CN116983980A - High-dispersion platinum-supported oxygen-defect zinc oxide photocatalyst, preparation method and application thereof in preparation of propylene by photocatalytic propane dehydrogenation - Google Patents
High-dispersion platinum-supported oxygen-defect zinc oxide photocatalyst, preparation method and application thereof in preparation of propylene by photocatalytic propane dehydrogenation Download PDFInfo
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- CN116983980A CN116983980A CN202310969409.3A CN202310969409A CN116983980A CN 116983980 A CN116983980 A CN 116983980A CN 202310969409 A CN202310969409 A CN 202310969409A CN 116983980 A CN116983980 A CN 116983980A
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- oxide photocatalyst
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 152
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 116
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 76
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 71
- 239000001294 propane Substances 0.000 title claims abstract description 58
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 58
- 239000006185 dispersion Substances 0.000 title claims abstract description 23
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 16
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 118
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 67
- 239000001301 oxygen Substances 0.000 claims abstract description 67
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 67
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 57
- 239000000243 solution Substances 0.000 claims abstract description 30
- 230000007547 defect Effects 0.000 claims abstract description 24
- DLINORNFHVEIFE-UHFFFAOYSA-N hydrogen peroxide;zinc Chemical compound [Zn].OO DLINORNFHVEIFE-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229940105296 zinc peroxide Drugs 0.000 claims abstract description 15
- 238000001354 calcination Methods 0.000 claims abstract description 13
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 238000007146 photocatalysis Methods 0.000 claims abstract description 9
- 239000000843 powder Substances 0.000 claims abstract description 9
- 239000002244 precipitate Substances 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 7
- 239000002243 precursor Substances 0.000 claims abstract description 7
- 150000003751 zinc Chemical class 0.000 claims abstract description 7
- 239000012266 salt solution Substances 0.000 claims abstract description 5
- 238000000227 grinding Methods 0.000 claims abstract description 4
- 230000002950 deficient Effects 0.000 claims description 40
- 238000000034 method Methods 0.000 claims description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 230000000630 rising effect Effects 0.000 claims description 6
- 239000011592 zinc chloride Substances 0.000 claims description 6
- 235000005074 zinc chloride Nutrition 0.000 claims description 6
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 claims description 5
- 238000003837 high-temperature calcination Methods 0.000 claims description 5
- 239000002105 nanoparticle Substances 0.000 claims description 5
- 239000003570 air Substances 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- -1 platinum ions Chemical class 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 238000002485 combustion reaction Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 54
- 229910000510 noble metal Inorganic materials 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 230000009849 deactivation Effects 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract 3
- 238000002791 soaking Methods 0.000 abstract 1
- 230000008569 process Effects 0.000 description 11
- 239000007789 gas Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 6
- 239000010453 quartz Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 3
- 229910001863 barium hydroxide Inorganic materials 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- 238000003775 Density Functional Theory Methods 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000001362 electron spin resonance spectrum Methods 0.000 description 2
- 238000000731 high angular annular dark-field scanning transmission electron microscopy Methods 0.000 description 2
- 238000007327 hydrogenolysis reaction Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000004227 thermal cracking Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000001016 Ostwald ripening Methods 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
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000004231 fluid catalytic cracking Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000005291 magnetic effect Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000001291 vacuum drying Methods 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
- B01J23/60—Platinum group metals with zinc, cadmium or mercury
-
- 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
-
- 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
- B01J37/0207—Pretreatment of the support
-
- 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
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
-
- 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
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C11/00—Aliphatic unsaturated hydrocarbons
- C07C11/02—Alkenes
- C07C11/06—Propene
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
Abstract
A high-dispersion platinum-supported oxygen-defect zinc oxide photocatalyst, a preparation method and application thereof in preparing propylene by catalyzing propane dehydrogenation belong to the technical field of photocatalysis. Generating white precipitate from zinc salt solution under alkaline condition and stirring, adding the white precipitate into hydrogen peroxide, stirring in an oil bath, and drying to obtain zinc peroxide powder; grinding zinc peroxide powder, calcining at high temperature to obtain an oxygen defect zinc oxide carrier, soaking in a platinum precursor solution, drying and calcining at high temperature to obtain the photocatalyst. The photocatalyst takes zinc oxide with oxygen defects as a carrier, and trace noble metal platinum as an active component, wherein the mass percentage of the noble metal platinum is 0.2% -1.0%. The catalyst of the invention shows high reaction activity which breaks through thermodynamic limitation far under the conditions of low temperature and visible light irradiation, the selectivity of propylene can reach more than 99 percent, the catalyst has better stability, no obvious deactivation after continuous operation for 100 hours, and the catalyst has high noble metal atom utilization rate.
