CN111908490A - Horn-hole alumina and preparation method and application thereof - Google Patents
Horn-hole alumina and preparation method and application thereof Download PDFInfo
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- CN111908490A CN111908490A CN201910388509.0A CN201910388509A CN111908490A CN 111908490 A CN111908490 A CN 111908490A CN 201910388509 A CN201910388509 A CN 201910388509A CN 111908490 A CN111908490 A CN 111908490A
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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 113
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 238000001035 drying Methods 0.000 claims abstract description 55
- 239000003054 catalyst Substances 0.000 claims abstract description 50
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000008367 deionised water Substances 0.000 claims abstract description 36
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 36
- 239000002243 precursor Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000007788 liquid Substances 0.000 claims abstract description 19
- 238000000926 separation method Methods 0.000 claims abstract description 9
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 55
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 55
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 34
- 229910052759 nickel Inorganic materials 0.000 claims description 27
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 24
- 238000001354 calcination Methods 0.000 claims description 24
- 229910052750 molybdenum Inorganic materials 0.000 claims description 24
- 239000011733 molybdenum Substances 0.000 claims description 24
- 238000005406 washing Methods 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 238000005470 impregnation Methods 0.000 claims description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 5
- 238000007598 dipping method Methods 0.000 claims description 4
- 238000007654 immersion Methods 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 27
- 238000001816 cooling Methods 0.000 abstract description 15
- 230000002349 favourable effect Effects 0.000 abstract description 3
- 239000000295 fuel oil Substances 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 description 51
- 239000002245 particle Substances 0.000 description 25
- 238000001878 scanning electron micrograph Methods 0.000 description 24
- 239000011148 porous material Substances 0.000 description 17
- 239000000843 powder Substances 0.000 description 17
- 238000011049 filling Methods 0.000 description 14
- -1 polytetrafluoroethylene Polymers 0.000 description 14
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 14
- 239000004810 polytetrafluoroethylene Substances 0.000 description 14
- 238000005303 weighing Methods 0.000 description 13
- 238000005485 electric heating Methods 0.000 description 12
- 238000007789 sealing Methods 0.000 description 12
- 238000001291 vacuum drying Methods 0.000 description 12
- 238000007664 blowing Methods 0.000 description 9
- 238000009792 diffusion process Methods 0.000 description 9
- 239000010779 crude oil Substances 0.000 description 8
- 229910003294 NiMo Inorganic materials 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 230000002902 bimodal effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000012535 impurity Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 159000000013 aluminium salts Chemical class 0.000 description 3
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 3
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 3
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 3
- 229940010552 ammonium molybdate Drugs 0.000 description 3
- 235000018660 ammonium molybdate Nutrition 0.000 description 3
- 239000011609 ammonium molybdate Substances 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 description 2
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000001935 peptisation Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000003483 aging Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention provides a bell-mouthed alumina and a preparation method and application thereof. The method comprises the following steps: (1) uniformly mixing soluble aluminum salt, deionized water and alcohol, carrying out thermal reaction at 220 ℃ for 12-48h at 180 ℃, then cooling, carrying out solid-liquid separation, and drying to obtain a precursor; (2) and (2) roasting the precursor obtained in the step (1). The flared alumina carrier provided by the invention has a flared structure, and the structure is favorable for macromolecular shuttling and is not easy to block. The alumina carrier with the horn holes can be used as a catalyst carrier, and particularly can be used as a carrier for preparing a hydrodesulfurization catalyst for heavy oil processing and the like.
Description
Technical Field
The invention relates to the technical field of chemical materials, in particular to a bell-mouthed alumina and a preparation method and application thereof.
Background
With the increasing deterioration of crude oil, the sulfur content of the produced crude oil is increasing and the hydrogen supply is insufficient in the oil processing process, and the problem of deep desulfurization becomes more troublesome in recent years. Especially in China, a large amount of high-sulfur crude oil is imported for reducing the purchasing cost, and a more effective desulfurization means is needed for reaching the international emission standard. The crude oil containing other impurities, such as nitrogen, metal and the like, can also be removed in the hydrogenation process, so that cleaner chemical raw materials are obtained. However, crude oil contains a large amount of macromolecular reactants such as asphaltene and colloid, the macromolecular reactants have large molecular weight, complex structure and difficult diffusion, and the activity of the catalyst in the hydrodesulfurization reaction is directly influenced in the diffusion process in the catalyst. There is therefore a need for a catalyst support having a good pore structure in order to improve the activity and stability of the catalyst during hydrodesulfurization.
