CN113304779B - Carbon tetraolefin cracking propylene yield-increasing catalyst containing all-silicon mesoporous microspheres and preparation method and application thereof - Google Patents
Carbon tetraolefin cracking propylene yield-increasing catalyst containing all-silicon mesoporous microspheres and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 130
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 92
- 239000010703 silicon Substances 0.000 title claims abstract description 92
- 239000004005 microsphere Substances 0.000 title claims abstract description 89
- 238000005336 cracking Methods 0.000 title claims abstract description 73
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 229910052799 carbon Inorganic materials 0.000 title abstract description 15
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- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 70
- 239000002808 molecular sieve Substances 0.000 claims abstract description 66
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 66
- 150000001336 alkenes Chemical class 0.000 claims abstract description 65
- 239000011148 porous material Substances 0.000 claims abstract description 42
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- 238000000034 method Methods 0.000 claims description 18
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 17
- 238000001125 extrusion Methods 0.000 claims description 15
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- 239000003795 chemical substances by application Substances 0.000 claims description 13
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 11
- 229910017604 nitric acid Inorganic materials 0.000 claims description 11
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 238000004523 catalytic cracking Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 8
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 8
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
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- 230000002378 acidificating effect Effects 0.000 claims description 4
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- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 1
- -1 C 4 Olefin Chemical class 0.000 abstract description 14
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
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- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
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- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 4
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- 239000002253 acid Substances 0.000 description 2
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- 239000005977 Ethylene Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
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- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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- B01J35/617—
-
- 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
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J35/40—
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- B01J35/51—
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- B01J35/635—
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- B01J35/638—
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
- C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
- C07C4/06—Catalytic processes
-
- 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
- B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C07C2529/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention relates to the field of petrochemical industry, and discloses a carbon tetraolefin cracking propylene yield-increasing catalyst containing all-silicon mesoporous microspheres, and a preparation method and application thereof. Wherein the catalyst comprises a zeolite molecular sieve with an MFI structure, all-silicon mesoporous microspheres, an oxide and a heteropoly acid; wherein the average grain diameter of the all-silicon mesoporous microspheres is 0.5-1.5 mu m, and the specific surface area is 600-900m 2 Per g, pore volume of 0.8-1.5mL/g, average pore diameter of 7-9nm. The catalyst provided by the invention is used for the catalyst C 4 The cracking reaction of olefin can effectively increase C 4 Olefin conversion and propylene selectivity, and significantly improves catalyst stability.
Description
Technical Field
The invention relates to the field of petrochemical industry, in particular to a carbon tetraolefin cracking propylene yield-increasing catalyst containing all-silicon mesoporous microspheres and a preparation method and application thereof.
Background
Among the basic organic feedstocks, propylene plays a dominant role. With the rapid development of national economy, the demand of downstream products of propylene is continuously increased, and the current situation of insufficient supply and demand of propylene is caused. In recent years, zeolite molecular sieves have been used as catalystsCracking with lower added value of C 4 And C 4 The method for obtaining the high-yield propylene from the olefin-rich raw materials is a propylene yield increasing technical route with high economic benefit, and has recently attracted high attention of relevant scholars at home and abroad.
C 4 The catalyst for cracking olefin to produce propylene is mainly zeolite molecular sieve catalyst. Catalyst systems that are gaining more attention now include ZSM series molecular sieves and SAPO series molecular sieves. At present, C 4 The olefin catalytic cracking technology has an industrial application device in China, and the main component of the catalyst is an MFI molecular sieve. However, it now appears that C 4 The propylene selectivity of olefin cracking catalysts is also relatively low. In order to improve the performance of the catalyst, many researchers have made intensive studies on the synthesis and modification of MFI molecular sieves (CN 1611471A, CN1611472A, and CN 1490288). Through the control and modification treatment of synthesis conditions, the number and the strength of acid centers on the surface of the MFI molecular sieve are changed, but the relatively fixed pore channel structure of the zeolite molecular sieve is not obviously changed. Structural characteristics of MFI molecular sieve with narrower pore diameter (less than 0.6 nm) for C 4 The olefin cracking reaction is still a disadvantage that side reactions are liable to occur.
In conclusion, C with higher propylene selectivity and better stability 4 Olefin cracking catalysts are yet to be further researched and developed.
Disclosure of Invention
The object of the present invention is to overcome the existing C of the prior art 4 The olefin cracking catalyst has the defects of low propylene yield and poor stability, provides a carbon tetraolefin cracking propylene yield-increasing catalyst containing all-silicon mesoporous microspheres and a preparation method and application thereof, and applies the catalyst to the catalyst C 4 The cracking reaction of olefin can effectively increase C 4 Olefin conversion and propylene selectivity, and significantly improves catalyst stability.
