CN113856738A - 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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- CN113856738A CN113856738A CN202010615415.5A CN202010615415A CN113856738A CN 113856738 A CN113856738 A CN 113856738A CN 202010615415 A CN202010615415 A CN 202010615415A CN 113856738 A CN113856738 A CN 113856738A
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- molecular sieve
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- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 239000003054 catalyst Substances 0.000 title claims abstract description 85
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 238000000034 method Methods 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 53
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 7
- 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 46
- 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 46
- 239000002243 precursor Substances 0.000 claims description 25
- 238000011068 loading method Methods 0.000 claims description 20
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 239000012752 auxiliary agent Substances 0.000 claims description 13
- 230000003197 catalytic effect Effects 0.000 claims description 12
- 238000005470 impregnation Methods 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 11
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 239000002135 nanosheet Substances 0.000 claims description 9
- -1 small-molecule quaternary ammonium salt Chemical class 0.000 claims description 9
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 229910000510 noble metal Inorganic materials 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052725 zinc 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
- 229910052791 calcium Inorganic materials 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 239000011148 porous material Substances 0.000 claims description 7
- 230000002194 synthesizing effect Effects 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
- 239000002671 adjuvant Substances 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Inorganic materials [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 239000007788 liquid Substances 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
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 2
- 239000004480 active ingredient Substances 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
- 229910021653 sulphate ion Inorganic materials 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 6
- 230000008021 deposition Effects 0.000 abstract description 6
- 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 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 238000003756 stirring Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229910052697 platinum Inorganic materials 0.000 description 5
- 238000002390 rotary evaporation Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000000052 comparative effect Effects 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
- 230000000694 effects Effects 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 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
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000000643 oven drying Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004230 steam cracking Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 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
- 239000006227 byproduct Substances 0.000 description 1
- 239000000969 carrier 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
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 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
- 239000002055 nanoplate Substances 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
- 238000011056 performance test Methods 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
- 239000013598 vector Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- 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
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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
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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- 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
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- 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
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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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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
- C07C5/3335—Catalytic processes with metals
- C07C5/3337—Catalytic processes with metals of the platinum group
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- 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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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 one-way service life, low carbon deposition rate, good product selectivity, high stability and the like. The selectivity of the catalyst on propylene can reach more than 90%, the one-way service life of the catalyst exceeds 200h, 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, and particularly relates 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 one of the basic raw materials of three large synthetic materials, and the demand of the propylene is huge in industry. The traditional propylene preparation process comprises steam cracking, catalytic cracking, methanol synthesis from coal and propylene preparation and the like. However, both steam cracking and catalytic cracking processes are routes to propylene from oil, and their costs are directly related to the price of petroleum, and as the price of petroleum increases, their costs also increase. The process for preparing propylene after synthesizing methanol from coal is realized by adopting a method for preparing olefins such as ethylene, propylene and the like by using methanol after synthesizing methanol from coal, but the process 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 price, short process route, less byproducts and higher yield.
At present, the commercial propane dehydrogenation propylene preparation catalyst mainly adopts an alumina carrier, and has the problems of poor catalyst stability, short one-way catalytic life and the like. Frequent catalyst regeneration increases production energy consumption, and a fluidized bed process is adopted in the process, so that the problems of complex matched reaction device, high construction cost and the like are caused. Therefore, it is desired to develop a novel catalyst carrier for propane dehydrogenation to propylene to overcome the above disadvantages.
The all-silicon molecular sieve has weak acidity, so that the isomerization of intermediate products and the secondary hydrogenation reaction can be inhibited to a certain extent, the occurrence of carbon deposition is reduced, and the selectivity of products, the one-way catalytic life of the catalyst and the catalytic stability are improved. In addition, when the all-silicon molecular sieve is used as a carrier, the all-silicon molecular sieve and the active component have weaker interaction, 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 channel structure and higher specific surface area, and the pore channels have shape selection selectivity and can be used for dehydrogenation reactions of small molecules. Although weakly acidic carriers can reduce the rate of carbon deposition, diffusion limitations can still promote the generation of carbon deposition due to the smaller pore channels of the all-silicon molecular sieve, thereby reducing the catalytic life.
