CN113019412A - Catalyst for preparing olefin by light alkane dehydrogenation, preparation method and application thereof - Google Patents
Catalyst for preparing olefin by light alkane dehydrogenation, preparation method and application thereof Download PDFInfo
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- CN113019412A CN113019412A CN202110250208.9A CN202110250208A CN113019412A CN 113019412 A CN113019412 A CN 113019412A CN 202110250208 A CN202110250208 A CN 202110250208A CN 113019412 A CN113019412 A CN 113019412A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 78
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 33
- 150000001335 aliphatic alkanes Chemical class 0.000 title claims abstract description 27
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims abstract description 35
- 229910052751 metal Inorganic materials 0.000 claims abstract description 27
- 239000002184 metal Substances 0.000 claims abstract description 27
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000001294 propane Substances 0.000 claims abstract description 13
- 230000003197 catalytic effect Effects 0.000 claims abstract description 12
- 239000001282 iso-butane Substances 0.000 claims abstract description 11
- 229910002056 binary alloy Inorganic materials 0.000 claims abstract description 9
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 8
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 6
- 229910052718 tin Inorganic materials 0.000 claims abstract description 6
- 229910052802 copper Inorganic materials 0.000 claims abstract description 4
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 4
- 229910052984 zinc sulfide Inorganic materials 0.000 claims abstract description 4
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 3
- 229910052738 indium Inorganic materials 0.000 claims abstract description 3
- 150000003839 salts Chemical class 0.000 claims description 38
- 239000002243 precursor Substances 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 30
- 239000012298 atmosphere Substances 0.000 claims description 23
- 239000012018 catalyst precursor Substances 0.000 claims description 23
- 239000012266 salt solution Substances 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 19
- 238000002791 soaking Methods 0.000 claims description 16
- 238000000498 ball milling Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000005470 impregnation Methods 0.000 claims description 11
- 238000007598 dipping method Methods 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 230000003301 hydrolyzing effect Effects 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000012495 reaction gas Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 230000001476 alcoholic effect Effects 0.000 claims description 2
- 239000003125 aqueous solvent Substances 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 7
- 229910045601 alloy Inorganic materials 0.000 abstract description 6
- 239000000956 alloy Substances 0.000 abstract description 6
- 230000009467 reduction Effects 0.000 abstract description 6
- 230000008929 regeneration Effects 0.000 abstract description 4
- 238000011069 regeneration method Methods 0.000 abstract description 4
- 238000005530 etching Methods 0.000 abstract description 3
- 238000011068 loading method Methods 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 25
- 229910052799 carbon Inorganic materials 0.000 description 21
- 238000001354 calcination Methods 0.000 description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 15
- 238000012360 testing method Methods 0.000 description 13
- 230000008021 deposition Effects 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 229910002621 H2PtCl6 Inorganic materials 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 7
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- 230000004913 activation Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910018509 Al—N Inorganic materials 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000010606 normalization Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910002844 PtNi Inorganic materials 0.000 description 1
- 229910002847 PtSn Inorganic materials 0.000 description 1
- 229910002846 Pt–Sn Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals 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
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
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- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
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- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
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- 230000000704 physical effect Effects 0.000 description 1
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- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 1
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- 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
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/60—Platinum group metals with zinc, cadmium or mercury
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
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- B01J23/56—Platinum group metals
- B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
- B01J23/622—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead
- B01J23/626—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead with tin
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
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- 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
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- C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
- C07C2523/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
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- C—CHEMISTRY; METALLURGY
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- C—CHEMISTRY; METALLURGY
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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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
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- Y02P20/50—Improvements relating to the production of bulk chemicals
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Abstract
The invention discloses a catalyst for preparing olefin by light alkane dehydrogenation, a preparation method and application thereof, wherein the catalyst is a supported type, wurtzite type high-specific-surface-area porous aluminum nitride nano powder is used as a carrier, and a catalytic active phase is a Pt-M binary alloy nano cluster, wherein Pt is an active component, M is a metal auxiliary agent and is Zn, Cu, Sn, Ga or In; the mass percent of Pt in the catalyst is 0.1-5.0 wt%, and the mass percent of M is 0.1-10 wt%. The preparation method of the catalyst comprises the steps of prehydrolysis of the surface of an aluminum nitride carrier, loading of active and auxiliary components on the surface of the aluminum nitride carrier, and roasting, reduction and self-etching to generate the nano alloy cluster. Compared with the traditional alumina supported catalyst, the catalyst obtained by the invention is used for propane and isobutane dehydrogenation reaction, the selectivity and the space-time yield of a target olefin product are obviously improved, and excellent reaction stability and recycling regeneration performance are shown.
