CN113856738B - Catalyst with function of catalyzing propane dehydrogenation to prepare propylene, preparation method and application thereof, and method for preparing propylene - Google Patents
Catalyst with function of catalyzing propane dehydrogenation to prepare propylene, preparation method and application thereof, and method for preparing propylene Download PDFInfo
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- CN113856738B CN113856738B CN202010615415.5A CN202010615415A CN113856738B CN 113856738 B CN113856738 B CN 113856738B CN 202010615415 A CN202010615415 A CN 202010615415A CN 113856738 B CN113856738 B CN 113856738B
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- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 239000003054 catalyst Substances 0.000 title claims abstract description 85
- 238000000034 method Methods 0.000 title claims abstract description 67
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 65
- 239000001294 propane Substances 0.000 title claims abstract description 52
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229910052710 silicon Inorganic materials 0.000 claims description 47
- 239000010703 silicon Substances 0.000 claims description 47
- 239000002808 molecular sieve Substances 0.000 claims description 44
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 44
- 239000002243 precursor Substances 0.000 claims description 28
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 14
- 238000005470 impregnation Methods 0.000 claims description 12
- 238000011068 loading method Methods 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 11
- 239000012752 auxiliary agent Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 239000002135 nanosheet Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 8
- 229910000510 noble metal Inorganic materials 0.000 claims description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 7
- 239000011148 porous material Substances 0.000 claims description 7
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- -1 small-molecule quaternary ammonium salt Chemical class 0.000 claims description 6
- 230000002194 synthesizing effect Effects 0.000 claims description 6
- 239000002671 adjuvant Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052799 carbon Inorganic materials 0.000 abstract description 6
- 230000008021 deposition Effects 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 230000008929 regeneration Effects 0.000 abstract description 4
- 238000011069 regeneration method Methods 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 22
- 239000000047 product Substances 0.000 description 12
- 230000003197 catalytic effect Effects 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 239000002245 particle Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 229910052697 platinum Inorganic materials 0.000 description 5
- 238000010025 steaming Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000002064 nanoplatelet Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000004230 steam cracking Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000003863 ammonium salts Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
-
- 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
-
- 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
-
- 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
-
- 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
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/40—Special temperature treatment, i.e. other than just for template removal
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
- C01P2004/24—Nanoplates, i.e. plate-like particles with a thickness from 1-100 nanometer
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
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- 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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- 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
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Abstract
The invention relates to the field of catalysts, and discloses a catalyst with a function of catalyzing propane dehydrogenation to prepare propylene, a preparation method and application thereof, and a method for preparing propylene. The catalyst provided by the invention has the characteristics of long single-pass service life, low carbon deposition rate, good product selectivity, high stability and the like. The selectivity of the catalyst to propylene can reach more than 90%, the single-pass service life is longer than 200 hours, compared with the existing catalyst, the regeneration frequency can be reduced, the production efficiency is effectively improved, and the requirement of large-scale industrial production can be met.
Description
Technical Field
The invention relates to the field of catalysts, in particular to a catalyst with a function of catalyzing propane dehydrogenation to prepare propylene, a preparation method and application thereof, and a method for preparing propylene.
Background
Propylene is a major industrial requirement as one of the basic raw materials for three synthetic materials. The traditional propylene preparation process comprises steam cracking, catalytic cracking, preparing propylene after synthesizing methanol by coal, and the like. However, both steam cracking and catalytic cracking processes are routes for producing propylene from oil, the cost of which is directly related to the price of petroleum, and the cost of which is increasing as the price of petroleum increases. The process for preparing propylene after synthesizing methanol by using coal is realized by adopting a method for preparing olefins such as ethylene, propylene and the like by using coal as a raw material to synthesize methanol, but has the problem of long process route. Compared with the traditional propylene preparation process, the process for directly preparing propylene by propane dehydrogenation has the advantages of low raw material cost, short process route, few byproducts and higher yield.
