid and ester, epichlorohydrin and the like; production of fine chemicals, such as: synthetic resins, synthetic fibers, synthetic rubbers, and the like. In addition, the product can be used as raw material in the oil refining industry to produce laminated gasoline, thus alleviating energy crisis. In addition, the method can also be applied to the fields of environmental protection, medical science, basic research and the like.
So far, the catalyst capable of realizing industrialization of propane dehydrogenation is only PtSn/Al2O3Or CrOx/Al2O3A catalyst. Therefore, extensive research has been focused on Pt-based and CrO for decadesxThe modification of the base catalyst, the reduction of the dosage and the design of the catalyst structure improve the catalytic efficiency, reduce the cost, protect the environment and prolong the reaction life. Therefore, the development of an alternative, low cost, controllable propane dehydrogenation catalyst is still necessary for the utilization of natural gas resources.
Has higher heat absorption rate (Δ Htheta 298 = 124.3 kJ. mol) due to the direct dehydrogenation process of propane-1) Higher reaction temperatures (550 ℃ C. and 700 ℃ C.) are required. Such harsh reaction conditions pose challenges to the thermal stability of the catalyst. The realization of propane dehydrogenation at a lower temperature has a series of advantages of reducing energy consumption, realizing green chemistry, inhibiting coking, sintering and the like, and arouses more and more interests of researchers. Considering the thermodynamic equilibrium limitations of propane direct dehydrogenation, how to achieve a propane direct dehydrogenation process with good catalytic performance at low temperatures is an emerging significant challenge. Therefore, the development of a highly stable catalyst having good low-temperature catalytic performance is highly desired.
Among the most promising catalysts for direct propane dehydrogenation, the monatomic Pt catalyst has been widely studied and applied due to its advantages such as a definite and isolated active site, and a unique and superior catalytic performance. Under low temperature conditions, the atom dispersed Pt sites can easily dissociate the first and second C-H bonds of the alkane, and the side reaction of generating coke is effectively reduced. However, the isolated Pt active sites have high surface Gibbs free energy, and agglomeration and sintering can occur in the catalytic process, thereby further causing the catalyst to be deactivated. To rationally design PDH catalysts, a number of strategies have been proposed. For example, post-transition metal elements (e.g., Sn, Zn, Ga, In) have been explored as co-catalysts to improve the dispersion, geometry, and electronic properties of Pt, and to improve activity, selectivity, stability, and anti-coking properties. And alumina has a stronger carrier effect on gallium oxide, thereby being beneficial to maintaining the dispersion of Pt species. On the other hand, the inorganic oxide shell layer is wrapped on the upper surface of the catalyst to serve as a physical barrier, so that the aggregation of Pt species is prevented, and the thermal stability and the coking resistance of the catalyst can be improved.
CN112135687A discloses an impregnation method for loading K-doped PtGa/Al2O3-SiO2The composite catalyst is used for a fixed bed reactor, the reaction temperature is 570 ℃, 10 percent of propane is used under the pressure of 5 bar, and the space velocity is 12h-1Under the reaction conditions of (1), 5 wt% SiO was introduced2The catalyst (A) is the catalyst with the best performance, the conversion rate is 41% in the initial 1 minute, and is reduced to 40% after 11 minutes. And pure Al2O3Comparison of Supported catalysts, different SiO2The stability of the introduced catalyst is firstly followed by SiO2Is increased, and the introduced B acid site also causes side reactions to occur more easily. Thus, an optimum SiO exists2The amount is in the range, but deactivation due to side reactions still occurs.
CN112221493A discloses a method for preparing trace precious metal modified uniformly distributed Pt-Ga2O3/Al2O3And Rh-Ga2O3/Al2O3Catalyst, the loaded active component is Ga2O3Trace noble metal as assistant at reaction pressure 0.1 MPa and reaction temperature 600 deg.c3H8/H2=1/1, nitrogen as balance gas, mass space velocity 10h-1Under the condition, the initial conversion rate of the catalyst with different Pt loading amounts is 19-27%, the initial conversion rate after 4 hours of reaction is 8-17%, the selectivity is basically maintained at about 88-99%, and the catalyst shows a rapid inactivation property.
CN110237840B discloses a method for preparing monoatomic Pt/TiO by adopting electrostatic adsorption2The catalyst has the reaction pressure of normal pressure and the reaction temperature of 580 ℃ and C3H8/H2=1/1 space velocity 3200 h-1Under the conditions of (1), the conversion rate is 20%, the selectivity is 98%, and the superiority of the monatomic Pt catalyst in the direct dehydrogenation of propane is fully shown.
The Jingulong topic group (ACS Catalysis, 2016, 6, 2158-2O3Catalyst, 500 mg of catalyst is under normal pressure, reaction temperature of 600 ℃ and space velocity of 3h−1，C3H8/H2=1/1, nitrogen as balance gas, total flow 50 mL/min. The initial equilibrium conversion was 35%, after 4h 31%, the selectivity 94% and the deactivation rate parameter 15%. Although Pt as an adjuvant can reduce Zn as an active site2+To achieve good dehydrogenation activity and minimized Pt usage, but carbon deposition and unstable active structure still cause significant deactivation to occur.
The Weckhuysen project group (Angewandte Chemie-International Edition, 2014, 53, 9251-one 9256) adopts an equal volume impregnation method to synthesize Al loaded with 1000 ppm Pt, 3 wt% Ga and 0.25 wt% K2O3The catalyst of (1). At atmospheric pressure, 0.15g of catalyst was used at 620oC reaction temperature, propane flow rate 9 mL/Min-1The catalyst was evaluated under conditions such that a conversion of 42% was achieved in the first cycle with a selectivity of 97%, and after 15 minutes of each cycle, a conversion of 750% was required oUsing 6% of O under C2Regeneration is carried out. The doped K covers acid sites, so that the generation of carbon deposition can be inhibited to a certain extent, but the generation of carbon deposition is still observed to be more through an online ultraviolet-visible Raman spectrum. And the dispersion before and after Pt regeneration has not changed significantly, indicating the presence of metal carrierStrong interaction between them.
Taoufik (ACS Catalysis, 2018, 8, 7566-one 7577) subject group adopts a grafting method to graft Ga (i-Bu)3The difference between different active sites was investigated by grafting onto alumina and silica supports, indicating that Al-O-Ga active sites have better capacity for heterolytic cleavage of C-H bonds than Si-O-Ga active sites. However, the catalyst loaded with active metal by the grafting method has poor activity and stability (initial conversion rate is 24%, reaction time is 25h later, 9%, and selectivity is maintained at about 90%).
The Luan Hui topic group (Science, 2012, 335, 1205-2O3The coating can well adjust Pd/Al2O3The catalyst surface and the performance study of the oxidative dehydrogenation reaction of ethane at high temperature. Due to Al2O3The limit function of the atomic layer greatly improves the anti-sintering capability of the Pd particles, and simultaneously weakens the adsorption affinity of product molecules to Pd species, thereby well improving the anti-sintering capability and the anti-carbon deposition capability of the catalyst.
The Somorjai topic group (Nature Materials, 2009, 8, 126-131) designs a stable high-temperature-resistant mesoporous amorphous silica coated Pt nanoparticle core-shell structure for CO oxidation and ethylene hydrogenation research at high temperature, and shows good stability. The synthesis is realized by adopting a three-step strategy: (1) synthesizing nano Pt particles by taking tetradecyl trimethyl ammonium bromide as a blocking agent; (2) silica polymerization around Pt core to form Pt @ SiO2A mesoporous structure; (3) removing organic molecules by calcination to generate Pt @ SiO2Core-shell nanoparticles.
The Schluth group of topics (Angewandte Chemie-International Edition, 2006, 118, 8404-. Au gel is synthesized and then reduced to obtain Au nano particles which are uniformly distributed, then silicon dioxide is wrapped on the surfaces of the Au nano particles, and monodisperse Au @ SiO is obtained after the growth of a silicon shell is finished2A nanoparticle. At Au @ SiO2Nano-ball surface coatingCoating a surfactant, reacting with n-butyl zirconium to coat zirconium oxide, and calcining to obtain Au @ SiO2@ZrO2. Finally, SiO is treated by NaOH2Dissolving to obtain hollow Au @ ZrO2A catalyst.
The research shows that the Pt-based catalysts obtained by the conventional synthesis strategy have the defects of high reaction temperature, low conversion rate, easy inactivation of the catalysts and the like.
Disclosure of Invention
The invention aims to provide a catalyst for preparing propylene by direct propane dehydrogenation and a preparation method thereof.
The catalyst provided by the invention comprises the following components in percentage by mass: 1. pt: 0.001 to 0.1%, Ga: 1% -10%, Al: 23.100% -51.635%, Si: 0.5-20%, O: 44.200-49.475%.
