CN113304779A - 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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- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 91
- 239000010703 silicon Substances 0.000 title claims abstract description 91
- 239000004005 microsphere Substances 0.000 title claims abstract description 90
- 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 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
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- 150000001336 alkenes Chemical class 0.000 claims abstract description 63
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000011148 porous material Substances 0.000 claims abstract description 42
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 34
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- 238000004523 catalytic cracking Methods 0.000 claims description 9
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- 238000003756 stirring Methods 0.000 claims description 9
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 9
- 241000219782 Sesbania Species 0.000 claims description 7
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- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 7
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- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
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- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 7
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- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
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- 239000004743 Polypropylene Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
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- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J35/617—500-1000 m2/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—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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- 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
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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
- 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
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
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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
- 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
- B01J35/63—Pore volume
- B01J35/638—Pore volume more than 1.0 ml/g
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/20—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
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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Abstract
The invention relates to the field of 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 particle diameter of the all-silicon mesoporous microspheres is 0.5-1.5 mu m, and the specific surface area is 600-900m2Per g, pore volume of 0.8-1.5mLg, the average pore diameter is 7-9 nm. The catalyst provided by the invention is used for C4The cracking reaction of olefin can effectively increase C4Olefin 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 sieve is adopted as catalyst to crack C with lower added value4And C4The 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.
C4The 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, C4The 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 C4The propylene selectivity of olefin cracking catalysts is also relatively low. In order to improve the performance of the catalyst, many researchers have conducted intensive studies on the synthesis and modification of MFI molecular sieves (CN1611471A, 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 0.6nm) for C4The olefin cracking reaction is still a disadvantage that side reactions are liable to occur.
In conclusion, the propylene has higher and stable selectivityBetter qualitative C4Olefin 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 art4The 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 C4The cracking reaction of olefin can effectively increase C4Olefin 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 microspheres4The 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 600-900m2Per g, pore volume of 0.8-1.5mL/g, average pore diameter of 7-9 nm.
The second aspect of the invention provides a C containing the all-silicon mesoporous microspheres4The 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 microspheres4The catalyst for cracking olefin to increase the yield of propylene.
The third aspect of the invention provides the C containing the all-silicon mesoporous microspheres4The 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 invention4Catalyst for cracking olefin to increase yield of propyleneOne of the components is zeolite molecular sieve raw material with MFI structure, which is low in price and easy to obtain.
(2) C provided by the invention4The other main component of the olefin cracking propylene-increasing catalyst is the all-silicon mesoporous microspheres, the preparation method is simple, and the preparation process is environment-friendly.
(3) C provided by the invention4Catalyst for increasing yield of propylene by cracking olefin4The cracking reaction of mono-olefin not only effectively improves C4Olefin conversion and propylene selectivity, while improving catalyst stability.
(4) Said C of the invention4The 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 an all-silicon mesoporous microsphere A prepared in example 1;
fig. 2 is a scanning electron microscope image of the all-silicon mesoporous microspheres 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 C4When 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, C4The 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 zeolite molecular sieve is structurally stabilizedThe combination of the characteristics of the surface of the mesoporous material and the surface of the mesoporous material with proper acid centers and the structural characteristic of wide pore channels of the mesoporous material can improve C4Propylene 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 C4An olefin cracking catalyst.
The invention provides a C containing all-silicon mesoporous microspheres in a first aspect4The 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 600-900m2Per g, pore volume of 0.8-1.5mL/g, average pore diameter of 7-9 nm.
According to the invention, the specific surface area of the all-silicon mesoporous microsphere is 704-780m2Per g, pore volume of 1.2-1.4mL/g, average pore diameter of 8-8.4 nm.
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 SiO2/Al2O3Is 100-800, preferably 150-500, and more preferably 300-500.
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 mole ratio of the template agent to the glycerol to the ethyl orthosilicate 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 2-30 h.
According to the invention, the crystallization conditions are: the crystallization temperature is 90-150 ℃, and the crystallization time is 10-40 h.
According to the invention, the drying conditions are: the drying temperature is 70-150 ℃, and the drying time is 3-20 h.
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, 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, it is noted that the all-silicon mesoporous microsphere-containing C4The total amount of each component in the olefin cracking propylene-increasing catalyst is one hundred percent.
According to the invention, the catalyst having an MFI structure is preferably used in the catalyst systemWhen the content of the zeolite molecular sieve 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 content of the cracking catalyst is increased4Olefin conversion, propylene selectivity, and catalyst stability.
The second aspect of the invention provides a C containing the all-silicon mesoporous microspheres4The 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 microspheres4The catalyst for cracking olefin to increase the yield of propylene.
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 the zeolite molecular sieve with MFI structure, the all-silicon mesoporous microspheres and phosphotungstic acid, adding the adhesive, the extrusion aid and the dilute nitric acid, uniformly stirring, then carrying out extrusion forming, drying at 70-150 ℃ for 5-20h, and roasting at 500-600 ℃ for 3-15h to obtain C4The catalyst for cracking olefin to increase the yield of propylene.