The existing commercial catalyst for preparing propylene by propane dehydrogenation mainly adopts an alumina carrier, and has the problems of poor stability, short single-pass catalytic life and the like. The frequent catalyst regeneration increases the production energy consumption, and meanwhile, the fluidized bed technology is adopted in the technology, so that the problems of complex matched reaction devices, high construction cost and the like are caused. Therefore, there is a need to develop a novel propylene catalyst support for the dehydrogenation of propane to overcome the above disadvantages.
The all-silicon molecular sieve has weak acidity, can inhibit isomerization and secondary hydrogenation of intermediate products to a certain extent, reduces carbon deposition, and is beneficial to improving the selectivity of the products, the single-pass catalytic life of the catalyst and the catalytic stability. In addition, when the all-silicon molecular sieve is used as a carrier, the interaction between the all-silicon molecular sieve and an active component is weaker, so that the activity of the catalyst can be further improved. The microporous molecular sieve is favorable for the dispersion of active components due to a specific pore structure and a higher specific surface area, and meanwhile, the pore canal has shape selectivity and can be used for some small molecule dehydrogenation reactions. Although weakly acidic supports can reduce the rate of carbon deposition, diffusion limitations can still promote carbon deposition due to the smaller pore channels of all-silica molecular sieves, thereby reducing catalytic life.
Disclosure of Invention
The invention aims to solve the problems of poor stability, short single-pass catalytic life, frequent regeneration and the like of a catalyst for preparing propylene by propane dehydrogenation in the prior art, and provides a catalyst with a function of preparing propylene by catalyzing propane dehydrogenation, a preparation method and application thereof, and a method for preparing propylene. The catalyst provided by the invention has the characteristics of long single-pass service life, low carbon deposition rate, good product selectivity, high stability and the like.
In order to achieve the above object, in one aspect, the present invention provides a catalyst having a function of catalyzing the dehydrogenation of propane to prepare propylene, the catalyst comprising a support comprising a two-dimensional all-silicon molecular sieve and an active component comprising a noble metal.
In a second aspect, the present invention provides a method for preparing a catalyst having a function of catalyzing the dehydrogenation of propane to prepare propylene, the method comprising the steps of:
(1) Synthesizing a two-dimensional all-silicon molecular sieve;
(2) An active component and optional adjuvants are supported on the two-dimensional all-silicon molecular sieve, the active component comprising a noble metal.
In a third aspect the present invention provides a catalyst prepared by the above process.
In a fourth aspect the present invention provides the use of the above catalyst and the above process for the catalytic dehydrogenation of propane to produce propylene.
In a fifth aspect the present invention provides a process for the preparation of propylene comprising contacting propane under dehydrogenation conditions to produce propylene with the catalyst described above.
Through the technical scheme, the catalyst provided by the invention has the advantages of long single-pass service life, low carbon deposition rate and high stability, and the selectivity of the catalyst to propylene can reach more than 90%. The catalyst provided by the invention is used for the reaction of preparing propylene by propane dehydrogenation, so that the regeneration frequency of the catalyst can be reduced, the production efficiency is effectively improved, the selectivity of the product is improved, and the requirement of large-scale industrial production can be met.
Drawings
FIGS. 1-2 are graphs showing the propane conversion and propylene selectivity of the propylene-producing reaction by dehydrogenation of propane for the catalyst A1 prepared in example 1, respectively, over time;
FIGS. 3 to 4 are graphs showing the propane conversion and propylene selectivity of the propylene-producing reaction by dehydrogenation of propane for the catalyst A2 prepared in example 2, respectively, over time;
FIGS. 5 to 6 are graphs showing the propane conversion and propylene selectivity of the propylene-producing reaction by dehydrogenation of propane for the catalyst A3 prepared in example 3, respectively, over time.
Detailed Description
The following detailed description of the invention will be further explained and illustrated with the understanding that the following detailed description is merely illustrative of the invention and is not intended to limit the invention.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
Under the condition that no special description is made, the two-dimensional all-silicon molecular sieve disclosed by the invention refers to: MFI molecular sieves having two-dimensional platelet morphology features.
