CN115487795A - Spherical alumina carrier and preparation method thereof, dehydrogenation catalyst and application - Google Patents
Spherical alumina carrier and preparation method thereof, dehydrogenation catalyst and application Download PDFInfo
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- CN115487795A CN115487795A CN202110677830.8A CN202110677830A CN115487795A CN 115487795 A CN115487795 A CN 115487795A CN 202110677830 A CN202110677830 A CN 202110677830A CN 115487795 A CN115487795 A CN 115487795A
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 120
- 239000003054 catalyst Substances 0.000 title claims abstract description 58
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 239000002243 precursor Substances 0.000 claims abstract description 59
- 238000000034 method Methods 0.000 claims abstract description 52
- 239000007864 aqueous solution Substances 0.000 claims abstract description 26
- 239000002245 particle Substances 0.000 claims abstract description 26
- 230000002378 acidificating effect Effects 0.000 claims abstract description 15
- 238000001125 extrusion Methods 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000002131 composite material Substances 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims description 26
- 238000007493 shaping process Methods 0.000 claims description 24
- 239000008188 pellet Substances 0.000 claims description 19
- 238000004519 manufacturing process Methods 0.000 claims description 16
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 15
- 238000005520 cutting process Methods 0.000 claims description 14
- 239000011148 porous material Substances 0.000 claims description 12
- 239000008187 granular material Substances 0.000 claims description 10
- 238000012216 screening Methods 0.000 claims description 10
- 229910001593 boehmite Inorganic materials 0.000 claims description 4
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- 229940024546 aluminum hydroxide gel Drugs 0.000 claims description 3
- SMYKVLBUSSNXMV-UHFFFAOYSA-K aluminum;trihydroxide;hydrate Chemical compound O.[OH-].[OH-].[OH-].[Al+3] SMYKVLBUSSNXMV-UHFFFAOYSA-K 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 2
- 229910001679 gibbsite Inorganic materials 0.000 claims description 2
- 238000005453 pelletization Methods 0.000 claims description 2
- 238000003776 cleavage reaction Methods 0.000 claims 1
- 230000007017 scission Effects 0.000 claims 1
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 abstract description 42
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 abstract description 22
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 abstract description 22
- 239000001294 propane Substances 0.000 abstract description 21
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 4
- 239000011805 ball Substances 0.000 description 27
- 239000000843 powder Substances 0.000 description 23
- 238000005516 engineering process Methods 0.000 description 12
- 238000000465 moulding Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 238000004898 kneading Methods 0.000 description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 6
- 229910017604 nitric acid Inorganic materials 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000005096 rolling process Methods 0.000 description 5
- 241000219782 Sesbania Species 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 4
- 239000000969 carrier Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000011806 microball Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 238000002447 crystallographic data Methods 0.000 description 2
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000004230 steam cracking Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000011865 Pt-based catalyst Substances 0.000 description 1
- 101100442269 Shewanella piezotolerans (strain WP3 / JCM 13877) dapB gene Proteins 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229940024545 aluminum hydroxide Drugs 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000007084 catalytic combustion reaction Methods 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000003915 liquefied petroleum gas Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000004148 unit process Methods 0.000 description 1
Images
Classifications
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/60—Platinum group metals with zinc, cadmium or mercury
-
- B01J35/51—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
- C07C5/3332—Catalytic processes with metal oxides or metal sulfides
-
- 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 catalyst carrier preparation and application, and discloses a spherical alumina carrier, a preparation method thereof, a dehydrogenation catalyst and application. The preparation method comprises the following steps: (1) Mixing an alumina precursor, an acidic aqueous solution and an extrusion aid, and carrying out pellet-making treatment on the obtained mixture to obtain a spherical precursor; (2) And drying and roasting the spherical precursor to obtain the spherical composite carrier. The spherical alumina carrier prepared by the method is used in the reaction of preparing propylene by propane dehydrogenation, not only can ensure that the catalyst has higher mechanical strength and better particle surface uniformity, but also can obtain better dehydrogenation activity, propylene selectivity and catalyst stability.
Description
Technical Field
The invention relates to the field of catalyst carrier preparation and application, in particular to a spherical alumina carrier and a preparation method thereof, a dehydrogenation catalyst and application.
Background
The alumina is low in price and easy to obtain, has the advantages of porosity, large specific surface area, high dispersibility, high thermal stability and the like, is commonly used as a catalyst carrier, and is widely applied in the fields of hydrorefining, hydrocracking, aromatic hydrocarbon preparation by catalytic reforming, catalytic combustion, hydrogen production by methane steam reforming, ethylene epoxidation reaction, automobile exhaust control and the like. It is generally believed that the crystal phase, channel structure and surface chemistry of the alumina support may affect the performance of the catalyst. In order to be industrially applicable, most alumina carriers need to satisfy mechanical strength and abrasion strength required for process production conditions through a molding process. In any molding method, the original physical structure or chemical structure of the carrier may be changed, thereby affecting the performance of the catalyst.