The pore structure of the catalyst has a very important influence on hydrodesulfurization. The hydrodesulfurization of crude oil is a typical internal diffusion control process, and the channel circulation can promote the diffusion and reaction of macromolecular substances in the crude oil, and can also avoid the deactivation of a catalyst in the catalytic process caused by the blockage of a catalyst hole due to the deposition of metal and coke, thereby improving the activity and stability of the catalyst. Therefore, it is critical that the catalyst have open channels for hydrodesulfurization.
In order to improve the pore volume of the alumina carrier and obtain smooth pore channels, a method of adding a pore-expanding agent is generally adopted at present, for example, the US4,448,896 patent introduces that a pseudo-boehmite is used as a raw material, carbon black powder is added as the pore-expanding agent, and the alumina carrier is obtained by kneading, extruding, drying and roasting. The disadvantages are that: adding a small amount of carbon black powder, an ink bottle-shaped hole is easy to form; the addition of excessive carbon black powder results in a significant reduction in the strength of the carrier.
Patents US4,066,574, US4,113,661 and US4,341,625 disclose a process for preparing an alumina carrier, wherein an aqueous solution of nitric acid is added to an alpha-alumina monohydrate for reaction, and then ammonia water is added to achieve the purpose of enlarging the pore volume of the carrier. However, the pore size is relatively single, which is not favorable for maximizing the functions of the inner surface and the outer surface of the particle.
In addition, the catalyst diffusion performance can be improved by preparing a bimodal pore structure. The pore diameter distribution of the bimodal pore channel structure is concentrated in the range of 5-30nm and more than 100 nm. Wherein, the aperture of 5-30nm provides a reaction surface and a deposition place for the reaction of impurities, and the aperture of more than 100nm provides a channel for the diffusion of macromolecular substances, thereby increasing the diffusion and the reaction of the impurities to the inside of the catalyst. Through the combined action of the two pore diameters, the diffusion performance of the catalyst is improved, and the impurity-containing capacity is enhanced.
Chinese patent CN201610840120 discloses a preparation method of a bimodal pore alumina carrier, which comprises mixing pseudoboehmite dry glue powder, an aluminum sol and water, and then carrying out peptization to obtain an aluminum hydroxide sol, wherein the aluminum/chlorine mass ratio of the aluminum sol is 1.0-1.4; mixing the obtained aluminium hydroxide sol with gelatinizer solution, dropping it into hot oil column to form balls, taking out the balls, ageing, washing, drying and calcining.
Chinese patent CN1047957C discloses a method for preparing a bimodal porous alumina carrier, which is prepared by uniformly mixing two or more pseudo-boehmite dry glue powders prepared by different raw material route methods, and then carrying out peptization, molding, drying and roasting treatment. The carrier obtained by the method has a pore volume of 0.7-1.6mL/g and a specific surface of 100-200m2The pore volume of the pores with the diameter of more than 100nm accounts for 10-56 percent of the total pore volume.
The bimodal pore structure, despite the diffusion properties and impurity-tolerant capacity of the catalyst, inevitably the small pores tend to plug during the reaction.
Disclosure of Invention
One object of the present invention is to provide a method for preparing alumina having a bell-mouth shape;
the invention also aims to provide the trumpet-hole alumina prepared by the preparation method;
the invention further aims to provide application of the trumpet-hole alumina.
In order to achieve the above object, in one aspect, the present invention provides a method for preparing alumina having a bell-mouth shape, wherein the method comprises the following steps:
(1) uniformly mixing soluble aluminum salt, deionized water and alcohol, carrying out hydrothermal reaction at 220 ℃ of 180-;
(2) and (2) roasting the precursor obtained in the step (1) to obtain the flared alumina, wherein the roasting temperature is controlled at 450-600 ℃.
According to some specific embodiments of the present invention, in the step (1), the soluble aluminum salt, the deionized water and the alcohol are mixed uniformly and poured into the liner of the hydrothermal reaction kettle made of polytetrafluoroethylene, the filling degree is controlled at 75%, the hydrothermal reaction kettle is sealed and placed into an electrothermal constant temperature air blast drying box, the hydrothermal temperature is controlled at 180-.
According to some embodiments of the invention, the soluble aluminium salt is crystalline aluminium chloride or anhydrous aluminium chloride.
According to some embodiments of the invention, the crystalline aluminum chloride is AlCl3·6H2O。
According to some embodiments of the invention, the alcohol is ethanol or methanol.
According to some embodiments of the invention, in step (1), the soluble aluminum salt and the deionized water are mixed first and then mixed with the alcohol.
According to some embodiments of the invention, the ratio of the volume of the deionized water to the volume of the alcohol is 1:1 to 2: 1.
According to some embodiments of the invention, wherein the mass ratio of the soluble aluminium salt to the alcohol is from 1:5 to 1: 15.