The first aspect of the invention provides a catalyst with the function of catalyzing propane dehydrogenation to prepare propylene, which comprises a carrier and an active component, wherein the carrier comprises a two-dimensional all-silicon molecular sieve, and the active component comprises noble metal.
According to a preferred embodiment of the invention, wherein the support comprises two-dimensional MFI-type molecular sieve nanoplatelets.
Preferably, the specific surface area of the carrier is 200-500m 2 /g。
Preferably, the average pore size of the support is 5-15nm.
According to a preferred embodiment of the invention, wherein the active component is Pt.
According to a preferred embodiment of the invention, the active ingredient is present in an amount of 0.1 to 1% by weight, based on the weight of the carrier. That is, the weight ratio of the active component to the carrier is 1 based on the total weight of the catalyst: 100-1000.
According to a preferred embodiment of the present invention, wherein the catalyst may further comprise an auxiliary agent.
Preferably, the auxiliary comprises at least one of Zn, sn, K and Ca. More preferably at least one of Zn, K and Ca.
More preferably, the adjuvant is present in an amount of 0.01 to 1% by weight based on the weight of the carrier.
In a second aspect, the present invention provides a method for preparing a catalyst having a function of catalyzing the dehydrogenation of propane to prepare propylene, the method comprising the steps of:
(1) Synthesizing a two-dimensional all-silicon molecular sieve;
(2) An active component and optional adjuvants are supported on the two-dimensional all-silicon molecular sieve, the active component comprising a noble metal.
The inventor of the invention skillfully discovers that the axial growth of crystals can be inhibited by adopting a method of using a long-chain quaternary ammonium salt and a small-molecular quaternary ammonium salt as double templates, and the problem that the crystal structure tends to grow in a three-dimensional structure in the synthesis process of the two-dimensional molecular sieve is solved.
According to a preferred embodiment of the present invention, the mode of synthesizing the two-dimensional all-silicon molecular sieve in the step (1) includes: and mixing the template agent with a silicon source, performing hydrothermal reaction, and sequentially performing solid-liquid separation, drying and roasting on a hydrothermal reaction product to obtain the two-dimensional all-silicon molecular sieve. Wherein the template agent comprises a mixture of long-chain quaternary ammonium salt and small-molecule quaternary ammonium salt.
Preferably, the long-chain quaternary ammonium salt is a long-chain quaternary ammonium salt with more than 10 carbon atoms. More preferably a C12-C22 long chain quaternary ammonium salt.
Preferably, the small molecule quaternary ammonium salt comprises tetrapropylammonium hydroxide.
More preferably, the molar ratio of long chain quaternary ammonium salt to small molecular quaternary ammonium salt in the mixture is 1:1-5.
The template agent can be long-chain quaternary ammonium salt and small-molecular quaternary ammonium salt which are prepared by self according to the prior art and can also be a commercial product with the characteristics. For example, an Organic Structure Directing Agent (OSDA) having a long chain alkyl group and a bisquaternary ammonium salt, tetrapropylammonium hydroxide (TPAOH), and the like can be mentioned.
The silicon source may be any of the available silicon-containing compounds that can be used in the preparation of all-silicon molecular sieves. According to a preferred embodiment of the invention, wherein the silicon source comprises at least one of ethyl silicate and a silica sol.
Preferably, the molar ratio of the template to the silicon source is 1:0.5-5.
More preferably, the molar ratio of the templating agent to the silicon source is 1:1-5.
Further preferably, the molar ratio of the templating agent to the silicon source is 1:1-4.
According to a preferred embodiment of the present invention, for the purpose of sufficiently mixing the silicon source and the template, the mixing manner of the template and the silicon source may include: the templating agent is gradually added to the silicon source while stirring.
Preferably, the stirring conditions include: the temperature is 20-30 ℃ and the time is 2-6 hours, and the stirring speed is 200-300rpm relative to 24g of the mixture of the template agent and the silicon source.
According to a preferred embodiment of the present invention, wherein the conditions of the hydrothermal reaction comprise: the time is 40-55h, and the temperature is 160-180 ℃.