Description
Technical Field
The invention belongs to the technical field of photocatalysis, and particularly relates to a high-dispersion platinum-supported oxygen defect zinc oxide photocatalyst, a preparation method and application thereof in preparing propylene by directly dehydrogenating photocatalytic propane at a low temperature.
Background
Propylene is one of the most important raw materials for producing various industrial products such as acrolein, polypropylene, acetone, polyacrylonitrile, propylene oxide and the like. Traditional industrial processes for propylene production are fluid catalytic cracking and steam cracking of naphtha, light diesel and other petroleum byproducts. With the rapid consumption of fossil energy, traditional propylene production processes have failed to meet the increasing propylene demand. Therefore, it is very important to develop an efficient and economical propylene production process. Over the past several decades, many processes have been developed for the efficient production of propylene, such as the direct dehydrogenation of propane to Propylene (PDH), methanol-to-olefins processes, and Fischer-Tropsch olefin processes. Among these processes, the direct dehydrogenation of propane to produce Propylene (PDH) is a direct process for producing propylene, since the development of shale gas extraction processes has produced a large amount of lower paraffins in recent years. The PDH technology is therefore considered one of the most promising propylene production processes.
The direct dehydrogenation of propane to propylene is a reversible reaction, and the chemical reaction formula is:△H 298K =124.3 KJ/mol. It can be seen that the reaction is thermodynamically equilibrium limited and highly endothermic, thus requiring higher reaction temperatures and/or lower paraffin partial pressures to achieve high conversion according to the Le Chatelier principle. In actual production, C 2 ～C 4 The dehydrogenation of low paraffins generally requires a temperature of 550 to 750 ℃ to obtain an alkane conversion of > 50% at 1 bar. In the current industrial production, propylene is prepared mainly using two processes, lummus Catofin and UOP alleflex (chem. Rev.2014,114, 10613-10653). The Lummus Catofin process uses a chromium/aluminum based photocatalyst and shows good performanceThe propylene selectivity is higher than 87% but the process is inefficient due to frequent switching to high temperature conditions and high propylene yield; in addition, chromium-based photocatalysts are not an environmentally friendly photocatalyst due to the toxicity of chromium. The UOP Oleflex process adopts a platinum/aluminum-based photocatalyst, has higher propylene selectivity and catalytic activity, and is more environment-friendly than a chromium-based photocatalyst.
Noble metal platinum has good activity for the direct dehydrogenation of propane due to its affinity for paraffinic C-H bonds. The active component of the platinum-based photocatalyst is a metal platinum cluster or platinum nanoparticle. XingGui Zhou and its colleagues have shown by Density Functional Theory (DFT) that the dehydrogenation energy barrier and desorption barrier of propylene on Pt (111) are similar, while the dehydrogenation energy barrier (0.29 eV) on Pt (211) is much lower than the desorption barrier of propylene (1.43 eV). Thus, the main problem with platinum nanoparticles is that the cracking of carbon-carbon bonds and deep dehydrogenation lead to coke formation. Meanwhile, due to the Ostwald ripening mechanism, the high temperatures required for the direct dehydrogenation of propane and the regeneration of the photocatalyst can lead to severe sintering of the platinum nanoparticles (platinum having a Tammann temperature of 750 ℃, chem. Soc. Rev.,2021,50,3315-3354). Therefore, in order to obtain higher activity of directly dehydrogenating propane, the reaction temperature is often required to be increased to more than 500 ℃, however, under the condition of high temperature, the photocatalyst is easy to deactivate, and side reactions such as thermal cracking, hydrogenolysis or carbon deposition of propane are easy to occur, so that the restriction relationship limits the development of the direct dehydrogenation of propane in industrial catalysis.
Disclosure of Invention
The invention aims to provide a high-dispersion platinum-supported oxygen-defect zinc oxide photocatalyst, a preparation method and application thereof in preparing propylene by directly dehydrogenating propane under low-temperature photocatalysis.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the preparation method of the high-dispersion platinum-supported oxygen defect zinc oxide photocatalyst comprises the following steps:
(1) Generating white precipitate from zinc salt solution under alkaline condition and stirring, washing and suction filtering for multiple times to remove excessive alkali metal ions;
(2) Adding the white precipitate obtained in the step (1) into hydrogen peroxide, stirring in an oil bath, washing and filtering for multiple times, and drying at 60-120 ℃ to obtain zinc peroxide powder;
(3) Grinding the zinc peroxide powder obtained in the step (2), and calcining at a high temperature to obtain an oxygen defect zinc oxide carrier;
(4) And (3) immersing the oxygen defect zinc oxide carrier obtained in the step (3) in a platinum precursor solution, taking out, drying, and calcining at a high temperature to obtain the high-dispersion platinum-loaded oxygen defect zinc oxide photocatalyst.
The solvents of the solutions used in the present invention are deionized water unless otherwise specified.
Further, in the step (1), zinc salt is zinc chloride, zinc nitrate, zinc sulfate or zinc acetate, and the concentration of zinc ions in the zinc salt solution is 0.01-10 mol/L; the alkaline condition is ammonia water, lithium hydroxide solution, sodium hydroxide solution, potassium hydroxide solution, cesium hydroxide solution or urea solution, and the concentration is 0.01-10 mol/L.
Further, in the step (1), deionized water is used for washing for 3-5 times, and a water pump is used for carrying out suction filtration after each washing;
further, in the step (2), the concentration of hydrogen peroxide is 0.1-10 mol/L, the treatment temperature is 20-90 ℃, and the treatment time is 0.1-20 h; filtering by a water pump and washing with deionized water for 3-5 times;
further, the high-temperature calcination in the step (3) specifically refers to calcination for 0.1 to 20 hours in an atmosphere of vacuum, argon, nitrogen, oxygen or air at a temperature rising rate of 1 to 10 ℃ to 200 to 800 ℃;
further, the platinum precursor solution in the step (4) is a chloroplatinic acid solution, a sodium chloroplatinate solution or a tetraammine platinum nitrate solution, and the mass concentration of platinum ions is 0.1 mg/mL-10 mg/mL; the mass percentage of the impregnated platinum is 0.2 to 1.0 percent based on the mass of the oxygen defect zinc oxide carrier.
Further, the high-temperature calcination in the step (4) specifically means that the high-temperature calcination is performed for 0.1 to 20 hours in an atmosphere of vacuum, argon, nitrogen, hydrogen, oxygen or air at a temperature rising rate of 1 to 10 ℃ to 200 to 600 ℃ (lower than the calcination temperature in the step (3); the platinum precursor is heated to decompose to form platinum monoatomic/monoatomic clusters, platinum sub-nanoclusters with the particle size of 0.8-2 nm or platinum nanoparticles with the particle size of 2-5 nm.
The invention also relates to a high-dispersion platinum-supported oxygen defect zinc oxide photocatalyst which is prepared by the method.
The invention also relates to application of the high-dispersion platinum-supported oxygen defect zinc oxide photocatalyst in preparing propylene by directly dehydrogenating propane under low-temperature photocatalysis.
The low temperature range is 0-300 ℃.
The light source of the photocatalysis is ultraviolet light, visible light or near infrared light, and the wavelength range is 180 nm-2500 nm.
The reaction process for preparing propylene by directly dehydrogenating photocatalytic propane comprises the steps of precisely controlling the reaction temperature by using a constant-temperature reaction bath device, introducing high-purity propane gas into a quartz reactor, and detecting the types of reactants by gas chromatography, wherein the illumination time is 0-12 h; further using a propane gas mobile phase reaction device to test the stability of the photocatalyst, wherein the test duration is 0-100 h; on-line gas chromatography detection, the conversion rate of propane and the selectivity of propylene are quantitatively calculated.
Compared with the prior art, the invention has the advantages that:
(1) The photocatalyst of the invention has simple synthesis steps and short time consumption in the whole process; in the preparation process, deionized water is mostly used as a solvent, so that the pollution is small; the requirements on equipment are not high, and the reaction conditions are easy to realize;
(2) The invention adopts the zinc oxide with oxygen defect as the carrier, can well anchor platinum atoms, realizes the stability and the circularity of the photocatalyst, adopts the impregnation method to load the active component platinum, has easily controlled component content and high repeatability;
(3) The photocatalyst is used for directly dehydrogenating photocatalytic propane to prepare propylene for the first time, and under the condition of irradiation of visible light (lambda is more than or equal to 400 nm) at room temperature (20 ℃), the propane can be subjected to dehydrogenation reaction, the conversion rate is higher, and the thermodynamic limit of the reaction is greatly broken through;
(4) According to the invention, the direct dehydrogenation of the low-temperature photocatalytic propane is realized for the first time to prepare propylene, and side reactions such as thermal cracking, hydrogenolysis and the like of the propane caused by high temperature (more than or equal to 500 ℃) in thermal catalysis are effectively avoided, so that the selectivity of the propylene is better, more than 99%, and the photocatalyst is free from obvious deactivation after continuous operation for 100 hours.
Drawings
FIG. 1 is a XRD spectrum of a comparison of the zinc peroxide, oxygen deficient zinc oxide support and commercial zinc oxide synthesized in example 1 of the present invention, znO noted in the zinc peroxide correspondence 2 Curve, znO noted in the oxygen-deficient zinc oxide support map 1-x Curve, commercial zinc oxide corresponds to the ZnO curve noted in the figure.
FIG. 2 is a transmission electron micrograph of an oxygen-deficient zinc oxide carrier synthesized in example 1 of the present invention, and a histogram of the particle size distribution of the oxygen-deficient zinc oxide carrier is attached to the blank of the photograph.
FIG. 3 is an electron paramagnetic resonance spectrum of the oxygen deficient zinc oxide photocatalyst synthesized in example 1 of the present invention.
FIG. 4 is a scanning transmission high angle annular dark field photograph (HAADF-STEM) of a highly dispersed platinum-supported oxygen-deficient zinc oxide photocatalyst prepared in example 1 of the present invention (the mass percentage of platinum is 0.5% based on the mass of the oxygen-deficient zinc oxide photocatalyst).
Fig. 5 is a standard curve (left graph) of propane and a standard curve (right graph) of propylene for amounts of different substances measured using a gas chromatograph GC, wherein the ordinate represents peak areas of the responses of propane (left graph) and propylene (right graph) for amounts of different substances on the gas chromatograph GC, so that the conversion of propane and the selectivity of propylene can be quantitatively described.
Fig. 6 is a XRD spectrum (left graph) of the oxygen-deficient zinc oxide photocatalyst synthesized using different alkali solutions and a yield bar graph (right graph) of propylene in the direct dehydrogenation of propane of the high-dispersion platinum-supported oxygen-deficient zinc oxide photocatalyst synthesized using different alkali solutions in examples 1 to 5 of the present invention.
FIG. 7 shows examples 6 to 6 of the present invention9, a bar graph shows the yield of propylene of the oxygen-deficient zinc oxide photocatalysts with different platinum contents, a dotted line graph shows the conversion frequency of the oxygen-deficient zinc oxide photocatalysts with different platinum contents, namely the number of propane molecules converted per minute of each platinum atom, and a calculation formula is shown in the specification: conversion frequency tof= ([ n (C) 3 H 8 )] in -n(C 3 H 8 )] out ) From the calculation, it was found that the utilization of platinum atoms was the highest when the mass percentage of the impregnated platinum was 0.5%.
Fig. 8 is a graph of mobile phase catalytic stability of a highly dispersed platinum supported 4 oxygen deficient zinc oxide photocatalyst (0.5% platinum mass%) of example 10 of the present invention for the direct dehydrogenation of propane. The figure shows that the photocatalyst of the high-dispersion platinum loaded on the oxygen-deficient zinc oxide photocatalyst has good stability, and the high propane conversion rate and the propylene selectivity of more than 99% are still maintained after a stability test for 100 hours.
FIG. 9 shows the final conversion of propane after 12 hours of continuous reaction of the oxygen deficient zinc oxide photocatalyst with highly dispersed platinum supported in example 11 of the present invention. The curve shows the equilibrium conversion of propane at different temperatures, and the pentagram shows the conversion of propane after 12 hours of irradiation of the photocatalyst with visible light at room temperature (20 ℃), which illustrates that the photocatalyst breaks the thermodynamic limit of the reaction for preparing propylene by directly dehydrogenating propane under the low-temperature photocatalysis.
Detailed Description
The present invention is described in further detail below with reference to specific examples, in which the specific operation process may enable one skilled in the art to more fully understand the present invention. The embodiments described below are only some of the embodiments of the present invention, but not all of them, and thus the scope of the present invention is not limited to the embodiments described below.
Example 1:
(1) Preparing a 100mL round-bottom flask, adding 25mL deionized water into the round-bottom flask, placing the flask on a magnetic stirrer, weighing 1.36g of anhydrous zinc chloride, slowly adding the anhydrous zinc chloride into the deionized water, and stirring for dissolution to obtain a zinc chloride aqueous solution; weighing 0.40g of sodium hydroxide to dissolve in a beaker containing 25mL of deionized water, slowly adding the prepared sodium hydroxide solution into the zinc chloride aqueous solution under stirring, and continuously stirring for 2 hours at 1000 revolutions per minute to generate white precipitate; washing with deionized water for 4 times, and suction filtration with a water pump was performed after each washing to remove the residual alkali metal ions.
(2) Transferring the white precipitate obtained in the step (1) into a 250mL round-bottom flask, then adding 100mL of hydrogen peroxide with concentration of 1mol/L prepared in advance, placing the round-bottom flask into an oil bath with the temperature of 75 ℃, and continuously stirring for 2 hours at 1000 revolutions per minute; after stirring is finished, cooling the suspension in the round-bottom flask to room temperature, washing with deionized water for 4 times, filtering with a water pump after each washing, and vacuum drying the obtained product overnight to obtain zinc peroxide powder.
(3) Grinding the zinc peroxide powder obtained in the step (2), then placing the ground zinc peroxide powder into a quartz boat, transferring the quartz boat into a vacuum tube furnace, and calcining the quartz boat for 2 hours at the temperature rising rate of 4 ℃/min to 400 ℃ to obtain the oxygen defect zinc oxide photocatalyst.
As shown in FIG. 1, X-ray diffraction was tested to obtain XRD spectra of zinc peroxide, oxygen-deficient zinc oxide and commercial zinc oxide, respectively, wherein the positions of the synthesized zinc peroxide peaks are consistent with PDF#13-0311 standard cards of zinc peroxide, and the positions of the synthesized oxygen-deficient zinc oxide and commercial zinc oxide peaks are consistent with PDF#36-1451 standard cards of zinc oxide, which indicates that zinc peroxide and zinc oxide of corresponding crystal forms are successfully synthesized.
As shown in FIG. 2, a transmission electron microscope was tested to obtain a TEM image of the oxygen-deficient zinc oxide photocatalyst, and the average particle diameter of the oxygen-deficient zinc oxide synthesized by the above method was measured to be 10nm to 15nm.
As shown in fig. 3, the electron paramagnetic resonance spectrum of the oxygen defect zinc oxide photocatalyst synthesized by the method is obtained through testing, wherein the g=1.960 positions marked on the graph are metal cation defect positions, and the g=2.003 positions are surface oxygen defect positions, so that the zinc oxide with oxygen defects is proved to be synthesized.
(4) Preparing a chloroplatinic acid solution with the mass concentration of platinum ions of 2mg/mL by taking deionized water as a solvent, taking 50 mu L of the chloroplatinic acid solution by a pipette, dipping the solution on the surface of the oxygen defect zinc oxide photocatalyst obtained in the step (3), drying by an infrared lamp, transferring the solution into a quartz reactor, and calcining the solution for 0.5h at the temperature rising rate of 5 ℃/min in a vacuum state to obtain the oxygen defect zinc oxide photocatalyst loaded by high-dispersion platinum, wherein the mass percentage of the dipped platinum is 0.5 percent based on the mass of the oxygen defect zinc oxide photocatalyst.
As shown in FIG. 4, the high-angle annular dark field patterns (HAADF-STEM) of the scanning transmission of the highly dispersed platinum-supported oxygen-deficient zinc oxide photocatalyst prepared by the above method were tested, and it can be seen from the patterns that platinum is highly dispersed on oxygen-deficient zinc oxide.
(5) And after the quartz reactor is cooled to room temperature, 100 mu mol of high-purity propane gas is introduced, the reactor is transferred to a constant temperature reaction device at 20 ℃, a xenon lamp light source with a 400nm optical filter is utilized to directly catalyze propane to prepare propylene for reaction, the illumination time is 5min, the reaction product is quantitatively analyzed by using gas chromatography, and the conversion rate of propane and the selectivity of propylene can be calculated by combining the standard curve of the amounts of propane and propylene substances in the gas chromatography.
As shown in fig. 5, by recording the correspondence between the peak area and the amount of the substance shown by the gas chromatograph GC, standard curves of propane and propylene are respectively drawn, and the conversion rate of propane and the selectivity of propylene can be calculated by the following formulas:
selectivity is as follows: sel (%) = ([ n (C) 3 H 6 )] out /([n(C 3 H 8 )] in -[n(C 3 H 8 )] out ))x100
Conversion rate: con (%) = (([ n (C)) 3 H 8 )] in -n(C 3 H 8 )] out )/[n(C 3 H 8 )] in )x100
Wherein [ n (C) 3 H 8 )] in And [ n (C) 3 H 8 )] out The amount of propane introduced before the reaction and the amount of propane remaining after the reaction, respectively, [ n (C) 3 H 6 )] out The amount of the propylene substance formed after the reaction.
Example 2:
the preparation and reaction were carried out by the method of example 1, except that 0.56g of potassium hydroxide was weighed in step (1).
Example 3:
the preparation and reaction were carried out in the same manner as in example 1 except that 1.50g of cesium hydroxide was weighed in step (1).
Example 4:
the preparation and reaction were carried out in the same manner as in example 1 except that 1.71g of barium hydroxide was weighed in step (1).
Example 5:
the preparation and reaction were carried out by the method of example 1, except that in step (1), concentrated aqueous ammonia having a concentration of 10mol/L was measured and the pH was adjusted to 9 to 10.
As shown in fig. 6, the left graph shows XRD patterns of the oxygen-deficient zinc oxide photocatalysts synthesized using different alkali solutions, wherein the XRD patterns of the oxygen-deficient zinc oxide photocatalysts synthesized using sodium hydroxide, potassium hydroxide, cesium hydroxide and ammonia water are substantially identical, and the XRD patterns of the oxygen-deficient zinc oxide photocatalysts synthesized using barium hydroxide are weaker; the right graph shows the propylene yield of the high-dispersion platinum-supported oxygen-defect zinc oxide photocatalyst synthesized by different alkali solutions in the direct dehydrogenation of propane, wherein the propylene yield of the oxygen-defect zinc oxide photocatalyst synthesized by using sodium hydroxide, potassium hydroxide, cesium hydroxide and ammonia water is basically consistent, and the propylene yield of the oxygen-defect zinc oxide photocatalyst synthesized by using barium hydroxide is weaker and is consistent with the rule of the left graph.
Example 6:
the preparation and reaction were carried out in the same manner as in example 1 except that in step (4), 20. Mu.L of an aqueous solution of chloroplatinic acid was removed by a pipette, and the mass percentage of the impregnated platinum was 0.2% based on the mass of the oxygen deficient zinc oxide photocatalyst.
Example 7:
the preparation and reaction were carried out in the same manner as in example 1 except that 30. Mu.L of an aqueous solution of chloroplatinic acid was removed by a pipette in step (4), and the mass percentage of the impregnated platinum was 0.3% based on the mass of the oxygen-deficient zinc oxide photocatalyst.
Example 8:
the preparation and reaction were carried out in the same manner as in example 1 except that 80. Mu.L of an aqueous solution of chloroplatinic acid was removed by a pipette in step (4), and the mass percentage of the impregnated platinum was 0.8% based on the mass of the oxygen-deficient zinc oxide photocatalyst.
Example 9:
the preparation and reaction were carried out in the same manner as in example 1 except that 100. Mu.L of an aqueous solution of chloroplatinic acid was removed by a pipette in step (4), and the mass percentage of the impregnated platinum was 1.0% based on the mass of the oxygen-deficient zinc oxide photocatalyst.
As shown in fig. 7, the bar graph shows the propylene yield of the oxygen-deficient zinc oxide photocatalysts loaded with different platinum contents, and the dotted line graph shows the conversion frequency of the oxygen-deficient zinc oxide photocatalysts loaded with different platinum contents, that is, the number of propane molecules converted per minute per platinum atom, and it is known that the propylene yield increases with increasing platinum content, and the conversion frequency decreases with increasing platinum content, and that the platinum atom utilization is highest when the mass percentage of impregnated platinum is 0.5%.
Example 10:
the preparation and reaction were carried out by the method of example 1, except that in step (5), a mobile phase photoreaction device was used, 100% high purity propane was introduced at a propane flow rate of 20mL/min, whsv=106.5, a direct dehydrogenation reaction of propane was carried out by photocatalysis using a xenon lamp light source with a 400nm filter, the reaction product was quantitatively analyzed on line by gas chromatography, and the conversion rate of propane and the selectivity of propylene to propylene could be calculated by combining the standard curves of the amounts of propane and propylene substances in gas chromatography.
Analysis of the results and data of the above examples, as shown in fig. 8, the triangle indicates the conversion rate of propane in the reaction for preparing propylene by directly dehydrogenating propane, the circle indicates the selectivity of propylene in the reaction for preparing propylene by directly dehydrogenating propane, and it is clear from the figure that the high dispersion platinum is loaded on the photocatalyst of oxygen-deficient zinc oxide photocatalyst, the stability test is good, the high conversion rate of propane can still be maintained after continuous operation for 100 hours, and the selectivity of propylene is still higher than 99%.
Example 11:
the preparation and reaction were carried out by the method of example 1, except that the illumination time in step (5) was 12 hours.
The results and data of the above examples were analyzed, and as shown in FIG. 9, the curves represent the equilibrium conversion of propane at different temperatures, and the pentagram represents the conversion of propane after irradiation of the photocatalyst with visible light for 12 hours at room temperature of 20 ℃. From this, it can be seen that the high dispersion platinum loading breaks through the thermodynamic equilibrium of the reaction in the reaction of preparing propylene by directly dehydrogenating propane under low temperature photocatalysis by oxygen-deficient zinc oxide photocatalyst.
Claims (10)
1. A preparation method of a high-dispersion platinum-supported oxygen-deficient zinc oxide photocatalyst comprises the following steps:
(1) Generating white precipitate from zinc salt solution under alkaline condition and stirring, washing and suction filtering for multiple times to remove excessive alkali metal ions;
(2) Adding the white precipitate obtained in the step (1) into hydrogen peroxide, stirring in an oil bath, washing and filtering for multiple times, and drying at 60-120 ℃ to obtain zinc peroxide powder;
(3) Grinding the zinc peroxide powder obtained in the step (2), and calcining at a high temperature to obtain an oxygen defect zinc oxide carrier;
(4) And (3) immersing the oxygen defect zinc oxide carrier obtained in the step (3) in a platinum precursor solution, taking out, drying, and calcining at a high temperature to obtain the high-dispersion platinum-loaded oxygen defect zinc oxide photocatalyst.
2. The method for preparing the high-dispersion platinum-supported oxygen-deficient zinc oxide photocatalyst according to claim 1, wherein the method comprises the following steps: the zinc salt in the step (1) is zinc chloride, zinc nitrate, zinc sulfate or zinc acetate, and the concentration of zinc ions in the zinc salt solution is 0.01-10 mol/L; the alkaline condition is ammonia water, lithium hydroxide solution, sodium hydroxide solution, potassium hydroxide solution, cesium hydroxide solution or urea solution, and the concentration is 0.01-10 mol/L; is filtered by a water pump and washed 3-5 times by deionized water.
3. The method for preparing the high-dispersion platinum-supported oxygen-deficient zinc oxide photocatalyst according to claim 1, wherein the method comprises the following steps: in the step (2), the concentration of hydrogen peroxide is 0.1-10 mol/L, the treatment temperature is 20-90 ℃ and the treatment time is 0.1-20 h; is filtered by a water pump and washed 3-5 times by deionized water.
4. The method for preparing the high-dispersion platinum-supported oxygen-deficient zinc oxide photocatalyst according to claim 1, wherein the method comprises the following steps: the high-temperature calcination in the step (3) refers to calcination for 0.1 to 20 hours in an atmosphere of vacuum, argon, nitrogen, oxygen or air at a temperature rising rate of 1 to 10 ℃ to 200 to 800 ℃.
5. The method for preparing the high-dispersion platinum-supported oxygen-deficient zinc oxide photocatalyst according to claim 1, wherein the method comprises the following steps: the platinum precursor solution in the step (4) is a chloroplatinic acid solution, a sodium chloroplatinate solution or a tetraammine platinum nitrate solution, and the mass concentration of platinum ions is 0.1 mg/mL-10 mg/mL; the mass percentage of the impregnated platinum is 0.2 to 1.0 percent based on the mass of the oxygen defect zinc oxide carrier.
6. The method for preparing the high-dispersion platinum-supported oxygen-deficient zinc oxide photocatalyst according to claim 1, wherein the method comprises the following steps: the high-temperature calcination in the step (4) means calcination for 0.1 to 20 hours in an atmosphere of vacuum, argon, nitrogen, hydrogen, oxygen or air at a temperature rising rate of 1 to 10 ℃ to 200 to 600 ℃, and the combustion temperature in the step (4) is lower than the calcination temperature in the step (3); the platinum precursor is heated to decompose to form platinum monoatomic/monoatomic clusters, platinum sub-nanoclusters with the particle size of 0.8-2 nm or platinum nanoparticles with the particle size of 2-5 nm.
7. A high dispersion platinum loaded oxygen defect zinc oxide photocatalyst is characterized in that: is prepared by the method of any one of claims 1 to 6.
8. The use of a highly dispersed platinum supported oxygen deficient zinc oxide photocatalyst in the preparation of propylene by direct dehydrogenation of propane under low temperature photocatalysis as defined in claim 7.
9. The use of a highly dispersed platinum supported oxygen deficient zinc oxide photocatalyst in the direct dehydrogenation of propane at low temperature to produce propylene according to claim 8, wherein: the low temperature range is 0-300 ℃.
10. The use of a highly dispersed platinum supported oxygen deficient zinc oxide photocatalyst in the direct dehydrogenation of propane at low temperature to produce propylene according to claim 8, wherein: the photocatalytic light source is ultraviolet light, visible light or near infrared light, and the wavelength range is 180 nm-2500 nm.
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