CN117339622A - Non-noble metal propane dehydrogenation catalyst and preparation method and application thereof - Google Patents
Non-noble metal propane dehydrogenation catalyst and preparation method and application thereof Download PDFInfo
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- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 116
- 239000001294 propane Substances 0.000 title claims abstract description 58
- 239000003054 catalyst Substances 0.000 title claims abstract description 56
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 34
- 239000002184 metal Substances 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 24
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 21
- 239000002808 molecular sieve Substances 0.000 claims abstract description 20
- 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 20
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims abstract description 19
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 11
- 239000010703 silicon Substances 0.000 claims abstract description 11
- 230000008569 process Effects 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 4
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 29
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 239000012298 atmosphere Substances 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 229910052738 indium Inorganic materials 0.000 claims description 5
- 239000003085 diluting agent Substances 0.000 claims description 4
- 238000007873 sieving Methods 0.000 claims description 4
- 238000000498 ball milling Methods 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 3
- 229910001338 liquidmetal Inorganic materials 0.000 claims description 2
- 238000005265 energy consumption Methods 0.000 abstract description 6
- 238000005054 agglomeration Methods 0.000 abstract description 4
- 230000002776 aggregation Effects 0.000 abstract description 4
- 239000002912 waste gas Substances 0.000 abstract description 4
- 239000002351 wastewater Substances 0.000 abstract description 4
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 230000002411 adverse Effects 0.000 abstract 1
- 230000009849 deactivation Effects 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- 239000002699 waste material Substances 0.000 abstract 1
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 description 14
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 14
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 14
- 230000003197 catalytic effect Effects 0.000 description 11
- 238000001354 calcination Methods 0.000 description 10
- 238000001035 drying Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 description 6
- 239000002245 particle Substances 0.000 description 5
- 239000012495 reaction gas Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229940044658 gallium nitrate Drugs 0.000 description 3
- 229910001195 gallium oxide Inorganic materials 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910002847 PtSn Inorganic materials 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 239000002082 metal nanoparticle Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- WVSMEHKNDSWLEM-LGDJGHNWSA-N Ins-1-P-Cer(t20:0/2,3-OH-26:0) Chemical compound CCCCCCCCCCCCCCCCCCCCCCCC(O)C(O)C(=O)N[C@H]([C@H](O)C(O)CCCCCCCCCCCCCCCC)COP(O)(=O)O[C@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](O)[C@H]1O WVSMEHKNDSWLEM-LGDJGHNWSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 102100033118 Phosphatidate cytidylyltransferase 1 Human genes 0.000 description 1
- 101710178747 Phosphatidate cytidylyltransferase 1 Proteins 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 241000219793 Trifolium Species 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 150000002258 gallium Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 150000002471 indium Chemical class 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 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
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/04—Mixing
-
- 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
- C07C5/3332—Catalytic processes with metal oxides or metal sulfides
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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
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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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)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention belongs to the field of catalysts, and particularly relates to a non-noble metal propane dehydrogenation catalyst, and a preparation method and application thereof. The invention mainly solves the problems of complex process, high energy consumption, long production period, high cost, waste gas and wastewater emission, environmental pollution and easy agglomeration and deactivation of active metal species of the catalyst in the existing preparation method. The invention adopts the technical scheme that liquid gallium or gallium metal solution and pure silicon molecular sieve with a certain aperture are fully mixed and mechanically molded to prepare the propane dehydrogenation catalyst, so that the problems are well solved, and the synthesis method effectively avoids adverse factors caused by high-temperature roasting, and can be used in the industrial production of the propane dehydrogenation catalyst with low cost, low energy consumption, no three waste discharge, simplicity, rapidness and stability.
Description
Technical Field
The invention belongs to the field of catalysts, and particularly relates to a non-noble metal propane dehydrogenation catalyst, and a preparation method and application thereof.