In order to achieve the above object, the present invention provides, in a first aspect, a C-containing all-silicon mesoporous microsphere 4 The catalyst for increasing the yield of propylene by cracking olefin comprises a zeolite molecular sieve with an MFI structure and all-silicon mediumPore microspheres, oxides and heteropolyacids; wherein the average particle diameter of the all-silicon mesoporous microspheres is 0.5-1.5 mu m, and the specific surface area is 600-900m 2 Per g, pore volume of 0.8-1.5mL/g, average pore diameter of 7-9nm.
The second aspect of the invention provides a C containing the all-silicon mesoporous microspheres 4 The preparation method of the catalyst for increasing the yield of propylene by olefin cracking comprises the following steps:
(1) Carrying out ball milling on a zeolite molecular sieve with an MFI structure, all-silicon mesoporous microspheres and phosphotungstic acid to obtain a mixture;
(2) Uniformly stirring the mixture with an adhesive, an extrusion aid and dilute nitric acid, then carrying out extrusion forming and roasting treatment to obtain C containing all-silicon mesoporous microspheres 4 The catalyst for cracking olefin to increase the yield of propylene.
The third aspect of the invention provides the C containing the all-silicon mesoporous microspheres 4 The application of the catalyst for increasing the yield of propylene by cracking olefin in catalytic cracking reaction.
Compared with the prior art, the technical scheme of the invention has the following advantages:
(1) C provided by the invention 4 One of the main components of the olefin cracking propylene-increasing catalyst is zeolite molecular sieve raw material with MFI structure, which has low price and is easy to obtain.
(2) C provided by the invention 4 The other main component of the olefin cracking propylene yield-increasing catalyst is the all-silicon mesoporous microsphere, the preparation method is simple, and the preparation process is environment-friendly.
(3) C provided by the invention 4 Catalyst for increasing yield of propylene by olefin cracking 4 The cracking reaction of mono-olefin not only effectively improves C 4 Olefin conversion and propylene selectivity, while improving catalyst stability.
(4) Said C of the invention 4 The preparation method of the olefin cracking propylene yield-increasing catalyst has the advantages of simple process, easily controlled conditions and good product repeatability.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
Fig. 1 is an XRD spectrum of the all-silicon mesoporous microsphere a prepared in example 1;
fig. 2 is a scanning electron microscope image of the all-silicon mesoporous microsphere a prepared in example 1.
Detailed Description
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.
The inventors of the present invention carried out C 4 When the preparation research of the catalyst for increasing the yield of propylene by cracking olefin is carried out, the finding shows that in the prior art, C 4 The olefin cracking catalyst uses zeolite molecular sieve or modified zeolite molecular sieve as main component. Since the zeolite molecular sieve belongs to a microporous molecular sieve, the pore channel structure is narrow, and side reactions are easy to occur. The mesoporous material has the structural characteristics of large specific surface area, large pore diameter and large pore volume. If the characteristics of stable structure, proper amount of acid centers on the surface of the zeolite molecular sieve and the structural characteristics of wide pore channels of the mesoporous material are combined, the C can be improved 4 Propylene selectivity and stability of olefin cracking catalysts. Therefore, in the present invention, a proper amount of all-silicon mesoporous microspheres are mixed with a zeolite molecular sieve having an MFI structure and modified with a heteropoly acid to prepare C 4 An olefin cracking catalyst.
The invention provides a C containing all-silicon mesoporous microspheres in a first aspect 4 The olefin cracking propylene yield increasing catalyst comprises a zeolite molecular sieve with an MFI structure, all-silicon mesoporous microspheres, oxides and heteropoly acid; wherein the average particle diameter of the all-silicon mesoporous microspheres is 0.5-1.5 mu m, and the specific surface area is 600-900m 2 Per g, pore volume of 0.8-1.5mL/g, average pore diameter of 7-9nm.
According to the invention, the all-silicon mesoporous structureThe specific surface area of the micron sphere is 704-780m 2 Per g, pore volume of 1.2-1.4mL/g, average pore diameter of 8-8.4nm.
According to the invention, the zeolite molecular sieve with MFI structure is a ZSM-5 molecular sieve and/or a ZRP molecular sieve; both the ZSM-5 molecular sieve and the ZRP molecular sieve are zeolite molecular sieves with specific structures, and the structures of the two molecular sieves are the same, but the ZRP molecular sieve contains a P element. In addition, it should be noted that the structural characteristics of ZSM-5 molecular sieves and ZRP molecular sieves are known to those skilled in the art from the nomenclature, and therefore, the structures thereof will not be described herein.
Preferably, the zeolite molecular sieve having the MFI structure has a silica to alumina molar ratio of SiO 2 /Al 2 O 3 Is 100 to 800, preferably 150 to 500, more preferably 300 to 500.