According to the invention, the C containing all-silicon mesoporous microspheres prepared by the method4The catalyst for cracking olefin to increase the yield of propylene.
According to the invention, the C containing all-silicon mesoporous microspheres4The specific surface area of the catalyst for increasing the yield of propylene by cracking olefin is 150-400m2Per g, pore volume0.3-0.7 mL/g; preferably, the specific surface area is 221-2(iii) a pore volume of 0.40-0.46 mL/g.
The third aspect of the invention provides the C containing the all-silicon mesoporous microspheres4The 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 C4-C8The 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 C4An olefin cracking catalyst.
According to the invention, said compound contains C4The 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 methanol.
Preference is given to using C4C of olefin production from raffinate I or methanol4And fractions containing more than five carbons are used as the raw materials of the invention.
According to the invention, the method comprises the following specific operations: at the temperature of 460 ℃ and 560 ℃, the pressure of 0.02-0.5MPa and the weight hourly space velocity of 0.5-30h-1Under the conditions of (1) will contain C4-C8Reacting a feed of monoolefins with C in a fixed bed reactor4The 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; x-ray diffraction analysis of the samples was performed on an X-ray diffractometer, model D8 Advance, available 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 corporation, model CWF 1100.
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 illustrates the preparation of all-silicon mesoporous microspheres by the method of the present invention4The catalyst for cracking olefin to increase the yield of propylene.
(1) Preparation of all-silicon mesoporous microspheres
58 g of P123(0.01mol) and 73.6 g of glycerol (0.8mol) 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 (0.6mol) 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 735m2Pore volume 1.3ml/g, average pore diameter 8.1 nm.
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)C4Preparation of olefin cracking catalyst
53 g of ZSM-5 molecular Sieve (SiO)2/Al2O3300), 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 C4Olefin cracking catalyst A.
C4The specific surface area of the olefin cracking catalyst A was 238m2(ii)/g; the pore volume was 0.42 mL/g.
In terms of weight percent, C4The 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 invention4The catalyst for cracking olefin to increase the yield of propylene.
(1) Preparation of all-silicon mesoporous microspheres
58 g of P123(0.01mol) and 27.6 g of glycerol (0.3mol) 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 (0.2mol) into the solution, slowly stirring for 10 minutes at 25 ℃, and 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 780m2Pore volume 1.4ml/g, average pore diameter 8.0 nm.
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)C4Preparation of olefin cracking catalyst
55 g of ZRP-5 molecular Sieve (SiO)2/Al2O3300), 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 time is 24 hours. 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 C4Olefin cracking catalyst A.
C4The specific surface area of the olefin cracking catalyst B was 221m2(ii)/g; the pore volume was 0.40 ml/g.
In terms of weight percent, C4The composition of olefin cracking catalyst B (wt.%): 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 invention4The catalyst for cracking olefin to increase the yield of propylene.
(1) Preparation of all-silicon mesoporous microspheres
58 g of P123(0.01mol) and 147.2 g of glycerol (1.6mol) 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 (1.0mol) 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 704m2Pore volume 1.2ml/g, average pore diameter 8.4 nm.
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)C4Preparation of olefin cracking catalyst
48 g of ZSM-5 molecular Sieve (SiO)2/Al2O3500), 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 0.5 h. 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 C4Olefin cracking catalyst C.
C4The specific surface area of the olefin cracking catalyst A was 257m2(ii)/g; the pore volume was 0.46 ml/g.
In terms of weight percent, C4The composition of 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 invention4The catalyst for cracking olefin to increase the yield of propylene.
Method according to example 1Preparing the catalyst D by a method except that the specific surface area of the all-silicon mesoporous microspheres is 600m2Pore volume 1.5mL/g, average pore diameter 7 nm.
Example 5
This example illustrates the preparation of all-silicon mesoporous microspheres by the method of the present invention4The 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 percent4The 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, step (2) was only retained, and 75g of ZSM-5 molecular Sieve (SiO) was used2/Al2O3300) instead of "53 g ZSM-5 molecular Sieve (SiO)2/Al2O3300), 22 g of all-silicon mesoporous microspheres A ".
C4The specific surface area of the olefin cracking catalyst D1 was 137m2(ii)/g; the pore volume was 0.28 ml/g.
In terms of weight percent, C4The composition of the olefin cracking catalyst D1 (wt.%) was: 75% of ZSM-5 molecular sieve, 15% of alumina and 10% of phosphotungstic acid.
Comparative example 2
Catalyst D2 was prepared according to the method of example 1, except that the high-silicon ZSM-5 zeolite molecular Sieve (SiO) in step (1)2/Al2O3300) is replaced by low-silicon ZSM-5 zeolite molecular Sieve (SiO)2/Al2O3Is 25).
C4The specific surface area of the olefin cracking catalyst D2 was 204m2(ii)/g; the pore volume was 0.39 ml/g.