According to some embodiments of the invention, wherein the mass ratio of the soluble aluminium salt to the alcohol is 1: 10.
According to some embodiments of the invention, wherein the thermal reaction in step (1) is carried out in a reaction vessel. The inner container of the reaction kettle is made of polytetrafluoroethylene.
The filling degree of the reaction kettle is controlled to be 50-80% of the volume of the reaction kettle.
And (2) naturally cooling to room temperature in the cooling in the step (1).
According to some embodiments of the present invention, the hydrothermal reaction temperature in step (1) is 180-220 ℃.
According to some embodiments of the present invention, the hydrothermal reaction time in step (1) is 12-24 h.
According to some embodiments of the present invention, the solid-liquid separation in step (1) is performed by separating the solid from the liquid in a high speed centrifuge, washing the solid, performing the separation again, and repeating the separation 2 to 3 times.
According to some embodiments of the present invention, the solid-liquid separation in step (1) is performed by performing solid-liquid separation at 7500rpm, using a high speed centrifuge at 5000-.
According to some embodiments of the invention, wherein the drying temperature in step (1) is 60-100 ℃.
According to some embodiments of the invention, the drying time in step (1) is 10-14 h.
According to some embodiments of the present invention, step (2) is to bake the precursor obtained in step (1) at 450 ℃ and 550 ℃.
According to some embodiments of the invention, the calcination time in step (2) is 4 to 7 hours.
On the other hand, the invention also provides the trumpet-hole alumina prepared by the preparation method.
In still another aspect, the invention also provides the application of the flared alumina in serving as a hydrodesulfurization catalyst carrier.
In still another aspect, the invention further provides a hydrodesulfurization catalyst, wherein the hydrodesulfurization catalyst takes the trumpet-shaped alumina as a catalyst carrier.
According to some specific embodiments of the present invention, the hydrodesulfurization catalyst comprises metallic nickel and molybdenum as active components, wherein the total loading amount of the nickel and the molybdenum is 25%, and the molar ratio of the nickel to the molybdenum is 1: 4.
according to some embodiments of the invention, the hydrodesulfurization catalyst is prepared by a process comprising the steps of: and (2) carrying out dipping treatment on the bell-mouthed alumina by using a nickel precursor aqueous solution, drying the dipped bell-mouthed alumina to obtain nickel-loaded bell-mouthed alumina, carrying out dipping treatment on the nickel-loaded bell-mouthed alumina by using a molybdenum precursor aqueous solution, and drying and calcining the dipped bell-mouthed alumina to obtain the hydrodesulfurization catalyst.
According to some embodiments of the invention, the precursor of nickel is a water-soluble salt of nickel; preferably nickel nitrate.
According to some embodiments of the invention, the precursor of molybdenum is a water-soluble salt of molybdenum; preferably ammonium molybdate.
According to some embodiments of the invention, the concentration of the nickel precursor in the nickel precursor aqueous solution is 1-7 w/w%; the concentration of the precursor of the molybdenum in the precursor water solution of the molybdenum is 15-25 w/w%.
According to some specific embodiments of the present invention, the drying temperature after the immersion treatment of the bell-mouthed alumina with the nickel precursor aqueous solution and after the immersion treatment of the nickel-loaded bell-mouthed alumina with the molybdenum precursor aqueous solution is 80-100 ℃, preferably 100 ℃ respectively; the drying time is 8-12h, preferably 10 h.
According to some specific embodiments of the present invention, the calcination temperature after the impregnation treatment of the nickel-loaded trumpet-hole alumina by using the molybdenum precursor aqueous solution is 400-450 ℃; preferably 400 deg.c.
According to some specific embodiments of the invention, the calcination time after the impregnation treatment of the nickel-loaded trumpet-hole alumina by using the molybdenum precursor aqueous solution is 4-8 h; preferably 5 h.
In conclusion, the invention provides the alumina with the horn holes, and the preparation method and the application thereof. The trumpet-hole alumina has the following advantages:
the flared alumina carrier provided by the invention has a flared structure, and the structure is favorable for macromolecular shuttling and is not easy to block. The alumina carrier with the horn holes can be used as a catalyst carrier, and particularly can be used as a carrier for preparing a hydrodesulfurization catalyst for heavy oil processing and the like.