According to the invention, the weight ratio of the zeolite molecular sieve with MFI structure to the all-silicon mesoporous microspheres is (1-5): 1, preferably (1.5-4): 1, more preferably (1.8-3.67): 1.
according to the invention, the preparation method of the all-silicon mesoporous microspheres comprises the following steps: in the presence of a template agent and glycerol, ethyl orthosilicate is contacted with an acidic aqueous solution, and a mixture obtained after the contact is crystallized, washed, filtered, dried and subjected to template agent removal, so that the all-silicon mesoporous microspheres are obtained.
According to the invention, the templating agent is a triblock copolymer polyoxyethylene-polyoxypropylene-polyoxyethylene, preferably P123;
preferably, the acidic aqueous solution is a hydrochloric acid aqueous solution prepared from water and hydrogen chloride;
the molar ratio of the template agent to the glycerol to the tetraethoxysilane to the water to the hydrogen chloride is 1:10-400:10-200:5000-50000:50-900, preferably 1:20-200:20-100:10000-30000:150-500.
According to the invention, the conditions of the contact are: the contact temperature is 25-60 ℃, and the contact time is 2-30h.
According to the invention, the crystallization conditions are: the crystallization temperature is 90-150 ℃, and the crystallization time is 10-40h.
According to the invention, the drying conditions are: the drying temperature is 70-150 ℃, and the drying time is 3-20h.
According to the invention, the conditions for removing the template agent are as follows: roasting in air atmosphere at 400-600 deg.c for 8-20 hr.
According to the invention, the oxide is obtained by roasting a binder, and is preferably silicon oxide and/or aluminum oxide; more preferably, the binder is selected from one or more of silica sol, aluminum sol and pseudo-boehmite.
According to the invention, the heteropolyacid is preferably phosphotungstic acid.
According to the invention, based on the total weight of the catalyst, the content of the zeolite molecular sieve with the MFI structure is 40-60 wt%, the content of the all-silicon mesoporous microspheres is 15-30 wt%, the content of the oxide is 10-20 wt%, and the content of the heteropoly acid is 5-20 wt%.
According to the present invention, the C containing all-silicon mesoporous microspheres 4 The total amount of each component in the olefin cracking propylene-increasing catalyst is one hundred percent.
According to the invention, preferably, based on the total weight of the catalyst, when the content of the zeolite molecular sieve with MFI structure is 45-55 wt%, the content of the all-silicon mesoporous microspheres is 15-25 wt%, the content of the oxide is 12-18 wt%, and the content of the heteropoly acid is 7-14 wt%, the C of the cracking catalyst is increased 4 Olefin conversion, propylene selectivity, and catalyst stability.
The invention provides a second aspect of the C containing the all-silicon mesoporous microspheres 4 The preparation method of the catalyst for increasing the yield of propylene by olefin cracking comprises the following steps:
(1) Carrying out ball milling on a zeolite molecular sieve with an MFI structure, all-silicon mesoporous microspheres and phosphotungstic acid to obtain a mixture;
(2) Uniformly stirring the mixture with an adhesive, an extrusion aid and dilute nitric acid, then carrying out extrusion forming and roasting treatment to obtain C containing all-silicon mesoporous microspheres 4 Olefin cracking yield increase propyleneA catalyst.
According to the invention, the mass ratio of the zeolite molecular sieve with MFI structure, the all-silicon mesoporous microspheres, the phosphotungstic acid, the adhesive, the extrusion aid and the dilute nitric acid is 1:0.25-0.75:0.08-0.5:0.15-2.0:0.08-0.4:0.15-1.0.
According to the invention, the mass concentration of the dilute nitric acid is 1-10%.
According to the invention, the extrusion aid is one or more of sesbania powder, polyacrylamide and cellulose, and preferably sesbania powder.
According to the invention, after mixing and ball-milling zeolite molecular sieve with MFI structure, all-silicon mesoporous microsphere and phosphotungstic acid, adding adhesive, extrusion aid and dilute nitric acid, stirring uniformly, extruding and forming, drying at 70-150 ℃ for 5-20h, roasting at 500-600 ℃ for 3-15h to obtain C 4 The catalyst for cracking olefin to increase the yield of propylene.
According to the invention, the C containing all-silicon mesoporous microspheres prepared by the method 4 The catalyst for cracking olefin to increase the yield of propylene.
According to the invention, the C containing all-silicon mesoporous microspheres 4 The specific surface area of the catalyst for increasing the yield of propylene by cracking olefin is 150-400m 2 Per gram, pore volume is 0.3-0.7mL/g; preferably, the specific surface area is 221-257m 2 (iii) a pore volume of 0.40-0.46mL/g.