The invention adopts an impregnation-cladding method to prepare the catalyst, and the preparation steps are as follows:
1) commercial gamma-Al2O31-5 times of airoThe temperature rise rate of C/min is increased to 700oAnd C, maintaining for 2-3 hours, and vacuumizing for 2 hours at the low pressure of 0.01MPa for later use.
2) Weighing a certain mass of Ga (NO)3)3·xH2O, weighing Pt (NH) according to the mass ratio of Pt/Ga = 0.0001-0.13)4(NO3)2Dissolved in Pt/H2And (4) marking the solution A as the water with the weight ratio of O = 0.000008-0.0008. With Pt/Al2O3Weighing Al in a weight ratio of = 0.00001-0.0012O3. Dropwise adding the solution A into the weighed Al2O3Standing for 2-3 h, drying, grinding and calcining to obtain PtGa/Al2O3A catalyst.
3) With ethanol/ammonia = 20: 1-40: 1 in the volume ratio of PtGa to Al as a B solution2O3(g) Ammonia water (ml) = 0.15-0.3, and weighing PtGa/Al2O3Adding the mixture into the solution B, and carrying out ultrasonic treatment to obtain a suspension C.
4）And (3) preparing a solution D according to the proportion of Tetraethoxysilane (TEOS) (g)/ethanol (ml) = 0.00058-0.02332, dripping the solution D into the suspension C at the speed of 1-5 ml/h, stirring for 10-20 h, and centrifuging to obtain the product. Drying and grinding the obtained product at 353K, and calcining the product in air at 623-673K for 2-4 hours (the heating rate is 1-2)oC·min-1) The obtained mass percentages are respectively as follows: pt: 0.001 to 0.1%, Ga: 1% -10%, Al: 23.100% -51.635%, Si: 0.5-20%, O: 44.200-49.475%.
The prepared catalyst has the following application: mixing the catalyst and quartz sand in a ratio of 1: 5, and filling the mixture into the middle section of a fixed bed quartz tube with the inner diameter of 6 mm. Under pure argon (20 mL. min)-1) Under the condition of raising the temperature of the reactor bed to 450 deg.CoAnd C, maintaining for 1-2 hours, and aiming at blowing off impurities on the surface of the catalyst. The ratio of propane/hydrogen (volume ratio) = 1: 1, argon is used as balance gas, the formed mixed gas is used as raw material, and the reaction temperature is 450 DEGoC, the reaction pressure is 0.1 MPa, and the airspeed is 1-3 h-1Then, propylene was synthesized.
The invention principle is as follows: the strategy of coating inorganic oxide can physically obstruct the migration of metal particles to a certain extent, and simultaneously change Ga by changing metal-carrier interface2O3The high-dispersion Pt sites are anchored by Ga species with different valence states after reduction, so that the catalytic performance, the sintering resistance and the carbon deposition resistance are improved. Therefore, the novel low-temperature catalyst with high activity, high propylene selectivity, high stability and carbon deposition resistance is prepared by using the Pt with ultra-low loading as an active phase, based on the strong carrier effect of gallium oxide and aluminum oxide, radiating and forming high-dispersion Pt sites by using the gallium oxide as a substrate, and wrapping a silicon dioxide shell layer on the surface of active metal.
Compared with the prior art, the Pt-based catalyst for preparing propylene by directly dehydrogenating propane wrapped by amorphous silica on the surface layer has the beneficial effects that:
1) the active component of the catalyst has small particle size and uniform distribution, and Ga clusters are uniformly dispersed in Al2O3High dispersion Pt active site fast anchor on carrierThe Pt catalyst is fixed on a Ga cluster, and is limited to migrate on the surface by a silicon dioxide thin shell layer to form a Pt active site structure with a stable structure, so that the catalytic activity at low temperature, high propylene selectivity and thermal stability of the catalyst are improved.
2) The catalyst is wrapped on the surface of the amorphous silicon dioxide shell layer, so that the occurrence of side reactions such as cracking, polymerization, deep dehydrogenation and the like is effectively inhibited, and the inactivation of the catalyst is slowed down.
3) The low-load high-dispersion Pt locus effectively improves the utilization rate of noble metal atoms and reduces the economic cost.
Drawings
FIG. 1 (a-d) 2.5% Si @0.1Pt5Ga/Al after reaction2O3Spherical aberration electron micrographs of the catalyst.
FIG. 2 (a-c) 0.1Pt5Ga/Al after reaction2O32.5% Si @0.1Pt5Ga/Al after reaction of catalyst and (d-f)2O3Spherical aberration electron micrographs of the catalyst.
FIG. 3 (a-b) 0.1Pt5Ga/Al after reaction2O32.5% Si @0.1Pt5Ga/Al after reaction of catalyst and (c-d)2O3Electron micrograph of catalyst.
FIG. 4 (a-f) 2.5% Si @0.1Pt5Ga/Al after reaction2O3Spherical aberration electron micrographs of the catalyst.
Figure 5 (a-b) DRIFT-CO plot of catalyst after reaction.
Detailed Description
In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
Example 1:
commercial gamma-Al2O3In the air by 5oThe temperature rise rate of C/Min is increased to 700oAnd C, maintaining for 2 hours, and vacuumizing for 2 hours by using a vacuum oven under the pressure of 0.01MPa for later use. Firstly weighing 2g of calcined gamma-Al2O3Put in a 50 mL beaker, and 0.0040g of Pt (NH) was weighed3)4(NO3)2，36.68gGa(NO3)3·xH2O was dissolved in 250 mL of water to prepare a mixed salt aqueous solution of Pt and Ga, which was designated as solution A. Taking 2.5 mL of solution A, dropwise adding the solution A into a beaker by using a 100 uL liquid transfer gun, stirring by using a glass rod while dropwise adding, continuously stirring for 1h after completely dropwise adding, sealing the beaker by using a sealing film, standing for 3h at room temperature, and putting the beaker into an oven 80%oAnd C, 12 h. Drying, grinding, and air drying at a speed of 5%oThe temperature rise rate of C/Min is increased to 500oC, maintaining for 3 hours, and recording the obtained medicine as 0.001Pt5Ga/Al2O3。
0.3g of synthesized 0.001Pt5Ga/Al was weighed2O3The catalyst was put into a 100 mL round-bottom flask, and 40 mL of absolute ethanol and 2 mL of concentrated aqueous ammonia were added thereto, and the mixture was sonicated for 30 Min and recorded as solution C. 0.1166 g of TEOS was weighed out and dissolved in 20mL of absolute ethanol and recorded as solution D. Solution D was drawn into a syringe and added to the round bottom flask containing solution A using a micro syringe pump at a dropping rate of 3 mL/min, at which time the stirring was vigorous at 1200 revolutions per minute. Stirring is continued for 15h after the dripping is finished. The solution was then centrifuged at 4000 rpm and placed in an oven 80oAnd C, 12 h. After grinding, the mixture is treated with 1 in airoThe temperature rise rate of C/Min is increased to 350oC, maintaining for 4h, and obtaining the content Pt: 0.001 percent; ga: 5 percent; al: 43.687%%; si: 5 percent; o: 46.312% catalyst, noted 5% Si @0.001Pt5Ga/Al2O3. Granulating into 40-60 mesh.