In terms of weight percent, C4The composition of the olefin cracking catalyst D2 (wt.%) was: 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 500m2Pore volume 1.6mL/g, average pore diameter 5 nm.
Comparative example 4
Catalyst D4 was prepared according to the method of example 1, except that the charge of the components was varied such that the result: in terms of weight percent, C4The composition of olefin cracking catalyst a (wt.%): ZSM-5 molecular sieve 35%, full-silicon mesoporous microspheres 40%, alumina 22% and heteropoly acid 3%.
Test example 1
C4Test 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 has the following composition (wt%): 11.92 parts of isobutane, 26.10 parts of n-butane, 22.02 parts of trans-2-butene, 23.48 parts of 1-butene, 0.38 parts of isobutene, 15.29 parts of cis-2-butene and C parts5The above component is 0.76.
The specific test method is as follows:
c of catalyst on fixed bed reactor4And (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-1After cooling and gas-liquid separation of the product, the gas composition is prepared with Al2O3-agilent 6890 gas chromatograph analysis of S capillary chromatography column and hydrogen flame detector (FID), using programmed temperature, quantitative analysis with correction factors; the liquid composition was analyzed by Agilent 6890 gas chromatograph equipped with PONA chromatographic column, using programmed temperature rise, and quantitative analysis with light gasoline standard. The reaction results are shown in Table 1, C4And (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 used4The catalyst for increasing the yield of propylene by olefin cracking has excellent performance when used for catalyzing the cracking reaction of carbon tetraolefin. A part of all-silicon mesoporous microspheres are added in the catalyst A, and all-silicon mesoporous microspheres are not added in the catalyst D1. Compared with catalyst D1, catalyst A has obviously raised carbon four olefin converting rate, propylene selectivity and catalyst stability. The above results show that the invention provides C4The 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 silica-alumina 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 relatively low, the pore volume is relatively high, and the average pore diameter is relatively small, 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 C4In 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 C4The contents of all components in the olefin cracking catalyst are not in the range defined by the invention, and the obtained carbon four-olefin cracking catalyst has poor performance, low carbon four-olefin conversion rate, low propylene selectivity and stable catalystThe properties were also poor.
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 (12)
1. C containing all-silicon mesoporous microspheres4The 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 average particle diameter of the all-silicon mesoporous microspheres is 0.5-1.5 mu m, and the specific surface area is 600-900m2Per g, pore volume of 0.8-1.5mL/g, average pore diameter of 7-9 nm.
2. The catalyst as claimed in claim 1, wherein the specific surface area of the all-silicon mesoporous microspheres is 704-780m2Per g, pore volume of 1.2-1.4mL/g, average pore diameter of 8-8.4 nm.
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; preferably, the zeolite molecular sieve having the MFI structure has a silica to alumina molar ratio of SiO2/Al2O3Is 100-;
preferably, the weight ratio of the zeolite molecular sieve with MFI structure to the all-silicon mesoporous microspheres is (1-5): 1.
4. the catalyst according to any one of claims 1 to 3, 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.
5. The catalyst of claim 4, wherein the templating agent is polyoxyethylene-polyoxypropylene-polyoxyethylene;
preferably, the acidic aqueous solution is a hydrochloric acid aqueous solution prepared from water and hydrogen chloride;
the mole ratio of the template agent to the glycerol to the ethyl orthosilicate 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.
6. The catalyst according to claim 1, wherein the oxide is an oxide obtained by calcining a binder, preferably silica and/or alumina;
more preferably, the binder is selected from one or more of silica sol, aluminum sol and pseudo-boehmite;
preferably, the heteropolyacid is preferably phosphotungstic acid.
7. The catalyst of any one of claims 1 to 6, wherein the zeolite molecular sieve having an MFI structure is present in an amount of 40 to 60 wt%, the all-silicon mesoporous microspheres are present in an amount of 15 to 30 wt%, the oxide is present in an amount of 10 to 20 wt%, and the heteropoly acid is present in an amount of 5 to 20 wt%, based on the total weight of the catalyst.
8. The catalyst according to any one of claims 1 to 7, wherein the specific surface area of the catalyst is 150-400m2(iii) a pore volume of 0.3-0.7 mL/g.
9. The all-silicon mesoporous microsphere C according to any one of claims 1 to 84The 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 microspheres4The catalyst for cracking olefin to increase the yield of propylene.
10. The method of claim 9, wherein the zeolite molecular sieve having an 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;
preferably, the mass concentration of the dilute nitric acid is 1-10%;
preferably, the extrusion aid is one or more of sesbania powder, polyacrylamide and cellulose, and is preferably sesbania powder.
11. The method of claim 9 or 10, wherein the firing conditions include: the temperature is 500-600 ℃, and the time is 3-15 h.
12. The method according to any one of claims 1 to 8, wherein the mesoporous microspheres are all-silicon microspheres4The application of the catalyst for increasing the yield of propylene by cracking olefin in catalytic cracking reaction.
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