The third aspect of the invention provides the C containing the all-silicon mesoporous microspheres 4 The application of the catalyst for increasing the yield of propylene by cracking olefin in catalytic cracking reaction.
According to the invention, the catalytic cracking reaction comprises: will contain C 4 -C 8 The raw material of mono-olefin is contacted with a catalyst in a fixed bed adiabatic reactor to carry out catalytic cracking reaction, wherein the catalyst is the C 4 An olefin cracking catalyst.
According to the invention, said compound contains C 4 The mono-olefin feedstock may be selected from:
(1) C four raffinate I of an ethylene plant, namely a product obtained by extracting butadiene in C four fraction;
(2) A carbon four fraction obtained from the catalytic cracking unit;
(3) And C four and C five or more fractions of the olefins prepared from the methanol.
Preference is given to using C 4 C of olefin production from raffinate I or methanol 4 And a fraction containing more than five carbons is used as the raw material of the invention.
According to the invention, the method comprises the following specific operations: at the temperature of 460-560 ℃, the pressure of 0.02-0.5MPa and the weight hourly space velocity of 0.5-30h -1 Under the conditions of (1) will contain C 4 -C 8 Reacting a feed of monoolefins with C in a fixed bed reactor 4 The olefin cracking can increase the propylene catalyst contact.
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples, the pore structure parameter analysis of the samples was carried out on an adsorption apparatus available from Micromeritics, USA, model ASAP2020-M + C; the X-ray diffraction analysis of the samples was carried out on an X-ray diffractometer, model D8 Advance, from Bruker AXS, germany; the scanning electron microscope picture of the sample is obtained on an XL-30 type field emission environment scanning electron microscope produced by FEI company in America; the elemental analysis experiments of the samples were performed on an Eagle III energy dispersive X-ray fluorescence spectrometer manufactured by EDAX, USA.
The drying box is produced by Shanghai-Hengchang scientific instruments Co., ltd, and is of a type DHG-9030A.
The muffle furnace is manufactured by CARBOLITE, inc. under the model number CWF1100.
The polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123) used in the examples and comparative examples was purchased from Sigma-Aldrich Chemistry; ZSM-5 molecular sieves with different silica-alumina ratios were purchased from Shanghai Korea molecular sieves Co., ltd; the ZRP zeolite molecular sieve is purchased from Hezhong Biochemical manufacturing company, inc. in Wuhan city; the alumina sol and the silica sol are purchased from Zibo Jiarun chemical Co., ltd; pseudoboehmite was purchased from Zibo Hengqi powder New Material Co., ltd; other reagents were purchased from the national pharmaceutical group chemical reagents, ltd.
Example 1
This example is to illustrate the preparation by the process of the inventionPrepared C containing all-silicon mesoporous microspheres 4 The catalyst for cracking olefin to increase the yield of propylene.
(1) Preparation of all-silicon mesoporous microspheres
58 g of P123 (0.01 mol) and 73.6 g of glycerol (0.8 mol) are mixed with 2777 g of aqueous hydrochloric acid (containing 2.1 mol of HCl) and stirred at 35 ℃ until the P123 and glycerol are completely dissolved; adding 124.8 g of tetraethoxysilane (0.6 mol) into the solution, slowly stirring for 4 minutes at 35 ℃, and standing for 24 hours; transferring the obtained solution into a reaction kettle with a polytetrafluoroethylene lining, and crystallizing for 24 hours at 100 ℃; then filtering and washing for 4 times by using deionized water, and then carrying out suction filtration to obtain mesoporous material raw powder; calcining the raw powder mesoporous material in a muffle furnace at 500 ℃ for 16h, and removing the template agent to obtain the all-silicon mesoporous microspheres A.
The specific surface area of the all-silicon mesoporous microsphere A is 735m 2 Pore volume 1.3ml/g, average pore diameter 8.1nm.
FIG. 1 is an XRD spectrum of an all-silicon mesoporous microsphere A. According to a small-angle spectrum peak appearing in an XRD spectrogram, the all-silicon mesoporous microsphere A has a typical mesoporous two-dimensional hexagonal pore channel structure.
FIG. 2 is an SEM scanning electron micrograph of the all-silicon mesoporous microspheres A. As can be seen, the microscopic morphology of the all-silicon mesoporous microspheres A is of small nearly spherical particles, the particle size is uniform, and the particle diameter is between 0.5 and 1 mu m.