The shapes of the alumina carriers used in the current industrial devices mainly include microspheric, spherical, strip-shaped, flaky, trilobal, ring-shaped and the like. Under the same composition, the spherical carrier has high bulk density, large loading capacity and handling capacity, low abrasion, small dust during loading, fast mass transfer and high adsorption efficiency or reaction efficiency. The carriers with strip shapes or other shapes are mostly used for fixed bed reactors, and the spherical carriers are more used for complex process devices such as moving beds or fluidized beds, so that the industrial reaction is more efficient, and the productivity and the product yield are improved. The upgrading of strip products into spherical products in domestic markets is a great trend.
The catalytic dehydrogenation of propane to Propylene (PDH) is a process for the production of propylene. Compared with the traditional cracking technology for preparing propylene, the propane dehydrogenation technology has three advantages: firstly, the technology takes propane as the only raw material and propylene as the only target product, so that the liquefied petroleum gas resource can be effectively utilized to be converted into olefin with wider application, and the propylene yield can reach 85 percent; secondly, the investment of the propane dehydrogenation device is about 33 percent lower than that of hydrocarbon steam cracking; third, propane dehydrogenation technology can produce more propylene than hydrocarbon steam cracking technology. The technology for preparing propylene by catalytic dehydrogenation of propane has been developed for nearly 40 years and has been industrially applied in the early 90 s of the 20 th century.
Alumina is a common carrier for industrial catalysts, and the research work related to the alumina is more. The forming method of industrial spherical alumina carrier mainly includes rolling ball method and oil column method. The uniformity degree of the surface of the alumina carrier obtained by the rolling ball method, the strength of the particles after high-temperature treatment and the sphericity degree of the particles can not meet the requirements of a moving bed process. The oil column forming method has low yield, low production efficiency and high production cost.
Currently, the Oleflex technology developed by UOP corporation is the most widely used worldwide. The Oleflex process employs 4 series-connected adiabatic moving bed reactors, and the catalyst can be continuously regenerated using alumina-supported Pt-based catalyst. The propane dehydrogenation catalysts developed by UOP company in the United states are DeH series, and are gradually improved to DeH-14 and DeH-16 from the initial DeH-6, deH-8 and DeH-10 catalysts, and the latest generation catalyst is DeH-26. The DeH series catalysts all use spherical alumina as a carrier. However, in order to meet the special requirements of the moving bed production mode, the performance requirements of the DeH catalyst on spherical alumina are extremely strict. In addition, UOP company adopts an oil column molding method to prepare a spherical alumina carrier, but the oil column molding method has low yield, low production efficiency and high production cost.
Therefore, it is urgent to develop a new molding process and method for a high-quality spherical alumina carrier.
Disclosure of Invention
The invention aims to overcome the defects of high production cost, low production efficiency, non-uniform spherical particle surface and low particle mechanical strength and abrasion strength of the spherical alumina carrier in the prior art, and provides the spherical alumina carrier, a preparation method thereof, a dehydrogenation catalyst and application thereof. The spherical alumina carrier prepared by the method is used in the reaction of preparing propylene by propane dehydrogenation, not only can ensure that the catalyst has higher mechanical strength and better particle surface uniformity, but also can obtain better dehydrogenation activity, propylene selectivity and catalyst stability.
In order to achieve the above object, a first aspect of the present invention provides a method for preparing a spherical alumina support, wherein the method comprises:
(1) Mixing an alumina precursor, an acidic aqueous solution and an extrusion aid, and carrying out pellet-making treatment on the obtained mixture to obtain a spherical precursor;
(2) And drying and roasting the spherical precursor to obtain the spherical composite carrier.
In a second aspect, the invention provides a spherical alumina carrier prepared by the preparation method.
The third aspect of the present invention provides a dehydrogenation catalyst, wherein the dehydrogenation catalyst comprises a carrier and an active component loaded on the carrier, wherein the carrier is the spherical alumina carrier.
The fourth aspect of the invention provides an application of the dehydrogenation catalyst in the dehydrogenation reaction of the light alkane.
Through the technical scheme, compared with the prior art, the technical scheme provided by the invention has the following advantages:
(1) The spherical alumina carrier prepared by the method has the advantages of good sphericity, smooth and uniform surface, uniform size, high mechanical strength of particles and high abrasion strength.