Description
Technical Field
The invention belongs to the technical field of chemical catalysis, and particularly relates to a catalyst for preparing olefin by light alkane dehydrogenation, and a preparation method and application thereof.
Background
The low-carbon olefin is the most important basic chemical raw material, is the basis for supporting the modern chemical industry, takes propylene/isobutene as a representative, is mainly used for synthesizing important chemicals such as polymers, rubber, acrylonitrile, oxygen-containing organic matters and the like, and is closely related to the production life of human beings. The traditional low-carbon olefin production processes mainly comprise oil-based steam cracking, catalytic cracking and coal-based methanol-to-olefin reaction, and the production processes involve the breakage and rearrangement of various chemical bonds of C-H, C-C, C-O, have low atom utilization efficiency, and often have a series of problems of high energy consumption, large carbon emission and the like. Compared with the traditional route, the light alkane (ethane/propane/isobutane) catalytic dehydrogenation process is specially used for producing low-carbon olefin and byproduct hydrogen, has high atom economy, simple flow and low investment cost, develops an important way for increasing the yield of the olefin in industry, and effectively relieves the excessive dependence of the low-carbon olefin raw material in China on petroleum resources.
The alumina-loaded Pt-Sn catalyst is a main system used by the existing light alkane catalytic dehydrogenation industrial device, however, carbon deposition and inactivation are easy to occur under the working condition, frequent oxidation and carbon burning and reduction regeneration are needed, sintering of Pt and Sn components is aggravated by high temperature and atmosphere switching, the service life of the catalyst is short, and the cost is high. Therefore, the problems of inhibiting the generation of carbon deposit to the maximum extent, reducing the regeneration process and prolonging the service life of the catalyst are to be solved urgently in the technical process. In order to solve the problems, the industry and academia select alkali metal or alkaline earth metal components to modify PtSn/Al2O3Catalyst supported by neutralizationThe surface acidity of the body relieves the generation of carbon deposition on the surface of the catalyst, but the low-boiling point elements usually cover active sites to lose reaction activity, so that the utilization efficiency of the precious metal Pt is reduced, the input cost is increased, and meanwhile, the alkali metal or alkaline earth metal elements are very volatile in a working condition environment, corrode reaction equipment and pipelines, and have very serious potential safety hazard and economic loss.
The selection of inert carriers comprising silicon oxide, silicon carbide and the like is a possible solution path, for example, Chinese patent [ CN106311311A ] reports that a mesoporous silicon oxide (SBA-15) supported Pt catalyst effectively inhibits carbon deposition side reaction caused by acidic surface in the propane dehydrogenation reaction, and shows good reaction stability. However, in contrast to activated alumina supports which are surface-rich in hydroxyl, amphoteric acid-base pairs, the surface inertness of these supports also directly entails a low dispersion of the active component Pt, albeit at the expense of a large proportion of the reactivity, despite an increase in the selectivity and stability of the dehydrogenation reaction. Therefore, further development of a novel carrier replacing alumina, simultaneous improvement of dehydrogenation activity and stability and noble metal platinum utilization efficiency remains an urgent need in this field.
Aluminum nitride (AlN) is an atomic crystal containing an Al-N covalent bond, belongs to a diamond-like compound, a hexagonal system and a wurtzite crystal form, is widely applied to the fields of superhard materials, high-temperature ceramics, electronic packaging and the like, has the characteristics of high hardness, high melting point, good thermal conductivity, chemical corrosion resistance and the like, and is also desired as an excellent catalytic carrier material, but is traditionally regarded as an inert material due to high hardness, small specific surface area, few surface defects and few functional groups, and hardly gets attention in the industrial catalytic field for many years.
Disclosure of Invention
The invention aims to adopt novel aluminum nitride with unique nano-morphology and porous structure as a carrier, regulate and control Pt active phase composition and structure by utilizing carrier effect, couple the surface alkaline characteristics of the carrier, and synchronously improve the activity, selectivity and stability of a Pt catalyst in the reaction of preparing olefin by light alkane dehydrogenation, namely, the activity and selectivity are improved, the generation of carbon deposit is inhibited to the greatest extent, the regeneration process is reduced, the service life of the catalyst is prolonged, and the catalytic efficiency is improved.