In a fixed bed, 0.1 g (40-60 mesh) of 5% Si @0.001Pt5Ga/Al2O3The catalyst is evenly mixed with 0.5 g (40-60 meshes) of quartz sand and then is filled into the middle section of a fixed bed quartz tube with the inner diameter of 6 mm. Under pure argon (20 mL. min)-1) Under the condition of raising the temperature of the reactor bed to 450 deg.CoC and maintaining for 2h, then introducing propane: hydrogen = 1: 1 (airspeed 1 h)-1) Catalytic evaluation was performed. The conversion rate of propane is 5.8 percent, the selectivity of propylene is 90.1 percent, and the inactivation rate constant is 0.059 h-1。
Example 2:
commercial gamma-Al2O3In the air by 5oThe temperature rise rate of C/Min is increased to 700oC, maintaining for 2 hours, and vacuum oven 0Vacuumizing at 01MPa for 2h for later use. Firstly weighing 2g of calcined gamma-Al2O3Put in a 50 mL beaker, and 0.0040g of Pt (NH) was weighed3)4(NO3)2，3.668gGa(NO3)3·xH2O was dissolved in 25 mL of water to prepare a mixed salt aqueous solution of Pt and Ga, which was designated as solution A. Taking 2.5 mL of solution A, dropwise adding the solution A into a beaker by using a 100 uL liquid transfer gun, stirring by using a glass rod while dropwise adding, continuously stirring for 1h after completely dropwise adding, sealing the beaker by using a sealing film, standing for 3h at room temperature, and putting the beaker into an oven 80%oAnd C, 12 h. Drying, grinding, and air drying at a speed of 5%oThe temperature rise rate of C/Min is increased to 500oC, maintaining for 3 hours, and recording the obtained medicine as 0.01Pt5Ga/Al2O3。
0.3g of synthesized 0.01Pt5Ga/Al was weighed2O3The catalyst was put into a 100 mL round-bottom flask, and 40 mL of absolute ethanol and 2 mL of concentrated aqueous ammonia were added thereto, and the mixture was sonicated for 30 Min and recorded as solution C. 0.1166 g of TEOS was weighed out and dissolved in 20mL of absolute ethanol and recorded as solution D. Solution D was drawn into a syringe and added to the round bottom flask containing solution A using a micro syringe pump at a dropping rate of 3 mL/min, at which time the stirring was vigorous at 1200 revolutions per minute. Stirring is continued for 15h after the dripping is finished. The solution was then centrifuged at 4000 rpm and placed in an oven 80oAnd C, 12 h. After grinding, the mixture is treated with 1 in airoThe temperature rise rate of C/Min is increased to 350oC, maintaining for 4h, and obtaining the content Pt: 0.01 percent; ga: 5 percent; al: 43.68 percent; si: 5 percent; o: 46.31% catalyst, reported as 5% Si @0.01Pt5Ga/Al2O3. Granulating into 40-60 mesh.
In a fixed bed, 0.1 g (40-60 mesh) of 5% Si @0.01Pt5Ga/Al2O3The catalyst is evenly mixed with 0.5 g (40-60 meshes) of quartz sand and then is filled into the middle section of a fixed bed quartz tube with the inner diameter of 6 mm. Under pure argon (20 mL. min)-1) Under the condition of raising the temperature of the reactor bed to 450 deg.CoC and maintaining for 2h, then introducing propane: hydrogen = 1: 1 (space velocity of 1.2 h)-1) Catalytic evaluation was performed. Propane conversion 9.5%, propylene selectivity 90.4%, deactivation rate constant 0.043 h-1。
Example 3:
commercial gamma-Al2O3In the air by 5oThe temperature rise rate of C/Min is increased to 700oAnd C, maintaining for 2 hours, and vacuumizing for 2 hours by using a vacuum oven under the pressure of 0.01MPa for later use. Firstly weighing 2g of calcined gamma-Al2O3Put in a 50 mL beaker, and 0.0040g of Pt (NH) was weighed3)4(NO3)2，0.3668gGa(NO3)3·xH2O was dissolved in 2.5 mL of water to prepare a mixed salt aqueous solution of Pt and Ga, which was designated as solution A. Dropwise adding the solution A into a beaker by using a 100 uL liquid transfer gun, stirring by using a glass rod while dropwise adding, continuously stirring for 1h after the dropwise adding is completed, sealing the beaker by using a sealing film, standing for 3h at room temperature, and putting into an oven 80oAnd C, 12 h. Drying, grinding, and air drying at a speed of 5%oThe temperature rise rate of C/Min is increased to 500oC, maintaining for 3 hours, and recording the obtained medicine as 0.1Pt5Ga/Al2O3。
0.3g of synthesized 0.1Pt5Ga/Al was weighed2O3The catalyst was put into a 100 mL round-bottom flask, and 40 mL of absolute ethanol and 2 mL of concentrated aqueous ammonia were added thereto, and the mixture was sonicated for 30 Min and recorded as solution C. Then, 0.0116g of TEOS was weighed and dissolved in 20mL of absolute ethanol and the solution was designated as D solution. Solution D was drawn into a syringe and added to the round bottom flask containing solution A using a micro syringe pump at a 5 mL/min drop rate with vigorous stirring at 1200 rpm. Stirring is continued for 10h after the dripping is finished. The solution was then centrifuged at 4000 rpm and placed in an oven 80oAnd C, 12 h. After grinding, the mixture is treated with 1 in airoThe temperature rise rate of C/Min is increased to 350oC, maintaining for 2h, obtaining the content Pt: 0.1 percent; ga: 5 percent; al: 48.7 percent; si: 0.5 percent; o: 45.7% catalyst, reported as 0.5% Si @0.1Pt5Ga/Al2O3. Granulating into 40-60 mesh.
In a fixed bed, 0.1 g (40-60 mesh) of 0.5% Si @0.1Pt5Ga/Al2O3The catalyst is evenly mixed with 0.5 g (40-60 meshes) of quartz sand and then is filled into the middle section of a fixed bed quartz tube with the inner diameter of 6 mm. Under pure argon (20 mL. min)-1) Under the condition of the reactor bedThe layer temperature is raised to 450 deg.CoC and maintaining for 2h, then introducing propane: hydrogen = 1: 1 (space velocity of 1.2 h)-1) Catalytic evaluation was performed. Propane conversion rate is 22.5%, propylene selectivity is 90.0%, and inactivation rate constant is 0.019 h-1。
Example 4:
commercial gamma-Al2O3In the air by 5oThe temperature rise rate of C/Min is increased to 700oAnd C, maintaining for 2 hours, and vacuumizing for 2 hours by using a vacuum oven under the pressure of 0.01MPa for later use. Firstly weighing 2g of calcined gamma-Al2O3Put in a 50 mL beaker, and 0.0040g of Pt (NH) was weighed3)4(NO3)2，0.3668gGa(NO3)3·xH2O was dissolved in 2.5 mL of water to prepare a mixed salt aqueous solution of Pt and Ga, which was designated as solution A. Dropwise adding the solution A into a beaker by using a 100 uL liquid transfer gun, stirring by using a glass rod while dropwise adding, continuously stirring for 1h after the dropwise adding is completed, sealing the beaker by using a sealing film, standing for 3h at room temperature, and putting into an oven 80oAnd C, 12 h. Drying, grinding, and air drying at a speed of 5%oThe temperature rise rate of C/Min is increased to 500oC, maintaining for 3 hours, and recording the obtained medicine as 0.1Pt5Ga/Al2O3。
0.3g of synthesized 0.1Pt5Ga/Al was weighed2O3The catalyst was put into a 100 mL round-bottom flask, and 40 mL of absolute ethanol and 2 mL of concentrated aqueous ammonia were added thereto, and the mixture was sonicated for 30 Min and recorded as solution C. 0.0583 g of TEOS was weighed out and dissolved in 20mL of absolute ethanol and recorded as solution D. Solution D was drawn into a syringe and added to the round bottom flask containing solution A using a micro syringe pump at a 4 mL/min drop rate with vigorous stirring at 1200 rpm. Stirring is continued for 12h after the dripping is finished. The solution was then centrifuged at 4000 rpm and placed in an oven 80oAnd C, 12 h. After grinding, the mixture is treated with 1 in airoThe temperature rise rate of C/Min is increased to 350oC, maintaining for 3 hours, and obtaining the content Pt: 0.1 percent; ga: 5 percent; al: 46.4 percent; si: 2.5 percent; o: 46.0%% of catalyst, noted as 2.5% Si @0.1Pt5Ga/Al2O3. Granulating into 40-60 mesh.