(2) The preparation method of the spherical alumina carrier has the advantages of simple process, high yield, low preparation cost and good preparation repeatability.
(3) The spherical alumina carrier prepared by the method can be used as a carrier of a catalyst for preparing propylene by propane dehydrogenation. All performance indexes of the prepared dehydrogenation catalyst completely meet the requirements of a moving bed process.
(4) The spherical alumina carrier prepared by the method is loaded with metal components to prepare the dehydrogenation catalyst, and the catalyst has good dehydrogenation activity, high propylene selectivity and good catalyst stability when used for preparing propylene by propane dehydrogenation.
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 a spherical alumina carrier A prepared in example 1 of the present invention;
FIG. 2 is an XRD spectrum of B, a spherical alumina carrier prepared in example 2 of the present invention;
FIG. 3 is a photograph of a spherical alumina carrier A prepared in example 1 of the present invention.
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 invention provides a preparation method of a spherical alumina carrier, wherein the preparation method comprises the following steps:
(1) Mixing an alumina precursor, an acidic aqueous solution and an extrusion aid, and carrying out pellet-making treatment on the obtained mixture to obtain a spherical precursor;
(2) And drying and roasting the spherical precursor to obtain the spherical composite carrier.
The inventors of the present invention found that: the molding refers to a unit process of preparing solid particles with certain shape, size and strength by mutually aggregating various powders, particles, solutions or molten raw materials under the action of certain external force. With the development of production and scientific technology, the molding process has penetrated into many important industries, and the development of the chemical industry relies heavily on the development of catalysts, while the preparation of any solid catalyst does not leave the molding process. However, under the condition of unchanged raw materials and formula, the catalyst or catalyst carrier has different use effects due to different forming methods and processes.
In addition, the performance requirements of the DeH series catalyst used by UOP company in the united states on spherical alumina are very strict, and the specific parameters are as follows: spherical alumina particles with diameter of 1.5-1.9mm, average particle diameter of 1.6-1.8mm, bulk density of 0.58-0.65g/ml, average particle strength higher than 25N, and specific surface area higher than 80m 2 Pore volume is between 0.5 and 0.7ml/g. Furthermore, UOP company uses an oil column molding method to prepare a spherical alumina carrier. However, the oil column molding method has low yield, low production efficiency, and high production cost.
In order to solve the above problems, the inventors of the present invention found that: by adopting the method of the invention and further adopting a pellet-making treatment method, the prepared alumina can meet the performance requirements of the DeH series catalyst used by the U.S. UOP company on spherical alumina, and the preparation method has the advantages of simple process, high yield, low preparation cost and good preparation repeatability.
According to the invention, in the step (1), the pellet pelletizing method comprises the following steps:
(1-1) extruding the mixture into strips, and then cutting and extruding the strips into raw material balls;
(1-2) shaping the raw material ball to obtain a standard ball;
and (1-3) screening the standard round balls to obtain a spherical precursor.
According to a specific embodiment of the present invention, a method for preparing a spherical alumina carrier, the pellet preparation process comprises the following steps: (1) Uniformly mixing a first aluminum oxide precursor, a second aluminum oxide precursor, an acidic aqueous solution and an extrusion aid in a kneader; (2) Transferring the mixture into a miniature ball making machine, extruding a long strip with a circular section, cutting and extruding into a raw material ball; (3) Shaping the raw material balls in a pellet shaping machine to form standard spherical shapes, wherein the obtained products are shaped raw material balls; (4) And (3) putting the shaped raw material balls into a pellet screening machine to screen out spherical precursors with proper sizes.
According to the invention, in the step (1-1), after an alumina precursor, an acidic aqueous solution and an extrusion aid are uniformly mixed, the obtained mixture is transferred to a miniature ball making machine to extrude a strip with a circular section, and then the strip is extruded into a raw material ball after being cut; wherein the conditions for extruding into a bar comprise: the extrusion speed is 0.5-5m/min, preferably 1-3m/min; the circular cross-sectional diameter of the strip may be 1.5 to 5.0mm, preferably 1.5 to 2.0mm; the cutting conditions include: the cutting speed is 100-3500 granules/min.
According to the invention, in the step (1-2), the raw material ball is put into a pellet shaping machine for shaping, so that the raw material ball becomes a standard round ball shape; wherein the shaping conditions include: the rounding time is 0.5-10 min/time, the rounding times are 1-5 times, and the rotating speed of the sample cavity is 50-1400r/min, preferably 200-500r/min.
According to the invention, in step (1-3), the standard round balls are placed in a pellet screening machine to screen out spherical precursors of suitable size.