Drawings
FIG. 1 is an SEM image of alumina particles obtained in example 1;
FIG. 2 is an SEM image of the alumina particles obtained in example 2;
FIG. 3 is an SEM image of the alumina particles obtained in example 3;
FIG. 4 is an SEM image of the alumina particles obtained in example 4;
FIG. 5 is an SEM image of the alumina particles obtained in example 5;
FIG. 6 is an SEM image of the alumina particles obtained in example 6;
FIG. 7 is an SEM image of the alumina particles obtained in example 7;
FIG. 8 is an SEM image of the alumina particles obtained in example 8;
FIG. 9 is an SEM image of the alumina particles obtained in example 9;
FIG. 10 is an SEM image of alumina particles obtained in example 10;
FIG. 11 is an SEM image of the alumina particles obtained in example 11;
FIG. 12 is an SEM image of alumina particles obtained in example 12;
FIG. 13 is a graph showing the evaluation results of the catalyst obtained in example 15.
Detailed Description
The following detailed description is provided for the purpose of illustrating the embodiments and the advantageous effects thereof, and is not intended to limit the scope of the present disclosure.
Example 1
The preparation method of the alumina with the horn holes comprises the following steps:
1) weighing crystalline aluminum chloride (AlCl)3·6H2O)2g, adding into 50mL of deionized water, stirring for 5min, adding 25mL of ethanol while stirring, and stirring for 5min to obtain solution A.
2) Pouring the solution A into a liner of a hydrothermal reaction kettle made of polytetrafluoroethylene, controlling the filling degree to be 75%, sealing the hydrothermal reaction kettle, putting the hydrothermal reaction kettle into an electric heating constant-temperature air blowing drying oven, controlling the hydrothermal temperature to be 200 ℃, reacting for 24 hours, and naturally cooling to room temperature after the reaction is finished.
3) And opening the hydrothermal reaction kettle, uniformly stirring, pouring into a centrifuge tube, centrifuging in a high-speed centrifuge, pouring the upper-layer liquid, washing with deionized water, centrifuging again, repeating for three times, drying in a vacuum drying oven at 80 ℃ for 12 hours, and calcining at 500 ℃ for 4 hours after drying is completed to obtain the horn-hole alumina powder.
The SEM image of the alumina speaker particles of this example is shown in fig. 1, and it can be seen from fig. 1 that the product obtained in this example is alumina speaker.
Example 2
The preparation method of the alumina with the horn holes comprises the following steps:
1) weighing crystalline aluminum chloride (AlCl)3·6H2O)2g, adding into 50mL of deionized water, stirring for 5min, adding 25mL of ethanol while stirring, and stirring for 5min to obtain solution A.
2) Pouring the solution A into a liner of a hydrothermal reaction kettle made of polytetrafluoroethylene, controlling the filling degree to be 75%, sealing the hydrothermal reaction kettle, putting the hydrothermal reaction kettle into an electric heating constant-temperature air blast drying oven, controlling the hydrothermal temperature to be 180 ℃, reacting for 24 hours, and naturally cooling to room temperature after the reaction is finished.
3) And opening the hydrothermal reaction kettle, uniformly stirring, pouring into a centrifuge tube, centrifuging in a high-speed centrifuge, pouring the upper-layer liquid, washing with deionized water, centrifuging again, repeating for three times, drying in a vacuum drying oven at 80 ℃ for 12 hours, and calcining at 500 ℃ for 4 hours after drying is completed to obtain the horn-hole alumina powder.
The SEM image of the alumina speaker particles of this example is shown in fig. 2, and it can be seen from fig. 2 that the product obtained in this example is alumina speaker.
Example 3
The preparation method of the alumina with the horn holes comprises the following steps:
1) weighing crystalline aluminum chloride (AlCl)3·6H2O)2g, adding into 50mL of deionized water, stirring for 5min, adding 25mL of ethanol while stirring, and stirring for 5min to obtain solution A.
2) Pouring the solution A into a liner of a hydrothermal reaction kettle made of polytetrafluoroethylene, controlling the filling degree to be 75%, sealing the hydrothermal reaction kettle, putting the hydrothermal reaction kettle into an electric heating constant-temperature air blowing drying oven, controlling the hydrothermal temperature to be 220 ℃, reacting for 24 hours, and naturally cooling to room temperature after the reaction is finished.
3) And opening the hydrothermal reaction kettle, uniformly stirring, pouring into a centrifuge tube, centrifuging in a high-speed centrifuge, pouring the upper-layer liquid, washing with deionized water, centrifuging again, repeating for three times, drying in a vacuum drying oven at 80 ℃ for 12 hours, and calcining at 500 ℃ for 4 hours after drying is completed to obtain the horn-hole alumina powder.
The SEM image of the alumina speaker particles of this example is shown in fig. 3, and it can be seen from fig. 3 that the product obtained in this example is alumina speaker.
Example 4
The preparation method of the alumina with the horn holes comprises the following steps:
1) weighing crystalline aluminum chloride (AlCl)3·6H2O)2g, adding into 50mL of deionized water, stirring for 5min, adding 25mL of ethanol while stirring, and stirring for 5min to obtain solution A.