Any existing solid-liquid separation, drying and roasting modes suitable for preparing the two-dimensional all-silicon molecular sieve can be used for the method provided by the invention.
According to a preferred embodiment of the present invention, the manner and condition of the solid-liquid separation may include, for the purpose of improving production efficiency: the centrifugal separation mode is adopted, the centrifugal speed is 4500-5500rpm, and the time is 20-40min.
According to a preferred embodiment of the present invention, wherein the drying conditions include: the temperature is 90-120 ℃ and the time is 1-5h.
According to a preferred embodiment of the present invention, wherein the conditions of the firing include: 550-600 ℃, 6-8 hours, and 1-5 ℃/min heating rate.
According to a preferred embodiment of the present invention, step (2) comprises loading an active component precursor and an optional auxiliary precursor on the two-dimensional all-silicon molecular sieve by an impregnation method, and then sequentially drying and calcining to obtain the catalyst.
The active component precursor can be any water-soluble compound containing noble metal elements which can be used in the preparation of noble metal catalysts. According to a preferred embodiment of the invention, wherein the active component precursor comprises a platinum group metal precursor, preferably chloroplatinic acid.
According to a preferred embodiment of the present invention, wherein the active component precursor is used in an amount such that the active component is supported on the support in an amount of 0.1 to 1% by weight of the support in terms of metal element.
According to a preferred embodiment of the invention, wherein the auxiliary precursor comprises a water-soluble inorganic salt of the auxiliary.
Preferably, the promoter precursor comprises at least one of a sulfate, nitrate and chloride of the promoter.
More preferably, the auxiliary precursor comprises ZnNO 3 、SnCl 4 、KNO 3 And Ca (NO) 3 ) 2 At least one of, preferably ZnNO 3 、KNO 3 And Ca (NO) 3 ) 2 At least one of them.
According to a preferred embodiment of the present invention, wherein the auxiliary precursor is used in such an amount that the auxiliary is supported on the support in an amount of 0.01 to 1% by weight of the support, based on the metal element.
According to a preferred embodiment of the invention, the impregnation method is an isovolumetric impregnation method and/or an overdose impregnation method.
Preferably, the impregnation method employs an isovolumetric impregnation method.
According to a preferred embodiment of the present invention, wherein the drying conditions include: the temperature is 100-150 ℃ and the time is 1-5h.
Preferably, the drying conditions include: the temperature is 120-130 ℃ and the time is 2-3h.
According to a preferred embodiment of the present invention, wherein the conditions of the firing include: the temperature is 550-650 ℃ and the time is 1-10h.
Preferably, the roasting conditions include: the temperature is 580-620 ℃ and the time is 5-6h.
According to a preferred embodiment of the invention, wherein, according to practical needs, a step of crushing can be further included after roasting.
Preferably, the conditions of the crushing are such that the particle size of the catalyst is 40-60 mesh.
In a third aspect the invention provides a catalyst prepared by the process as described above.
According to a preferred embodiment of the present invention, wherein the catalyst has a particle size of 40 to 60 mesh and a specific surface area of 200 to 500m 2 And/g, the average pore diameter is 5-15nm.
In a fourth aspect the present invention provides the use of a catalyst as described above or a process as described above for the catalytic dehydrogenation of propane to propylene.
In a fifth aspect the present invention provides a process for the preparation of propylene, characterised in that the process comprises contacting propane with a catalyst as described above under dehydrogenation conditions to prepare propylene.
According to a preferred embodiment of the present invention, wherein the conditions for the dehydrogenation to propylene comprise: the temperature is 550-650 ℃, the pressure is 0.08-0.12MPa, and the mass airspeed is 1-3h -1 . In the present invention, the pressure refers to gauge pressure.
The present invention will be described in detail by examples. It should be understood that the following examples are provided for further explanation and illustration of the present invention and are not intended to limit the present invention.