(2)C 4 Preparation of olefin cracking catalyst
53 g of ZSM-5 molecular Sieve (SiO) 2 /Al 2 O 3 300), 22 g of all-silicon mesoporous microspheres A and 10 g of phosphotungstic acid are put into a 300ml ball milling tank for ball milling. Wherein the ball milling tank is made of polytetrafluoroethylene, the grinding balls are made of agate, the diameter of each grinding ball is 3mm, the number of the grinding balls is 4, the rotating speed is 500r/min, the temperature in the ball milling tank is 50 ℃, and the ball milling time is 2 hours. And uniformly mixing the ball-milled mixture with 20 g of pseudo-boehmite and 8g of sesbania powder, adding 65 g of 5% dilute nitric acid, uniformly stirring, and performing extrusion forming. Drying the formed product at 120 deg.C for 15h, and burning at 550 deg.C for 6h to obtain C 4 Olefin cracking catalyst A.
C 4 Ratio of olefin cracking catalyst ASurface area of 238m 2 (iv) g; the pore volume was 0.42mL/g.
In terms of weight percent, C 4 The composition of olefin cracking catalyst a (wt.%): 53% of ZSM-5 molecular sieve, 22% of all-silicon mesoporous microspheres, 15% of alumina and 10% of phosphotungstic acid.
Example 2
This example illustrates the preparation of all-silicon mesoporous microspheres by the method of the present invention 4 The catalyst for cracking olefin to increase the yield of propylene.
(1) Preparation of all-silicon mesoporous microspheres
58 g of P123 (0.01 mol) and 27.6 g of glycerol (0.3 mol) are mixed with 1855 g of aqueous hydrochloric acid (containing 1.5 mol of HCl) and stirred at 25 ℃ until the P123 and glycerol are completely dissolved; adding 41.6 g of tetraethoxysilane (0.2 mol) into the solution, slowly stirring for 10 minutes at 25 ℃, and then standing for 24 hours; transferring the obtained solution into a reaction kettle with a polytetrafluoroethylene lining, and crystallizing for 40 hours at 90 ℃; then filtering and washing for 4 times by using deionized water, and then carrying out suction filtration to obtain mesoporous material raw powder; calcining the raw powder mesoporous material in a muffle furnace at 400 ℃ for 20h, and removing the template agent to obtain the all-silicon mesoporous microspheres B.
The specific surface area of the all-silicon mesoporous microsphere B is 780m 2 Pore volume 1.4ml/g, average pore diameter 8.0nm.
The XRD spectrogram of the all-silicon mesoporous microsphere B is similar to that in figure 1, and the sample is proved to have a typical mesoporous two-dimensional hexagonal pore channel structure.
The SEM scanning electron micrograph of the all-silicon mesoporous microsphere B is similar to that of the SEM scanning electron micrograph shown in figure 2, the microscopic morphology of the sample is nearly spherical small particles, the particle size is uniform, and the particle diameter is 0.5-1 μm.
(2)C 4 Preparation of olefin cracking catalyst
55 g of ZRP-5 molecular Sieve (SiO) 2 /Al 2 O 3 300), 15 g of all-silicon mesoporous microspheres B and 14 g of phosphotungstic acid are put into a 300ml ball milling tank for ball milling. Wherein the ball milling tank is made of polytetrafluoroethylene, the grinding balls are made of agate, the diameter of each grinding ball is 3mm, the number of the grinding balls is 4, the rotating speed is 500r/min, the temperature in the ball milling tank is 20 ℃, and the ball milling tank is used for ball millingThe time is 24h. And uniformly mixing the ball-milled mixture with 57 g of 28% silica sol and 5g of sesbania powder, adding 30 g of 10% dilute nitric acid, uniformly stirring, and performing extrusion forming. Drying the formed product at 150 deg.C for 5h, and firing at 500 deg.C for 15h to obtain C 4 Olefin cracking catalyst A.
C 4 The specific surface area of the olefin cracking catalyst B was 221m 2 (ii)/g; the pore volume was 0.40ml/g.
In terms of weight percent, C 4 The composition of olefin cracking catalyst B (% by weight) was: 55% of ZRP-5 molecular sieve, 15% of all-silicon mesoporous microspheres, 16% of silicon oxide and 14% of phosphotungstic acid.
Example 3
This example illustrates the preparation of all-silicon mesoporous microspheres by the method of the present invention 4 The catalyst for cracking olefin to increase the yield of propylene.
(1) Preparation of all-silicon mesoporous microspheres
58 g of P123 (0.01 mol) and 147.2 g of glycerol (1.6 mol) are mixed with 5583 g of aqueous hydrochloric acid (containing 5.0 mol of HCl) and stirred at 60 ℃ until the P123 and glycerol are completely dissolved; then 208 g of tetraethoxysilane (1.0 mol) is added into the solution, slowly stirred for 4 minutes at 60 ℃ and then kept stand for 24 hours; transferring the obtained solution into a reaction kettle with a polytetrafluoroethylene lining, and crystallizing for 15 hours at 130 ℃; then filtering and washing for 4 times by using deionized water, and then carrying out suction filtration to obtain mesoporous material raw powder; calcining the raw powder mesoporous material in a muffle furnace at 600 ℃ for 8h, and removing the template agent to obtain the all-silicon mesoporous microsphere C.