The technical scheme of the invention is as follows:
a supported light alkane dehydrogenation olefin preparation catalyst comprises a carrier and a catalytic active phase, wherein the carrier is wurtzite crystal aluminum nitride nano powder, and the catalytic active phase is a Pt-M binary alloy nano cluster, wherein Pt is an active component, M is a metal auxiliary agent and is Zn, Cu, Sn, Ga or In; the mass percent of Pt in the catalyst is 0.1-5.0 wt%, and the mass percent of M is 0.1-10 wt%.
The mass percentage of Pt in the catalyst is 0.1-0.5 wt%.
The mass percentage of M is 0.1-1 wt%.
The Pt-M binary alloy is attached to the surface of an aluminum nitride carrier in a low-dimensional nano cluster form, and the grain size of the Pt-M binary alloy nano cluster ranges from 0.5 nm to 5nm and is concentrated at 2 nm.
Preferably, the aluminum nitride is spherical, granular, flaky, filamentous or fibrous physical mesostructure, and further, the aluminum nitride is spherical, the particle size is 50-500 nm, and the specific surface area is 50-300 m2(ii)/g, the pore size distribution is 1-10 nm.
Preferably, the metal auxiliary agent is Zn, Cu or Sn; further, the metal promoter is Zn.
The invention also provides a preparation method of the supported light alkane catalyst for olefin preparation by dehydrogenation, which comprises the following steps:
firstly, pre-hydrolyzing an aluminum nitride carrier: ball milling treatment or acid water solution treatment is carried out,
a) ball milling treatment: ball milling the aluminum nitride carrier for 0.1-10 h at room temperature, wherein the ball milling speed is less than 800r/min, and the atmosphere is air or oxygen;
b) and (3) treating with an acidic aqueous solution: aluminum nitride support isovolumic impregnation of HNO at room temperature3And/or HCl solution, standing at room temperature, pre-hydrolyzing, and drying;
step two, catalyst preparation:
introducing an active component Pt and a metal auxiliary agent M on the prehydrolyzed aluminum nitride carrier by adopting a co-impregnation method, a step-by-step impregnation method or a soaking method to obtain a catalyst precursor, roasting and reducing the catalyst precursor at 400-800 ℃ to obtain a supported light alkane dehydrogenation olefin catalyst, and recording the catalyst as a Pt-M/AlN catalyst.
The preparation method of the catalyst precursor by the co-impregnation method comprises the following steps: a) dissolving Pt salt and metal rib agent salt in an aqueous solvent to obtain a metal precursor salt solution; b) dipping a metal precursor solution on the prehydrolyzed aluminum nitride carrier, standing at room temperature, and drying to obtain a catalyst precursor; the metal rib agent salt is Zn salt or Cu salt;
the step-by-step impregnation method for preparing the catalyst precursor comprises the following steps: a) respectively dissolving Pt salt and Sn salt in an aqueous solution and an alcoholic solution to obtain a Pt precursor salt solution and a Sn precursor salt solution dipping solution; b) dipping the Sn precursor salt solution on a prehydrolyzed aluminum nitride carrier, stirring at room temperature for 0.05-2 h, drying and roasting to obtain SnO/AlN, dipping the Pt precursor salt solution on the SnO/AlN, standing at room temperature and drying to obtain a catalyst precursor;
the soaking method for preparing the catalyst precursor comprises the following steps: a) dissolving Pt salt and metal auxiliary agent salt in an aqueous solution to obtain a metal precursor salt solution; b) soaking the prehydrolyzed aluminum nitride carrier in a metal precursor salt solution, stirring at room temperature for 0.05-2 h, and drying to obtain a catalyst precursor; the metal rib agent salt is Ga salt or In salt.
The Pt salt is chloroplatinic acid, and the Zn salt, the Cu salt, the Sn salt, the Ga salt or the In salt is nitrate, chloride or acetate.
Preferably, the concentration of Pt salt in the metal precursor salt solution in the co-soaking method or the soaking method is 0.025-0.25 g/mL, and the concentration of metal auxiliary salt is 0.01-0.4 g/mL; the concentration of Pt salt in the Pt precursor salt solution is 0.025-0.25 g/mL by a stepwise dipping method, and the concentration of Sn salt in the Sn precursor salt solution is 0.01-0.4 g/mL.