In the following examples, OSDA was purchased from the national drug company, TPAOH was purchased from the chemical industry of ridge, and ethyl silicate was purchased from the optical company of Tianjin. Other conventional instrumentation and chemicals are purchased from standardized chemical instrumentation and reagent suppliers.
In the following examples, the conditions of the vacuum spin-steaming method are: water bath at 60℃and vacuum of 95kPa.
In the following test examples, analysis of the reaction product components was performed on a gas chromatograph available from Agilent under the model 7890A, in which propane and propylene were detected by an alumina column FID detector. The calculation method of the propane conversion rate adopts a normalization method, and the main formula is as follows:
propane conversion = moles of propane converted/moles of propane fed
Propylene selectivity = moles of propylene converted/moles of propane converted
In the following examples, the single pass lifetime refers to: the catalyst is maintained for a period of time under conditions of use at activity levels including CO conversion and product selectivity. Specifically, the single-pass life is calculated from the start of the reaction until when any one of the indices fails to be maintained stable.
Example 1
The first step: synthesis of two-dimensional MFI type all-silicon molecular sieve
Adopting ethyl silicate as a silicon source, adopting OSDA and TPAOH as dual-template agents, and mixing the dual-template agents with the ethyl silicate according to the molar ratio of 0.5:1:1, mixing and stirring. Magnetic stirring for 2h at 250rpm relative to 24g of the mixture of the template and the silicon source, transferring to a hydrothermal kettle, crystallizing at constant temperature of 180 ℃ for 48h, taking out, and centrifuging (5000 rpm,30 min). Oven dried (120 ℃,2 h) and calcined at 550 ℃ for 6h. Obtaining the two-dimensional MFI type all-silicon molecular sieve nanosheets S1.
And a second step of: catalyst with function of catalyzing propane dehydrogenation to prepare propylene
With chloroplatinic acid and ZnNO 3 Is prepared into an aqueous solution by using an active component precursor and an auxiliary agent precursor. And (3) dipping by adopting a vacuum rotary steaming method, and loading the Pt loaded amount of 0.1 weight percent and the Zn loaded amount of 0.1 weight percent on the two-dimensional MFI type all-silicon molecular sieve nano-sheet S1 prepared in the first step according to the weight of the carrier and calculated by metal elements. And then dried at 120℃for 2 hours. The dried product was then calcined at 600℃for 5h.
Tabletting and crushing the roasted product to the particle size of 40-60 meshes. Catalyst A1 was obtained.
Example 2
The first step: synthesis of two-dimensional MFI type all-silicon molecular sieve
Adopting ethyl silicate as a silicon source, adopting OSDA and TPAOH as dual-template agents, and mixing the dual-template agents with the ethyl silicate according to a molar ratio of 1:1:1, mixing and stirring. Magnetically stirring for 2h at 250rpm, transferring to a hydrothermal kettle, crystallizing at 180deg.C for 48h, taking out, and centrifuging (5000 rpm,30 min). Oven dried (120 ℃,2 h) and calcined at 550 ℃ for 6h. Obtaining the two-dimensional MFI type all-silicon molecular sieve nanosheets S2.
And a second step of: catalyst with function of catalyzing propane dehydrogenation to prepare propylene
With chloroplatinic acid and ZnNO 3 Is prepared into an aqueous solution by using an active component precursor and an auxiliary agent precursor. And (3) dipping by adopting a vacuum rotary steaming method, and loading the Pt loaded amount of 0.1 weight percent and the Zn loaded amount of 0.5 weight percent on the two-dimensional MFI type all-silicon molecular sieve nano-sheet S2 prepared in the first step according to the weight of the carrier and calculated by metal elements. And then dried at 120℃for 2 hours. The dried product was then calcined at 600℃for 3h.
Tabletting and crushing the roasted product to the particle size of 40-60 meshes. Catalyst A2 was obtained.
Example 3
The first step: synthesis of two-dimensional MFI type all-silicon molecular sieve
Two-dimensional MFI-type all-silicon molecular sieve synthesis was performed using the method in example 2.