The specific surface area of the all-silicon mesoporous microsphere A is 704m 2 Pore volume 1.2ml/g, average pore diameter 8.4nm.
The XRD spectrogram of the all-silicon mesoporous microsphere C is similar to that in figure 1, and the sample is proved to have a typical mesoporous two-dimensional hexagonal pore channel structure.
The SEM scanning electron micrograph of the all-silicon mesoporous microsphere C is similar to that of the SEM scanning electron micrograph shown in figure 2, the microscopic morphology of the sample is nearly spherical small particles, the particle size is uniform, and the particle diameter is 0.5-1 μm.
(2)C 4 Preparation of olefin cracking catalyst
48 g of ZSM-5 molecular Sieve (SiO) 2 /Al 2 O 3 500), 25 g of all-silicon mesoporous microspheres C and 9 g of phosphotungstic acid are put into a 300ml ball milling tank for ball milling. Wherein the ball milling tank is made of polytetrafluoroethylene, the grinding balls are made of agate, the diameter of each grinding ball is 3mm, the number of the grinding balls is 4, the rotating speed is 500r/min, the temperature in the ball milling tank is 70 ℃, and the ball milling time is 0.5h. And uniformly mixing the ball-milled mixture with 24 g of pseudo-boehmite and 12g of sesbania powder, adding 55 g of 5% dilute nitric acid, uniformly stirring, and performing extrusion forming. Drying the formed product at 70 deg.C for 20h, and burning at 600 deg.C for 3h to obtain C 4 Olefin cracking catalyst C.
C 4 The specific surface area of the olefin cracking catalyst A was 257m 2 (ii)/g; the pore volume was 0.46ml/g.
In terms of weight percent, C 4 The composition of the olefin cracking catalyst a (wt.%): 48% of ZSM-5 molecular sieve, 25% of all-silicon mesoporous microspheres, 18% of alumina and 9% of phosphotungstic acid.
Example 4
This example illustrates the preparation of all-silicon mesoporous microspheres by the method of the present invention 4 The catalyst for cracking olefin to increase the yield of propylene.
Catalyst D was prepared according to the method of example 1, except that the all-silicon mesoporous microspheres had a specific surface area of 600m 2 Pore volume 1.5mL/g, average pore diameter 7nm.
Example 5
This example illustrates the preparation of all-silicon mesoporous microspheres by the method of the present invention 4 The catalyst for cracking olefin to increase the yield of propylene.
Catalyst E was prepared as in example 1, except that C was added in weight percent 4 The composition of olefin cracking catalyst a (wt.%): 51% of ZSM-5 molecular sieve, 30% of all-silicon mesoporous microspheres, 12% of alumina and 7% of phosphotungstic acid.
Comparative example 1
Catalyst D1 was prepared according to the method of example 1, except that step (1) was eliminated and only step (2) was retained, using 75g of ZSM-5 molecular Sieve (SiO) 2 /Al 2 O 3 300) instead of "53 g ZSM-5 molecular Sieves (SiO) 2 /Al 2 O 3 300) and 22 g of all-silicon mesoporous microspheres A ".
C 4 The specific surface area of the olefin cracking catalyst D1 was 137m 2 (iv) g; the pore volume was 0.28ml/g.
In terms of weight percent, C 4 The composition of the olefin cracking catalyst D1 (wt.%): 75% of ZSM-5 molecular sieve, 15% of alumina and 10% of phosphotungstic acid.
Comparative example 2
Catalyst D2 was prepared as in example 1, except that the high-silicon ZSM-5 zeolite molecular Sieve (SiO) in step (1) was used 2 /Al 2 O 3 300) is replaced by low-silicon ZSM-5 zeolite molecular Sieve (SiO) 2 /Al 2 O 3 Is 25).
C 4 The specific surface area of the olefin cracking catalyst D2 was 204m 2 (ii)/g; the pore volume was 0.39ml/g.
In terms of weight percent, C 4 The composition of the olefin cracking catalyst D2 (wt.%): 53% of ZSM-5 molecular sieve, 22% of all-silicon mesoporous microspheres, 15% of alumina and 10% of phosphotungstic acid.
Comparative example 3
Catalyst D3 was prepared according to the method of example 1, except that the all-silicon mesoporous microspheres had a specific surface area of 500m 2 Pore volume 1.6mL/g, average pore diameter 5nm.
Comparative example 4
Catalyst D4 was prepared as in example 1, except that the charge of the individual components was varied such that the result: in terms of weight percent, C 4 The composition of the olefin cracking catalyst a (wt.%): ZSM-5 molecular sieve 35%, full-silicon mesoporous microsphere 40%, alumina 22% and heteropoly acid 3%.