The roasting atmosphere is 20 vol% O2/N2The reducing atmosphere is 1-20 vol% H2/N2。
An appropriate prehydrolysis mode is selected based on physical properties such as structural properties and surface properties of aluminum nitride, and the prehydrolysis mode of acidic aqueous solution treatment is preferred.
The invention also provides an application of the catalyst in the preparation of olefin by light alkane dehydrogenation, which is to mix light alkane with gas (H)2And N2) And mixing at room temperature, and introducing the mixture into a reactor filled with the catalyst, wherein the concentration of the light alkane is 1-30 vol%, the total flow rate of gas is 10-300 mL/min, the reaction temperature is 450-650 ℃, and the reaction pressure is 0-0.2 MPa.
Preferably, the reactor is a fixed bed differential reactor.
Preferably the light alkane is propane or isobutane; when the reaction gas is propane, the reaction temperature is 550-650 ℃, and further, the reaction temperature is 590 ℃; when the reaction gas is isobutane, the reaction temperature is 450-550 ℃, and further, the reaction temperature is 500 ℃.
The reaction pressure is preferably 0.1 MPa.
The invention has the beneficial effects of reacting with Pt-M/Al2O3Compared with the catalyst, the Pt-M/AlN catalyst disclosed by the invention is applied to light alkane dehydrogenation, so that the selectivity and the space-time yield of an olefin product are obviously improved, the generation of carbon deposition is greatly reduced, the reaction stability of the catalyst is improved, and the catalyst has a good application prospect. The surface of the aluminum nitride carrier is beneficial to the generation of the Pt-M binary alloy, the alloy state ensures that the dehydrogenated Pt active center is in an electron-rich state, the desorption of olefin is facilitated, the secondary deep dehydrogenation reaction of olefin is inhibited, the selectivity of a dehydrogenation reaction product on a catalyst is effectively improved, and the generation of carbon deposit is correspondingly inhibited. On the other hand, the unique hydrolysis characteristic of Al-N bonds on the surface of the aluminum nitride drives the etching process around Pt-M alloy particles (water is generated in the reduction process, the generated water hydrolyzes the Al-N bonds around the PtM and ammonia is released by etching, Pt-M particles are embedded in an aluminum nitride carrier), the high dispersion and stability of a Pt-M active phase are promoted, and the reaction activity of the catalyst is ensured. Meanwhile, the specific alkaline characteristics of the aluminum nitride carrier can cut off the occurrence of carbon deposition side reactions such as alkane cracking and the like, the alkaline sites further eliminate the polymerization reaction of the carbon deposition precursor, and the carbon deposition reaction rate is effectively reduced, so that the excellent carbon deposition resistance is shown. The invention applies the aluminum nitride to the dehydrogenation reaction of the loaded Pt-M catalyst and the light alkane for the first timeThe obtained catalyst has obvious effects on the aspects of improving the reaction activity, the carbon deposition resistance and the catalyst stability.
Drawings
FIG. 1 is a graph comparing conversion and selectivity for catalyst B versus catalyst G.
FIG. 2 is an optical photograph of the sample after reaction of catalyst B with catalyst G.
FIG. 3 is a transmission electron microscope image of catalyst B obtained in example 1 of the present invention.
FIG. 4 is a comparison of the powder X-ray diffraction results for catalyst B and catalyst G.
Detailed Description
The present invention will be described in detail below with reference to specific examples, but the present invention is not limited to the following examples.
The carrier is expressed by AlN-bm/H, wherein: bm represents activation treatment using a ball milling method; h represents activation treatment using an acidic aqueous solution. The specific process is as follows:
a) activation treatment of a ball milling method: ball milling the aluminum nitride carrier for 5 hours at room temperature, wherein the ball milling speed is 400r/min, and the atmosphere is air or oxygen;
b) acid aqueous solution activation treatment: the aluminum nitride carrier is dipped in 2M HNO in the same volume at room temperature3And/or HCl solution, standing at room temperature, pre-hydrolyzing, and drying;
the amounts of active component and promoter of the catalyst are in mass percent, for example 0.5Pt1Sn/AlN-H, which means that the mass percent of Pt is 0.5% and the mass percent of Sn is 1%.
