CN117482981A - Platinum cluster catalyst for preparing propylene by directly dehydrogenating propane and preparation method and application thereof - Google Patents
Platinum cluster catalyst for preparing propylene by directly dehydrogenating propane and preparation method and application thereof Download PDFInfo
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- CN117482981A CN117482981A CN202311448288.4A CN202311448288A CN117482981A CN 117482981 A CN117482981 A CN 117482981A CN 202311448288 A CN202311448288 A CN 202311448288A CN 117482981 A CN117482981 A CN 117482981A
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- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 214
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 163
- 239000001294 propane Substances 0.000 title claims abstract description 107
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 103
- 239000003054 catalyst Substances 0.000 title claims abstract description 101
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 28
- 239000002808 molecular sieve Substances 0.000 claims abstract description 22
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
- 238000001354 calcination Methods 0.000 claims abstract description 16
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims abstract description 13
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 12
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 11
- 239000010703 silicon Substances 0.000 claims abstract description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 239000003223 protective agent Substances 0.000 claims abstract description 8
- 239000002243 precursor Substances 0.000 claims abstract description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 80
- 239000000243 solution Substances 0.000 claims description 65
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 33
- 238000003756 stirring Methods 0.000 claims description 26
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 22
- 239000010453 quartz Substances 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 16
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims description 7
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 7
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 2
- QLBHNVFOQLIYTH-UHFFFAOYSA-L dipotassium;2-[2-[bis(carboxymethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [K+].[K+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O QLBHNVFOQLIYTH-UHFFFAOYSA-L 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 abstract description 6
- 229910000510 noble metal Inorganic materials 0.000 abstract description 3
- 238000011068 loading method Methods 0.000 abstract description 2
- 238000005342 ion exchange Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 238000001035 drying Methods 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 11
- 239000006004 Quartz sand Substances 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 238000010586 diagram Methods 0.000 description 10
- 238000004817 gas chromatography Methods 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 239000000376 reactant Substances 0.000 description 10
- 238000010335 hydrothermal treatment Methods 0.000 description 9
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 9
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 229960001484 edetic acid Drugs 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 230000018109 developmental process Effects 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 239000011865 Pt-based catalyst Substances 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- MGDKBCNOUDORNI-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetic acid;potassium Chemical compound [K].[K].OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O MGDKBCNOUDORNI-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910002847 PtSn Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001212 derivatisation Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0316—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing iron group metals, noble metals or copper
- B01J29/0325—Noble metals
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0316—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing iron group metals, noble metals or copper
- B01J29/0333—Iron group metals or copper
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/035—Microporous crystalline materials not having base exchange properties, such as silica polymorphs, e.g. silicalites
- B01J29/0352—Microporous crystalline materials not having base exchange properties, such as silica polymorphs, e.g. silicalites containing iron group metals, noble metals or copper
- B01J29/0354—Noble metals
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/035—Microporous crystalline materials not having base exchange properties, such as silica polymorphs, e.g. silicalites
- B01J29/0352—Microporous crystalline materials not having base exchange properties, such as silica polymorphs, e.g. silicalites containing iron group metals, noble metals or copper
- B01J29/0356—Iron group metals or copper
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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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- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
The invention discloses a platinum cluster catalyst for preparing propylene by directly dehydrogenating propane, and a preparation method and application thereof; the method comprises the steps of preparing a heteroatom molecular sieve by a hydrothermal method under standing, taking tetrapropylammonium hydroxide as a guiding agent, water and a silicon source, and ethylenediamine tetraacetic acid bi-metal salt as a metal precursor protecting agent, and then loading Pt precursor salt on the surface of a heteroatom molecular sieve carrier through ion exchange and calcination to prepare a platinum cluster catalyst; the platinum cluster catalyst is used in the propane direct dehydrogenation reaction, so that the high-efficiency generation of propylene is realized, the dehydrogenation stability of low-load noble metal is obviously improved, and the catalyst has high single-pass propylene yield and high stability; relates to the field of petrochemical industry.
Description
Technical Field
The invention relates to a platinum cluster catalyst for preparing propylene by directly dehydrogenating propane, and also relates to a preparation method and application of the catalyst, belonging to the field of petrochemical industry.
Background
Propylene is one of the key components of the chemical industry, and due to the advent of shale gas, the source of propylene is slowly being transferred from naphtha to light paraffins, which has led to the derivatization of propane direct dehydrogenation (PDH) propylene production technology. In 1990, the first set of PDH devices worldwide was put into production in thailand, which has been thirty years old. While the PDH project starts from 2013 in China, and the development process is over ten years. In 10 months 2013, 60 ten thousand tons of PDH projects are put into production smoothly in China of Tianjin Bohai petrochemical limited company investment construction. Under the drive of good profit expectations, one-wave PDH investment hot tide is raised in China. Up to the present, about 1000 ten thousand tons of PDH devices are put into production in China, and the PDH devices account for 19.29% of the total propylene productivity in China, and the PDH devices are not as fast as petroleum refining, but the development potential is rapid, and still have a predicted lifting space. Meanwhile, due to the fact that the byproduct hydrogen in the PDH technology is high in purity and high in yield, according to the forecast of a TrendBank (silver potential) company, with the development of hydrogen energy application and the construction and production of national propane dehydrogenation projects, PDH is the main force of domestic hydrogen energy supply. In addition, with the further development of the fracturing technology, the large-scale production of shale gas condensate oil rich in propane can be realized, and the price of propane, a raw material of the PDH technology, is further reduced. Therefore, PDH technology has been considered as one of the most promising propylene production processes in recent years.