Disclosure of Invention
The invention aims to overcome the problems of poor stability, short one-way 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 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 one-way service life, low carbon deposition rate, good product selectivity, high stability and the like.
In order to achieve the above objects, according to one aspect of the present invention, there is provided a catalyst having a function of catalyzing dehydrogenation of propane to produce propylene, the catalyst comprising a support and an active component, the support comprising a two-dimensional all-silica molecular sieve, and the 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 dehydrogenation of propane to produce propylene, the method comprising the steps of:
(1) synthesizing a two-dimensional all-silicon molecular sieve;
(2) and loading an active component and an optional auxiliary agent on the two-dimensional all-silicon molecular sieve, wherein the active component comprises a noble metal.
In a third aspect, the present invention provides a catalyst prepared by the above method.
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 propene.
In a fifth aspect, the present invention provides a process for producing propylene, said process comprising contacting propane with the above-described catalyst under conditions for dehydrogenation to produce propylene.
Through the technical scheme, the catalyst provided by the invention has the advantages of long one-way service life, low carbon deposition rate and high stability, and the selectivity of the catalyst on 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 of propane conversion and propylene selectivity over time, respectively, for the propane dehydrogenation to propylene reaction of catalyst A1 prepared in example 1;
FIGS. 3-4 are graphs of propane conversion and propylene selectivity over time, respectively, for the propane dehydrogenation to propylene reaction of catalyst A2 prepared in example 2;
fig. 5-6 are graphs of propane conversion and propylene selectivity over time, respectively, for the propane dehydrogenation to propylene reaction of catalyst a3 prepared in example 3.
Detailed Description
While specific embodiments of the present invention will be further explained and illustrated below, it should be understood that the following specific embodiments are only intended to explain and illustrate the contents of the present invention and are not intended to limit the present invention.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
Under the condition that no special description is made, the two-dimensional all-silicon molecular sieve of the invention refers to: an MFI type molecular sieve with two-dimensional sheet shape feature.
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-silica molecular sieve, and the active component comprises a noble metal.
According to a preferred embodiment of the invention, wherein the support comprises two-dimensional MFI-type molecular sieve nanoplates.
Preferably, the specific surface area of the carrier is 200-500m2/g。
Preferably, the support has an average pore size of 5-15 nm.
According to a preferred embodiment of the present 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 support is 1: 100-1000.
According to a preferred embodiment of the present invention, wherein the catalyst may further comprise an auxiliary.
Preferably, the auxiliary agent 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 dehydrogenation of propane to produce propylene, the method comprising the steps of:
(1) synthesizing a two-dimensional all-silicon molecular sieve;
(2) and loading an active component and an optional auxiliary agent on the two-dimensional all-silicon molecular sieve, wherein the active component comprises a noble metal.
The inventor of the invention skillfully discovers that the crystal axial growth can be inhibited by adopting the method of the long-chain quaternary ammonium salt and the small-molecule quaternary ammonium salt double-template agent, and the problem that the crystal structure tends to grow towards 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 method for synthesizing the two-dimensional all-silicon molecular sieve in step (1) comprises: mixing a template agent and a silicon source, carrying out hydrothermal reaction, and then sequentially carrying out 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 having 10 or more carbon atoms. More preferably C12-C22 long chain quaternary ammonium salts.
Preferably, the small molecule quaternary ammonium salt comprises tetrapropylammonium hydroxide.
More preferably, the molar ratio of the long-chain quaternary ammonium salt to the small-molecule quaternary ammonium salt in the mixture is 1: 1-5.
The template agent can be long-chain quaternary ammonium salt and small-molecule quaternary ammonium salt which are prepared by the prior art and have the characteristics, and can also be a commercial product with the characteristics. For example, Organic Structure Directing Agents (OSDA) and tetrapropylammonium hydroxide (TPAOH) and the like having a long chain alkyl group and a biquaternary ammonium salt composition may be mentioned.