Example 1
4.543-227.3 mg Zn (NO)3)2·6H2O and 13.27mg H2PtCl6·6H2Dissolving the O precursor in 500 mul of water, soaking the O precursor in 1g of AlN-H carrier, standing the soaked sample at room temperature for 2H, drying the sample at 50 ℃ overnight to obtain a catalyst precursor, and adding the catalyst precursor into 20 vol% O2/N2Calcining at 500 deg.C for 4H in atmosphere, and then calcining at 20 vol% H2/N2And reducing for 2h at 590 ℃ in an atmosphere to obtain catalyst samples A, B and C. As can be seen from fig. 3, catalyst B: 0.5PtZn/AlN-HThe Pt-Zn metal particles are highly dispersed on the bulk in the form of small clusters. The grain size of the Pt-Zn binary alloy nano cluster ranges from 0.5 nm to 5nm and is concentrated at 2 nm. Fig. 4 gives information on the crystal structure of the 0.5PtZn/AlN-H catalyst, where the peak at the position of 40.8 ° 2 θ corresponds to the as-alloyed Pt1Zn1(111) The diffraction peak of (1).
Testing the reaction performance of the propane dehydrogenation catalyst:
taking 100mg of catalyst, loading the catalyst into a fixed bed micro-reaction device, and controlling the flow rate to be 48mL min-1C of (A)3H8/H2/N2(1: 1.25: 4) mixed gas is used as a reaction raw material, the reaction is carried out for 6 hours at 590 ℃ and 0.1MPa, the dehydrogenation product is analyzed by a GC7900 gas chromatograph, propane and propane in the product are analyzed, the conversion rate, the selectivity and the like of the reaction are calculated by a normalization method, and the evaluation result is shown in Table 1.
Testing the reaction performance of the isobutane dehydrogenation catalyst:
taking 100mg of catalyst, loading the catalyst into a fixed bed micro-reaction device, and controlling the flow rate to be 52mL min-1C of (A)4H10/H2/N2(1: 3.2) using mixed gas as a reaction raw material, reacting for 12h at 500 ℃ and 0.1MPa, analyzing isobutane and isobutene in a dehydrogenation product by a GC7900 gas chromatograph, calculating the conversion rate, selectivity and the like of the reaction by adopting a normalization method, and obtaining an evaluation result shown in Table 1.
Example 2
1g of AlN-H carrier was immersed in 2ml of a solution containing 59.9mg of Ga (NO)3)3·9H2O and 13.27mg H2PtCl6·6H2Stirring a sample in an O precursor water solution for 2h at room temperature, drying at 120 ℃ to obtain a catalyst precursor, and putting the catalyst precursor in 20 vol% O2/N2Calcining at 500 deg.C for 4H in atmosphere, and then calcining at 20 vol% H2/N2The catalyst sample D was obtained by reduction in an atmosphere at 590 ℃ for 2 hours, and the propane dehydrogenation test was carried out under the test conditions of example 1, and the evaluation results are shown in Table 1.
Example 3
19.01mg of SnCl is taken2·2H2O was dissolved in 500. mu.l of ethanol solution, and the solution (Sn front)Flooding solution) on a 1g AlN-H carrier, standing the impregnated sample at room temperature for 2H, drying at 50 ℃ overnight, and adding 20 vol% O2/N2Roasting for 4 hours at 500 ℃ in the atmosphere to obtain SnO/AlN-H; 13.27mg of H2PtCl6·6H2Dissolving an O precursor in 500 mu l of water solution, soaking the solution (Pt precursor salt solution) on a 1g SnO/AlN-H carrier in the same volume, standing the soaked sample at room temperature for 2H, drying at 50 ℃ overnight to obtain a catalyst precursor, and putting the catalyst precursor in 20 vol% O2/N2Calcining at 500 deg.C for 4H in atmosphere, and then calcining at 20 vol% H2/N2The catalyst sample E was obtained by reduction in an atmosphere at 590 ℃ for 2 hours, and the propane dehydrogenation test was carried out under the test conditions of example 1, and the evaluation results are shown in Table 1.