Industrially, catalysts used for the direct dehydrogenation of propane are mainly Pt-based catalysts and Cr-based catalysts, such as Oleflex process from UOP company using PtSn/Al 2 O 3 Catalyst, catofin Process from Lummus Co., ltd., cr 2 O 3 /Al 2 O 3 A catalyst. Noble metal Pt has high activity when being used for propane dehydrogenation, is environment-friendly, but has high price, improves the production cost, and is easy to generate sintering phenomenon and catalyst carbon deposition under the severe production conditions of high temperature and low pressure, so that the activity is reduced. Thus, the Pt-based catalyst active sites are enhancedThe performance stability and propylene selectivity in PDH reactions can be strategically improved by reducing the structurally sensitive side reactions (cracking, deep dehydrogenation, etc.) caused by larger Pt nanoparticles. Based on the method, the optimization of the carrier besides the addition of the auxiliary metal ensures that Pt can be well stabilized, is an effective measure, and has great practical significance when the heteroatom molecular sieve stabilized platinum cluster catalyst is used in the reaction of preparing propylene by directly dehydrogenating propane.
Disclosure of Invention
The first object of the invention is to provide a platinum cluster catalyst for preparing propylene by directly dehydrogenating propane, wherein the catalyst carrier is a heteroatom molecular sieve (M-S-1) with the size of 200-1000nm; the active center contains only one metal, pt, present as ultra-small clusters or single sites.
The second object of the invention is to provide a preparation method of the platinum cluster catalyst for preparing propylene by directly dehydrogenating propane.
A third object of the present invention is to provide a method for producing propylene by directly dehydrogenating propane using the platinum group metal catalyst for producing propylene by directly dehydrogenating propane.
The preparation method of the platinum cluster catalyst for preparing propylene by directly dehydrogenating propane sequentially comprises the following steps:
1) Mixing a protective agent and metal salt to form a solution, stirring for 20-40 minutes at room temperature, adding a mixed solution of a silicon source containing water and a guiding agent, stirring for 6-12 hours, transferring to a reaction kettle, carrying out hydrothermal reaction at 180 ℃ for 3-4 days in an oven, cooling to room temperature, washing with water, centrifuging, and calcining to obtain a heteroatom molecular sieve;
2) Adding the hybrid molecular sieve into a Pt-containing precursor solution, stirring at 70-80 ℃ for 6-8 hours, washing with water, centrifuging, and calcining at high temperature to obtain a corresponding Pt/M-S-1 platinum cluster catalyst;
the metal salt is Fe (NO) 3 ) 3 ·9H 2 O，Co(NO 3 ) 2 ·6H 2 O，Ni(NO 3 ) 2 ·6H 2 O，Cu(NO 3 ) 2 ·3H 2 O，Zn(NO 3 ) 2 ·6H 2 O，Ga(NO 3 ) 2 ·9H 2 O，In(NO 3 ) 2 ·4H 2 One of O;
the guiding agent is one of 40% or 25% tetrapropylammonium hydroxide solution;
the molar ratio of the protective agent, the metal salt, the silicon source and the guiding agent is as follows in sequence: 1.0/0.4/40/x/y (where x=y=0.006-0.045);
the mass ratio of the impurity original molecular sieve to the Pt-containing precursor solution is as follows: 1/(5-500).
Preferably, the preparation method of the platinum cluster catalyst for preparing propylene by directly dehydrogenating propane sequentially comprises the following steps:
1) Mixing a protective agent of ethylenediamine tetraacetic acid dimetal salt and metal salt with water to form a complex solution, and stirring for 30 minutes at room temperature until the complex solution is clear;
2) Adding the solution in the step 1) into a mixed solution of a water-containing silicon source and a directing agent, stirring and reacting for 12 hours, transferring to an oven, carrying out hydrothermal treatment for 3 days, centrifuging, washing with water, drying and calcining to obtain M-S-1.
3) And (3) adding the M-S-1 in the step (2) into the solution containing the Pt precursor, stirring for 6 hours, centrifuging, washing with water, drying, and grinding to obtain a sample.
4) And 3) placing the sample in the step 3) in the atmosphere of air in a muffle furnace, heating from room temperature to 400 ℃ at a heating rate of 2 ℃/min, preserving heat for 2 hours, and cooling to room temperature to obtain the Pt/M-S-1 platinum cluster catalyst.
Further, in the preparation method of the platinum cluster catalyst for preparing propylene by directly dehydrogenating propane, the protective agent is one of dipotassium ethylenediamine tetraacetate or disodium ethylenediamine tetraacetate.