And a second step of: catalyst with function of catalyzing propane dehydrogenation to prepare propylene
Chloroplatinic acid as active component precursor and ZnNO 3 And Ca (NO) 3 ) 2 Is an auxiliary agent precursor, and is prepared into an aqueous solution. And (3) dipping by adopting a vacuum rotary steaming method, and loading Pt, zn and Ca on the two-dimensional MFI type all-silicon molecular sieve nano-sheet S2 prepared in the first step according to the proportion of 0.1 weight percent of loading amount by metal elements relative to the weight of the carrier. And then dried at 120℃for 2 hours. The dried product was then calcined at 600℃for 3h.
Tabletting and crushing the roasted product to the particle size of 40-60 meshes. Catalyst A3 was obtained. The XRD pattern thereof shows typical two-dimensional layered MFI-type catalyst characteristics.
Example 4
The first step: synthesis of two-dimensional MFI type all-silicon molecular sieve
Two-dimensional MFI-type all-silicon molecular sieve synthesis was performed using the method in example 2.
And a second step of: catalyst with function of catalyzing propane dehydrogenation to prepare propylene
Chloroplatinic acid is used as an active component precursor, znNO 3 、KNO 3 And Ca (NO) 3 ) 2 Is an auxiliary agent precursor, and is prepared into an aqueous solution. And (3) dipping by adopting a vacuum rotary steaming method, and loading Pt, zn, ca and K on the two-dimensional MFI type all-silicon molecular sieve nano sheet S2 prepared in the first step according to the proportion of 0.1 weight percent of loading capacity by using metal elements relative to the weight of the molecular sieve. And then dried at 120℃for 2 hours. The dried product was calcined at 600℃for 6h.
Tabletting and crushing the roasted product to the particle size of 40-60 meshes. Catalyst A4 was obtained.
Example 5
The method of example 1 was employed, except that the loading amounts of Pt and Zn were each 0.2 wt% in terms of metal element, relative to the weight of the molecular sieve in the second step. Catalyst A5 was obtained.
Example 6
The method of example 1 was employed, except that the loading amounts of Pt, zn and Ca were each 0.2 wt% in terms of metal element with respect to the weight of the molecular sieve in the second step. Catalyst A6 was obtained.
Example 7
The method of example 1 was employed, except that the loading amounts of Pt, zn, ca and K in terms of metal elements were all 0.2 wt% with respect to the weight of the molecular sieve in the second step. Catalyst A7 was obtained.
Comparative example 1:
the method of example 1 was employed, except that alumina (support S3) was used instead of the two-dimensional MFI-type all-silicon molecular sieve nanoplatelets S1 therein as a support. Catalyst D1 was obtained.
Comparative example 2
The method of example 1 was used, except that MFI-type all-silicon molecular sieve crystal grains (carrier S4, available from Aldrich company) were used instead of the two-dimensional MFI-type all-silicon molecular sieve nanoplatelets S1 therein as a carrier. Catalyst D2 was obtained.
Test example 1
The carriers prepared in the above examples and comparative examples were subjected to feature detection such as pore diameter and specific surface area.
Wherein, the aperture and specific surface area of the carrier are detected by adopting a nitrogen adsorption and desorption method.
The results are detailed in tables 1 and 2.
TABLE 1 Carrier characterization
Test example 2
The catalysts obtained in the above examples and comparative examples were subjected to performance evaluation of catalytic propane dehydrogenation to prepare propylene by the following methods.
Before the reaction started, the temperature was raised to 600 ℃, and the catalyst was reduced for 2 hours under a hydrogen atmosphere.