Example 4
4.543mgZn (NO)3)2·6H2O and 13.27mg H2PtCl6·6H2Dissolving the O precursor in 500 μ l of water, soaking the O precursor in 1g of AlN-bm carrier, standing the soaked sample at room temperature for 2h, drying the sample at 50 ℃ overnight, and treating the sample with 20 vol% of O2/N2Calcining at 500 deg.C for 4H in atmosphere, and then calcining at 20 vol% H2/N2The catalyst sample F was obtained by reduction in an atmosphere at 590 ℃ for 2 hours, and the propane dehydrogenation test was carried out under the test conditions of example 1, and the evaluation results are shown in Table 1.
Example 5
4.543mgZn (NO)3)2·6H2O and 2.654mg H2PtCl6·6H2Dissolving the O precursor in 500 μ l of water, soaking the O precursor in 1g of AlN-bm carrier, standing the soaked sample at room temperature for 2h, drying the sample at 50 ℃ overnight, and treating the sample with 20 vol% of O2/N2Calcining at 500 deg.C for 4H in atmosphere, and then calcining at 20 vol% H2/N2The catalyst sample was obtained as H by reduction in an atmosphere at 590 ℃ for 2 hours, and the evaluation results of the isobutane dehydrogenation test conducted under the test conditions of example 1 are shown in Table 1.
Comparative example 1
Al used in this comparative example2O3Com is prepared by leaving high purity pseudoboehmite developed by Sasol company, Germany at 500 ℃ and standingRoasting in air for 4h to obtain gamma-Al2O3. 4.543mg of Zn (NO)3)2·6H2O and 13.27mg H2PtCl6·6H2The O precursor was dissolved in 500. mu.l of water and immersed in 1gAl2O3Com support, after impregnation the sample was left to stand at room temperature for 2h, dried at 50 ℃ overnight in 20 vol% O2/N2Calcining at 500 deg.C for 4H in atmosphere, and then calcining at 20 vol% H2/N2Reducing the catalyst for 2 hours at 590 ℃ in an atmosphere to obtain a catalyst sample G, wherein as can be seen from FIG. 4, the catalyst G does not form a PtZn alloy, performing an isobutane dehydrogenation test according to the test conditions of example 1, and the evaluation results are shown in Table 1, and comparing the isobutane dehydrogenation catalytic test results, the following results are obtained: from the conversion point of view, the catalyst using AlN-H as a carrier and Al2O3Com as a carrier and a catalyst; however, from the viewpoint of the selectivity of isobutene in the product and the catalytic stability, the catalyst using AlN-H as a carrier has better performance. Meanwhile, from the color comparison of the catalyst after the reaction in FIG. 2, it can be seen that the catalyst having AlN-H as a carrier has a higher Al content than Al content2O3The catalyst taking com as a carrier has the advantage of resisting carbon deposition.
Comparative example 2
Mixing 15.75mgAgNO3And 13.27mg H2PtCl6·6H2Dissolving the O precursor in 500 μ l of water, soaking the mixture in 1g of AlN-bm carrier, standing the soaked sample at room temperature for 2h, drying the sample at 50 ℃ overnight, and treating the sample with 20 vol% O2/N2Calcining at 500 deg.C for 4H in atmosphere, and then calcining at 20 vol% H2/N2Reduction was carried out at 590 ℃ for 2h in an atmosphere to obtain a catalyst sample I, 0.5Pt1Ag/AlN, and no PtAg alloy was formed in the catalyst I.
Comparative example 3
49.55mgNi (NO)3)2·6H2O and 13.27mg H2PtCl6·6H2Dissolving the O precursor in 500 μ l of water, soaking the O precursor in 1g of AlN-bm carrier, standing the soaked sample at room temperature for 2h, drying the sample at 50 ℃ overnight, and treating the sample with 20 vol% of O2/N2Calcining at 500 deg.C for 4H in atmosphere, and then calcining at 20 vol% H2/N2Reduction was carried out at 590 ℃ for 2h in an atmosphere to obtain a catalyst sample J, 0.5Pt1Ni/AlN, and no PtNi alloy was formed in the catalyst J.
TABLE 1 correspondence of dehydrogenation activities of low-carbon alkanes in different samples
Claims (8)
1. A supported catalyst for preparing olefin by dehydrogenating light alkane is characterized in that: the catalyst comprises a carrier and a catalytic active phase, wherein the carrier is wurtzite crystal aluminum nitride nano powder, and the catalytic active phase is a Pt-M binary alloy nano cluster, wherein Pt is an active component, and M is a metal auxiliary agent which is Zn, Cu, Sn, Ga or In; the mass percent of Pt in the catalyst is 0.1-5.0 wt%, and the mass percent of M is 0.1-10 wt%.