Further, the silicon source is one of ethyl orthosilicate, amorphous silica and colloidal silicon solution.
Further, the preparation method of the platinum cluster catalyst for preparing propylene by directly dehydrogenating propane, wherein the size of the heteroatom molecular sieve is 200-1000nm; the proportion of metal in the heteroatom molecular sieve is within 5 wt%.
Further, in the preparation method of the platinum group catalyst for preparing propylene by directly dehydrogenating propane, the M element is one of Fe, co, ni, cu, zn, ga, in.
The second object of the present invention is a platinum cluster catalyst for the direct dehydrogenation of propane to propylene prepared by the first technical solution.
Furthermore, the platinum cluster catalyst for preparing propylene by directly dehydrogenating propane comprises the platinum cluster catalyst, wherein the mass fraction of Pt metal in the platinum cluster catalyst is one ten thousandth to three percent of that of the catalyst, the Pt metal exists in M-S-1 in the form of ultra-small clusters or single points, and the whole catalyst exists in the shape of a hexagonal prism and has the size of 200-1000nm.
The final object of the present invention is to provide the method for preparing propylene by directly dehydrogenating propane, wherein a fixed bed is adopted as a reactor, the platinum cluster catalyst of claim 6 is added into a quartz tube matched with the fixed bed, and the propane is directly dehydrogenated to prepare propylene at 550-600 ℃ under the atmosphere of normal pressure reactive propane.
Further, in the above method for producing propylene by directly dehydrogenating propane, the inner diameter of the tube is 7mm, the outer diameter is 10mm, and the length is 45cm.
Further, the method for preparing propylene by directly dehydrogenating propane is characterized in that the propane atmosphere is 25% C 3 H 8 And pure C 3 H 8 。
Compared with the prior art, the invention has the following advantages:
(1) According to the technical scheme provided by the invention, other hetero atoms are doped into the all-silicon molecular sieve, and the obtained hetero atom molecular sieve can uniformly disperse Pt species, so that the controllable preparation of the ultra-small platinum cluster catalyst is realized, the excellent selectivity and yield are shown in the reaction of directly preparing propylene by propane dehydrogenation, the preparation is simple, the noble metal loading is low, and the environment is friendly;
(2) The platinum cluster catalyst prepared by the method is applied to the reaction of directly preparing propylene by propane dehydrogenation, so that the high-efficiency utilization of active components and the high-efficiency generation of propylene are realized; the propylene yield is low, and the byproducts are few in the reaction process. After oxygen regeneration, the initial propylene yield can still reach more than 40 percent, and no deactivation phenomenon exists.
(3) The platinum cluster catalyst prepared by the invention is applied to the reaction of directly preparing propylene by dehydrogenating propane, realizes high utilization rate of propane raw material and reduces cost.
Description of the drawings:
FIG. 1 is a schematic diagram of PtZnNa3000 platinum group catalyst synthesis;
FIG. 2 is an XRD pattern for PtZnNa750, ptZnNa3000, ptZnNa6000 platinum cluster catalysts;
FIG. 3 is a graph of a PtZnNa3000 platinum group catalyst spherical aberration correcting transmission electron microscope;
FIG. 4 is a view of PtZnNa3000 platinum group catalyst XAS;
FIG. 5 is a graph showing the performance of PtZnNa750, ptZnNa1500, ptZnNa3000, ptZnNa6000 platinum cluster catalysts.
FIG. 6 is a transmission electron microscope image of a PtZnNa750 platinum cluster catalyst;
FIG. 7 is a transmission electron microscope image of a PtZnNa6000 platinum cluster catalyst;
FIG. 8 is an XRD pattern of PtZn3000, ptZnK3000 platinum group catalysts;
fig. 9 is a graph showing the performance of PtZn3000, ptZnK3000 platinum group catalysts:
FIG. 10 shows performance graphs of PtFeNa3000, ptCoNa3000, ptNiNa3000 platinum group catalysts.
FIG. 11 is a graph showing the performance of propylene production by dehydrogenation of propane.
Detailed Description
The present invention will be further described with reference to examples, but the scope of the present invention is not limited to the examples.
Example 1 preparation of Pt/Zn-S-1 (PtZnNa 3000; zn content 0.8 wt.%)
0.74g Zn (NO) was weighed out 3 ) 2 ·6H 2 O is dissolved in 10mL of deionized water, 0.92g of disodium ethylenediamine tetraacetate is added, and stirring is carried out for 30min, so as to obtain solution A; 7g of tetraethyl orthosilicate (TEOS) and 6.6g of 40% tetrapropylammonium hydroxide solution are added to 17g of water and stirred for 30min to obtain solution B; 3ml of solution A was added to solution B and stirredAfter 12h, hydrothermal treatment is carried out for 3d at 180 ℃, and Zn-S-1 is obtained through centrifugal washing, drying and calcining for 6h at 550 ℃;
1g of Zn-S-1 is weighed and dispersed in an aqueous solution containing 3mg of tetramine platinum nitrate, stirred for 6 hours at 80 ℃, centrifugally washed, dried, finally placed in a muffle furnace, heated to 400 ℃ at a heating rate of 2 ℃/min, kept for 2 hours, and cooled to room temperature to obtain the Pt/Zn-S-1 platinum cluster catalyst (PtZnNa 3000).