The silicon source can be any existing silicon-containing compound which can be used for preparing the all-silicon molecular sieve. According to a preferred embodiment of the present invention, wherein the silicon source comprises at least one of ethyl silicate and 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 template 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 agent, the mixing manner of the template agent and the silicon source may include: the template agent is gradually added to the silicon source while stirring.
Preferably, the conditions of the stirring include: the temperature is 20-30 ℃, the time is 2-6h, 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 hydrothermal reaction conditions include: the time is 40-55h, and the temperature is 160-.
Any existing solid-liquid separation, drying and roasting mode 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, wherein for the purpose of improving production efficiency, the means and conditions of the solid-liquid separation may include: adopts a centrifugal separation mode, the centrifugal speed is 4500-5500rpm, and the time is 20-40 min.
According to a preferred embodiment of the present invention, wherein the drying conditions include: the temperature is 90-120 ℃, and the time is 1-5 h.
According to a preferred embodiment of the present invention, wherein the firing conditions include: 550 ℃ and 600 ℃, the time is 6-8h, and the heating rate is 1-5 ℃/min.
According to a preferred embodiment of the present invention, step (2) comprises loading an active component precursor and an optional auxiliary agent 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 for preparing noble metal catalysts. According to a preferred embodiment of the present 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 amount of the active component supported on the carrier is 0.1 to 1% by weight of the carrier, in terms of the metal element.
According to a preferred embodiment of the invention, wherein the promoter precursor comprises a water-soluble inorganic salt of the promoter.
Preferably, the promoter precursor comprises at least one of a sulphate, nitrate and chloride of the promoter.
More preferably, the promoter precursor comprises ZnNO3、SnCl4、KNO3And Ca (NO)3)2Preferably ZnNO3、KNO3And Ca (NO)3)2At least one of (1).
According to a preferred embodiment of the present invention, wherein the amount of the auxiliary agent precursor is such that the supporting amount of the auxiliary agent supported on the carrier is 0.01 to 1% by weight of the carrier, in terms of the metal element.
According to a preferred embodiment of the present invention, wherein the impregnation method employs an equal volume impregnation method and/or an excess impregnation method.
Preferably, the impregnation method is an equal volume impregnation method.
According to a preferred embodiment of the present invention, wherein the drying conditions include: the temperature is 100 ℃ and 150 ℃, and the time is 1-5 h.
Preferably, the drying conditions include: the temperature is 120 ℃ and 130 ℃, and the time is 2-3 h.
According to a preferred embodiment of the present invention, wherein the firing conditions include: the temperature is 550 ℃ and 650 ℃, and the time is 1-10 h.
Preferably, the conditions of the calcination include: the temperature is 580-620 ℃ and the time is 5-6 h.
According to a preferred embodiment of the present invention, a crushing step may be further included after the firing according to actual needs.
Preferably, the crushing conditions are such that the particle size of the catalyst is 40-60 mesh.
A third aspect of the invention provides a catalyst prepared by the method as described above.
According to a preferred embodiment of the present invention, wherein the catalyst has a particle size of 40-60 mesh and a specific surface area of 200-500m2(ii)/g, the average pore diameter is 5-15 nm.
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.
A fifth aspect of the present invention provides a process for the production of propylene, characterised in that the process comprises contacting propane with a catalyst as described above under conditions whereby propane is dehydrogenated to produce propylene.
According to a preferred embodiment of the present invention, wherein the conditions for producing propylene by dehydrogenation include: the temperature is 550--1. In the present invention, the pressure refers to gauge pressure.
The present invention will be described in detail below by way of examples. It should be understood that the following examples are only intended to further illustrate and explain the present invention, and are not intended to limit the present invention.
In the examples below, OSDA was obtained from national medicine, TPAOH was obtained from west longa chemical company, and ethyl silicate was obtained from tianjin shin company. Other conventional instrumentation and chemical reagents are commercially available from normal chemical instrumentation and reagent suppliers.
In the following examples, the conditions of the vacuum rotary evaporation method are: the water bath is carried out at 60 ℃ and the vacuum degree is 95 kPa.