According to the invention, the alumina precursor comprises a first alumina precursor and/or a second alumina precursor, wherein the first alumina precursor is a main alumina precursor; the second alumina precursor is a secondary alumina precursor; the first alumina precursor is necessary; the second alumina precursor may be optionally used or not used according to specific needs. Preferably, the first alumina precursor and the second alumina precursor are the same or different and are each selected from one or more of pseudo-boehmite, aluminum hydroxide gel, alumina sol, gibbsite or boehmite. In the present invention, the pseudoboehmite may be commercially available or prepared, and in the present invention, specifically, the pseudoboehmite includes: pseudoboehmite powder (produced by Shandong aluminum industry, ltd., specific surface area 257 m) 2 0.32ml/g pore volume and PB-0101 type macroporous pseudoboehmite powder (produced by Zibo Hezi powder new material Co., ltd., specific surface area of 327 m) 2 Pore volume 1.02 ml/g) of TY-101 aluminum hydroxide gelPowder (purchased from Shandong Zibo Tong chemical engineering Co., ltd., ignition loss of 34.6%) and boehmite powder (purchased from Shandong Zibo Bai chemical Co., ltd., specific surface area of 269 m) with the model number of BD-BS03 2 Per g, pore volume of 0.41 ml/g) and type SB, which is imported from Germany original package of pseudo-boehmite powder (purchased from Beijing Atoa Chemicals Co., ltd., specific surface area of 241m 2 Per g, pore volume of 0.53 ml/g), type P-DF-09-LSi (manufactured by Shandong aluminum Limited company, having a specific surface area of 286m 2 Pore volume of 1.08 ml/g) and type CY-L-10A alumina sol (available from Nippon New materials, inc. of Hangzhou, having a specific surface area of 187m 2 Per g, pore volume of 0.38 ml/g) and model PB-0104 (Zibo constant powder new material Co., ltd., specific surface area of 270 m) 2 Pore volume of 0.43 ml/g).
According to the invention, the dosage of the first alumina precursor is more than that of the second alumina precursor; preferably, the weight ratio of the dosage of the first alumina precursor to the dosage of the second alumina precursor is 1: (0-1); more preferably, the weight ratio of the first alumina precursor to the second alumina precursor is 1: (0-0.8).
According to the present invention, the acidic aqueous solution may be an organic acid aqueous solution or an inorganic acid aqueous solution, preferably, the acidic aqueous solution is selected from one or more of a formic acid aqueous solution, an acetic acid aqueous solution, a citric acid aqueous solution, a nitric acid aqueous solution and a hydrochloric acid aqueous solution, more preferably, the acidic aqueous solution is a nitric acid aqueous solution or a citric acid aqueous solution; in the present invention, the mass concentration of the acidic aqueous solution is 1 to 20%, preferably 2 to 10%.
According to the invention, the extrusion aid is selected from one or more of sesbania powder, polyethylene glycol, polyvinyl alcohol, polyacrylamide and cellulose; preferably, the auxiliary agent is sesbania powder.
According to the invention, the weight ratio of the first alumina precursor, the extrusion aid and the acidic aqueous solution is 1: (0.02-0.5): (0.2-5); preferably, the weight ratio of the first alumina precursor, the extrusion aid and the acidic aqueous solution is 1: (0.05-0.2): (0.2-1.0).
According to the invention, the spherical precursor may have a diameter of 1.5 to 5.0mm, preferably 1.5 to 2.0mm.
According to the invention, in the step (1), the alumina precursor, the acidic aqueous solution and the extrusion assistant are contacted and mixed, and the mixing conditions comprise that: stirring at a speed of 50-300r/min and at a temperature of 20-60 deg.C for 0.5-6h; preferably, the stirring speed is 100-200r/min, the temperature is 30-50 ℃, and the time is 1-3h.
According to the invention, in step (2), the drying conditions include: the temperature is 70-150 ℃, and the time is 3-24h; preferably, the temperature is 110-130 ℃ and the time is 5-8h.
According to the present invention, in the step (2), the conditions of the calcination include: the temperature is 400-1200 ℃, and the time is 2-30h; preferably, the temperature is 600-1050 ℃ and the time is 8-15h.
In a second aspect, the invention provides a spherical alumina carrier prepared by the preparation method.
According to the invention, the diameter of the particles of the spherical alumina carrier can be 1.5-5.0mm, preferably 1.5-1.9mm; the average particle diameter may be from 1.5 to 5mm, preferably from 1.5 to 1.9mm; the bulk density is 0.58-0.65g/ml, the mechanical strength of the particles is higher than 35N, and the specific surface area is higher than 100m 2 Pore volume of 0.5-0.7ml/g.