Background
Propylene is an important basic organic chemical raw material, and is a precursor of various fine chemicals such as propylene oxide, acrylic acid or polymers such as polypropylene. Traditional propylene production methods include naphtha steam cracking, naphtha catalytic cracking and synthesis gas to produce propylene. The propane dehydrogenation process has the advantages of low investment, high yield and high purity due to rich raw materials and high propylene selectivity, and is rapidly developed in recent years. Industrial propane dehydrogenation processes are based on Oleflex process (U.S. Pat. No. 3,2022-06-30) and Catofin process (U.S. Pat. No. 3, 201113236971A, 2013-03-01), respectively using PtSn/Al 2 O 3 Catalyst and Cr 2 O 3 /Al 2 O 3 A catalyst. The PtSn catalyst has high catalytic activity, but has high price and high requirement on raw materials, pt particles are easy to sinter in the reduction process before catalysis, and the activity and stability of the catalyst are seriously affected. The Cr-based catalyst has lower cost and higher activity at low temperature, but has poor stability and serious influence on environment. Therefore, the preparation of a novel catalyst with high stability, low cost and environmental friendliness is key to the propane dehydrogenation reaction while maintaining high catalytic activity.
Researches show that the gallium oxide-based catalyst has good catalytic performance on propane dehydrogenation reaction, has low cost and low toxicity, and can improve the catalytic propane dehydrogenation performance by adding other metal species. The existing preparation methods of the gallium oxide-based catalyst mainly comprise two types: impregnation and coprecipitation. Yang man prepared Ga by dipping method 2 O 3 Soaking the MgO/ZSM-5 catalyst in a magnesium nitrate solution, stirring uniformly, drying and calcining to obtain MgO/ZSM-5, soaking the MgO/ZSM-5 in a gallium nitrate solution, stirring uniformly, drying and calcining to obtain Ga 2 O 3 MgO/ZSM-5 catalyst, at 600 ℃, 0.1MPa, 20% C 3 H 8 、WHSV＝4.7h -1 Under the condition that the conversion rate of propane reaches 16 percent, the propylene selectivity is 90 percent (Applied catalyst A, general 643 (2022) 118778). Tan person prepared In by coprecipitation method 2 O 3 -Ga 2 O 3 -Al 2 O 3 Dissolving gallium salt, indium salt and aluminum salt in ethanol, dripping a mixture of ammonia water and ethanol to precipitate metal salt, stirring uniformly, centrifuging, drying, calcining to obtain the catalyst, and heating at 600deg.C, 0.1MPa and 5%C 3 H 8 、WHSV＝1h -1 Under the conditions, the conversion of propane reached 17% and the propylene selectivity was 85% (ChemCatChem 2016,8,214-221).
In conclusion, the gallium oxide-based catalyst has high activity, low cost and low toxicity, is a novel propane dehydrogenation catalyst with great potential, but has the advantages of complex synthesis steps, long production period, energy consumption and cost rise caused by drying and calcining links, agglomeration of active metal species of the catalyst, and waste water, waste gas and environmental pollution caused by impregnating, precipitating and calcining metal salts. These factors have greatly limited the development and industrial application of propane dehydrogenation catalysts.
Disclosure of Invention
The invention aims to solve the technical problems of lengthy and complex preparation process, high energy consumption and cost, environment friendliness and agglomeration of catalyst active metal species in the prior art, and provides a novel preparation method of a propane dehydrogenation catalyst. The method is simple and quick, has low cost and low energy consumption, avoids waste gas and waste water generated in the process of calcining the metal salt, and the obtained catalyst loaded metal nano particles are uniformly dispersed and stable, and the particle size is kept about 3nm (shown in figure 3).
In order to solve the technical problems, the application provides the following technical scheme:
the invention provides a preparation method of a non-noble metal propane dehydrogenation catalyst, which comprises the following steps:
s11: dissolving a metal simple substance in liquid metal gallium to obtain a gallium metal solution; the mass ratio of the metal simple substance to the liquid gallium is 0-1:1, a step of; the metal simple substance is selected from one or more of In, sn, zn, al, ag, cu, ni, co and Fe;
s12: and mixing the gallium metal solution with a pure silicon molecular sieve, and mechanically forming to obtain the non-noble metal propane dehydrogenation catalyst.
Preferably, the mass ratio of the metal solution to the molecular sieve is 0.01-1:1.
preferably, the pure silicon molecular sieve has a microporous character.
Preferably, the pure silicon molecular sieve has one or more of BEC, CDO, EWO, IFR, ITW, MEL, MFI, MWW, OKO, PCR, RRO and RTE structures in the international molecular sieve association CODE.
Preferably, the pure silicon molecular sieve is selected from Silicalite-1 molecular sieves.
Preferably, in the step S12, the mixing is performed by one of stirring, friction, extrusion, impact, grinding and ball milling.
Preferably, in the step S12, the mechanical molding method is tabletting and sieving.