Test example 1
C 4 Test of performance of olefin cracking propylene-increasing catalyst in catalytic cracking reaction of carbon tetraolefin
The test catalysts were example catalyst a, catalyst B, catalyst C, catalyst D, catalyst E, comparative catalyst D1, catalyst D2, catalyst D3 and catalyst D4, respectively.
The reaction raw material is a carbon-carbon four mixture after etherification, a mixture after part of isobutane is separated, and the reaction raw material is provided by Luoyang refining metadynamics chemical industry Limited liability company and comprises the following components in percentage by weight: 11.92 of isobutane, 26.10 of n-butane, 22.02 of trans-2-butene, 23.48 of 1-butene, 0.38 of isobutene, 15.29 of cis-2-butene 5 The above component is 0.76.
The specific test method is as follows:
c of catalyst on fixed bed reactor 4 And (4) evaluating the catalytic cracking reaction performance of the olefin. The loading of the catalyst is 5.0 g, the reaction temperature is 500 ℃, the reaction pressure is 0.05MPa, and the weight space velocity of the raw material is 16h -1 After cooling and gas-liquid separation of the product, the gas composition is prepared with Al 2 O 3 -agilent 6890 gas chromatograph analysis of S capillary chromatographic column and hydrogen flame detector (FID), quantitative analysis with correction factors using temperature programming; the liquid composition is analyzed by an Agilent 6890 gas chromatograph equipped with a PONA chromatographic column, and the quantitative analysis is carried out by adopting the temperature programming and the light gasoline standard sample. The reaction results are shown in Table 1, C 4 And (3) evaluating the reaction performance of the olefin cracking propylene-increasing catalyst.
TABLE 1
As can be seen from Table 1, C provided by the present invention was used 4 The catalyst for increasing the yield of propylene by olefin cracking has excellent performance when used for catalyzing the cracking reaction of carbon tetraolefin. Part of all-silicon mesoporous microspheres are added into the catalyst A, and all-silicon mesoporous microspheres are not added into the catalyst D1. Compared with the catalyst D1, the catalyst A has the advantages that the carbon tetraene conversion rate, the propylene selectivity and the catalyst stability are obviously improved. The above results show that the invention provides C 4 The excellent performance of the catalyst for increasing the yield of propylene by cracking olefin is because of containing all-silicon mesoporous microspheres.
Comparing the data of catalyst a and catalyst D2, it can be seen that the carbon tetraolefin cracking catalyst prepared using the zeolite molecular sieve having a lower silicon to aluminum ratio has a poorer performance, a lower carbon tetraolefin conversion rate, a lower propylene selectivity, and a poorer catalyst stability. And the catalyst prepared by the zeolite molecular sieve with high silicon-aluminum ratio has obviously improved various performances.
Comparing the data of catalyst a and catalyst D3, it can be seen that the specific surface area of the all-silicon mesoporous microspheres in D3 is lower, the pore volume is higher, and the average pore size is smaller, i.e., the parameters of the all-silicon mesoporous microspheres are not within the range defined by the present invention, and the resulting carbon tetraolefin cracking catalyst has poor performance, low carbon tetraolefin conversion rate, low propylene selectivity, and poor catalyst stability.
Comparing the data for catalyst A and catalyst D4, it can be seen that C 4 In the composition of the olefin cracking catalyst A, the ZSM-5 molecular sieve content is lower, the all-silicon mesoporous microspheres content is higher, the alumina (oxide) content from the binder is higher, and the heteropoly acid content is lower, namely C 4 The contents of the components in the olefin cracking catalyst are not in the range defined by the invention, and the prepared carbon four-olefin cracking catalyst has poor performance, low carbon four-olefin conversion rate, low propylene selectivity and poor catalyst stability.
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 various technical features being combined 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 (18)
1. C containing all-silicon mesoporous microspheres 4 The catalyst for increasing the yield of propylene by cracking olefin is characterized by comprising a zeolite molecular sieve with an MFI structure, all-silicon mesoporous microspheres, an oxide and a heteropoly acid; wherein the zeolite molecular sieve with MFI structure has a silica-alumina molar ratio SiO 2 /Al 2 O 3 Is 100-800; said is fullThe average grain diameter of the silicon mesoporous microsphere is 0.5-1.5 mu m, and the specific surface area is 600-900m 2 Per g, pore volume of 0.8-1.5mL/g, average pore diameter of 7-9nm; the oxide is silicon oxide and/or aluminum oxide; the heteropoly acid is phosphotungstic acid;
based on the total weight of the catalyst, the content of the zeolite molecular sieve with the MFI structure is 40-60 wt%, the content of the all-silicon mesoporous microspheres is 15-30 wt%, the content of the oxide is 10-20 wt%, and the content of the heteropoly acid is 5-20 wt%.