In a fixed bed, 0.1 g (40-60 mesh) of 2.5% Si @0.1Pt5Ga/Al2O3The catalyst is evenly mixed with 0.5 g (40-60 meshes) of quartz sand and then is filled into the middle section of a fixed bed quartz tube with the inner diameter of 6 mm. Under pure argon (20 mL. min)-1) Under the condition of raising the temperature of the reactor bed to 450 deg.CoC, maintaining for 1h, and then introducing propane: hydrogen = 1: 1 (space velocity of 1.2 h)-1) Catalytic evaluation was performed. The conversion rate of propane is 23.0 percent, the selectivity of propylene is 95.0 percent, and the inactivation rate constant is 0.008 h-1。
Example 5:
commercial gamma-Al2O3In the air by 5oThe temperature rise rate of C/Min is increased to 700oAnd C, maintaining for 2 hours, and vacuumizing for 2 hours by using a vacuum oven under the pressure of 0.01MPa for later use. Firstly weighing 2g of calcined gamma-Al2O3Put in a 50 mL beaker, and 0.0040g of Pt (NH) was weighed3)4(NO3)2，0.3668gGa(NO3)3·xH2O was dissolved in 2.5 mL of water to prepare a mixed salt aqueous solution of Pt and Ga, which was designated as solution A. Dropwise adding the solution A into a beaker by using a 100 uL liquid transfer gun, stirring by using a glass rod while dropwise adding, continuously stirring for 1h after the dropwise adding is completed, sealing the beaker by using a sealing film, standing for 3h at room temperature, and putting into an oven 80oAnd C, 12 h. Drying, grinding, and air drying at a speed of 5%oThe temperature rise rate of C/Min is increased to 500oC, maintaining for 3 hours, and recording the obtained medicine as 0.1Pt5Ga/Al2O3。
0.3g of synthesized 0.1Pt5Ga/Al was weighed2O3The catalyst was put into a 100 mL round-bottom flask, and 40 mL of absolute ethanol and 2 mL of concentrated aqueous ammonia were added thereto, and the mixture was sonicated for 30 Min and recorded as solution C. 0.1166 g of TEOS was weighed out and dissolved in 20mL of absolute ethanol and recorded as solution D. Solution D was drawn into a syringe and added to the round bottom flask containing solution A using a micro syringe pump at a dropping rate of 3 mL/min, at which time the stirring was vigorous at 1200 revolutions per minute. Stirring is continued for 15h after the dripping is finished. The solution was then centrifuged at 4000 rpm and placed in an oven 80oAnd C, 12 h. After grinding, the mixture is treated with 1 in airoThe temperature rise rate of C/Min is increased to 350oC, maintaining for 4h, and obtaining the content Pt: 0.1 percent; ga: 5 percent; al: 43.6 percent(ii) a Si: 5 percent; o: 46.3% catalyst, reported as 5% Si @0.1Pt5Ga/Al2O3. Granulating into 40-60 mesh.
In a fixed bed, 0.1 g (40-60 mesh) of 5% Si @0.1Pt5Ga/Al2O3The catalyst is evenly mixed with 0.5 g (40-60 meshes) of quartz sand and then is filled into the middle section of a fixed bed quartz tube with the inner diameter of 6 mm. Under pure argon (20 mL. min)-1) Under the condition of raising the temperature of the reactor bed to 450 deg.CoC and maintaining for 2h, then introducing propane: hydrogen = 1: 1 (space velocity of 1.2 h)-1) Catalytic evaluation was performed. The conversion rate of propane is 22.3 percent, the selectivity of propylene is 93.0 percent, and the inactivation rate constant is 0.016 h-1。
Example 6:
commercial gamma-Al2O3In the air by 5oThe temperature rise rate of C/Min is increased to 700oAnd C, maintaining for 2 hours, and vacuumizing for 2 hours by using a vacuum oven under the pressure of 0.01MPa for later use. Firstly weighing 2g of calcined gamma-Al2O3Put in a 50 mL beaker, and 0.0040g of Pt (NH) was weighed3)4(NO3)2，0.5868gGa(NO3)3·xH2O was dissolved in 2.5 mL of water to prepare a mixed salt aqueous solution of Pt and Ga, which was designated as solution A. Dropwise adding the solution A into a beaker by using a 100 uL liquid transfer gun, stirring by using a glass rod while dropwise adding, continuously stirring for 1h after the dropwise adding is completed, sealing the beaker by using a sealing film, standing for 3h at room temperature, and putting into an oven 80oAnd C, 12 h. Drying, grinding, and air drying at a speed of 5%oThe temperature rise rate of C/Min is increased to 500oC, maintaining for 3 hours, and recording the obtained medicine as 0.1Pt8Ga/Al2O3。
0.3g of synthesized 0.1Pt8Ga/Al was weighed2O3The catalyst was put into a 100 mL round-bottom flask, and 40 mL of absolute ethanol and 1mL of concentrated aqueous ammonia were added thereto, and the mixture was sonicated for 30 Min and recorded as solution C. 0.1166 g of TEOS was weighed out and dissolved in 20mL of absolute ethanol and recorded as solution D. Solution D was drawn into a syringe and added to the round bottom flask containing solution A using a micro syringe pump at a dropping rate of 3 mL/min, at which time the stirring was vigorous at 1200 revolutions per minute. Stirring is continued for 15h after the dripping is finished. The solution is then washed with 4Centrifuging at 000 rpm, placing in oven 80oAnd C, 12 h. After grinding, the mixture is treated with 1 in airoThe temperature rise rate of C/Min is increased to 350oC, maintaining for 4h, and obtaining the content Pt: 0.1 percent; ga: 8 percent; al: 41.5 percent; si: 5 percent; o: 45.4% catalyst, reported as 0.5% Si @0.1Pt8Ga/Al2O3. Granulating into 40-60 mesh.
In a fixed bed, 0.1 g (40-60 mesh) of 0.5% Si @0.1Pt8Ga/Al2O3The catalyst is evenly mixed with 0.5 g (40-60 meshes) of quartz sand and then is filled into the middle section of a fixed bed quartz tube with the inner diameter of 6 mm. Under pure argon (20 mL. min)-1) Under the condition of raising the temperature of the reactor bed to 450 deg.CoC, maintaining for 1h, and then introducing propane: hydrogen = 1: 1 (space velocity of 1.2 h)-1) Catalytic evaluation was performed. The conversion rate of propane is 22.8 percent, the selectivity of propylene is 90.8 percent, and the inactivation rate constant is 0.019 h-1。
Example 7:
commercial gamma-Al2O3In the air by 5oThe temperature rise rate of C/Min is increased to 700oAnd C, maintaining for 2 hours, and vacuumizing for 2 hours by using a vacuum oven under the pressure of 0.01MPa for later use. Firstly weighing 2g of calcined gamma-Al2O3Put in a 50 mL beaker, and 0.0040g of Pt (NH) was weighed3)4(NO3)2，7.33gGa(NO3)3·xH2O was dissolved in 250 mL of water to prepare a mixed salt aqueous solution of Pt and Ga, which was designated as solution A. Taking 2.5 mL of solution A, dropwise adding the solution A into a beaker by using a 100 uL liquid transfer gun, stirring by using a glass rod while dropwise adding, continuously stirring for 1h after completely dropwise adding, sealing the beaker by using a sealing film, standing for 3h at room temperature, and putting the beaker into an oven 80%oAnd C, 12 h. Drying, grinding, and air drying at a speed of 5%oThe temperature rise rate of C/Min is increased to 500oC, maintaining for 3 hours, and recording the obtained medicine as 0.001Pt1Ga/Al2O3。
0.3g of synthesized 0.001Pt1Ga/Al was weighed2O3The catalyst was put into a 100 mL round-bottom flask, and 40 mL of absolute ethanol and 1mL of concentrated aqueous ammonia were added thereto, and the mixture was sonicated for 30 Min and recorded as solution C. Then 0.0116g of TEOS was weighed and dissolved in 20mL of absolute ethanolAnd is referred to as D solution. Solution D was drawn into a syringe and added to the round bottom flask containing solution A using a micro syringe pump at a 5 mL/min drop rate with vigorous stirring at 1200 rpm. Stirring is continued for 10h after the dripping is finished. The solution was then centrifuged at 4000 rpm and placed in an oven 80oAnd C, 12 h. After grinding, the mixture is treated with 1 in airoThe temperature rise rate of C/Min is increased to 350oC, maintaining for 2h, obtaining the content Pt: 0.001 percent; ga: 1 percent; al: 51.635 percent; si: 0.5 percent; o: 46.864% catalyst, reported as 0.5% Si @0.001Pt1Ga/Al2O3. Granulating into 40-60 mesh.