Preferably, the non-noble metal propane dehydrogenation catalyst obtained after mechanical shaping is spherical, clover-leaf-shaped, flake-shaped or irregular cube-shaped.
The invention also provides a non-noble metal propane dehydrogenation catalyst prepared by the preparation method.
The invention also provides a method for catalyzing the dehydrogenation of propane, which comprises the following steps:
heating the non-noble metal propane dehydrogenation catalyst to 300-850 ℃, and reacting under the condition of mixed gas atmosphere and pressure of 0.01-10 MPa; the mixed gas is propane and diluent gas.
Preferably, the mass space velocity is 0.1-10h during the reaction -1 The total flow of the gas is 1-200mL/min.
Preferably, the diluent gas is nitrogen.
Preferably, the volume concentration of propane in the mixed gas is 1-100%.
Preferably, the reaction is carried out in a fixed bed reactor.
Compared with the prior art, the technical scheme of the invention has the following advantages:
according to the scheme, the metal simple substance is used for replacing metal salt, so that the high-temperature roasting process is effectively avoided, the active site tightly combined with the carrier can be obtained by mechanical mixing, and the complexity, the preparation cost and the environmental pollution of the catalyst preparation process are greatly reduced. The metal single matter is preferably one of In, sn, zn, al, ag, cu, ni, co, fe metals; the metallic gallium or gallium-based metal is in a liquid state; the pure silicon molecular sieve is preferably selected from one of Silicalite-1, silicalite-2, ITQ-1, SSZ-48, CDS-1, CIT-15, IPC-4, RUB-41, ITQ-4, COK-14, ITQ-12 and RUB-3 with micropore characteristics; the mixing mode is one of stirring, friction, extrusion, impact, grinding and ball milling mechanical methods; the mechanical shaping causes the catalyst to exhibit one of a spherical, clover, platelet, irregular cube shape. Compared with other preparation methods, the method reduces the steps of dipping, drying and calcining, and has shorter period, lower energy consumption and lower cost. And the metal simple substance is used as the raw material to replace metal salt, so that NO waste water and waste gas are discharged in the processes of dipping, precipitation and calcination, and compared with nitrate (NO is generated) 2 ) Chloride salts (formation of HCl or Cl) 2 ) Is more environment-friendly. In addition, the synthesized metal nano particles are uniformly dispersed, the particle size distribution is about 3nm (shown in figure 3), the particles do not agglomerate after the catalytic propane dehydrogenation reaction (shown in figure 4), and the catalytic propane dehydrogenation performance is more stable.
Drawings
FIG. 1 is a Silicalite-1 molecular sieve and Ga 2 O 3 -In 2 O 3 XRD pattern of Silicalite-1 catalyst.
FIG. 2 is a TEM image of Silicalite-1 molecular sieves.
FIG. 3 is Ga 2 O 3 -In 2 O 3 TEM image of Silicalite-1 catalyst.
FIG. 4 is Ga 2 O 3 -In 2 O 3 TEM image of a Silicalite-1 after catalytic propane dehydrogenation.
FIG. 5 is a graph of 3% Ga in example 1 2 O 3 Silicalite-1 catalyst at 4.5h -1 Propane dehydrogenation performance activity profile at mass space velocity.
FIG. 6 is a graph of 3% Ga in example 2 2 O 3 -1％In 2 O 3 Silicalite-1 catalyst at 4.5h -1 Propane dehydrogenation performance activity profile at mass space velocity.
Detailed Description
The present invention will be further described with reference to the accompanying drawings and specific examples, which are not intended to be limiting, so that those skilled in the art will better understand the invention and practice it.
Example 1
Mixing 0.03g of metallic gallium and 1g of Silicalite-1 molecular sieve uniformly by grinding, tabletting, forming and sieving to obtain spherical Ga 2 O 3 Silicalite-1 catalyst and catalytic evaluation of propane dehydrogenation was carried out in a fixed bed reactor. The specific conditions are as follows: 0.3g Ga 2 O 3 Silicalite-1 catalyst (40-60 mesh), reaction temperature of 600 ℃, reaction pressure of normal pressure, total flow of reaction gas of 50mL/min, propane flow of 12.5mL/min and nitrogen flow of 37.5mL/min. Ga 2 O 3 The Silicalite-1 catalyst was heated to 600℃under a nitrogen atmosphere, and was reacted by introducing a mixture of propane and nitrogen, with an initial propane conversion of 21.3%, a propylene selectivity of 75.1%, a propane conversion after 3 hours of reaction of 19.4% and a propylene selectivity of 78.6% (as shown in FIG. 5).