In the following test examples, the analysis of the reaction product composition was carried out on a gas chromatograph available from Agilent under the model number 7890A, in which propane and propylene were detected by means of an alumina column FID detector. The method for calculating the conversion rate of the propane 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 one-way lifetime refers to: the catalyst is maintained at the conditions of use for a period of time at an activity level, wherein the activity level includes CO conversion and product selectivity. Specifically, the one-way lifetime is calculated from the start of the reaction to when any one of the indices fails to remain stable.
Example 1
The first step is as follows: synthesis of two-dimensional MFI type all-silicon molecular sieve
Adopting ethyl silicate as a silicon source, adopting OSDA and TPAOH as double templates, and mixing the silicon source, the OSDA and the TPAOH with ethyl silicate according to a molar ratio of 0.5: 1:1, mixing and stirring. Magnetically stirring for 2h at 250rpm relative to 24g of the mixture of the template agent and the silicon source, transferring to a hydrothermal kettle, crystallizing at 180 ℃ for 48h, taking out, and centrifuging (5000rpm, 30 min). Oven-drying (120 deg.C, 2h) and calcining at 550 deg.C for 6 h. Obtaining the two-dimensional MFI type all-silicon molecular sieve nanosheet S1.
The second step is that: catalyst with function of catalyzing propane dehydrogenation to prepare propylene
With chloroplatinic acid and ZnNO3Is prepared into aqueous solution by active component precursor and assistant precursor. And (2) impregnating by adopting a vacuum rotary evaporation method, and loading the carrier on the two-dimensional MFI-type all-silicon molecular sieve nanosheet S1 prepared in the first step according to the proportion that the Pt loading amount is 0.1 wt% and the Zn loading amount is 0.1 wt% in terms of metal elements relative to the weight of the carrier. Then dried at 120 ℃ for 2 h. The dried product was then calcined at 600 ℃ for 5 h.
And tabletting and crushing the roasted product to obtain a particle size of 40-60 meshes. Catalyst a1 was obtained.
Example 2
The first step is as follows: synthesis of two-dimensional MFI type all-silicon molecular sieve
Adopting ethyl silicate as a silicon source, adopting OSDA and TPAOH as double templates, and mixing the silicon source, the OSDA and the TPAOH with ethyl silicate according to a molar ratio of 1: 1:1, mixing and stirring. Magnetically stirring for 2h at 250rpm, transferring into hydrothermal kettle, crystallizing at 180 deg.C for 48h, taking out, and centrifuging (5000rpm, 30 min). Oven-drying (120 deg.C, 2h) and calcining at 550 deg.C for 6 h. Obtaining the two-dimensional MFI type all-silicon molecular sieve nanosheet S2.
The second step is that: catalyst with function of catalyzing propane dehydrogenation to prepare propylene
With chloroplatinic acid and ZnNO3Is prepared into aqueous solution by active component precursor and assistant precursor. And (2) impregnating by adopting a vacuum rotary evaporation method, and loading the carrier on the two-dimensional MFI-type all-silicon molecular sieve nanosheet S2 prepared in the first step according to the proportion that the Pt loading amount is 0.1 wt% and the Zn loading amount is 0.5 wt% in terms of metal elements relative to the weight of the carrier. Then dried at 120 ℃ for 2 h. The dried product was then calcined at 600 ℃ for 3 h.
And tabletting and crushing the roasted product to obtain a particle size of 40-60 meshes. Catalyst a2 was obtained.
Example 3
The first step is as follows: synthesis of two-dimensional MFI type all-silicon molecular sieve
The method of example 2 was used to synthesize a two-dimensional MFI-type all-silica molecular sieve.
The second step is that: catalyst with function of catalyzing propane dehydrogenation to prepare propylene
Uses chloroplatinic acid as active component precursor and ZnNO3And Ca (NO)3)2Is used as an auxiliary agent precursor and is prepared into an aqueous solution. And (2) impregnating by adopting a vacuum rotary evaporation method, and loading Pt, Zn and Ca on the two-dimensional MFI-type all-silicon molecular sieve nanosheet S2 prepared in the first step according to the loading amount of 0.1 weight percent in terms of metal elements relative to the weight of the carrier. Then dried at 120 ℃ for 2 h. The dried product was then calcined at 600 ℃ for 3 h.