In a fixed bed, 0.1 g (40-60 mesh) of 0.5% Si @0.001Pt1Ga/Al2O3The catalyst is evenly mixed with 0.5 g (40-60 meshes) of quartz sand and then is filled into the middle section of a fixed bed quartz tube with the inner diameter of 6 mm. Under pure argon (20 mL. min)-1) Under the condition of raising the temperature of the reactor bed to 450 deg.CoC and maintaining for 2h, then introducing propane: hydrogen = 1: 1 (space velocity of 1.2 h)-1) Catalytic evaluation was performed. Propane conversion rate 12.3%, propylene selectivity 84.7%, deactivation rate constant 0.087 h-1。
Example 8:
commercial gamma-Al2O3In the air by 5oThe temperature rise rate of C/Min is increased to 700oAnd C, maintaining for 2 hours, and vacuumizing for 2 hours by using a vacuum oven under the pressure of 0.01MPa for later use. Firstly weighing 2g of calcined gamma-Al2O3Put in a 50 mL beaker, and 0.0040g of Pt (NH) was weighed3)4(NO3)2，0.3668gGa(NO3)3·xH2O was dissolved in 2.5 mL of water to prepare a mixed salt aqueous solution of Pt and Ga, which was designated as solution A. Dropwise adding the solution A into a beaker by using a 100 uL liquid transfer gun, stirring by using a glass rod while dropwise adding, continuously stirring for 1h after the dropwise adding is completed, sealing the beaker by using a sealing film, standing for 3h at room temperature, and putting into an oven 80oAnd C, 12 h. Drying, grinding, and air drying at a speed of 5%oThe temperature rise rate of C/Min is increased to 500oC, maintaining for 3 hours, and recording the obtained medicine as 0.1Pt5Ga/Al2O3。
0.3g of synthesized 0.1Pt5Ga/Al was weighed2O3The catalyst was put into a 100 mL round-bottom flask, and 40 mL of absolute ethanol and 2 mL of concentrated aqueous ammonia were added thereto, and the mixture was sonicated for 30 Min and recorded as solution C. 0.2332 g of TEOS was weighed out and dissolved in 20mL of absolute ethanol and recorded as solution D. Solution D was drawn into a syringe and added to the round bottom flask containing solution A using a micro syringe pump at a 2 mL/min drop rate with vigorous stirring at 1200 rpm. Stirring is continued for 18h after the dripping is finished. The solution was then centrifuged at 4000 rpm and placed in an oven 80oAnd C, 12 h. After grinding, the mixture is treated with 2 degrees of stirring in airoThe temperature rise rate of C/Min is increased to 400oC, maintaining for 3 hours, and obtaining the content Pt: 0.1 percent; ga: 5 percent; al: 37.9 percent; si: 10 percent; o: 47.0% catalyst, reported as 10% Si @0.1Pt5Ga/Al2O3. Granulating into 40-60 mesh.
In a fixed bed, 0.1 g (40-60 mesh) of 10% Si @0.1Pt5Ga/Al2O3The catalyst is evenly mixed with 0.5 g (40-60 meshes) of quartz sand and then is filled into the middle section of a fixed bed quartz tube with the inner diameter of 6 mm. Under pure argon (20 mL. min)-1) Under the condition of raising the temperature of the reactor bed to 450 deg.CoC, maintaining for 1h, and then introducing propane: hydrogen = 1: 1 (space velocity of 1.2 h)-1) Catalytic evaluation was performed. Propane conversion 21.3%, propylene selectivity 91.6%, deactivation rate constant 0.025 h-1。
Example 9:
commercial gamma-Al2O3In the air by 5oThe temperature rise rate of C/Min is increased to 700oAnd C, maintaining for 2 hours, and vacuumizing for 2 hours by using a vacuum oven under the pressure of 0.01MPa for later use. Firstly weighing 2g of calcined gamma-Al2O3Put in a 50 mL beaker, and 0.0040g of Pt (NH) was weighed3)4(NO3)2，0.3668gGa(NO3)3·xH2O was dissolved in 2.5 mL of water to prepare a mixed salt aqueous solution of Pt and Ga, which was designated as solution A. Dropwise adding the solution A into a beaker by using a 100 uL liquid transfer gun, stirring by using a glass rod while dropwise adding, continuously stirring for 1h after the dropwise adding is completed, sealing the beaker by using a sealing film, standing for 3h at room temperature, and putting into an oven 80oAnd C, 12 h. Drying, grinding, and air drying at a speed of 5%oThe temperature rise rate of C/Min is increased to 500oC, maintaining for 3 hours, and recording the obtained medicine as 0.1Pt5Ga/Al2O3。
0.3g of synthesized 0.1Pt5Ga/Al was weighed2O3The catalyst was put into a 100 mL round-bottom flask, and 40 mL of absolute ethanol and 2 mL of concentrated aqueous ammonia were added thereto, and the mixture was sonicated for 30 Min and recorded as solution C. 0.4664g of TEOS was weighed out and dissolved in 20mL of absolute ethanol and recorded as solution D. Solution D was drawn into a syringe and added to the round bottom flask containing solution A using a micro syringe pump at a 1 mL/min drop rate with vigorous stirring at 1200 rpm. Stirring is continued for 20h after the dripping is finished. The solution was then centrifuged at 4000 rpm and placed in an oven 80oAnd C, 12 h. After grinding, the mixture is treated with 2 degrees of stirring in airoThe temperature rise rate of C/Min is increased to 400oC, maintaining for 4h, and obtaining the content Pt: 0.1 percent; ga: 5 percent; al: 26.6 percent; si: 20 percent; o: 48.3% catalyst, reported as 20% Si @0.1Pt5Ga/Al2O3. Granulating into 40-60 mesh.
In a fixed bed, 0.1 g (40-60 mesh) of 20% Si @0.1Pt5Ga/Al2O3The catalyst is evenly mixed with 0.5 g (40-60 meshes) of quartz sand and then is filled into the middle section of a fixed bed quartz tube with the inner diameter of 6 mm. Under pure argon (20 mL. min)-1) Under the condition of raising the temperature of the reactor bed to 450 deg.CoC, maintaining for 1h, and then introducing propane: hydrogen = 1: 1 (space velocity of 1.2 h)-1) Catalytic evaluation was performed. The conversion rate of propane is 20.0 percent, the selectivity of propylene is 89.4 percent, and the inactivation rate constant is 0.058 h-1。
Example 10:
commercial gamma-Al2O3In the air by 5oThe temperature rise rate of C/Min is increased to 700oAnd C, maintaining for 2 hours, and vacuumizing for 2 hours by using a vacuum oven under the pressure of 0.01MPa for later use. Firstly weighing 2g of calcined gamma-Al2O3Put in a 50 mL beaker, and 0.0040g of Pt (NH) was weighed3)4(NO3)2，7.33gGa(NO3)3·xH2O was dissolved in 250 mL of water to prepare a mixed salt aqueous solution of Pt and Ga, which was designated as solution A.Taking 2.5 mL of solution A, dropwise adding the solution A into a beaker by using a 100 uL liquid transfer gun, stirring by using a glass rod while dropwise adding, continuously stirring for 1h after completely dropwise adding, sealing the beaker by using a sealing film, standing for 3h at room temperature, and putting the beaker into an oven 80%oAnd C, 12 h. Drying, grinding, and air drying at a speed of 5%oThe temperature rise rate of C/Min is increased to 500oC, maintaining for 3 hours, and recording the obtained medicine as 0.001Pt1Ga/Al2O3。
0.3g of synthesized 0.001Pt1Ga/Al was weighed2O3The catalyst was put into a 100 mL round-bottom flask, and 40 mL of absolute ethanol and 2 mL of concentrated aqueous ammonia were added thereto, and the mixture was sonicated for 30 Min and recorded as solution C. 0.4664g of TEOS was weighed out and dissolved in 20mL of absolute ethanol and recorded as solution D. Solution D was drawn into a syringe and added to the round bottom flask containing solution A using a micro syringe pump at a 1 mL/min drop rate with vigorous stirring at 1200 rpm. Stirring is continued for 20h after the dripping is finished. The solution was then centrifuged at 4000 rpm and placed in an oven 80oAnd C, 12 h. After grinding, the mixture is treated with 2 degrees of stirring in airoThe temperature rise rate of C/Min is increased to 400oC, maintaining for 4h, and obtaining the content Pt: 0.001 percent; ga: 1 percent; al: 29.524%%; si: 20%%; o: 49.475% catalyst, noted 20% Si @0.001Pt1Ga/Al2O3. Granulating into 40-60 mesh.
In a fixed bed, 0.1 g (40-60 mesh) of 20% Si @0.001Pt1Ga/Al2O3The catalyst is evenly mixed with 0.5 g (40-60 meshes) of quartz sand and then is filled into the middle section of a fixed bed quartz tube with the inner diameter of 6 mm. Under pure argon (20 mL. min)-1) Under the condition of raising the temperature of the reactor bed to 450 deg.CoC, maintaining for 1h, and then introducing propane: hydrogen = 1: 1 (space velocity of 1.2 h)-1) Catalytic evaluation was performed. 4.6 percent of propane conversion rate, 89.2 percent of propylene selectivity and 0.068 h of inactivation rate constant-1。
Example 11:
commercial gamma-Al2O3In the air with 1oThe temperature rise rate of C/Min is increased to 700oAnd C, maintaining for 3 hours, and vacuumizing for 2 hours in a vacuum oven under the pressure of 0.01MPa for later use. Firstly weighing 2g of calcined gamma-Al2O3Put in a 50 mL beaker, and 0.0040g of Pt (NH) was weighed3)4(NO3)2，0.7336gGa(NO3)3·xH2O was dissolved in 2.5 mL of water to prepare a mixed salt aqueous solution of Pt and Ga, which was designated as solution A. Dropwise adding the solution A into a beaker by using a 100 uL liquid transfer gun, stirring by using a glass rod while dropwise adding, continuously stirring for 1h after the dropwise adding is completed, sealing the beaker by using a sealing film, standing for 3h at room temperature, and putting into an oven 80oAnd C, 12 h. Drying, grinding, and air drying at a speed of 5%oThe temperature rise rate of C/Min is increased to 500oC, maintaining for 3 hours, and recording the obtained medicine as 0.1Pt10Ga/Al2O3。
0.3g of synthetic 0.1Pt10Ga/Al are weighed2O3The catalyst was put into a 100 mL round-bottom flask, and 40 mL of absolute ethanol and 1mL of concentrated aqueous ammonia were added thereto, and the mixture was sonicated for 30 Min and recorded as solution C. Then, 0.0116g of TEOS was weighed and dissolved in 20mL of absolute ethanol and the solution was designated as D solution. Solution D was drawn into a syringe and added to the round bottom flask containing solution A using a micro syringe pump at a 5 mL/min drop rate with vigorous stirring at 1200 rpm. Stirring is continued for 10h after the dripping is finished. The solution was then centrifuged at 4000 rpm and placed in an oven 80oAnd C, 12 h. After grinding, the mixture is treated with 1 in airoThe temperature rise rate of C/Min is increased to 350oC, maintaining for 2h, obtaining the content Pt: 0.1 percent; ga: 10 percent; al: 45.2 percent; si: 0.5 percent; o: 44.2% catalyst, reported as 0.5% Si @0.1Pt10Ga/Al2O3. Granulating into 40-60 mesh.