Example 2
Mixing 0.03g of metal gallium and 0.005g of metal indium uniformly to obtain gallium metal solution, mixing gallium metal solution and 1g of Silicalite-1 molecular sieve uniformly by grinding, tabletting, forming and sieving to obtain spherical Ga 2 O 3 -In 2 O 3 Silicalite-1 catalyst and catalytic evaluation of propane dehydrogenation was carried out in a fixed bed reactor. The specific conditions are as follows: 0.3g Ga 2 O 3 -In 2 O 3 Silicalite-2 catalyst (40-60 mesh), reaction temperature of 600 ℃, reaction pressure of normal pressure, total flow of reaction gas of 50mL/min, propane flow of 12.5mL/min and nitrogen flow of 37.5mL/min. Ga 2 O 3 -In 2 O 3 Silicalite-1 catalystThe temperature is raised to 600 ℃ under the nitrogen atmosphere, propane and nitrogen mixed gas are introduced to react, the initial propane conversion rate is 24.7%, the propylene selectivity is 88.1%, the propane conversion rate after 3 hours of reaction is 20.0%, and the propylene selectivity is 91.6% (shown in fig. 6).
Examples 3 to 30
According to the methods of examples 1 and 2, propane dehydrogenation catalysts of different non-noble metals were prepared by changing the metal simple substance type, the mass ratio of metal simple substance to gallium, the mass ratio of pure silicon molecular sieve type, gallium or gallium-based metal to pure silicon molecular sieve, the mixing mode and the catalyst molding shape (see table 1 for specific modes), and the propane dehydrogenation reaction was catalytically evaluated in a fixed bed reactor. The catalyst is heated to the reaction temperature in the inert gas atmosphere, propane and nitrogen are introduced to react, and different catalytic results of propane dehydrogenation reaction are obtained by changing the reaction pressure, the reaction temperature, the reaction mass space velocity and the total flow of the reaction gas.
Comparative example 1
According to literature [ RSCAAdvances, 2017,7,4710]Soaking gallium nitrate solution on an SBA-15 carrier, aging for 4 hours at room temperature, drying for one night at 100 ℃, and calcining for 4 hours at 550 ℃ in air atmosphere to obtain Ga with 3% loading capacity 2 O 3 SBA-15 catalyst and the catalytic performance of the propane dehydrogenation was determined in a fixed bed reactor. The specific conditions are as follows: 0.2g Ga 2 O 3 SBA-15 catalyst, the reaction temperature is 620 ℃, the reaction pressure is normal pressure, the total flow of reaction gas is 20mL/min, the flow of propane is 1mL/min, and the flow of argon is 19mL/min. The initial (t=10 min) propane conversion was 22%, the propylene selectivity was 91%, the propane conversion after 2h of reaction was 17% and the propylene selectivity was 92%.
Comparative example 2
According to document [ Applied Catalysis A, general 643 (2022) 118778]Soaking gallium nitrate solution on a Mg-modified ZSM-5 carrier, stirring at room temperature for 12h, drying at 120 ℃ for one night, and calcining at 600 ℃ for 4h in air atmosphere to obtain Ga with 5% loading capacity 2 O 3 MgO/ZSM-5 catalyst and determination of the catalyst for the dehydrogenation of propane in a fixed bed reactorChemical properties. The specific conditions are as follows: 0.2g Ga 2 O 3 The reaction temperature is 600 ℃, the reaction pressure is normal pressure, the total flow of reaction gas is 40mL/min, the flow of propane is 8mL/min, and the flow of argon is 32mL/min. The initial (t=10 min) propane conversion was 16%, the propylene selectivity was 89%, the propane conversion after 3h of reaction was 10% and the propylene selectivity was 92%.
Effect evaluation 1
In FIG. 1, after loading the metal oxide, there was no change in the diffraction peak position of Silicalite-1, and no diffraction peak of the metal oxide appeared, indicating that this method did not destroy the support itself, and that the metal oxide was uniformly dispersed on the support.
In FIGS. 2 to 4, the transmission electron microscope shows Silicalite-1 carrier and Ga 2 O 3 -In 2 O 3 The Silicalite-1 catalyst catalyzes the nano features before and after the propane dehydrogenation reaction. From the figure, it can be observed that the surface of Silicalite-1 is loaded with metal oxide with the particle size of about 3nm, the dispersion degree is high, and agglomeration does not exist after catalysis.