2. The supported catalyst for preparing olefin by dehydrogenating light alkane as claimed in claim 1, wherein: the mass percentage of Pt in the catalyst is 0.1-0.5 wt%.
3. The supported catalyst for preparing olefin by dehydrogenating light alkane as claimed in claim 1, wherein: the Pt-M binary alloy is attached to the surface of an aluminum nitride carrier in a low-dimensional nano cluster form, and the grain size of the Pt-M binary alloy nano cluster ranges from 0.5 nm to 5nm and is concentrated at 2 nm.
4. A method for preparing the supported catalyst for preparing olefin by dehydrogenating light alkane according to claim 1, which is characterized in that: the method comprises the following steps:
s1 prehydrolysis of aluminum nitride support: ball milling treatment or acid water solution treatment is carried out,
a) ball milling treatment: ball milling the aluminum nitride carrier for 0.1-10 h at room temperature, wherein the ball milling speed is less than 800r/min, and the atmosphere is air or oxygen;
b) and (3) treating with an acidic aqueous solution: aluminum nitride support isovolumic impregnation of HNO at room temperature3And/or HCl solution ofStanding at room temperature, pre-hydrolyzing, and drying;
s2 preparation of catalyst:
introducing an active component Pt and a metal auxiliary agent M on the prehydrolyzed aluminum nitride carrier by adopting a co-impregnation method, a step-by-step impregnation method or a soaking method to obtain a catalyst precursor, and roasting the catalyst precursor at 400-800 ℃ and reducing the catalyst precursor at 350-600 ℃ to obtain the supported light alkane dehydrogenation olefin catalyst.
5. The method of claim 4, wherein the method comprises the steps of:
the preparation method of the catalyst precursor by the co-impregnation method comprises the following steps: a) dissolving Pt salt and metal rib agent salt in an aqueous solvent to obtain a metal precursor salt solution; b) dipping a metal precursor solution on the prehydrolyzed aluminum nitride carrier, standing at room temperature, and drying to obtain a catalyst precursor; the metal rib agent salt is Zn salt or Cu salt;
the step-by-step impregnation method for preparing the catalyst precursor comprises the following steps: a) respectively dissolving Pt salt and Sn salt in an aqueous solution and an alcoholic solution to obtain a Pt precursor salt solution and a Sn precursor salt solution dipping solution; b) dipping the Sn precursor salt solution on a prehydrolyzed aluminum nitride carrier, stirring at room temperature for 0.05-2 h, drying and roasting to obtain SnO/AlN, dipping the Pt precursor salt solution on the SnO/AlN, standing at room temperature and drying to obtain a catalyst precursor;
the soaking method for preparing the catalyst precursor comprises the following steps: a) dissolving Pt salt and metal auxiliary agent salt in an aqueous solution to obtain a metal precursor salt solution; b) soaking the prehydrolyzed aluminum nitride carrier in a metal precursor salt solution, stirring at room temperature for 0.05-2 h, and drying to obtain a catalyst precursor; the metal rib agent salt is Ga salt or In salt.
6. The method of claim 5, wherein the method comprises the steps of: the concentration of Pt salt in the metal precursor salt solution in the co-soaking method or the soaking method is 0.025-0.25 g/mL, and the concentration of metal auxiliary salt is 0.01-0.4 g/mL; the concentration of Pt salt in the Pt precursor salt solution is 0.025-0.25 g/mL by a stepwise dipping method, and the concentration of Sn salt in the Sn precursor salt solution is 0.01-0.4 g/mL.
7. Use of the catalyst of claim 1 in the dehydrogenation of light alkanes to olefins, wherein: and (2) mixing the light alkane at room temperature, and introducing the mixture into a reactor filled with the catalyst, wherein the concentration of the light alkane is 1-30 vol%, the total flow rate of the gas is 10-300 mL/min, the reaction temperature is 450-650 ℃, and the reaction pressure is 0-0.2 MPa.
8. Use of the catalyst of claim 7 in the dehydrogenation of light alkanes to olefins, wherein: the light alkane is propane or isobutane; when the reaction gas is propane, the reaction temperature is 550-650 ℃; when the reaction gas is isobutane, the reaction temperature is 450-550 ℃.
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