In a fixed bed, 0.1 g (40-60 mesh) of 0.5% Si @0.1Pt10Ga/Al2O3The catalyst is evenly mixed with 0.5 g (40-60 meshes) of quartz sand and then is filled into the middle section of a fixed bed quartz tube with the inner diameter of 6 mm. Under pure argon (20 mL. min)-1) Under the condition of raising the temperature of the reactor bed to 450 deg.CoC, maintaining for 1h, and then introducing propane: hydrogen = 1: 1 (space velocity 3 h)-1) Catalytic evaluation was performed. The conversion rate of propane is 18.7 percent, the selectivity of propylene is 88.3 percent, and the inactivation rate constant is 0.023 h-1。
Example 12:
commercial gamma-Al2O3In the air with 1oThe temperature rise rate of C/Min is increased to 700oAnd C, maintaining for 3 hours, and vacuumizing for 2 hours in a vacuum oven under the pressure of 0.01MPa for later use. Firstly weighing 2g of calcined gamma-Al2O3Put in a 50 mL beaker, and 0.0040g of Pt (NH) was weighed3)4(NO3)2，0.7336gGa(NO3)3·xH2O was dissolved in 2.5 mL of water to prepare a mixed salt aqueous solution of Pt and Ga, which was designated as solution A. Dropwise adding the solution A into a beaker by using a 100 uL liquid transfer gun, stirring by using a glass rod while dropwise adding, continuously stirring for 1h after the dropwise adding is completed, sealing the beaker by using a sealing film, standing for 3h at room temperature, and putting into an oven 80oAnd C, 12 h. Drying, grinding, and air drying at a speed of 5%oThe temperature rise rate of C/Min is increased to 500oC, maintaining for 3 hours, and recording the obtained medicine as 0.1Pt10Ga/Al2O3。
0.3g of synthetic 0.1Pt10Ga/Al are weighed2O3The catalyst was put into a 100 mL round-bottom flask, and 40 mL of absolute ethanol and 1mL of concentrated aqueous ammonia were added thereto, and the mixture was sonicated for 30 Min and recorded as solution C. 0.0583 g of TEOS was weighed out and dissolved in 20mL of absolute ethanol and recorded as solution D. Solution D was drawn into a syringe and added to the round bottom flask containing solution A using a micro syringe pump at a 4 mL/min drop rate with vigorous stirring at 1200 rpm. Stirring is continued for 12h after the dripping is finished. The solution was then centrifuged at 4000 rpm and placed in an oven 80oAnd C, 12 h. After grinding, the mixture is treated with 1 in airoThe temperature rise rate of C/Min is increased to 350oC, maintaining for 3 hours, and obtaining the content Pt: 0.1 percent; ga: 10 percent; al: 42.9 percent; si: 2.5 percent; o: 44.5% catalyst, reported as 2.5% Si @0.1Pt10Ga/Al2O3. Granulating into 40-60 mesh.
In a fixed bed, 0.1 g (40-60 mesh) of 2.5% Si @0.1Pt10Ga/Al2O3The catalyst is evenly mixed with 0.5 g (40-60 meshes) of quartz sand and then is filled into the middle section of a fixed bed quartz tube with the inner diameter of 6 mm. Under pure argon (20 mL. min)-1) Under the condition of raising the temperature of the reactor bed to 450 deg.CoC, maintaining for 1h, and then introducing propane: hydrogen gas= 1: 1 (space velocity 3 h)-1) Catalytic evaluation was performed. Propane conversion rate is 20.3%, propylene selectivity is 93.8%, and deactivation rate constant is 0.012 h-1。
Example 13:
commercial gamma-Al2O3In the air with 1oThe temperature rise rate of C/Min is increased to 700oAnd C, maintaining for 3 hours, and vacuumizing for 2 hours in a vacuum oven under the pressure of 0.01MPa for later use. Firstly weighing 2g of calcined gamma-Al2O3Put in a 50 mL beaker, and 0.0040g of Pt (NH) was weighed3)4(NO3)2，0.7336gGa(NO3)3·xH2O was dissolved in 2.5 mL of water to prepare a mixed salt aqueous solution of Pt and Ga, which was designated as solution A. Dropwise adding the solution A into a beaker by using a 100 uL liquid transfer gun, stirring by using a glass rod while dropwise adding, continuously stirring for 1h after the dropwise adding is completed, sealing the beaker by using a sealing film, standing for 3h at room temperature, and putting into an oven 80oAnd C, 12 h. Drying, grinding, and air drying at a speed of 5%oThe temperature rise rate of C/Min is increased to 500oC, maintaining for 3 hours, and recording the obtained medicine as 0.1Pt10Ga/Al2O3。
0.3g of synthetic 0.1Pt10Ga/Al are weighed2O3The catalyst was put into a 100 mL round-bottom flask, and 40 mL of absolute ethanol and 2 mL of concentrated aqueous ammonia were added thereto, and the mixture was sonicated for 30 Min and recorded as solution C. 0.1166 g of TEOS was weighed out and dissolved in 20mL of absolute ethanol and recorded as solution D. Solution D was drawn into a syringe and added to the round bottom flask containing solution A using a micro syringe pump at a dropping rate of 3 mL/min, at which time the stirring was vigorous at 1200 revolutions per minute. Stirring is continued for 15h after the dripping is finished. The solution was then centrifuged at 4000 rpm and placed in an oven 80oAnd C, 12 h. After grinding, the mixture is treated with 1 in airoThe temperature rise rate of C/Min is increased to 350oC, maintaining for 4h, and obtaining the content Pt: 0.1 percent; ga: 10 percent; al: 40.1 percent; si: 5 percent; o: 44.8% catalyst, reported as 5% Si @0.1Pt10Ga/Al2O3. Granulating into 40-60 mesh.
In a fixed bed, 0.1 g (40-60 mesh) of 5% Si @0.1Pt10Ga/Al2O3The catalyst and 0.5 g (40-60 meshes) of quartz sand are mixedAfter being evenly mixed, the mixture is filled into the middle section of a quartz tube of a fixed bed with the inner diameter of 6 mm. Under pure argon (20 mL. min)-1) Under the condition of raising the temperature of the reactor bed to 450 deg.CoC, maintaining for 1h, and then introducing propane: hydrogen = 1: 1 (space velocity 3 h)-1) Catalytic evaluation was performed. Propane conversion rate is 20.5%, propylene selectivity is 91.3%, and deactivation rate constant is 0.026 h-1。
Example 14:
commercial gamma-Al2O3In the air with 1oThe temperature rise rate of C/Min is increased to 700oAnd C, maintaining for 3 hours, and vacuumizing for 2 hours in a vacuum oven under the pressure of 0.01MPa for later use. Firstly weighing 2g of calcined gamma-Al2O3Put in a 50 mL beaker, and 0.0040g of Pt (NH) was weighed3)4(NO3)2，0.7336gGa(NO3)3·xH2O was dissolved in 2.5 mL of water to prepare a mixed salt aqueous solution of Pt and Ga, which was designated as solution A. Dropwise adding the solution A into a beaker by using a 100 uL liquid transfer gun, stirring by using a glass rod while dropwise adding, continuously stirring for 1h after the dropwise adding is completed, sealing the beaker by using a sealing film, standing for 3h at room temperature, and putting into an oven 80oAnd C, 12 h. Drying, grinding, and air drying at a speed of 5%oThe temperature rise rate of C/Min is increased to 500oC, maintaining for 3 hours, and recording the obtained medicine as 0.1Pt10Ga/Al2O3。
0.3g of synthetic 0.1Pt10Ga/Al are weighed2O3The catalyst was put into a 100 mL round-bottom flask, and 40 mL of absolute ethanol and 2 mL of concentrated aqueous ammonia were added thereto, and the mixture was sonicated for 30 Min and recorded as solution C. 0.2332 g of TEOS was weighed out and dissolved in 20mL of absolute ethanol and recorded as solution D. Solution D was drawn into a syringe and added to the round bottom flask containing solution A using a micro syringe pump at a 2 mL/min drop rate with vigorous stirring at 1200 rpm. Stirring is continued for 18h after the dripping is finished. The solution was then centrifuged at 4000 rpm and placed in an oven 80oAnd C, 12 h. After grinding, the mixture is treated with 2 degrees of stirring in airoThe temperature rise rate of C/Min is increased to 400oC, maintaining for 3 hours, and obtaining the content Pt: 0.1 percent; ga: 10 percent; al: 34.4 percent; si: 10 percent; o: 45.5% catalyst, reported as 10% Si @0.1Pt10Ga/Al2O3. Granulating into 40-60 mesh.