FIG. 1 is a schematic diagram of the synthesis of a platinum cluster catalyst; FIG. 2 shows XRD patterns; FIG. 3 shows a TEM image of a spherical aberration electron microscope; FIG. 4 shows an XAS graph, which shows that the prepared platinum cluster catalyst is basically in a hexagonal prism shape, and the particle size is 200-500nm, and shows that the platinum cluster preparation is successful.
The prepared platinum cluster catalyst is applied to the reaction of preparing propylene by directly dehydrogenating propane, 100mg PtZnNa3000 is weighed and mixed with 900mg quartz sand to be matched with a fixed bed in a quartz tube, the quartz tube is reduced for 1h at 550 ℃, 25% propane is taken as a reactant (nitrogen is taken as balance gas, the volume ratio is adopted here), and the catalyst is used for preparing propylene at 550 ℃, normal pressure and weight hourly space velocity for 6h -1 The reaction is carried out under the condition of (1), the gas after the reaction is monitored in real time by gas chromatography to analyze the conversion rate of propane and the selectivity of propylene, and fig. 5 is a performance diagram of the preparation of propylene by the dehydrogenation of propane.
The catalyst activity was expressed as a propane conversion and a propylene selectivity, which were calculated as follows. The initial propane conversion was 43%, the propylene selectivity was 99.3%, and after 20h the reactions were 44.6% and 99.2%, respectively.
The conversion rate calculation method comprises the following steps:
the selective calculation method comprises the following steps:
example 2 preparation of Pt/Zn-S-1 (PtZnNa 750; zn content 0.3 wt.%)
0.18g Zn (NO) was weighed out 3 ) 2 ·6H 2 O is dissolved in 10mL of deionized water, and then 0.23g of disodium ethylenediamine tetraacetate is added and stirred for 30min to obtain solution A; 7g of tetraethyl orthosilicate (TEOS) and 6.6g of 40% tetrapropylammonium hydroxide solution are added to 17g of water and stirred for 30min to obtain solution B; adding 3ml of the solution A into the solution B, stirring for 12 hours, carrying out hydrothermal treatment at 180 ℃ for 3 days, and obtaining Zn-S-1 through centrifugal washing, drying and calcining at 550 ℃ for 6 hours;
1g of Zn-S-1 is weighed and dispersed in an aqueous solution containing 3mg of tetramine platinum nitrate, stirred for 6 hours at 80 ℃, centrifugally washed, dried, finally placed in a muffle furnace, heated to 400 ℃ at a heating rate of 2 ℃/min, kept for 2 hours, and cooled to room temperature to obtain the Pt/Zn-S-1 platinum cluster catalyst (PtZnNa 750).
FIG. 2 shows XRD patterns; FIG. 6 shows an electron microscope TEM image, and shows that the prepared platinum cluster catalyst is basically in a hexagonal prism shape, and the particle size is 200-500nm.
The prepared platinum cluster catalyst is applied to the reaction of preparing propylene by directly dehydrogenating propane, 100mg PtZnNa750 is weighed and mixed with 900mg quartz sand to be matched with a fixed bed in a quartz tube, the quartz tube is reduced for 1h at 550 ℃, 25% propane is taken as a reactant (nitrogen is taken as balance gas, the volume ratio is adopted here), and the catalyst is used for preparing propylene at 550 ℃, normal pressure and weight hourly space velocity for 6h -1 The reaction is carried out under the condition of (1), the gas after the reaction is monitored in real time by gas chromatography to analyze the conversion rate of propane and the selectivity of propylene, and fig. 5 is a performance diagram of the preparation of propylene by the dehydrogenation of propane.
The catalyst activity was expressed as propane conversion and propylene selectivity, which were calculated as the formula in example 1. The initial propane conversion was 43.1%, the propylene selectivity was 97%, and after 20h of reaction 42.1% and 99%, respectively.
Example 3 preparation of Pt/Zn-S-1 (PtZnNa 1500; zn content 0.55 wt.%)
0.37g Zn (NO) was weighed out 3 ) 2 ·6H 2 Dissolving O in 10mL of deionized water, adding 0.46g of disodium ethylenediamine tetraacetate, and stirring for 30min to obtain solution A; 7g of tetraethyl orthosilicate (TEOS) and 6.6g of 40% tetrapropylammonium hydroxide solution are added to 17g of water and stirred for 30min to obtain solution B; 3ml of solution A was added to solution B and after stirring for 12h, at 18Hydrothermal treatment is carried out for 3d at 0 ℃, and Zn-S-1 is obtained through centrifugal washing, drying and calcination for 6h at 550 ℃;
1g of Zn-S-1 is weighed and dispersed in an aqueous solution containing 3mg of tetramine platinum nitrate, stirred for 6 hours at 80 ℃, centrifugally washed, dried, finally placed in a muffle furnace, heated to 400 ℃ at a heating rate of 2 ℃/min, kept for 2 hours, and cooled to room temperature to obtain the Pt/Zn-S-1 platinum cluster catalyst (PtZnNa 1500).