Catalytic performance test: the performance evaluation of the catalyst propane dehydrogenation to propylene was carried out on a fixed bed microreactor (from deluxe, texas). 0.5g of catalyst is filled, the diameter of a reaction tube is 10mm, the reaction temperature is 600 ℃, and the mass space velocity of propane is 3h -1 At normal pressure, hydrogen is used as diluent gas, and the volume ratio of hydrogen to propane is 1:3.
the results of the dehydrogenation of propane to propylene for catalyst A1 are detailed in FIG. 1 (catalyst A1 propane conversion) and FIG. 2 (catalyst A1 propylene selectivity). The results of the dehydrogenation of propane to propylene for catalyst A2 are detailed in fig. 3 (catalyst A2 propane conversion) and fig. 4 (catalyst A2 propylene selectivity). The results of the dehydrogenation of propane to propylene for catalyst A3 are detailed in FIG. 5 (catalyst A3 propane conversion) and FIG. 6 (catalyst A2 propylene selectivity). As can be seen from FIGS. 1 to 6, the catalyst provided by the invention has the characteristics of high propane conversion rate, high propylene selectivity and good stability. The results of the propane dehydrogenation to propylene reactions for catalysts A4-A7 are also similar to those shown in FIGS. 1-6.
The results of the catalytic performance tests of catalysts A1-A7 and D1-D2 are shown in Table 2. Shown in table 2, among others, is the average propane conversion and average propylene selectivity of the catalyst over a single pass lifetime (the average was tested and calculated before there was no significant drop in both, respectively).
TABLE 2 catalytic Performance test results
| Catalyst | Average propane conversion (%) | Average propylene selectivity (%) | Single pass life (h) |
| A1 | 40 | 90.4 | 250 |
| A2 | 42 | 90.8 | 210 |
| A3 | 41 | 92.3 | 250 |
| A4 | 40 | 92.5 | 300 |
| A5 | 40 | 91.6 | 220 |
| A6 | 43 | 92.6 | 250 |
| A7 | 42 | 94.1 | 380 |
| D1 | 38 | 90.1 | 1 |
| D2 | 38 | 90.2 | 200 |
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (21)
1. The catalyst with the function of catalyzing propane dehydrogenation to prepare propylene comprises a carrier and an active component, and is characterized in that the carrier is a two-dimensional MFI molecular sieve nanosheet, and the active component comprises noble metal;
the catalyst also comprises an auxiliary agent, wherein the content of the auxiliary agent is 0.01-1 wt% of the weight of the carrier.
2. The catalyst according to claim 1, wherein the specific surface area of the carrier is 200-500m 2 /g；
And/or the average pore diameter of the carrier is 5-15nm.
3. The catalyst of claim 1, wherein the active component is Pt.
4. A catalyst according to claim 3, wherein the active component is present in an amount of 0.1 to 1% by weight based on the weight of the support.
5. The catalyst of claim 1, wherein the promoter is selected from at least one of Zn, sn, ca, and K.
6. A method for preparing a catalyst having a function of catalyzing the dehydrogenation of propane to prepare propylene, the method comprising the steps of:
(1) Synthesizing MFI type molecular sieve nano-sheets, which comprises the following steps: mixing a template agent with a silicon source, performing hydrothermal reaction, and sequentially performing solid-liquid separation, drying and roasting on a hydrothermal reaction product to obtain an MFI molecular sieve nanosheet;
the template agent comprises a mixture of long-chain quaternary ammonium salt and small-molecule quaternary ammonium salt, wherein the long-chain quaternary ammonium salt is long-chain quaternary ammonium salt with more than 10 carbon atoms;
(2) And loading an active component and an auxiliary agent on the MFI molecular sieve nanosheets, wherein the active component comprises noble metal, and the content of the auxiliary agent is 0.01-1 wt% of the weight of the carrier.
7. The method of claim 6, wherein in step (1), the silicon source comprises at least one of ethyl silicate and a silica sol;
and/or the molar ratio of the template agent to the silicon source is 1:0.5-5.
8. The method of claim 6, wherein the small molecule quaternary ammonium salt comprises tetrapropylammonium hydroxide.
9. The method of claim 6, wherein the molar ratio of long chain quaternary ammonium salt to small molecule quaternary ammonium salt is 1:1-5.