The invention provides a dehydrogenation catalyst, wherein the dehydrogenation catalyst comprises a carrier and an active component loaded on the carrier, and the carrier is the spherical alumina carrier.
According to the present invention, preferably, the active component is selected from one or more of Pt, zn, tin, lanthanum, sodium and potassium; more preferably, the active component is selected from Pt and/or Zn.
According to the present invention, preferably, the spherical alumina support is contained in an amount of 97.5 to 99.4 wt%, and the active component is contained in an amount of 0.6 to 2.5 wt%, based on the total weight of the dehydrogenation catalyst. More preferably, the spherical alumina carrier is 98.6-99.3 wt%, the active component Pt is 0.2-0.4 wt%, and the active component Zn is 0.5-1.0 wt%, based on the total weight of the dehydrogenation catalyst.
The fourth aspect of the invention provides an application of the dehydrogenation catalyst in the dehydrogenation reaction of the light alkane.
According to the invention, the low-carbon alkane dehydrogenation reaction comprises the following steps: and loading a metal component on the spherical alumina carrier by adopting an impregnation method to prepare the dehydrogenation catalyst.
According to the present invention, the above dehydrogenation catalyst is preferably used in a reaction for producing propylene by dehydrogenation of propane.
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples:
the kneader is FN-NH2 type kneader produced by Technology limited company of Tianshuihua round pharmaceutical equipment.
The micro ball making machine is a HWJ-100 type micro ball making machine produced by Tianshuihua round pharmaceutical equipment science and technology limited company.
The pellet screening machine is an SWP-1200 type pellet screening machine produced by Tianshuihua round pharmaceutical equipment science and technology limited company.
The pellet shaper is FN-XZXJ type pellet shaper produced by Tianshuihua round pharmaceutical equipment science and technology limited.
The pore structure parameter analysis of the samples was performed on an adsorption apparatus model ASAP2020-M + C, available from Micromeritics, USA.
The sample was degassed at 350 ℃ for 4 hours under vacuum before measurement, and the specific surface area of the sample was calculated by the BET method and the pore volume was calculated by the BJH model.
The elemental analysis experiments of the samples were performed on an Eagle III energy dispersive X-ray fluorescence spectrometer manufactured by EDAX, USA.
The rotary evaporator is produced by German IKA company, and the model is RV10 digital;
the drying box is produced by Shanghai-Hengheng scientific instruments Co., ltd., model number DHG-9030A.
The muffle furnace is manufactured by CARBOLITE, inc. under the model number CWF1100.
The reagents used in the examples and comparative examples were purchased from the national chemical group, chemical reagents, inc., and the purity of the reagents was analytical grade.
Example 1
This example consists in the preparation of the spherical alumina support of the invention.
100g of pseudo-boehmite powder (produced by Shandong aluminum industry, ltd.), 50g of pseudo-boehmite powder (purchased from Beijing Asia Tai ao Hua chemical auxiliary agent, ltd.) of Germany original package with the type of SB, 85g of dilute nitric acid with the concentration of 5% and 5g of sesbania powder are mixed, transferred to a kneader and stirred uniformly. The kneading temperature is 35 ℃, the rotation speed of the main shaft of the kneading machine is 150r/min, and the kneading time is 1h.
Putting the uniformly mixed raw materials into a hopper of a miniature ball making machine, selecting a strip extruding die with the aperture of 1.8mm, adjusting the strip extruding speed to be 2m/min and the cutting speed to be 1200 granules/min, extruding the raw materials into strips, and extruding and cutting the strips into round small granules.
The round small particles are put into a pellet shaping machine for shaping, and the shaping conditions are as follows: the rounding time is 3 minutes/time, the rounding times are 3 times, and the rotating speed of the sample cavity is 300r/min.
And putting the standard spherical raw material balls obtained after shaping into a pellet screening machine to screen out spherical precursors with the size of 1.7 mm. Drying the spherical precursor at 110 ℃ for 8h, and then roasting at 600 ℃ for 15h to obtain the spherical alumina carrier A.
The spherical alumina support A was characterized and its structural parameters are listed in Table 1.
FIG. 1 is an XRD spectrum of a spherical alumina carrier A prepared in accordance with example 1 of the present invention, and it can be seen from the spectrum of FIG. 1 that the x-ray diffraction angles of the sample are mainly: 2 theta is approximately equal to 19.3 degrees, 31.9 degrees, 37.5 degrees, 39.3 degrees, 45.7 degrees, 60.5 degrees and 66.6 degrees, and gamma-Al 2 O 3 The diffraction data are matched, which shows that the spherical alumina carrier A has typical gamma-Al after being roasted at 600 DEG C 2 O 3 A crystalline phase.