And tabletting and crushing the roasted product to obtain a particle size of 40-60 meshes. Catalyst a3 was obtained. The XRD pattern shows the characteristic of a typical two-dimensional layered MFI-type catalyst.
Example 4
The first step is as follows: synthesis of two-dimensional MFI type all-silicon molecular sieve
The method of example 2 was used to synthesize a two-dimensional MFI-type all-silica molecular sieve.
The second step is that: catalyst with function of catalyzing propane dehydrogenation to prepare propylene
ZnNO as the precursor of the active component of chloroplatinic acid3、KNO3And Ca (NO)3)2Is used as an auxiliary agent precursor and is prepared into an aqueous solution. Dipping by adopting a vacuum rotary evaporation method, and loading Pt, Zn, Ca and K on the two-dimensional MFI-type all-silicon molecular sieve nanosheet S2 prepared in the first step according to the loading amount of 0.1 weight percent in terms of metal elements relative to the weight of the molecular sieve. Then dried for 2h at 120 ℃. The dried product was calcined at 600 ℃ for 6 h.
And tabletting and crushing the roasted product to obtain a particle size of 40-60 meshes. Catalyst a4 was obtained.
Example 5
The process of example 1 was used except that the Pt and Zn loadings in the second step were 0.2 wt% as the metal element relative to the weight of the molecular sieve. Catalyst a5 was obtained.
Example 6
The process of example 1 was used except that the loadings of Pt, Zn and Ca in the second step were all 0.2 wt% as metal elements relative to the weight of the molecular sieve. Catalyst a6 was obtained.
Example 7
The process of example 1 was used except that the loadings of Pt, Zn, Ca and K in the second step were all 0.2 wt% as metal element relative to the weight of the molecular sieve. 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-silica molecular sieve nanosheet S1 therein as the support. Catalyst D1 was obtained.
Comparative example 2
The method of example 1 was used except that MFI-type all-silica molecular sieve crystal grains (support S4, available from Aldrich) were used instead of the two-dimensional MFI-type all-silica molecular sieve nanosheet S1 as the support. Catalyst D2 was obtained.
Test example 1
The supports prepared in the above examples and comparative examples were subjected to characteristic tests such as pore diameter and specific surface area.
Wherein, the aperture and the 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 characteristics of the vectors
Test example 2
The catalysts prepared in the above examples and comparative examples were subjected to the performance evaluation of catalytic propane dehydrogenation to produce propylene by the following method.
Before the reaction, the temperature was raised to 600 ℃ and the catalyst was reduced for 2 hours in a hydrogen atmosphere.
And (3) testing the catalytic performance: evaluation of the performance of the catalyst for propane dehydrogenation to propylene was carried out on a fixed-bed microreactor (from Dretyok, Tex.). 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-1At normal pressure, using hydrogen as diluent gas, wherein the volume ratio of hydrogen to propane is 1: 3.
the results of the propane dehydrogenation of catalyst a1 to propylene are detailed in fig. 1 (catalyst a1 propane conversion) and fig. 2 (catalyst a1 propylene selectivity). The results of the propane dehydrogenation of catalyst a2 to propylene are detailed in fig. 3 (catalyst a2 propane conversion) and fig. 4 (catalyst a2 propylene selectivity). The results of the propane dehydrogenation of catalyst A3 to propylene 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 reaction of catalysts A4-A7 to produce propylene also have similar characteristics to those of FIGS. 1-6.
The results of the catalytic performance tests on catalysts A1-A7 and D1-D2 are detailed in Table 2. Where the average propane conversion and average propylene selectivity of the catalyst over a single pass life are shown in table 2 (the average values were measured and calculated, respectively, before there was no significant drop in the two).
TABLE 2 results of catalytic Performance testing
| Catalyst and process for preparing same | Average propane conversion (%) | Average propylene selectivity (%) | One way life (h) |
| |
40 | 90.4 | 250 |
| A2 | 42 | 90.8 | 210 |
| A3 | 41 | 92.3 | 250 |
| |
40 | 92.5 | 300 |
| |
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 above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (13)
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 comprises a two-dimensional all-silica molecular sieve, and the active component comprises a noble metal.