In a fixed bed, 0.1 g (40-60 mesh) of 10% Si @0.1Pt10Ga/Al2O3The catalyst is evenly mixed with 0.5 g (40-60 meshes) of quartz sand and then is filled into the middle section of a fixed bed quartz tube with the inner diameter of 6 mm. Under pure argon (20 mL. min)-1) Under the condition of raising the temperature of the reactor bed to 450 deg.CoC, maintaining for 1h, and then introducing propane: hydrogen = 1: 1 (space velocity 3 h)-1) Catalytic evaluation was performed. Propane conversion 19.7%, propylene selectivity 88.9%, deactivation rate constant 0.041 h-1。
Example 15:
commercial gamma-Al2O3In the air with 1oThe temperature rise rate of C/Min is increased to 700oAnd C, maintaining for 3 hours, and vacuumizing for 2 hours in a vacuum oven under the pressure of 0.01MPa for later use. Firstly weighing 2g of calcined gamma-Al2O3Put in a 50 mL beaker, and 0.0040g of Pt (NH) was weighed3)4(NO3)2，0.7336gGa(NO3)3·xH2O was dissolved in 2.5 mL of water to prepare a mixed salt aqueous solution of Pt and Ga, which was designated as solution A. Dropwise adding the solution A into a beaker by using a 100 uL liquid transfer gun, stirring by using a glass rod while dropwise adding, continuously stirring for 1h after the dropwise adding is completed, sealing the beaker by using a sealing film, standing for 3h at room temperature, and putting into an oven 80oAnd C, 12 h. Drying, grinding, and air drying at a speed of 5%oThe temperature rise rate of C/Min is increased to 500oC, maintaining for 3 hours, and recording the obtained medicine as 0.1Pt10Ga/Al2O3。
0.3g of synthetic 0.1Pt10Ga/Al are weighed2O3The catalyst was put into a 100 mL round-bottom flask, and 40 mL of absolute ethanol and 2 mL of concentrated aqueous ammonia were added thereto, and the mixture was sonicated for 30 Min and recorded as solution C. 0.4664g of TEOS was weighed out and dissolved in 20mL of absolute ethanol and recorded as solution D. Solution D was drawn into a syringe and added to the round bottom flask containing solution A using a micro syringe pump at a 1 mL/min drop rate with vigorous stirring at 1200 rpm. Stirring is continued for 20h after the dripping is finished. The solution was then centrifuged at 4000 rpm and placed in an oven 80oAnd C, 12 h. GrindingThen in air by 2oThe temperature rise rate of C/Min is increased to 400oC, maintaining for 4h, and obtaining the content Pt: 0.1 percent; ga: 10 percent; al: 23.1 percent; si: 20 percent; o: 46.8% catalyst, reported as 20% Si @0.1Pt10Ga/Al2O3. Granulating into 40-60 mesh.
In a fixed bed, 0.1 g (40-60 mesh) of 20% Si @0.1Pt10Ga/Al2O3The catalyst is evenly mixed with 0.5 g (40-60 meshes) of quartz sand and then is filled into the middle section of a fixed bed quartz tube with the inner diameter of 6 mm. Under pure argon (20 mL. min)-1) Under the condition of raising the temperature of the reactor bed to 450 deg.CoC, maintaining for 1h, and then introducing propane: hydrogen = 1: 1 (space velocity 3 h)-1) Catalytic evaluation was performed. The conversion rate of propane is 17.9 percent, the selectivity of propylene is 79.8 percent, and the inactivation rate constant is 0.053 h-1。
FIG. 1 (a-d) 2.5% Si @0.1Pt5Ga/Al after reaction2O3Spherical aberration electron micrographs of the catalyst. Fig. a shows that the Ga metal clusters are uniformly dispersed on the surface of the catalyst by a spherical aberration electron microscope dark field graph; according to the atomic number contrast mechanism, isolated bright points in the clusters are Pt active sites, and Ga species are darker around the bright points; and d is a spherical aberration electron microscope bright field image, according to the atomic number contrast mechanism, isolated dark points in the cluster are Pt active sites, and the dark points around the bright points are Ga species.
FIG. 2 (a-c) 0.1Pt5Ga/Al after reaction2O32.5% Si @0.1Pt5Ga/Al after reaction of catalyst and (d-f)2O3Spherical aberration electron micrographs of the catalyst. FIG. (a-c) shows 0.1Pt5Ga/Al after reaction2O3The PtGa clusters of the catalyst are significantly agglomerated, and the graphs (d-f) show 2.5% Si @0.1Pt5Ga/Al after the reaction2O3The catalyst retained highly dispersed PtGa clusters. The comparison shows that highly dispersed Pt sites are anchored by Ga while being effectively restricted from migration by the silica shell.
FIG. 3 (a-b) 0.1Pt5Ga/Al after reaction2O32.5% Si @0.1Pt5Ga/Al after reaction of catalyst and (c-d)2O3Electron microscopy of the catalyst, (a-b) dotted micro Al2O3Boundary, (c-d) dotted line is epitaxialA long silica shell. The silicon dioxide shell layer grows at 0.1Pt5Ga/Al2O3The surface of the catalyst.
FIG. 4 (a-f) 2.5% Si @0.1Pt5Ga/Al after reaction2O3The spherical aberration electron microscope picture of the catalyst shows that the elements Si, Ga, Al and Pt are uniformly dispersed on the surface, and the silicon dioxide shell layer is tightly wrapped on the PtGa/Al2O3The surface of the catalyst.
Figure 5 (a-b) DRIFT-CO plot of the catalyst after reaction, illustrating that the Pt sites are still present as highly dispersed Pt sites after reaction and the peaks are shifted due to the interaction of the silica shell and the Pt sites, illustrating that the electronic properties of the Pt sites are modulated.
The catalysts in the above five figures are all catalysts after reaction, which illustrates that highly dispersed Pt sites are anchored on highly dispersed Ga clusters and silicon dioxide shell layers are tightly wrapped on PtGa/Al2O3The surface also shows that the silica shell layer can well limit the migration of active sites in the reaction process, thereby playing a role in resisting sintering.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (6)
1. A catalyst for preparing propylene by direct dehydrogenation of propane is characterized in that: the components by mass percent are as follows: pt: 0.001 to 0.1%, Ga: 1% -10%, Al: 23.100% -51.635%, Si: 0.5-20%, O: 44.200-49.475%.
2. A method of preparing the catalyst of claim 1, wherein: the catalyst is prepared by adopting an impregnation-cladding method, and the method comprises the following specific steps:
1) commercial gamma-Al2O3Raising the temperature to 700 ℃ at a heating rate of 1-5 ℃/min in the air, maintaining the temperature for 2-3 h, and vacuumizing for 2h under the low pressure of 0.01MPa to obtain Al2O3；
2) Ga (NO)3)3·xH2O and Pt(NH3)4(NO3)2Dissolved in water and added dropwise to Al2O3Standing for 2-3 h, drying, grinding and calcining to obtain PtGa/Al2O3；
3) PtGa/Al is mixed2O3Adding the mixture into a mixed solution of ethanol and ammonia water, and performing ultrasonic treatment to obtain a suspension;
4) dropwise adding the mixed solution of ethyl orthosilicate and ethanol into the suspension at the speed of 1-5 mL/h, stirring for 10-20 h, centrifuging, drying at 353K, grinding, and calcining in air at 623-673K for 2-4 h to obtain the catalyst for preparing propylene by direct propane dehydrogenation.