2) Pouring the solution A into a liner of a hydrothermal reaction kettle made of polytetrafluoroethylene, controlling the filling degree to be 75%, sealing the hydrothermal reaction kettle, putting the hydrothermal reaction kettle into an electric heating constant-temperature air blast drying oven, controlling the hydrothermal temperature to be 200 ℃, reacting for 12 hours, and naturally cooling to room temperature after the reaction is finished.
3) And opening the hydrothermal reaction kettle, uniformly stirring, pouring into a centrifuge tube, centrifuging in a high-speed centrifuge, pouring the upper-layer liquid, washing with deionized water, centrifuging again, repeating for three times, drying in a vacuum drying oven at 80 ℃ for 12 hours, and calcining at 500 ℃ for 4 hours after drying is completed to obtain the horn-hole alumina powder.
The SEM image of the alumina speaker particles of this example is shown in fig. 4, and it can be seen from fig. 4 that the product obtained in this example is alumina speaker.
Example 5
The preparation method of the alumina with the horn holes comprises the following steps:
1) weighing crystalline aluminum chloride (AlCl)3·6H2O)2g, adding into 50mL of deionized water, stirring for 5min, adding 25mL of ethanol while stirring, and stirring for 5min to obtain solution A.
2) Pouring the solution A into a liner of a hydrothermal reaction kettle made of polytetrafluoroethylene, controlling the filling degree to be 75%, sealing the hydrothermal reaction kettle, putting the hydrothermal reaction kettle into an electric heating constant-temperature air blast drying oven, controlling the hydrothermal temperature to be 200 ℃, reacting for 48 hours, and naturally cooling to room temperature after the reaction is finished.
3) And opening the hydrothermal reaction kettle, uniformly stirring, pouring into a centrifuge tube, centrifuging in a high-speed centrifuge, pouring the upper-layer liquid, washing with deionized water, centrifuging again, repeating for three times, drying in a vacuum drying oven at 80 ℃ for 12 hours, and calcining at 500 ℃ for 4 hours after drying is completed to obtain the horn-hole alumina powder.
The SEM image of the alumina speaker particles of this example is shown in fig. 5, and it can be seen from fig. 5 that the product obtained in this example is alumina speaker.
Example 6
The preparation method of the alumina with the horn holes comprises the following steps:
1) weighing crystalline aluminum chloride (AlCl)3·6H2O)2g, adding into 50mL of deionized water, stirring for 5min, and then25mL of ethanol was added while stirring, and the mixture was further stirred for 5min to obtain a solution A.
2) Pouring the solution A into a liner of a hydrothermal reaction kettle made of polytetrafluoroethylene, controlling the filling degree to be 75%, sealing the hydrothermal reaction kettle, putting the hydrothermal reaction kettle into an electric heating constant-temperature air blowing drying oven, controlling the hydrothermal temperature to be 200 ℃, reacting for 24 hours, and naturally cooling to room temperature after the reaction is finished.
3) And opening the hydrothermal reaction kettle, uniformly stirring, pouring into a centrifuge tube, centrifuging in a high-speed centrifuge, pouring the upper-layer liquid, washing with deionized water, centrifuging again, repeating for three times, drying in a vacuum drying oven at 60 ℃ for 12 hours, and calcining at 500 ℃ for 4 hours after drying is completed to obtain the horn-hole alumina powder.
The SEM image of the alumina speaker particles of this example is shown in fig. 6, and it can be seen from fig. 6 that the product obtained in this example is alumina speaker.
Example 7
The preparation method of the alumina with the horn holes comprises the following steps:
1) weighing crystalline aluminum chloride (AlCl)3·6H2O)2g, adding into 50mL of deionized water, stirring for 5min, adding 25mL of ethanol while stirring, and stirring for 5min to obtain solution A.
2) Pouring the solution A into a liner of a hydrothermal reaction kettle made of polytetrafluoroethylene, controlling the filling degree to be 75%, sealing the hydrothermal reaction kettle, putting the hydrothermal reaction kettle into an electric heating constant-temperature air blowing drying oven, controlling the hydrothermal temperature to be 200 ℃, reacting for 24 hours, and naturally cooling to room temperature after the reaction is finished.
3) And opening the hydrothermal reaction kettle, uniformly stirring, pouring into a centrifugal tube, centrifuging in a high-speed centrifuge, pouring the upper-layer liquid, washing with deionized water, centrifuging again, repeating for three times, drying in a vacuum drying oven at 80 ℃ for 12 hours, and calcining at 600 ℃ for 4 hours after drying is completed to obtain the horn-hole alumina powder.