2. The catalyst of claim 1, wherein the support is a two-dimensional MFI-type molecular sieve nanosheet;
preferably, the specific surface area of the carrier is 200-500m2/g；
Preferably, the support has an average pore size of 5-15 nm.
3. The catalyst according to claim 1 or 2, wherein the active component is Pt;
preferably, the active ingredient is present in an amount of 0.1 to 1% by weight based on the weight of the carrier.
4. The catalyst of claim 1, wherein the catalyst further comprises a promoter;
preferably, the auxiliary agent is selected from at least one of Zn, Sn, Ca and K;
more preferably, the adjuvant is present in an amount of 0.01 to 1% by weight based on the weight of the carrier.
5. A method for preparing a catalyst having a function of catalyzing dehydrogenation of propane to produce propylene, the method comprising the steps of:
(1) synthesizing a two-dimensional all-silicon molecular sieve;
(2) and loading an active component and an optional auxiliary agent on the two-dimensional all-silicon molecular sieve, wherein the active component comprises a noble metal.
6. The method of claim 5, wherein the step (1) of synthesizing the two-dimensional all-silicon molecular sieve comprises: mixing a template agent and a silicon source, carrying out hydrothermal reaction, and then sequentially carrying out solid-liquid separation, drying and roasting on a hydrothermal reaction product to obtain a 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; and/or the presence of a gas in the gas,
the silicon source comprises at least one of ethyl silicate and silica sol;
preferably, the molar ratio of the template agent to the silicon source is 1: 0.5-5;
preferably, the long-chain quaternary ammonium salt is a long-chain quaternary ammonium salt with the carbon atom number of more than 10, and the small-molecule quaternary ammonium salt comprises tetrapropylammonium hydroxide;
preferably, the molar ratio of the long-chain quaternary ammonium salt to the small-molecule quaternary ammonium salt is 1: 1-5.
7. The method of claim 6, wherein in step (1), the conditions of the hydrothermal reaction comprise: the time is 40-55h, and the temperature is 160-;
preferably, the drying conditions include: the temperature is 90-120 ℃, and the time is 1-5 h;
preferably, the conditions of the calcination include: the temperature is 550-.
8. The method of claim 5, wherein the step (2) comprises loading an active component precursor and an optional auxiliary agent precursor on the two-dimensional all-silicon molecular sieve by adopting 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 loading amount of the active component supported on the carrier is 0.1 to 1% by weight based on the weight of the carrier;
preferably, the active component precursor comprises a platinum group metal precursor, preferably chloroplatinic acid;
the dosage of the auxiliary agent precursor is that the loading amount of the auxiliary agent loaded on the carrier accounts for 0.01-1% of the weight of the carrier;
preferably, the adjuvant precursor comprises a water-soluble inorganic salt of the adjuvant, preferably at least one of a sulphate, nitrate and chloride of the adjuvant, more preferably ZnNO3、SnCl4、KNO3And Ca (NO)3)2At least one of (1), more preferably ZnNO3、KNO3And Ca (NO)3)2At least one of (1).
9. The method according to claim 8, wherein in step (2), the impregnation method adopts an equal-volume impregnation method and/or an excess impregnation method, preferably an equal-volume impregnation method;
and/or, the drying conditions include: the temperature is 100-;
and/or, the roasting conditions include: the temperature is 550 ℃ and 650 ℃, and the time is 1-10 h.
10. A catalyst prepared according to the process of any one of claims 5 to 9.
11. Use of a catalyst according to any one of claims 1 to 4 and 10 or a process according to any one of claims 5 to 9 for the catalytic dehydrogenation of propane to propylene.
12. A process for producing propylene, comprising: contacting propane with the catalyst of any one of claims 1 to 4 and 10 under conditions for dehydrogenation to produce propylene.
13. The process of claim 12, wherein the conditions for dehydrogenation to produce propylene comprise: the temperature is 550--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 |
| 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 |
| 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 |
| 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 |
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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 |
| 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 |
| 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 |
| 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 |
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