TABLE 1 results for specific examples 1-14
TABLE 2 example results 15-30 and comparative example results
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations and modifications of the present invention will be apparent to those of ordinary skill in the art in light of the foregoing description. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.
Claims (10)
1. A method for preparing a non-noble metal propane dehydrogenation catalyst, which is characterized by comprising the following steps:
s11: dissolving a metal simple substance in liquid metal gallium to obtain a gallium metal solution; the mass ratio of the metal simple substance to the liquid gallium is 0-1:1, a step of; the metal simple substance is selected from one or more of In, sn, zn, al, ag, cu, ni, co and Fe;
s12: and mixing the gallium metal solution with a pure silicon molecular sieve, and mechanically forming to obtain the non-noble metal propane dehydrogenation catalyst.
2. The preparation method according to claim 1, wherein the mass ratio of the metal solution to the molecular sieve is 0.01-1:1.
3. the method of manufacture of claim 1 wherein the pure silicon molecular sieve has microporous characteristics.
4. The method of claim 1, wherein the pure silicon molecular sieve is selected from the group consisting of Silicalite-1 molecular sieves.
5. The method of claim 1, wherein in the step S12, the mixing is performed by one of stirring, friction, extrusion, impact, grinding and ball milling.
6. The method of claim 1, wherein in step S12, the mechanical molding is tabletting and sieving.
7. A non-noble metal propane dehydrogenation catalyst prepared by the method of any one of claims 1-6.
8. A method of catalyzing the dehydrogenation of propane comprising the steps of:
heating the non-noble metal propane dehydrogenation catalyst according to claim 7 to 300-850 ℃, and reacting under the condition of mixed gas atmosphere and pressure of 0.01-10 MPa; the mixed gas is propane and diluent gas.
9. The process according to claim 8, wherein the mass space velocity is from 0.1 to 10h during the reaction -1 The total flow of the gas is 1-200mL/min.
10. The method of claim 8, wherein the diluent gas is nitrogen.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005052730A (en) * | 2003-08-04 | 2005-03-03 | National Institute Of Advanced Industrial & Technology | Catalyst for propane dehydrogenation reaction |
| CN106311214A (en) * | 2016-07-31 | 2017-01-11 | 湘潭大学 | Dehydrogenation catalyst for non-precious metal and preparation method thereof |
| CN110975925A (en) * | 2019-12-04 | 2020-04-10 | 中国科学院上海高等研究院 | Gallium indium tin metal catalyst, preparation method and application |
| CN111589464A (en) * | 2020-04-23 | 2020-08-28 | 台州学院 | Boron nitride-loaded rhodium-gallium-tin liquid alloy catalyst and preparation method and application thereof |
| CN113479849A (en) * | 2020-07-29 | 2021-10-08 | 宁波工程学院 | Preparation method of nano metal oxide |
| CN113509950A (en) * | 2021-04-28 | 2021-10-19 | 福州大学 | Preparation method of gallium-based catalyst taking alumina modified by non-metallic elements as carrier |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005052730A (en) * | 2003-08-04 | 2005-03-03 | National Institute Of Advanced Industrial & Technology | Catalyst for propane dehydrogenation reaction |
| CN106311214A (en) * | 2016-07-31 | 2017-01-11 | 湘潭大学 | Dehydrogenation catalyst for non-precious metal and preparation method thereof |
| CN110975925A (en) * | 2019-12-04 | 2020-04-10 | 中国科学院上海高等研究院 | Gallium indium tin metal catalyst, preparation method and application |
| CN111589464A (en) * | 2020-04-23 | 2020-08-28 | 台州学院 | Boron nitride-loaded rhodium-gallium-tin liquid alloy catalyst and preparation method and application thereof |
| CN113479849A (en) * | 2020-07-29 | 2021-10-08 | 宁波工程学院 | Preparation method of nano metal oxide |
| CN113509950A (en) * | 2021-04-28 | 2021-10-19 | 福州大学 | Preparation method of gallium-based catalyst taking alumina modified by non-metallic elements as carrier |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117960157A (en) * | 2024-03-29 | 2024-05-03 | 苏州大学 | Carbon monoxide oxidation catalyst and preparation method and application thereof |
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