The prepared platinum cluster catalyst is applied to the reaction of preparing propylene by directly dehydrogenating propane, 100mg PtZnNa1500 is weighed and mixed with 900mg quartz sand to be matched with a fixed bed in a quartz tube, the quartz tube is reduced for 1h at 550 ℃, 25% propane is taken as a reactant (nitrogen is taken as balance gas, the volume ratio is adopted here), and the catalyst is used for preparing propylene at 550 ℃, normal pressure and weight hourly space velocity for 6h -1 The reaction is carried out under the condition of (1), the gas after the reaction is monitored in real time by gas chromatography to analyze the conversion rate of propane and the selectivity of propylene, and fig. 5 is a performance diagram of the preparation of propylene by the dehydrogenation of propane.
The catalyst activity was expressed as propane conversion and propylene selectivity, which were calculated as the formula in example 1. The initial propane conversion was 42.8%, the propylene selectivity was 98.1%, and after 20h the reactions were 44.2% and 98.9%, respectively.
Example 4 preparation of Pt/Zn-S-1 (PtZnNa 6000; zn content 1.6 wt.%)
1.47g Zn (NO) was weighed out 3 ) 2 ·6H 2 O is dissolved in 10mL of deionized water, 1.84g of disodium ethylenediamine tetraacetate is added, and stirring is carried out for 30min, so as to obtain solution A; 7g of tetraethyl orthosilicate (TEOS) and 6.6g of 40% tetrapropylammonium hydroxide solution are added to 17g of water and stirred for 30min to obtain solution B; adding 3ml of the solution A into the solution B, stirring for 12 hours, carrying out hydrothermal treatment at 180 ℃ for 3 days, and obtaining Zn-S-1 through centrifugal washing, drying and calcining at 550 ℃ for 6 hours;
1g of Zn-S-1 is weighed and dispersed in an aqueous solution containing 3mg of tetramine platinum nitrate, stirred for 6 hours at 80 ℃, centrifugally washed, dried, finally placed in a muffle furnace, heated to 400 ℃ at a heating rate of 2 ℃/min, kept for 2 hours, and cooled to room temperature to obtain the Pt/Zn-S-1 platinum cluster catalyst (PtZnNa 6000).
FIG. 2 shows XRD patterns; FIG. 7 shows an electron microscope TEM image, and shows that the prepared platinum cluster catalyst is basically in a hexagonal prism shape, and the particle size is 200-500nm.
The prepared platinum cluster catalyst is applied to the reaction of preparing propylene by directly dehydrogenating propane, 100mg PtZnNa6000 is weighed and mixed with 900mg quartz sand to be matched with a fixed bed in a quartz tube, the quartz tube is reduced for 1h at 550 ℃, 25% propane is taken as a reactant (nitrogen is taken as balance gas, the volume ratio is adopted here), and the temperature is 550 ℃, the normal pressure and the weight hourly space velocity are respectively 6h -1 The reaction is carried out under the condition of (1), the gas after the reaction is monitored in real time by gas chromatography to analyze the conversion rate of propane and the selectivity of propylene, and fig. 5 is a performance diagram of the preparation of propylene by the dehydrogenation of propane.
The catalyst activity was expressed as propane conversion and propylene selectivity, which were calculated as the formula in example 1. The initial propane conversion was 43.3%, the propylene selectivity was 99.4%, and after 20h the reactions were 44.9% and 99%, respectively.
Example 5 preparation of Pt/Zn-S-1 (PtZnK 3000; zn content 0.6 wt%)
0.74g Zn (NO) was weighed out 3 ) 2 ·6H 2 O is dissolved in 10mL of deionized water, 1g of ethylene diamine tetraacetic acid dipotassium is added, and stirring is carried out for 30min, so as to obtain solution A; 7g of tetraethyl orthosilicate (TEOS) and 6.6g of 40% tetrapropylammonium hydroxide solution are added to 17g of water and stirred for 30min to obtain solution B; adding 3ml of the solution A into the solution B, stirring for 12 hours, carrying out hydrothermal treatment at 180 ℃ for 3 days, and obtaining Zn-S-1 through centrifugal washing, drying and calcining at 550 ℃ for 6 hours;
1g of Zn-S-1 is weighed and dispersed in an aqueous solution containing 3mg of tetramine platinum nitrate, stirred for 6 hours at 80 ℃, centrifugally washed, dried, finally placed in a muffle furnace, heated to 400 ℃ at a heating rate of 2 ℃/min, kept for 2 hours, and cooled to room temperature to obtain the Pt/Zn-S-1 platinum cluster catalyst (PtZnK 3000). Figure 8 shows the XRD pattern.
The prepared platinum cluster catalyst is applied to the reaction of preparing propylene by directly dehydrogenating propane, 100mg PtZnK3000 is weighed and mixed with 900mg quartz sand to be matched with a fixed bed in a quartz tube, the quartz tube is reduced for 1h at 550 ℃, 25% propane is taken as a reactant (nitrogen is taken as balance gas, the volume ratio is adopted here), and the catalyst is used for preparing propylene at 600 ℃, normal pressure and weight hourly space velocity for 6h -1 Is carried out under the condition of reaction and reactionThe gas after reaction was monitored by gas chromatography in real time to analyze the conversion of propane and the selectivity of propylene, and fig. 9 is a performance chart of the dehydrogenation of propane to propylene.