The SEM image of the alumina speaker particles of this example is shown in fig. 7, and it can be seen from fig. 7 that the product obtained in this example is alumina speaker.
Example 8
The preparation method of the alumina with the horn holes comprises the following steps:
1) weighing crystalline aluminum chloride (AlCl)3·6H2O)2g, adding into 50mL of deionized water, stirring for 5min, adding 25mL of ethanol while stirring, and stirring for 5min to obtain solution A.
2) Pouring the solution A into a liner of a hydrothermal reaction kettle made of polytetrafluoroethylene, controlling the filling degree to be 75%, sealing the hydrothermal reaction kettle, putting the hydrothermal reaction kettle into an electric heating constant-temperature air blowing drying oven, controlling the hydrothermal temperature to be 200 ℃, reacting for 24 hours, and naturally cooling to room temperature after the reaction is finished.
3) And opening the hydrothermal reaction kettle, uniformly stirring, pouring into a centrifuge tube, centrifuging in a high-speed centrifuge, pouring the upper-layer liquid, washing with deionized water, centrifuging again, repeating for three times, drying in a vacuum drying oven at 80 ℃ for 12 hours, and calcining at 450 ℃ for 4 hours after drying is completed to obtain the horn-hole alumina powder.
The SEM image of the alumina speaker particles of this example is shown in fig. 8, and it can be seen from fig. 8 that the product obtained in this example is alumina speaker.
Example 9
The preparation method of the alumina with the horn holes comprises the following steps:
1) weighing crystalline aluminum chloride (AlCl)3·6H2O)2g, adding into 50mL of deionized water, stirring for 5min, adding 50mL of ethanol while stirring, and stirring for 5min to obtain solution A.
2) Pouring the solution A into a liner of a hydrothermal reaction kettle made of polytetrafluoroethylene, controlling the filling degree to be 75%, sealing the hydrothermal reaction kettle, putting the hydrothermal reaction kettle into an electric heating constant-temperature air blowing drying oven, controlling the hydrothermal temperature to be 200 ℃, reacting for 24 hours, and naturally cooling to room temperature after the reaction is finished.
3) And opening the hydrothermal reaction kettle, uniformly stirring, pouring into a centrifuge tube, centrifuging in a high-speed centrifuge, pouring the upper-layer liquid, washing with deionized water, centrifuging again, repeating for three times, drying in a vacuum drying oven at 80 ℃ for 12 hours, and calcining at 500 ℃ for 5 hours after drying is completed to obtain the horn-hole alumina powder.
The SEM image of the alumina speaker particles of this example is shown in fig. 9, and it can be seen from fig. 9 that the product obtained in this example is alumina speaker.
Example 10
The preparation method of the alumina with the horn holes comprises the following steps:
1) weighing crystalline aluminum chloride (AlCl)3·6H2O)2g, adding into 50mL of deionized water, stirring for 5min, adding 25mL of ethanol while stirring, and stirring for 5min to obtain solution A.
2) Pouring the solution A into a liner of a hydrothermal reaction kettle made of polytetrafluoroethylene, controlling the filling degree to be 75%, sealing the hydrothermal reaction kettle, putting the hydrothermal reaction kettle into an electric heating constant-temperature air blowing drying oven, controlling the hydrothermal temperature to be 200 ℃, reacting for 24 hours, and naturally cooling to room temperature after the reaction is finished.
3) And opening the hydrothermal reaction kettle, uniformly stirring, pouring into a centrifuge tube, centrifuging in a high-speed centrifuge, pouring the upper-layer liquid, washing with deionized water, centrifuging again, repeating for three times, drying in a vacuum drying oven at 80 ℃ for 12 hours, and calcining at 500 ℃ for 5 hours after drying is completed to obtain the horn-hole alumina powder.
The SEM image of the alumina speaker particles of this example is shown in fig. 10, and it can be seen from fig. 10 that the product obtained in this example is alumina speaker.
Example 11
The preparation method of the alumina with the horn holes comprises the following steps:
1) weighing crystalline aluminum chloride (AlCl)3·6H2O)2g, adding into 50mL of deionized water, stirring for 5min, adding 25mL of ethanol while stirring, and stirring for 5min to obtain solution A.
2) Pouring the solution A into a liner of a hydrothermal reaction kettle made of polytetrafluoroethylene, controlling the filling degree to be 75%, sealing the hydrothermal reaction kettle, putting the hydrothermal reaction kettle into an electric heating constant-temperature air blowing drying oven, controlling the hydrothermal temperature to be 200 ℃, reacting for 24 hours, and naturally cooling to room temperature after the reaction is finished.