10. The method of claim 6, wherein in step (1), the hydrothermal reaction conditions comprise: the time is 40-55h, and the temperature is 160-180 ℃;
and/or, the drying conditions include: the temperature is 90-120 ℃ and the time is 1-5h;
and/or, the roasting conditions include: the temperature is 550-600 ℃, the time is 6-8h, and the temperature rising rate is 1-5 ℃/min.
11. The method of claim 6, wherein step (2) comprises loading an active component precursor and an auxiliary agent precursor on the two-dimensional all-silicon molecular sieve by an impregnation method, and then sequentially drying and roasting to obtain the catalyst;
wherein the active component precursor is used in an amount such that the active component is supported on the support in an amount of 0.1 to 1 wt% based on the weight of the support.
12. The method of claim 11, wherein the active component precursor comprises a platinum group metal precursor;
and/or the adjuvant precursor comprises a water-soluble inorganic salt of the adjuvant.
13. The method of claim 12, wherein the active component precursor comprises chloroplatinic acid;
and/or the promoter precursor comprises at least one of sulfate, nitrate and chloride of the promoter.
14. The method of claim 13, wherein the auxiliary precursor comprises ZnNO 3 、SnCl 4 、KNO 3 And Ca (NO) 3 ) 2 At least one of them.
15. The method of claim 14, wherein the auxiliary precursor comprises ZnNO 3 、KNO 3 And Ca (NO) 3 ) 2 At least one of them.
16. The method of claim 11, wherein in step (2), the impregnation method employs an isovolumetric impregnation method and/or an overdose impregnation method;
and/or, the drying conditions include: the temperature is 100-150 ℃ and the time is 1-5h;
and/or, the roasting conditions include: the temperature is 550-650 ℃ and the time is 1-10h.
17. The method of claim 16, wherein in step (2), the impregnation method employs an isovolumetric impregnation method.
18. A catalyst prepared according to the method of any one of claims 6-17.
19. Use of the catalyst of any one of claims 1-5 and 18 for catalyzing the dehydrogenation of propane to propylene.
20. A process for the preparation of propylene, said process comprising: contacting propane with the catalyst of any one of claims 1-5 and 18 under dehydrogenation conditions to produce propylene.
21. The process of claim 20, wherein the dehydrogenation to produce propylene conditions comprise: the temperature is 550-650 ℃, the pressure is 0.08-0.12MPa, and the mass airspeed is 1-3h -1 。
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| CN106311311A (en) * | 2015-06-19 | 2017-01-11 | 中国石油化工股份有限公司 | Catalyst for preparing propylene through propane dehydrogenation, preparation method of catalyst, and method for propylene through propane dehydrogenation |
| CN109745977A (en) * | 2017-11-03 | 2019-05-14 | 中国石油化工股份有限公司 | The method of propane dehydrogenation catalyst and preparation method thereof and preparing propylene by dehydrogenating propane |
| CN109745978A (en) * | 2017-11-03 | 2019-05-14 | 中国石油化工股份有限公司 | The method of propane dehydrogenation catalyst and preparation method thereof and preparing propylene by dehydrogenating propane |
| CN109746026A (en) * | 2017-11-03 | 2019-05-14 | 中国石油化工股份有限公司 | A kind of dehydrogenation and the preparation method and application thereof |
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| CN106311311A (en) * | 2015-06-19 | 2017-01-11 | 中国石油化工股份有限公司 | Catalyst for preparing propylene through propane dehydrogenation, preparation method of catalyst, and method for propylene through propane dehydrogenation |
| CN109745977A (en) * | 2017-11-03 | 2019-05-14 | 中国石油化工股份有限公司 | The method of propane dehydrogenation catalyst and preparation method thereof and preparing propylene by dehydrogenating propane |
| CN109745978A (en) * | 2017-11-03 | 2019-05-14 | 中国石油化工股份有限公司 | The method of propane dehydrogenation catalyst and preparation method thereof and preparing propylene by dehydrogenating propane |
| CN109746026A (en) * | 2017-11-03 | 2019-05-14 | 中国石油化工股份有限公司 | A kind of dehydrogenation and the preparation method and application thereof |
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