The catalyst activity was expressed as propane conversion and propylene selectivity, which were calculated as the formula in example 1. The initial propane conversion was 61.9%, the propylene selectivity was 97.7%, and after 20h the reaction was 17.9% and 96.1%, respectively.
Example 6 preparation of Pt/Zn-S-1 (PtZn 3000; zn content 0.4 wt%)
0.74g Zn (NO) was weighed out 3 ) 2 ·6H 2 Dissolving O in 10mL of deionized water, adding 0.72g of ethylenediamine tetraacetic acid, and stirring for 30min to obtain solution A; 7g of tetraethyl orthosilicate (TEOS) and 6.6g of 40% tetrapropylammonium hydroxide solution are added to 17g of water and stirred for 30min to obtain solution B; adding 3ml of the solution A into the solution B, stirring for 12 hours, carrying out hydrothermal treatment at 180 ℃ for 3 days, and obtaining Zn-S-1 through centrifugal washing, drying and calcining at 550 ℃ for 6 hours;
1g of Zn-S-1 is weighed and dispersed in an aqueous solution containing 3mg of tetramine platinum nitrate, stirred for 6 hours at 80 ℃, centrifugally washed with water, dried, finally placed in a muffle furnace, heated to 400 ℃ at a heating rate of 2 ℃/min, kept for 2 hours, and cooled to room temperature to obtain the Pt/Zn-S-1 platinum cluster catalyst (PtZn 3000). Figure 8 shows the XRD pattern.
The prepared platinum cluster catalyst is applied to the reaction of preparing propylene by directly dehydrogenating propane, 100mg PtZn3000 is weighed and mixed with 900mg quartz sand to be matched with a fixed bed in a quartz tube, the quartz tube is reduced for 1h at 550 ℃, 25% propane is taken as a reactant (nitrogen is taken as balance gas, the volume ratio is taken here), and the catalyst is used for preparing propylene at 600 ℃, normal pressure and weight hourly space velocity for 6h -1 The reaction is carried out under the condition of (1), and the gas after the reaction is monitored in real time by gas chromatography to analyze the conversion rate of propane and the selectivity of propylene, and fig. 9 is a performance diagram of the preparation of propylene by the dehydrogenation of propane.
The catalyst activity was expressed as propane conversion and propylene selectivity, which were calculated as the formula in example 1. The initial propane conversion was 54.7%, the propylene selectivity was 98.5%, and after 20h the reactions were 3.3% and 80.2%, respectively.
EXAMPLE 7 preparation of Pt/Fe-S-1 (PtFeNa 3000; fe content 1.6 wt%)
1g of Fe (NO) was weighed out 3 ) 2 ·9H 2 O is dissolved in 10mL of deionized water, 0.92g of ethylenediamine tetraacetic acid is added, and stirring is carried out for 30min, so as to obtain solution A; 7g of tetraethyl orthosilicate (TEOS) and 6.6g of 40% tetrapropylammonium hydroxide solution are added to 17g of water and stirred for 30min to obtain solution B; adding 3ml of solution A into solution B, stirring for 12h, performing hydrothermal treatment at 180 ℃ for 3d, and performing centrifugal washing, drying and calcination at 550 ℃ for 6h to obtain Fe-S-1;
1g of Fe-S-1 is weighed and dispersed in an aqueous solution containing 3mg of tetramine platinum nitrate, stirred for 6 hours at 80 ℃, centrifugally washed with water, dried, finally placed in a muffle furnace, heated to 400 ℃ at a heating rate of 2 ℃/min, kept for 2 hours, and cooled to room temperature to obtain the Pt/Fe-S-1 platinum cluster catalyst (PtFeNa 3000).
The prepared platinum cluster catalyst is applied to the reaction of preparing propylene by directly dehydrogenating propane, 100mg PtFeNa3000 is weighed and mixed with 900mg quartz sand to be matched with a fixed bed in a quartz tube, the quartz tube is reduced for 1h at 550 ℃, 25% propane is taken as a reactant (nitrogen is taken as balance gas, the volume ratio is adopted here), and the catalyst is used for preparing propylene at 550 ℃, normal pressure and weight hourly space velocity for 6h -1 The reaction is carried out under the condition of (1), and the gas after the reaction is monitored in real time by gas chromatography to analyze the conversion rate of propane and the selectivity of propylene, and fig. 10 is a performance diagram of the preparation of propylene by the dehydrogenation of propane.
The catalyst activity was expressed as propane conversion and propylene selectivity, which were calculated as the formula in example 1. The initial propane conversion was 47.5%, the propylene selectivity was 90.5%, and after 9.5h the reactions were 46.9% and 94.5%, respectively.
Example 8 preparation of Pt/Co-S-1 (PtCoNa 3000; co content 1 wt.%)
0.72g of Co (NO) was weighed out 3 ) 2 ·6H 2 O is dissolved in 10mL of deionized water, 0.92g of ethylenediamine tetraacetic acid is added, and stirring is carried out for 30min, so as to obtain solution A; 7g of tetraethyl orthosilicate (TEOS) and 6.6g of 40% tetrapropylammonium hydroxide solution are added to 17g of water and stirred for 30min to obtain solution B; 3ml of solution A is added into solution B, stirred for 12 hours, then hydrothermal for 3d at 180 ℃, and centrifugal water washing, drying,Calcining at 550 ℃ for 6 hours to obtain Co-S-1;
1g of Co-S-1 is weighed and dispersed in an aqueous solution containing 3mg of tetramine platinum nitrate, stirred for 6 hours at 80 ℃, centrifugally washed with water, dried, finally placed in a muffle furnace, heated to 400 ℃ at a heating rate of 2 ℃/min, kept for 2 hours, and cooled to room temperature to obtain the Pt/Co-S-1 platinum cluster catalyst (PtCoNa 3000).
The prepared platinum cluster catalyst is applied to the reaction of preparing propylene by directly dehydrogenating propane, 100mg PtCoNa3000 is weighed and mixed with 900mg quartz sand to be matched with a fixed bed in a quartz tube, the quartz tube is reduced for 1h at 550 ℃, 25% propane is taken as a reactant (nitrogen is taken as balance gas, the volume ratio is adopted here), and the catalyst is used for preparing propylene at 550 ℃, normal pressure and weight hourly space velocity for 6h -1 The reaction is carried out under the condition of (1), and the gas after the reaction is monitored in real time by gas chromatography to analyze the conversion rate of propane and the selectivity of propylene, and fig. 10 is a performance diagram of the preparation of propylene by the dehydrogenation of propane.
The catalyst activity was expressed as propane conversion and propylene selectivity, which were calculated as the formula in example 1. The initial propane conversion was 42.8%, the propylene selectivity was 92.4%, and after 9.5h the reactions were 18.3% and 98%, respectively.
Example 9 preparation of Pt/Ni-S-1 (PtNiNa 3000; ni content 1 wt%)
0.72g Ni (NO) was weighed out 3 ) 2 ·6H 2 O is dissolved in 10mL of deionized water, 0.92g of ethylenediamine tetraacetic acid is added, and stirring is carried out for 30min, so as to obtain solution A; 7g of tetraethyl orthosilicate (TEOS) and 6.6g of 40% tetrapropylammonium hydroxide solution are added to 17g of water and stirred for 30min to obtain solution B; adding 3ml of the solution A into the solution B, stirring for 12 hours, carrying out hydrothermal treatment at 180 ℃ for 3 days, and carrying out centrifugal washing, drying and calcination at 550 ℃ for 6 hours to obtain Ni-S-1;
1g of Ni-S-1 is weighed and dispersed in an aqueous solution containing 3mg of tetramine platinum nitrate, stirred for 6 hours at 80 ℃, centrifugally washed with water, dried, finally placed in a muffle furnace, heated to 400 ℃ at a heating rate of 2 ℃/min, kept for 2 hours, and cooled to room temperature to obtain the Pt/Ni-S-1 platinum cluster catalyst (PtNiNa 3000).
The prepared platinum cluster catalyst is applied to the reaction of preparing propylene by directly dehydrogenating propane, 100mg PtNiNa3000 is weighed and 900mg quartz sand is mixedIn a quartz tube matched with a fixed bed, the mixture is reduced for 1h at 550 ℃, 25% propane is taken as a reactant (nitrogen is taken as balance gas, and the volume ratio is adopted here), and the mixture is subjected to air velocity at 550 ℃ under normal pressure and at a weight hourly space velocity of 6h -1 The reaction is carried out under the condition of (1), and the gas after the reaction is monitored in real time by gas chromatography to analyze the conversion rate of propane and the selectivity of propylene, and fig. 10 is a performance diagram of the preparation of propylene by the dehydrogenation of propane.
The catalyst activity was expressed as propane conversion and propylene selectivity, which were calculated as the formula in example 1. The initial propane conversion was 49.7%, the propylene selectivity was 82.2%, and after 9.5h the reactions were 44.2% and 91.5%, respectively.
Example 10 preparation of Co/Zn-S-1 (CoZnNa 6000; zn content 1.6 wt.%)
1.47g Zn (NO) was weighed out 3 ) 2 ·6H 2 O is dissolved in 10mL of deionized water, 1.84g of disodium ethylenediamine tetraacetate is added, and stirring is carried out for 30min, so as to obtain solution A; 7g of tetraethyl orthosilicate (TEOS) and 6.6g of 40% tetrapropylammonium hydroxide solution are added to 17g of water and stirred for 30min to obtain solution B; adding 3ml of the solution A into the solution B, stirring for 12 hours, carrying out hydrothermal treatment at 180 ℃ for 3 days, and obtaining Zn-S-1 through centrifugal washing, drying and calcining at 550 ℃ for 6 hours;
1g of Zn-S-1 was weighed and dispersed in an aqueous solution containing 0.0988g of cobalt nitrate hexahydrate, stirred at 80℃for 6 hours, centrifugally washed with water, and dried to obtain a Co/Zn-S-1 cobalt cluster catalyst (CoZnNa 6000).