FIG. 3 is a photograph of spherical alumina support A prepared in example 1 of the present invention. As can be seen from FIG. 3, the spherical alumina carrier A is pure white, has smooth surface, uniform particles and uniform size.
Example 2
This example consists in the preparation of the spherical alumina support of the invention.
150g of pseudo-boehmite powder (manufactured by Zibo constant powder new material Co., ltd.) with the model number of PB-0101, 120g of alumina sol (manufactured by Nippon Hangzhou new material Co., ltd.) with the model number of CY-L-10A, 30g of citric acid aqueous solution with the concentration of 20% and 8g of cellulose are mixed, transferred into a kneader and stirred and mixed uniformly. The kneading temperature is 45 ℃, the rotation speed of the main shaft of the kneader is 200r/min, and the kneading time is 2h.
Putting the uniformly mixed raw materials into a hopper of a miniature ball making machine, selecting a strip extruding die with the aperture of 2.0mm, adjusting the strip extruding speed to be 1m/min and the cutting speed to be 500 granules/min, extruding the raw materials into strips, and extruding and cutting the strips into round small granules.
Putting the round small particles into a pellet shaping machine for shaping, wherein the shaping conditions are as follows: the rounding time is 2 minutes/time, the rounding times are 4 times, and the rotating speed of the sample cavity is 200r/min.
And (4) putting the standard spherical raw material balls obtained after shaping into a pellet screening machine to screen out spherical precursors with the size of 1.9 mm. Drying the spherical precursor at 110 ℃ for 12h, and then roasting at 1050 ℃ for 8h to obtain a spherical alumina carrier B.
The spherical alumina support B was characterized and its structural parameters are listed in Table 1.
Fig. 2 is an XRD spectrum of the spherical alumina support B prepared in example 2 of the present invention, and it can be seen from the spectrum of fig. 2 that the x-ray diffraction angle of the sample is mainly: 2 theta is about equal to 31.2 degrees, 32.9 degrees, 34.7 degrees, 36.8 degrees, 39.0 degrees, 39.8 degrees, 44.8 degrees, 46.5 degrees, 47.5 degrees, 50.8 degrees, 52.8 degrees, 59.8 degrees, 62.2 degrees, 64.1 degrees, 66.4 degrees and 67.5 degrees, and theta-Al 2 O 3 The diffraction data are matched, and the result shows that the spherical alumina carrier B has typical theta-Al after being calcined at 1050 DEG C 2 O 3 A crystalline phase.
Example 3
This example is the preparation of the spherical alumina support of the present invention.
200g of TY-101 type aluminum hydroxide gel powder (manufactured by Shandong Zibotong chemical science and technology Co., ltd.), 105g of dilute nitric acid with a concentration of 3% and 10g of sesbania powder were mixed, and transferred to a kneader and uniformly mixed. The kneading temperature is 40 ℃, the rotation speed of the main shaft of the kneading machine is 100r/min, and the kneading time is 3h.
Putting the uniformly mixed raw materials into a hopper of a micro ball making machine, selecting a strip extruding die with the aperture of 1.9mm, adjusting the strip extruding speed to be 2m/min and the cutting speed to be 1100 granules/min, extruding the raw materials into strips, and extruding and cutting the strips into round small granules.
Putting the round small particles into a pellet shaping machine for shaping, wherein the shaping conditions are as follows: the rounding time is 3 minutes/time, the rounding times are 3 times, and the rotating speed of the sample cavity is 300r/min.
And putting the standard spherical raw material balls obtained after shaping into a pellet screening machine to screen out spherical precursors with the size of 1.8 mm. Drying the spherical precursor at 130 ℃ for 5h, and then roasting at 900 ℃ for 10h to obtain the spherical alumina carrier C.
The spherical alumina support C was characterized and its structural parameters are listed in Table 1.
Example 4
This example consists in the preparation of the spherical alumina support of the invention.
120g of boehmite powder (purchased from Shandong Zibo Baida chemical Co., ltd.), 80g of pseudo-boehmite powder (manufactured by Zibo Hezi Tong powder New Material Co., ltd.) with the model of BD-BS03, 110g of acetic acid aqueous solution with the concentration of 10% and 15g of polyethylene glycol are mixed, transferred to a kneader and stirred and mixed uniformly. The kneading temperature is 35 ℃, the rotation speed of the main shaft of the kneader is 150r/min, and the kneading time is 1h.