3. The method of claim 2, wherein: step 2), raw materials in mass ratio: Pt/Ga = 0.0001 to 0.1, Pt/H2O=0.000008~0.0008，Pt/Al2O3=0.00001~0.001。
4. The method of claim 2, wherein: the volume ratio of the ethanol to the ammonia water in the step 3) is 20: 1-40: 1, PtGa/Al2O3The mass-volume ratio of the ammonia water to the ammonia water is 0.15-0.3 g: 1 mL.
5. The method of claim 2, wherein: in the step 4), the mass-volume ratio of the ethyl orthosilicate to the ethanol is 0.0116-0.4664 g: 20 mL; the temperature rise rate in the calcining process is 1-2 ℃ per minute-1。
6. Use of a catalyst according to claim 1, wherein: the catalyst is applied to direct dehydrogenation of propane to prepare propylene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110963865.8A CN113559853A (en) | 2021-08-21 | 2021-08-21 | Catalyst for preparing propylene by direct dehydrogenation of propane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110963865.8A CN113559853A (en) | 2021-08-21 | 2021-08-21 | Catalyst for preparing propylene by direct dehydrogenation of propane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113559853A true CN113559853A (en) | 2021-10-29 |
Family
ID=78172398
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110963865.8A Pending CN113559853A (en) | 2021-08-21 | 2021-08-21 | Catalyst for preparing propylene by direct dehydrogenation of propane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113559853A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114618476A (en) * | 2022-02-16 | 2022-06-14 | 中国科学院大连化学物理研究所 | Monoatomic platinum-based catalyst, and preparation method and application thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86104031A (en) * | 1985-06-17 | 1987-02-04 | 斯纳姆普罗吉蒂公司 | The method for preparing the C3-C5 paraffin hydrocarbon dehydrogenation catalyst |
| CN1098399A (en) * | 1993-08-06 | 1995-02-08 | 斯南普罗吉蒂联合股票公司 | The method for preparing light alkene by dehydrogenation of corresponding paraffins |
| US20040259727A1 (en) * | 2001-12-20 | 2004-12-23 | Andrea Bartolini | Catalytic composition for the dehydrogenation of alkylaromatic hydrocarbons |
| CN104226307A (en) * | 2013-06-09 | 2014-12-24 | 上海鼎际得工业技术有限公司 | Platinum-based catalyst, preparation method and application thereof, and preparation method for propylene |
| CN106492824A (en) * | 2016-08-30 | 2017-03-15 | 中国科学院山西煤炭化学研究所 | A kind of methyl hydride combustion catalyst, preparation method and application |
| CN106669666A (en) * | 2015-11-05 | 2017-05-17 | 中国石油化工股份有限公司大连石油化工研究院 | Light-alkane dehydrogenation-to-olefins catalyst and preparation method thereof |
| CN110548505A (en) * | 2019-08-20 | 2019-12-10 | 青岛科技大学 | Core-shell type catalyst, synthesis method thereof and method for preparing gamma-valerolactone by catalyzing levulinic acid by core-shell type catalyst |
| CN112135687A (en) * | 2018-05-22 | 2020-12-25 | 托普索公司 | Silica promoters for platinum and gallium based propane dehydrogenation catalysts |
| CN112221493A (en) * | 2020-10-13 | 2021-01-15 | 天津大学 | Noble metal modified gallium oxide catalyst and preparation method and application thereof |
| CN113042098A (en) * | 2021-03-24 | 2021-06-29 | 中国科学技术大学 | PtIn @ MFI catalyst and preparation method and application thereof |
-
2021
- 2021-08-21 CN CN202110963865.8A patent/CN113559853A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86104031A (en) * | 1985-06-17 | 1987-02-04 | 斯纳姆普罗吉蒂公司 | The method for preparing the C3-C5 paraffin hydrocarbon dehydrogenation catalyst |
| CN1098399A (en) * | 1993-08-06 | 1995-02-08 | 斯南普罗吉蒂联合股票公司 | The method for preparing light alkene by dehydrogenation of corresponding paraffins |
| US20040259727A1 (en) * | 2001-12-20 | 2004-12-23 | Andrea Bartolini | Catalytic composition for the dehydrogenation of alkylaromatic hydrocarbons |
| CN104226307A (en) * | 2013-06-09 | 2014-12-24 | 上海鼎际得工业技术有限公司 | Platinum-based catalyst, preparation method and application thereof, and preparation method for propylene |
| CN106669666A (en) * | 2015-11-05 | 2017-05-17 | 中国石油化工股份有限公司大连石油化工研究院 | Light-alkane dehydrogenation-to-olefins catalyst and preparation method thereof |
| CN106492824A (en) * | 2016-08-30 | 2017-03-15 | 中国科学院山西煤炭化学研究所 | A kind of methyl hydride combustion catalyst, preparation method and application |
| CN112135687A (en) * | 2018-05-22 | 2020-12-25 | 托普索公司 | Silica promoters for platinum and gallium based propane dehydrogenation catalysts |
| CN110548505A (en) * | 2019-08-20 | 2019-12-10 | 青岛科技大学 | Core-shell type catalyst, synthesis method thereof and method for preparing gamma-valerolactone by catalyzing levulinic acid by core-shell type catalyst |
| CN112221493A (en) * | 2020-10-13 | 2021-01-15 | 天津大学 | Noble metal modified gallium oxide catalyst and preparation method and application thereof |
| CN113042098A (en) * | 2021-03-24 | 2021-06-29 | 中国科学技术大学 | PtIn @ MFI catalyst and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| （美）P.H.爱梅特主编: "《催化基本原理 第1部分》", 30 November 1965, 上海科学技术出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114618476A (en) * | 2022-02-16 | 2022-06-14 | 中国科学院大连化学物理研究所 | Monoatomic platinum-based catalyst, and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110479248A (en) | A kind of preparation method of metal oxide supported monatomic catalyst | |
| KR20160147872A (en) | Cobalt-based fischer-tropsch synthesis catalyst coated with mesoporous materials and preparation method therefor | |
| CN114570415B (en) | Pt @ hierarchical pore zeolite catalyst for preparing propylene by propane dehydrogenation and preparation method thereof | |
| CN110479251B (en) | Macroporous-mesoporous supported palladium catalyst, and preparation method and application thereof | |
| CN112642448B (en) | Preparation method and application of copper catalyst for acetylene hydrochlorination | |
| CN115041188B (en) | Modification method of supported platinum-copper alloy catalyst and application of supported platinum-copper alloy catalyst in propylene preparation by propane dehydrogenation | |
| CN111514889A (en) | Ruthenium-based carbon dioxide hydromethanation catalyst and preparation method thereof | |
| CN111111666B (en) | Cobalt-based Fischer-Tropsch catalyst and preparation method and application thereof | |
| CN113559853A (en) | Catalyst for preparing propylene by direct dehydrogenation of propane | |
| CN111558392A (en) | Catalyst for dry reforming reaction of methane and carbon dioxide and preparation method and application thereof | |
| CN112604711A (en) | Preparation method and application of novel titanium silicalite molecular sieve | |
| CN109876804A (en) | A kind of titanium dioxide loaded ruthenium catalyst and preparation method thereof adding hydrogen cyclohexene for benzene selective | |
| CN112316945B (en) | Heterogeneous nano composite material, preparation method thereof, nitro reduction catalyst and application | |
| CN111437813B (en) | Isobutane dehydrogenation catalyst and preparation method and application thereof | |
| CN115400785B (en) | Core-shell structure catalyst for propane aromatization and preparation method and application thereof | |
| CN114602442B (en) | Preparation method of low-carbon alkane dehydrogenation catalyst for moving bed | |
| CN116618055A (en) | Carbon-modified nickel-based catalyst and application thereof in catalytic hydrogenation of lignin derivatives | |
| CN116474780A (en) | For direct CO 2 Catalyst for preparing ethanol by hydrogenation, and preparation method and application thereof | |
| CN114950439A (en) | Efficient water photolysis hydrogen production MOF TiO 2 -NiO material and preparation method and application thereof | |
| CN109926046B (en) | Catalyst for hydrogen production by hydroiodic acid decomposition and preparation method thereof | |
| CN112473721A (en) | PdAg/NH2-MCM-41 catalyst, preparation method and application thereof | |
| CN103566942B (en) | A kind of selective hydrogenation catalyst | |
| CN115770562B (en) | Reticular titanium dioxide photocatalyst material, preparation method, application and equipment thereof | |
| CN116786153A (en) | Preparation method and application of methane dry reforming nickel-based molecular sieve catalyst | |
| CN116618057B (en) | Supported nickel monoatomic catalyst and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |