CN111686778A - Supported platinum catalyst for preparing propylene by catalytic dehydrogenation of propane and preparation method thereof - Google Patents
Supported platinum catalyst for preparing propylene by catalytic dehydrogenation of propane and preparation method thereof Download PDFInfo
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- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 239000003054 catalyst Substances 0.000 title claims abstract description 98
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 239000001294 propane Substances 0.000 title claims abstract description 53
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 47
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 46
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 29
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title abstract description 22
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 57
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 35
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 35
- 238000001035 drying Methods 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 27
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims abstract description 13
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims abstract description 11
- 239000004926 polymethyl methacrylate Substances 0.000 claims abstract description 11
- 238000005470 impregnation Methods 0.000 claims abstract description 9
- 235000010333 potassium nitrate Nutrition 0.000 claims abstract description 9
- 239000004323 potassium nitrate Substances 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- 229910052718 tin Inorganic materials 0.000 claims abstract description 8
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000007598 dipping method Methods 0.000 claims abstract description 6
- 235000010344 sodium nitrate Nutrition 0.000 claims abstract description 6
- 239000004317 sodium nitrate Substances 0.000 claims abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 5
- 229910002846 Pt–Sn Inorganic materials 0.000 claims abstract description 4
- 239000011734 sodium Substances 0.000 claims abstract description 4
- 229910052708 sodium Inorganic materials 0.000 claims abstract 2
- 239000000243 solution Substances 0.000 claims description 24
- 238000002791 soaking Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 5
- 239000003995 emulsifying agent Substances 0.000 claims description 4
- 239000003999 initiator Substances 0.000 claims description 4
- 230000001795 light effect Effects 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 239000000839 emulsion Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical group [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 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 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 22
- 229910052799 carbon Inorganic materials 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 7
- 239000012752 auxiliary agent Substances 0.000 abstract description 6
- 230000008021 deposition Effects 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 5
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 230000002779 inactivation Effects 0.000 abstract description 4
- 238000011068 loading method Methods 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- 230000002776 aggregation Effects 0.000 abstract description 2
- 238000004220 aggregation Methods 0.000 abstract description 2
- 230000005012 migration Effects 0.000 abstract description 2
- 238000013508 migration Methods 0.000 abstract description 2
- 229910052684 Cerium Inorganic materials 0.000 abstract 1
- 229910052746 lanthanum Inorganic materials 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 229910052700 potassium Inorganic materials 0.000 abstract 1
- 238000000967 suction filtration Methods 0.000 abstract 1
- 239000000969 carrier Substances 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 4
- 229910002847 PtSn Inorganic materials 0.000 description 4
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 235000011150 stannous chloride Nutrition 0.000 description 4
- 239000001119 stannous chloride Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 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
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-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
- 239000004743 Polypropylene Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- FHMDYDAXYDRBGZ-UHFFFAOYSA-N platinum tin Chemical compound [Sn].[Pt] FHMDYDAXYDRBGZ-UHFFFAOYSA-N 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 1
Images
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- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a supported platinum catalyst for preparing propylene by propane catalytic dehydrogenation and a preparation method thereof, relates to the technical field of catalysis for preparing propylene by propane dehydrogenation, and provides the supported platinum catalyst for solving the problems of easy migration, aggregation and carbon deposition inactivation of active components, low activity and poor stability of the whole catalyst in the high-temperature use process of the existing catalyst. The catalyst comprises the components of Pt-Sn/N-Al2O3And N is metal modification auxiliary agents Na, K, Ce and La. The weight percentage of the material is as follows: 0.5 to 0.8 percent of Pt0, 0.1 to 0.2 percent of Sn0.5 to 3 percent of N, and the balance of three-dimensional ordered macroporous Al2O3. The preparation method comprises the following steps: preparing PMMA template agent, then pouring a proper amount of template agent into the mold containing Al (NO)3)·9H2In a 95% ethanol solution of O,the three-dimensional ordered macroporous Al is obtained by dipping, suction filtration, drying and roasting2O3A carrier; in Al2O3Loading sodium nitrate, potassium nitrate, cerium nitrate or lanthanum nitrate solution on a carrier, drying and roasting, loading Pt and Sn components on a modified carrier in an isometric impregnation mode, drying and roasting to obtain the Pt-Sn/N-Al2O3A catalyst. Three-dimensional ordered macroporous Al2O3The carrier supported catalyst has better conversion rate, selectivity and stability.
Description
Technical Field
The invention relates to a catalytic technology for preparing propylene by propane dehydrogenation, in particular to a supported platinum catalyst for preparing propylene by propane catalytic dehydrogenation and a preparation method thereof.
Background
Propylene (CH)3-CH＝CH2) Is an important petrochemical basic raw material, is mainly used for producing products such as polypropylene, acrylonitrile, propylene oxide, acrylic acid, butanol, octanol, cumene, isopropyl acid and the like, and has a steadily increasing trend of the world demand for propylene. At present, propylene supply mainly comes from ethylene prepared by naphtha cracking and byproducts generated in the petroleum catalytic cracking process, and due to the influence of factors such as petroleum supply, lighter catalytic cracking feed and the like, the yield of propylene is reduced, so that the propylene gap is increased, and the propylene prepared by the traditional process cannot meet the market demand of the current world on propylene. The propane gas in China is rich in resources and low in price, and the propane with abundant and low price is subjected to dehydrogenation catalytic reaction to prepare the propylene with high added value which is in short supply in the market, so that the method has important practical significance.
At present, the technology for preparing propylene by propane dehydrogenation mainly comprises the following steps: 1) catalytic dehydrogenation 2) non-oxidative catalytic dehydrogenation 3) membrane reactor dehydrogenation. Among them, non-oxidative catalytic dehydrogenation is attracting attention because of its high catalytic safety and good stability. The preparation of propylene by catalytic dehydrogenation of propane is a strong endothermic reaction, which is limited by thermodynamic equilibrium and needs to be carried out under low pressure and high temperature conditions in order to obtain higher conversion rate. However, the high temperature will cause the propane to be easily cracked to smallThe molecule causes the selectivity of the catalyst to be reduced, and simultaneously, the generated olefin is easy to polymerize and cyclize into macromolecules to cause carbon deposition and inactivation of the catalyst. Therefore, the development of a propane dehydrogenation propylene preparation catalyst with high activity, high selectivity and high stability is the key of non-oxidative catalytic dehydrogenation. In this regard, researchers have conducted a great deal of research. For example, U.S. Pat. No. 4, 4,506,032 uses Pt-Sn-K-Cl/γ -Al2O3The catalyst is prepared by soaking a chloroplatinic acid solution and a potassium nitrate solution in steps by using an Sn-doped alumina carrier, drying and roasting the solution, and then injecting chlorine into the solution, wherein the prepared catalyst is used for dehydrogenation of low-carbon alkane. US patent 4,595,673 on Pt-Sn-K-Li-Cl/gamma-Al2O3The catalyst is prepared by co-soaking chloroplatinic acid and lithium nitrate solution in Sn-doped alumina carrier, drying, roasting, soaking in potassium nitrate solution, and drying and roasting. The procedure is complicated and the catalytic repeatability is poor. The catalyst disclosed in the Chinese patent CN200710025372.X is a preparation method of impregnating a platinum-tin component on an alumina modified mesoporous molecular sieve serving as a carrier, wherein the conversion rate of propane is only 17 percent, and the selectivity of propylene is 93 percent; chinese patent CN101066532A reports a preparation method of a ZSM-5 molecular sieve skeleton carrier containing Sn for propane dehydrogenation propylene catalyst, the catalyst shows higher selectivity and stability, but the conversion rate is relatively lower, the preparation process of the ZSM-5 molecular sieve containing Sn is longer, the energy consumption is large, the content of each metal component is relatively higher, and the preparation cost of the catalyst is correspondingly increased.
Disclosure of Invention
Aiming at the problems of easy migration, aggregation and carbon deposition inactivation of active components, low activity and poor stability of the whole catalyst and gradual reduction of selectivity in the operation process of the existing catalyst in the high-temperature use process, the invention provides a supported platinum catalyst which is used for preparing propylene by propane dehydrogenation by a non-oxidation catalysis method.
The technical scheme adopted by the invention is as follows:
the supported platinum catalyst applied to the preparation of propylene by propane dehydrogenation comprises the components of Pt-Sn/N-Al2O3Wherein, metal Pt is used as active metal, Sn/N is used as auxiliary agent, N is selected from sodium nitrate, potassium nitrate, cerous nitrate, lanthanum nitrate and Al2O3Is a three-dimensional ordered macroporous carrier, and comprises the following components, by weight, 0.5-0.8% of Pt, 0.1-0.2% of Sn, 0.5-3% of N, and the balance of three-dimensional ordered macroporous Al2O3。
The preparation method of the supported platinum catalyst applied to preparing propylene by propane dehydrogenation comprises the following steps:
1) preparation of three-dimensional ordered macroporous Al2O3Firstly, preparing a PMMA template agent or a PS template agent: adding a certain amount of deionized water and methyl methacrylate into a 1000mL four-neck flask, introducing nitrogen for protection, adding a trace amount of emulsifier, heating to above 70 ℃, adding a proper amount of initiator, continuously reacting for more than 1 hour, taking out the emulsion, cooling to room temperature, washing for multiple times, carrying out centrifugal assembly, and drying in a water bath to obtain a PMMA template agent with a Bragg light effect; the PS template agent with the Bragg light effect is prepared by adopting the method by using (styrene) to replace methyl methacrylate; then pouring proper amount of PMMA template agent or PS template agent into the mold containing certain amount of Al (NO)3)·9H2Soaking in 95% ethanol solution of O, filtering, drying and roasting to obtain three-dimensional ordered macroporous Al2O3The carrier is the carrier of the catalyst for preparing propylene by propane dehydrogenation;
2) dipping the three-dimensional ordered macroporous Al prepared in the step 1) in a sodium nitrate, potassium nitrate, cerium nitrate and lanthanum nitrate solution by adopting an isometric dipping method2O3Drying and roasting the carrier to obtain the modified catalyst carrier N-Al2O3；
3) An isovolumetric impregnation method is adopted to load an active component Pt and an auxiliary agent Sn component to the modified catalyst carrier N-Al in a co-impregnation or step-by-step impregnation mode2O3Drying and roasting to obtain the supported platinum applied to preparing propylene by propane dehydrogenationIs a catalyst.
Further, in the step 1), the drying temperature may be 60 to 100 ℃;
further, the roasting temperature in the step 1) can be 550-800 ℃.
Further, in the step 2), the roasting temperature may be 550 to 650 ℃.
Further, the dipping time in the step 2) is 4-8 h;
further, the drying condition of the step 2) is drying for 6-10 hours in an oven at 60-100 ℃;
further, the roasting condition of the step 3) is roasting for 4-6 hours in a muffle furnace at 550-650 ℃.
The supported platinum catalyst is applied to the reaction of preparing propylene by propane dehydrogenation, and comprises the following specific steps:
1) placing 3.0-5.0 g of the supported platinum catalyst in a fixed bed stainless steel reaction tube, heating to 450-570 ℃ at a heating rate of 2 ℃/min at room temperature in a 10% hydrogen atmosphere, and carrying out reduction activation for 6-10 h, wherein the flow rate of hydrogen is 140-160 mL/min;
2) after the reduction is finished, raising the temperature of a bed layer of the reaction tube to 550-620 ℃ under the normal pressure condition, and introducing pure propane gas for reaction, wherein the flow rate of the propane gas is 60-100 mL/min.
The method comprises the steps of firstly preparing a three-dimensional ordered macroporous alumina precursor by using a colloidal crystal template method, drying and roasting to prepare a carrier of a propylene catalyst prepared by propane dehydrogenation, then impregnating N components of a modification auxiliary agent, namely sodium nitrate, potassium nitrate, cerium nitrate and lanthanum nitrate, on the alumina carrier by using an isometric impregnation method, and drying and roasting to obtain the modified catalyst carrier, namely N-Al2O3. And loading the Pt and Sn components by an equal-volume co-impregnation method or a step-by-step impregnation method.
The supported platinum catalyst applied to the preparation of propylene by propane dehydrogenation can effectively catalyze propane dehydrogenation to prepare propylene under mild conditions, the propane conversion rate is still higher than 35.5%, the selectivity of propylene is still higher than 87%, carbon deposition on the catalyst is less, the activity is slowly reduced, and the catalyst still has good catalytic activity after multiple regeneration after reaction for 10 hours in pure propane atmosphere without any diluent gas under the condition of 550-600 ℃.
Compared with the prior art, the invention has the following advantages:
1) the preparation method comprises the steps of firstly, when three-dimensional ordered macroporous alumina is used as a carrier, the carrier has good carrier structure performance, active components can be well loaded and uniformly dispersed on the carrier, the active components are efficiently utilized, after the auxiliary agent is added, the interaction between the active components and the carrier can be effectively enhanced, the active components do not migrate in the high-temperature reaction process, and the sintering inactivation of the active components is reduced. And after the modification of the auxiliary agent, the surface acidity of the alumina carrier can be obviously improved, the increase of side reactions and the deepening of carbon deposition caused by the influence of an acid position in the reaction process of the catalyst are prevented, the stability of the catalyst is effectively improved, the mass transfer resistance of a target product on the catalyst is reduced, and the separation of reactants and the product is enhanced.
2) In the invention, the catalyst is prepared by adopting an isometric saturated impregnation method, so that the using amount of each metal component is reduced, the utilization efficiency of the metal components is improved, the production cost is reduced, and the method is suitable for large-scale production and industrial application.
3) The catalyst has high reaction activity, high propane conversion rate and propylene selectivity, less carbon deposit on the catalyst, slow reduction of catalyst activity and strong regeneration.
Drawings
FIG. 1 is an SEM electron micrograph of a PMMA template prepared;
FIG. 2 is an SEM electron microscope image of a three-dimensional ordered catalyst for catalytic dehydrogenation of propane to propylene in example 2 after calcination;
FIG. 3 is a flow diagram of the preparation of the catalyst.
Detailed Description
The invention is further described below with reference to the figures and examples.
Firstly, a chloroplatinic acid solution and a stannous chloride solution are prepared.
Preparing a chloroplatinic acid solution: dissolving 2g of chloroplatinic acid in deionized water, transferring the solution into a 50mL volumetric flask, adding the deionized water to the scale mark of the volumetric flask, and placing the volumetric flask in the shade for later use.
Preparing a stannous chloride solution: dissolving 2g of stannous chloride in 10mL of concentrated hydrochloric acid, transferring the solution to a 100mL volumetric flask after the solution, and adding deionized water to the scale mark of the volumetric flask for later use.
Examples the catalyst preparation scheme is described in the specification with reference to figure 3.
Preparing a common alumina carrier according to the proportion:
mixing pseudo-boehmite and a binder, uniformly mixing the raw materials in a kneading machine, slowly adding deionized water, slowly stirring in the kneading machine to form the raw materials, transferring the raw materials into a strip extruding machine, slowly and uniformly extruding and forming an alumina carrier, transferring the alumina carrier into a constant-temperature drying oven to dry at 80 ℃ overnight, transferring the alumina carrier into a temperature programming muffle furnace to roast at 600 ℃ for 4 hours to obtain common Al2O3Vector, denoted as a.
Comparative example preparation of three-dimensionally ordered macroporous Al2O3Carrier:
firstly, preparing a PMMA template agent or a PS template agent: adding a certain amount of deionized water and methyl methacrylate into a 1000mL four-neck flask, introducing nitrogen for protection, adding a trace amount of emulsifier sodium dodecyl sulfate, heating to above 70 ℃, adding a proper amount of initiator potassium persulfate, continuously reacting for more than 1 hour, taking out the emulsion, cooling to room temperature, washing with water for multiple times, carrying out centrifugal assembly, and drying in a water bath to obtain a PMMA template agent with a Bragg light effect; styrene was used in place of methyl methacrylate, and a PS template having a Bragg effect was obtained in the same manner.
Then pouring a proper amount of PMMA template agent or PS template agent into 95 percent ethanol solution containing a certain amount of aluminum nitrate nonahydrate, dipping, filtering, drying, and finally roasting at 800 ℃ for 5 hours to obtain the three-dimensional ordered macroporous Al2O3The carrier, i.e. the carrier of the propane dehydrogenation to propylene catalyst, is denoted as O.
Example 1
(1) The carriers A and O were taken separately without treatment.
(2) Preparing a catalyst: respectively take 3Transferring 1.2mL (0.6 wt%) of chloroplatinic acid solution and 0.3mL (0.1 wt%) of stannous chloride solution by using a pipette, adding deionized water, uniformly mixing, soaking 3g of carrier in the mixed solution in an equal volume, standing overnight, drying at 80 ℃ in an air atmosphere for 10 hours, and roasting at 600 ℃ in an air atmosphere for 4 hours to obtain the catalyst PtSn/Al2O3。
The obtained catalyst is marked as Ac (common alumina supported catalyst) and Oc (three-dimensional ordered alumina supported catalyst), and the percentage content of each component is respectively as follows: pt: 0.6%, Sn: 0.1% and the balance of Al2O3。
Example 2
(1) Respectively taking 3g of carriers (A and O), weighing a proper amount of potassium nitrate to prepare a solution with the concentration of 0.31g/mL, then soaking 3g of carriers in the mixed solution in an equal volume, standing overnight, drying at 80 ℃ in an air atmosphere for 10h, and roasting at 600 ℃ in an air atmosphere for 4h to obtain the modified carrier K-Al of the propane dehydrogenation catalyst2O3。
(2) Respectively taking 3g of modified carrier K-Al2O3Then, the preparation method of the catalyst is the same as the step (2) in the example 1, and the propane dehydrogenation supported catalyst PtSnK/Al of the invention is prepared2O3。
The obtained catalyst is marked as Ac-K (common alumina supported catalyst) and Oc-K (three-dimensional ordered alumina supported catalyst, figure 2), and the percentage content of each component is respectively as follows: k: 1.2%, Pt: 0.6%, Sn: 0.1% and the balance of Al2O3。
Example 3
(1) Respectively taking 3g of carriers (A and O), weighing a proper amount of sodium nitrate to prepare a solution, then soaking 3g of carriers in the mixed solution in an equal volume, standing overnight, drying for 10 hours at 80 ℃ in an air atmosphere, and roasting for 4 hours at 600 ℃ in the air atmosphere to obtain the modified carrier Na-Al of the propane dehydrogenation catalyst2O3。
(2) Respectively taking 3g of modified carrier Na-Al2O3Then, the catalyst was prepared in the same manner as in the step (2) of example 1 to obtain a propane dehydrogenation supported catalyst of the present inventionReagent PtSn/Na-Al2O3。
The obtained catalyst is marked as Ac-Na (common alumina supported catalyst) and Oc-Na (three-dimensional ordered alumina supported catalyst), and the percentage content of each component is respectively as follows: na: 1.2%, Pt: 0.6%, Sn: 0.1% and the balance of Al2O3。
Example 4
(1) Respectively taking 3g of carriers (A and O), weighing a proper amount of lanthanum nitrate to prepare a solution, then soaking 3g of carriers in the mixed solution in an equal volume, standing overnight, drying for 10 hours at 80 ℃ in an air atmosphere, and roasting for 4 hours at 600 ℃ in the air atmosphere to obtain the propane dehydrogenation catalyst modified carrier La-Al2O3。
(2) Respectively taking 3g of modified carrier La-Al2O3Then, the catalyst preparation method was the same as that in the step (2) of example 1, to obtain the propane dehydrogenation supported catalyst PtSn/La-Al of the present invention2O3。
The obtained catalyst is marked as Ac-La (common alumina supported catalyst) and Oc-La (three-dimensional ordered alumina supported catalyst), and the percentage content of each component is respectively as follows: la: 1.2%, Pt: 0.6%, Sn: 0.1% and the balance of Al2O3。
Example 5
(1) Respectively taking 3g of carriers (A and O), weighing a proper amount of cerium nitrate to prepare a solution, then soaking 3g of carriers in the mixed solution in an equal volume, standing overnight, drying for 10 hours at 80 ℃ in an air atmosphere, and roasting for 4 hours at 600 ℃ in the air atmosphere to obtain the propane dehydrogenation catalyst modified carrier Ce-Al2O3。
(2) Respectively taking 3g of modified carrier Ce-Al2O3Then, the preparation method of the catalyst is the same as the step (2) in the example 1, and the propane dehydrogenation supported catalyst PtSn/Ce-Al of the invention is prepared2O3。
The obtained catalyst is marked as Ac-Ce (common alumina supported catalyst) and Oc-Ce (three-dimensional ordered alumina supported catalyst), and the percentage content of each component is respectively as follows: ce: 1.2%, Pt: 0.6%, Sn: 0.1% and the balance of Al2O3。
Application example
All the catalysts prepared in the examples were used for the catalytic dehydrogenation of propane to propylene to evaluate the reactivity, selectivity and stability. The specific operation steps are as follows: 1) putting 3.0g of catalyst into a fixed bed stainless steel reaction tube, heating to 500 ℃ at room temperature at the heating rate of 2 ℃/min in the atmosphere of 10% hydrogen, and carrying out reduction activation for 10h, wherein the flow rate of the hydrogen is 150 mL/min; 2) after the reduction is finished, raising the temperature of the bed layer of the reaction tube to 600 ℃ under normal pressure, introducing pure propane gas for reaction, wherein the flow rate of the propane gas is 80mL/min, and reacting for 15 h. The propane conversion per pass, propylene selectivity and propylene yield are shown in Table 2, both initially and after 12h of reaction.
TABLE 1 Metal Mass Supported by different example catalysts
TABLE 2 catalytic Performance of different example catalysts for dehydrogenation of propane to propylene
The catalyst is excellent in environmental adaptability, data are multiple evaluation results, the effect can be achieved in different types of reactors, the catalytic reaction handling capacity is large (the reaction space velocity is large), the catalytic performance of the three-dimensional ordered macroporous alumina supported catalyst is obviously superior to that of a common catalyst along with the reaction, active components are not easy to migrate, aggregate and carbon deposition to be inactivated, and the overall catalyst stability is good.
Claims (9)
1. A supported platinum catalyst for preparing propylene by propane catalytic dehydrogenation is characterized in that the catalyst comprises Pt-Sn/N-Al2O3Pt as the active metal and Sn/N as the aidN is selected from sodium nitrate, potassium nitrate, cerium nitrate, lanthanum nitrate and Al2O3Is a three-dimensional ordered macroporous carrier; the components are calculated according to the weight percentage: 0.5 to 0.8 percent of Pt, 0.1 to 0.2 percent of Sn, 0.5 to 3 percent of N and the balance of three-dimensional ordered macroporous Al2O3。
2. The method for preparing the supported platinum-based catalyst for preparing propylene by propane dehydrogenation according to claim 1, comprising the following steps:
1) preparing a PMMA template agent or a PS template agent: adding deionized water and methyl methacrylate into a 1000mL four-neck flask, introducing nitrogen for protection, adding an emulsifier, heating to above 70 ℃, adding an initiator, continuously reacting for more than 1 hour, taking out the emulsion, cooling to room temperature, centrifugally assembling, and drying in a water bath to obtain PMMA with a Bragg light effect; preparing a PS template agent by using styrene to replace methyl methacrylate according to the same method; pouring PMMA template or PS template into the mold containing Al (NO)3)·9H2Soaking in 95% ethanol solution of O, filtering, drying and roasting to obtain three-dimensional ordered macroporous Al2O3A carrier;
2) respectively soaking sodium, potassium nitrate, cerium nitrate and lanthanum nitrate solution in the three-dimensional ordered macroporous Al prepared in the step 1) by adopting an isometric soaking method2O3Drying and roasting the carrier to obtain the modified catalyst carrier N-Al2O3；
3) The modified catalyst carrier is N-Al2O3Co-dipping the catalyst in a mixed solution of an auxiliary Sn and an active component Pt, and drying and roasting to obtain the supported platinum catalyst applied to preparing propylene by propane dehydrogenation.
3. The method for preparing a supported platinum-based catalyst for propane dehydrogenation to propylene according to claim 2, wherein the calcination temperature in step 1) is 550 to 800 ℃.
4. The method for preparing a supported platinum-based catalyst for propane dehydrogenation to propylene according to claim 2, wherein the calcination temperature in step 2) is 550 to 650 ℃.
5. The method for preparing a supported platinum-based catalyst for propane dehydrogenation to propylene according to claim 2, wherein the calcination temperature in step 3) is 550 to 650 ℃.
6. The method for preparing a supported platinum-based catalyst for propane dehydrogenation to propylene according to claim 2, wherein the impregnation time in step 2) is 4 to 8 hours.
7. The method for preparing the supported platinum-based catalyst for preparing propylene by propane dehydrogenation according to claim 2, wherein in the step 3), the drying condition is drying in an oven at 80-100 ℃ for 6-10 h.
8. The method for preparing the supported platinum-based catalyst for preparing propylene by propane dehydrogenation according to claim 2, wherein in the step 3), the calcination time is 4-6 h.
9. The method for preparing a supported platinum-based catalyst for propane dehydrogenation to produce propylene according to claim 2, wherein the emulsifier in step 1) is sodium lauryl sulfate and the initiator is potassium persulfate.
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