Putting the uniformly mixed raw materials into a hopper of a miniature ball making machine, selecting a strip extruding die with the aperture of 1.8mm, adjusting the strip extruding speed to be 3m/min and the cutting speed to be 750 granules/min, extruding the raw materials into strips, and extruding and cutting the strips into round small granules.
Putting the round small particles into a pellet shaping machine for shaping, wherein the shaping conditions are as follows: the rounding time is 6 minutes/time, the rounding times are 1 time, and the rotating speed of the sample cavity is 500r/min.
And (4) putting the standard spherical raw material balls obtained after shaping into a pellet screening machine to screen out spherical precursors with the size of 1.7 mm. And drying the spherical precursor at 110 ℃ for 8h, and roasting at 700 ℃ for 12h to obtain a spherical alumina carrier D.
The spherical alumina support D was characterized and its structural parameters are listed in Table 1.
Comparative example 1
100g of pseudo-boehmite powder (produced by Shandong aluminum industry, inc.) with the model number of P-DF-03-LS, 50g of pseudo-boehmite powder (purchased from Beijing Atoa chemical auxiliary agent, inc.) imported from Germany with the model number of SB and 85g of dilute nitric acid with the concentration of 5 percent are uniformly mixed, and the spherical alumina carrier D1 is prepared by adopting an oil column molding method. The structural parameters of the spherical alumina support D1 are given in Table 1.
Comparative example 2
100g of pseudo-boehmite powder (produced by Shandong aluminum industry, inc.) with the model number of P-DF-03-LS, 50g of pseudo-boehmite powder (purchased from Beijing Atao Hua chemical auxiliary agent, inc.) imported from Germany with the model number of SB and 85g of dilute nitric acid with the concentration of 5 percent are uniformly mixed, and the spherical alumina carrier D2 is prepared by adopting a rolling ball forming method. The structural parameters of the spherical alumina support D2 are listed in Table 1.
TABLE 1
As can be seen from Table 1, the particle size of the spherical alumina carrier prepared by the method provided by the invention can be adjusted between 1.5 mm and 1.9mm, the mechanical strength of the particles can reach more than 35N, and the yield is higher than 90%. The spherical alumina carrier products obtained in examples 1-4 all meet the performance requirements of the DeH series catalysts used by UOP company in the United states on the spherical alumina.
Comparing example 1 with comparative example 1, it can be seen that the specific surface area and particle strength of the spherical alumina carrier prepared by the oil column molding method are equivalent to those of the product of the present invention, but the yield is far lower than that of the method.
As can be seen from the comparison between example 1 and comparative example 2, the yield of the spherical alumina carrier prepared by the rolling ball forming method is slightly lower than that of the method, but the particle strength is far lower than that of the product of the invention, and the requirements of moving bed process conditions can not be met completely.
Example 5
This example is intended to illustrate the preparation of the dehydrogenation catalyst of this invention.
(1) Preparation of dehydrogenation catalyst
0.080g of H 2 PtCl 6 ·6H 2 O and 0.321gZn (NO) 3 ) 2 ·6H 2 Dissolving O in 100mL of deionized water in a round-bottom flask to obtain a mixed solution; adding 10g of the spherical alumina carrier A obtained in the example 1 into the mixed solution, carrying out impregnation treatment, continuously stirring and reacting for 8 hours under the condition of a water bath at 50 ℃, and then evaporating solvent water in a system by using a rotary evaporator to obtain a solid product; the solid product was placed in a drying cabinet at 110 ℃ and dried for 6h. Then roasting the mixture in a muffle furnace at the temperature of 550 ℃ for 8h to obtain the dehydrogenation catalyst A-1. The content of the platinum component in terms of platinum element was 0.3% by weight and the content of the zinc component in terms of zinc element was 0.7% by weight based on the total weight of the dehydrogenation catalyst a-1.
(2) Evaluation of reaction Performance in production of propylene by dehydrogenation of propane
0.5g of dehydrogenation catalyst A-1 was charged into a fixed bed quartz reactor, the reaction temperature was controlled at 600 ℃, the reaction pressure was 0.1MPa, propane: the molar ratio of hydrogen is 1:0.5, the reaction time is 24h, and the mass space velocity of propane is 3h -1 . By Al 2 O 3 The reaction product separated by the S molecular sieve column was directly subjected to on-line analysis by an Agilent 7890A gas chromatograph equipped with a hydrogen flame detector (FID), and the obtained propane conversion and propylene selectivity were as shown in Table 2.
Examples 6 to 8
This example is presented to illustrate the preparation of a dehydrogenation catalyst of the present invention.