3) And opening the hydrothermal reaction kettle, uniformly stirring, pouring into a centrifuge tube, centrifuging in a high-speed centrifuge, pouring the upper-layer liquid, washing with deionized water, centrifuging again, repeating for three times, drying in a vacuum drying oven at 80 ℃ for 12 hours, and calcining at 500 ℃ for 7 hours after drying is finished to obtain the horn-hole alumina powder.
The SEM image of the alumina speaker particles of this example is shown in fig. 11, and it can be seen from fig. 11 that the product obtained in this example is alumina speaker.
Example 12
The preparation method of the alumina with the horn holes comprises the following steps:
1) weighing anhydrous aluminum chloride (AlCl)3)2g, adding into 50mL of deionized water, stirring for 5min, adding 25mL of ethanol while stirring, and stirring for 5min to obtain solution A.
2) Pouring the solution A into a liner of a hydrothermal reaction kettle made of polytetrafluoroethylene, controlling the filling degree to be 75%, sealing the hydrothermal reaction kettle, putting the hydrothermal reaction kettle into an electric heating constant-temperature air blowing drying oven, controlling the hydrothermal temperature to be 200 ℃, reacting for 24 hours, and naturally cooling to room temperature after the reaction is finished.
3) And opening the hydrothermal reaction kettle, uniformly stirring, pouring into a centrifuge tube, centrifuging in a high-speed centrifuge, pouring the upper-layer liquid, washing with deionized water, centrifuging again, repeating for three times, drying in a vacuum drying oven at 80 ℃ for 12 hours, and calcining at 500 ℃ for 4 hours after drying is completed to obtain the horn-hole alumina powder.
The SEM image of the alumina speaker particles of this example is shown in fig. 12, and it can be seen from fig. 12 that the product obtained in this example is alumina speaker.
Example 13
The catalyst is prepared by a step-by-step impregnation method, wherein the metal loading is 25 wt%, and the molar ratio of nickel to molybdenum is 1:4, and the preparation process comprises the following steps:
(1) 2g of trumpet Al prepared in example 1 were weighed2O3And (3) a carrier.
(2) 0.3g of nickel nitrate hexahydrate was weighed and dissolved in 1.4mL of deionized water.
(3) Adding nickel nitrate solution dropwise onto the carrier, stirring continuously to make the impregnation uniform, and placing the carrier into an oven at 100 ℃ for 10 min.
(4) 0.738g of ammonium molybdate tetrahydrate was weighed and dissolved in 1.4mL of deionized water.
(5) And (4) dropwise adding an ammonium molybdate solution into the sample prepared in the step (3), continuously stirring to ensure that the sample is uniformly soaked, and putting the sample into an oven at 100 ℃ for 12 hours.
(6) Calcining the sample prepared in the step (5) in a box-type resistance furnace at 400 ℃ for 5 hours to obtain the alumina carrier catalyst (NiMo/ur-Al) with horn holes2O3)。
Example 14
The catalyst is prepared by a step-by-step impregnation method, wherein the metal loading is 25 wt%, and the molar ratio of nickel to molybdenum is 1:4, and the preparation process comprises the following steps:
(1) weighing 2g of commercial Al2O3And (3) a carrier.
(2) 0.3g of nickel nitrate hexahydrate is weighed. It was dissolved in 1.4mL of deionized water.
(3) Adding nickel nitrate solution dropwise onto the carrier, stirring continuously to make the impregnation uniform, and placing the carrier into an oven at 100 ℃ for 10 min.
(4) 0.738g of ammonium molybdate tetrahydrate was weighed and dissolved in 1.4mL of deionized water.
(5) And (4) dropwise adding an ammonium molybdate solution into the sample prepared in the step (3), continuously stirring to ensure that the sample is uniformly soaked, and putting the sample into an oven at 100 ℃ for 12 hours.
(6) Calcining the sample prepared in the step (5) in a box-type resistance furnace at 400 ℃ for 5 hours to obtain the commercial alumina carrier catalyst (NiMo/com-Al)2O3)。
Example 15
The catalysts obtained in example 13 and example 14 were evaluated in the following manner:
(1) for horn-hole alumina carrier catalyst (NiMo/ur-Al)2O3) And commercial alumina supported catalyst (NiMo/com-Al)2O3) Using a 3% by volume CS2The cyclohexane solution is presulfided.
(2) First, nitrogen gas was purged through the line at a flow rate of 70ml/min while adjusting a back pressure valve to stabilize the reaction pressure at 3 MPa.
(3) The temperature was raised to 100 ℃ for 25 minutes and dried for 40 minutes under a nitrogen atmosphere.