2. The catalyst according to claim 1, wherein the all-silicon mesoporous microspheres have a specific surface area of 704 to 780m 2 Per g, pore volume of 1.2-1.4mL/g, average pore diameter of 8-8.4nm.
3. The catalyst of claim 1, wherein the zeolite molecular sieve having the MFI structure is a ZSM-5 molecular sieve and/or a ZRP molecular sieve.
4. The catalyst of claim 3, wherein the zeolite molecular sieve having the MFI structure has a silica to alumina molar ratio of from 150 to 500.
5. The catalyst of claim 1, wherein the weight ratio of the zeolite molecular sieve having the MFI structure to the all-silicon mesoporous microspheres is (1-5): 1.
6. the catalyst of claim 2, wherein the preparation method of the all-silicon mesoporous microspheres comprises the following steps: in the presence of a template agent and glycerol, ethyl orthosilicate is contacted with an acidic aqueous solution, and a mixture obtained after the contact is crystallized, washed, filtered, dried and subjected to template agent removal, so that the all-silicon mesoporous microspheres are obtained.
7. The catalyst of claim 6, wherein the templating agent is polyoxyethylene-polyoxypropylene-polyoxyethylene.
8. The catalyst according to claim 6, wherein the acidic aqueous solution is an aqueous hydrochloric acid solution prepared from water and hydrogen chloride.
9. The catalyst of claim 6, wherein the molar ratio of the template agent, glycerol, ethyl orthosilicate, water, and hydrogen chloride is 1:10-400:10-200:5000-50000:50-900.
10. The catalyst of claim 9, wherein the molar ratio of the template agent, glycerol, ethyl orthosilicate, water, and hydrogen chloride is 1:20-200:20-100:10000-30000:150-500.
11. The catalyst according to any one of claims 1 to 10, wherein the specific surface area of the catalyst is from 150 to 400m 2 (iii) a pore volume of 0.3-0.7mL/g.
12. The all-silicon mesoporous microsphere C according to any one of claims 1 to 11 4 The preparation method of the catalyst for increasing the yield of propylene by olefin cracking is characterized by comprising the following steps:
(1) Carrying out ball milling on a zeolite molecular sieve with an MFI structure, all-silicon mesoporous microspheres and phosphotungstic acid to obtain a mixture;
(2) Uniformly stirring the mixture with an adhesive, an extrusion aid and dilute nitric acid, then carrying out extrusion forming and roasting treatment to obtain C containing all-silicon mesoporous microspheres 4 The catalyst for cracking olefin to increase the yield of propylene.
13. The method as claimed in claim 12, wherein the zeolite molecular sieve having MFI structure, the all-silicon mesoporous microspheres, the phosphotungstic acid, the binder, the extrusion aid, and the dilute nitric acid are in a mass ratio of 1:0.25-0.75:0.08-0.5:0.15-2.0:0.08-0.4:0.15-1.0.
14. The method of claim 12, wherein the dilute nitric acid has a mass concentration of 1-10%.
15. The method of claim 12, wherein the extrusion aid is one or more of sesbania powder, polyacrylamide and cellulose.
16. The method of claim 15, wherein the extrusion aid is sesbania powder.
17. The method of claim 12, wherein the firing conditions include: the temperature is 500-600 ℃, and the time is 3-15h.
18. The method according to any one of claims 1 to 11, wherein the mesoporous microspheres are all-silicon microspheres 4 The application of the catalyst for increasing the yield of propylene by cracking olefin in catalytic cracking reaction.
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| CN101172247A (en) * | 2006-10-31 | 2008-05-07 | 中国石油化工股份有限公司 | Catalyst for production of propylene and ethylene with carbon alkatetraenes, regeneration and uses thereof |
| CN101927180A (en) * | 2009-06-19 | 2010-12-29 | 中国石油化工股份有限公司 | Catalyst for preparing propylene from C4 olefins, and application and regeneration method thereof |
| CN104107713A (en) * | 2013-04-16 | 2014-10-22 | 中国石油化工股份有限公司 | Catalyst for preparing propylene through C4 olefin cracking, and preparation method and use thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101172247A (en) * | 2006-10-31 | 2008-05-07 | 中国石油化工股份有限公司 | Catalyst for production of propylene and ethylene with carbon alkatetraenes, regeneration and uses thereof |
| CN101927180A (en) * | 2009-06-19 | 2010-12-29 | 中国石油化工股份有限公司 | Catalyst for preparing propylene from C4 olefins, and application and regeneration method thereof |
| CN104107713A (en) * | 2013-04-16 | 2014-10-22 | 中国石油化工股份有限公司 | Catalyst for preparing propylene through C4 olefin cracking, and preparation method and use thereof |
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