The prepared Co cluster catalyst is applied to the reaction of preparing propylene by directly dehydrogenating propane, 200mg CoZnNa6000 is weighed and mixed with 800mg quartz sand to be matched with a fixed bed in a quartz tube, the quartz tube is reduced for 1h at 550 ℃, 25% propane is taken as a reactant (nitrogen is taken as balance gas, the volume ratio is adopted here), and the temperature is 550 ℃, the normal pressure and the weight hourly space velocity are respectively 6h -1 The reaction is carried out under the condition that the gas after the reaction is monitored in real time through gas chromatography to analyze the conversion rate of propane and the selectivity of propylene, and fig. 11 is a performance chart of the preparation of propylene by the dehydrogenation of propane, and obviously, the method also has excellent performance, so that the method is not only suitable for platinum cluster catalysts, but also suitable for catalysts of the same type except Pt and including Co.
The catalyst activity was expressed as propane conversion and propylene selectivity, which were calculated as the formula in example 1. The initial propane conversion was 41.4%, the propylene selectivity was 96%, and after 8.5h of reaction 39.5% and 98%, respectively.
Claims (10)
1. The preparation method of the platinum cluster catalyst for preparing propylene by directly dehydrogenating propane is characterized by comprising the following steps in sequence:
1) Mixing a protective agent and metal salt to form a solution, stirring for 20-40 minutes at room temperature, adding a mixed solution of a silicon source containing water and a guiding agent, stirring for 6-12 hours, transferring to a reaction kettle, carrying out hydrothermal reaction at 180 ℃ for 3-4 days in an oven, cooling to room temperature, washing with water, centrifuging, and calcining to obtain a heteroatom molecular sieve;
2) Adding the hybrid molecular sieve into a Pt-containing precursor solution, stirring at 70-80 ℃ for 6-8 hours, washing with water, centrifuging, and calcining at high temperature to obtain a corresponding Pt/M-S-1 platinum cluster catalyst;
the metal salt is Fe (NO) 3 ) 3 ·9H 2 O，Co(NO 3 ) 2 ·6H 2 O，Ni(NO 3 ) 2 ·6H 2 O，Cu(NO 3 ) 2 ·3H 2 O，Zn(NO 3 ) 2 ·6H 2 O，Ga(NO 3 ) 2 ·9H 2 O，In(NO 3 ) 2 ·4H 2 One of O;
the guiding agent is one of 40% or 25% tetrapropylammonium hydroxide solution;
the molar ratio of the silicon source, the guiding agent, the water, the metal salt and the protecting agent is as follows in sequence: 1.0/0.4/40/x/y
Wherein x=y=0.006-0.045;
the mass ratio of the impurity original molecular sieve to the Pt-containing precursor solution is as follows: 1/(5-500).
2. The method for preparing a platinum group catalyst for the direct dehydrogenation of propane to propylene according to claim 1, wherein the protecting agent is one of dipotassium ethylenediamine tetraacetate or disodium ethylenediamine tetraacetate.
3. The method for preparing a platinum group catalyst for the direct dehydrogenation of propane to propylene according to claim 1, wherein the silicon source is one of ethyl orthosilicate, amorphous silica, and colloidal silicon solution.
4. The method for preparing a platinum cluster catalyst for the direct dehydrogenation of propane to propylene according to claim 1, wherein the heteroatom molecular sieve is 200-1000nm in size; the proportion of metal in the heteroatom molecular sieve is within 5 wt%.
5. The method for preparing a platinum group catalyst for the direct dehydrogenation of propane to propylene according to claim 1, wherein said M element is one of Fe, co, ni, cu, zn, ga, in.
6. A platinum group catalyst for the direct dehydrogenation of propane to propylene, characterized in that it is obtainable by the process according to any of claims 1 to 5.
7. The platinum cluster catalyst for preparing propylene by directly dehydrogenating propane according to claim 6, wherein the platinum cluster catalyst comprises Pt metal in an amount of one ten thousandth to three percent of the mass of the catalyst, and the platinum cluster catalyst exists in M-S-1 in the form of ultra-small clusters or units, and the whole catalyst exists in a hexagonal prism shape and has a size of 200-1000nm.
8. A method for preparing propylene by directly dehydrogenating propane is characterized in that a fixed bed is adopted as a reactor, the platinum cluster catalyst of claim 6 is added into a quartz tube matched with the fixed bed, and the propane is directly dehydrogenated at 550-600 ℃ under the atmosphere of normal pressure reaction propane to prepare propylene.
9. The process for the direct dehydrogenation of propane to propylene according to claim 8, characterized in that the tube has an inner diameter of 7mm, an outer diameter of 10mm and a length of 45cm.
10. The process for the direct dehydrogenation of propane to propylene according to claim 8, wherein the propane atmosphere is 25% c 3 H 8 And pure C 3 H 8 。
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