(4) After drying, introducing a vulcanizing agent at the flow rate of 0.2ml/min for about 10 minutes, soaking the catalyst, switching nitrogen into hydrogen, controlling the flow rate of the hydrogen at 30ml/min, continuously stabilizing the reaction pressure at 3MPa, starting temperature programming, and reacting at 340 ℃ for a period of time to obtain the activated catalyst.
(5) Two catalysts were evaluated with siberian crude oil under the following conditions: the temperature is 340 ℃, the pressure is 5MPa, the space-time is 0.5, the hydrogen-oil ratio is 600, and the result is shown in figure 13, and the trumpet-hole alumina carrier catalyst (NiMo/ur-Al) of the invention2O3) The effect is obviously better than that of a commercial alumina carrier catalyst (NiMo/com-Al)2O3) Good results are obtained.
Claims (21)
1. A preparation method of trumpet-hole alumina, wherein the method comprises the following steps:
(1) uniformly mixing soluble aluminum salt, deionized water and alcohol, carrying out hydrothermal reaction at 220 ℃ of 180-;
(2) and (2) roasting the precursor obtained in the step (1) to obtain the flared alumina, wherein the roasting temperature is controlled at 450-600 ℃.
2. The production method according to claim 1, wherein the soluble aluminum salt is crystalline aluminum chloride or anhydrous aluminum chloride.
3. The method according to claim 1, wherein the alcohol is ethanol or methanol.
4. The method according to claim 1, wherein the step (1) comprises mixing the soluble aluminum salt and deionized water, and then mixing with the alcohol.
5. The method of claim 1, wherein the ratio of the volume of deionized water to the volume of alcohol is 1:1 to 2: 1.
6. The production method according to claim 1, wherein the mass ratio of the soluble aluminum salt to the alcohol is 1:5 to 1: 15.
7. The preparation method according to claim 1, wherein the hydrothermal reaction time in step (1) is 12-24 h.
8. The preparation method according to claim 1, wherein the solid-liquid separation in step (1) is performed by separating the solid from the liquid in a high-speed centrifuge, washing the solid, performing the separation again, and repeating the separation 2 to 3 times.
9. The production method according to claim 1, wherein the drying of step (1) is drying at 60 to 100 ℃; the drying time is 10-14 h.
10. The method as claimed in claim 1, wherein the step (2) comprises calcining the precursor obtained in the step (1) at 550 ℃.
11. The method of claim 9, wherein the calcination time in step (2) is 4-7 hours.
12. The trumpet-hole alumina prepared by the preparation method of any one of claims 1 to 11.
13. Use of the flared alumina of claim 12 as a support for a hydrodesulphurisation catalyst.
14. A hydrodesulfurization catalyst wherein the catalyst support is the flared alumina of claim 12.
15. The hydrodesulfurization catalyst of claim 14 wherein the hydrodesulfurization catalyst comprises nickel and molybdenum as active components, wherein the total loading of nickel and molybdenum is 25%, and the molar ratio of nickel to molybdenum is 1: 4.
16. the hydrodesulfurization catalyst of claim 14 wherein the hydrodesulfurization catalyst is prepared by a process comprising: and (2) carrying out dipping treatment on the bell-mouthed alumina by using a nickel precursor aqueous solution, drying the dipped bell-mouthed alumina to obtain nickel-loaded bell-mouthed alumina, carrying out dipping treatment on the nickel-loaded bell-mouthed alumina by using a molybdenum precursor aqueous solution, and drying and calcining the dipped bell-mouthed alumina to obtain the hydrodesulfurization catalyst.
17. The hydrodesulfurization catalyst of claim 16 wherein the nickel precursor is a water soluble salt of nickel; the precursor of the molybdenum is water-soluble salt of the molybdenum.
18. The hydrodesulfurization catalyst of claim 16 wherein the nickel precursor concentration in the aqueous solution of nickel precursor is 1-7 w/w%; the concentration of the precursor of the molybdenum in the precursor water solution of the molybdenum is 15-25 w/w%.
19. The hydrodesulfurization catalyst of claim 16 wherein the temperatures of drying after the immersion treatment of the bell-mouthed alumina with an aqueous nickel precursor solution and after the immersion treatment of the nickel-loaded bell-mouthed alumina with an aqueous molybdenum precursor solution are each independently 80-100 ℃; the drying time is 8-12h respectively and independently.
20. The hydrodesulfurization catalyst of claim 16 wherein the calcination temperature after the impregnation treatment of the nickel-supported bell-mouthed alumina with an aqueous solution of a molybdenum precursor is 400-450 ℃.
21. The hydrodesulfurization catalyst of claim 16 wherein the calcination time after the impregnation treatment of the nickel-supported bell-mouthed alumina with an aqueous solution of a molybdenum precursor is from 4 to 8 hours.
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