Dehydrogenation catalysts B-1, C-1 and D-1 were prepared in the same manner as in step (1) in example 5, using the spherical alumina supports B, C and D obtained in examples 2, 3 and 4, respectively.
The catalytic performances of dehydrogenation catalysts B-1, C-1 and D-1 in the reaction of propane dehydrogenation to propylene were evaluated by the method of step (2) in example 5, respectively. The results of the experiment are shown in table 2.
Comparative example 3
A dehydrogenation catalyst D1-1 was prepared in the same manner as in step (1) in example 5, using the spherical alumina support D1 obtained in comparative example 1.
The catalytic performance of dehydrogenation catalyst D1-1 in the reaction of propane dehydrogenation to propylene was evaluated by the method of step (2) in example 5. The results of the experiment are shown in table 2.
Comparative example 4
A dehydrogenation catalyst D2-1 was prepared in the same manner as in step (1) in example 5, using the spherical alumina support D2 obtained in comparative example 2.
The catalytic performance of dehydrogenation catalyst D2-1 in the reaction of propane dehydrogenation to propylene was evaluated by the method of step (2) in example 5. The results of the experiment are shown in table 2.
TABLE 2
As can be seen from Table 2, compared with the spherical alumina prepared by the oil column forming method or the rolling ball method, the dehydrogenation catalyst prepared by using the spherical alumina carrier loaded with the metal component prepared by the method has more excellent performance when used for preparing propylene by propane dehydrogenation, and the propane conversion rate, the propylene selectivity and the catalyst stability are obviously improved.
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 (10)
1. A preparation method of a spherical alumina carrier is characterized by comprising the following steps:
(1) Mixing an alumina precursor, an acidic aqueous solution and an extrusion aid, and carrying out pellet-making treatment on the obtained mixture to obtain a spherical precursor;
(2) And drying and roasting the spherical precursor to obtain the spherical composite carrier.
2. The preparation method of claim 1, wherein in step (1), the pellet pelletizing method comprises:
(1-1) extruding the mixture into strips, and then cutting and extruding the strips into raw material balls;
(1-2) shaping the raw material ball to obtain a standard ball;
and (1-3) screening the standard round balls to obtain a spherical precursor.
3. The production method according to claim 2, wherein the conditions for extruding into a bar include: the extrusion speed is 0.5-5m/min, and the diameter of the circular section of the strip is 1.5-5.0mm;
preferably, the conditions for the cleavage include: the cutting speed is 100-3500 granules/min;
preferably, the shaping processing conditions include: the rounding time is 0.5-10 minutes/time, the rounding times are 1-5 times, and the rotating speed of the sample cavity is 50-1400r/min;
preferably, the spherical precursor may have a diameter of 1.5 to 5.0mm.
4. The production method according to claim 1, wherein the alumina precursor includes a first alumina precursor and/or a second alumina precursor;
preferably, the first alumina precursor and the second alumina precursor are the same or different and are each selected from one or more of pseudo-boehmite, aluminum hydroxide gel, alumina sol, gibbsite and boehmite;
preferably, the amount of the first alumina precursor is more than that of the second alumina precursor;
preferably, the weight ratio of the dosage of the first alumina precursor to the dosage of the second alumina precursor is 1: (0-1).
5. The preparation method according to claim 1, wherein the mass concentration of the acidic aqueous solution is 1-20%; preferably, the weight ratio of the first alumina precursor to the extrusion aid to the acidic aqueous solution is 1: (0.02-0.5): (0.2-5).
6. The method of claim 1, wherein the mixing conditions comprise: the temperature is 20-60 ℃, the time is 0.5-6h, and the rotating speed of the main shaft is 50-300r/min;
preferably, the drying conditions include: the temperature is 70-150 ℃, and the time is 3-24h;
preferably, the conditions of the calcination include: the temperature is 400-1200 ℃ and the time is 2-30h.
7. A spherical alumina support prepared by the preparation method of any one of claims 1 to 6.
8. A spherical alumina support according to claim 7, wherein the spherical alumina support has a particle diameter of 1.5 to 5.0mm, preferably 1.5 to 1.9mm; the average particle diameter is 1.5 to 5.0mm, preferably 1.6 to 1.8mm; the bulk density is 0.58-0.65g/ml, the mechanical strength of the particles is higher than 35N, and the specific surface area is higher than 100m 2 Pore volume of 0.5-0.7ml/g.
9. A dehydrogenation catalyst comprising a carrier and an active component supported on the carrier, wherein the carrier is the spherical alumina carrier of claim 7 or 8.
10. Use of the dehydrogenation catalyst of claim 9 in a dehydrogenation reaction of a lower alkane.
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