CN114452966B - Preparation method of macroporous alumina - Google Patents
Preparation method of macroporous alumina Download PDFInfo
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- CN114452966B CN114452966B CN202011135395.8A CN202011135395A CN114452966B CN 114452966 B CN114452966 B CN 114452966B CN 202011135395 A CN202011135395 A CN 202011135395A CN 114452966 B CN114452966 B CN 114452966B
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- boehmite
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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 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical group [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims abstract description 48
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000000034 method Methods 0.000 claims abstract description 31
- 239000000463 material Substances 0.000 claims abstract description 27
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 23
- 238000001935 peptisation Methods 0.000 claims abstract description 9
- 239000002243 precursor Substances 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims description 25
- 239000000843 powder Substances 0.000 claims description 17
- 238000009740 moulding (composite fabrication) Methods 0.000 claims description 13
- 238000000926 separation method Methods 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 8
- 238000000465 moulding Methods 0.000 claims description 8
- 238000005984 hydrogenation reaction Methods 0.000 claims description 7
- 238000004898 kneading Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 4
- 239000000295 fuel oil Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 239000007790 solid phase Substances 0.000 claims description 2
- 239000011148 porous material Substances 0.000 abstract description 21
- 230000000694 effects Effects 0.000 abstract description 5
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 229920002521 macromolecule Polymers 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 22
- 239000000243 solution Substances 0.000 description 16
- 239000012298 atmosphere Substances 0.000 description 10
- 238000005303 weighing Methods 0.000 description 9
- 230000032683 aging Effects 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 239000011343 solid material Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 241000219782 Sesbania Species 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- 238000009826 distribution Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical group S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 150000002191 fatty alcohols Chemical class 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000002336 sorption--desorption measurement Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 229910001593 boehmite Inorganic materials 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical group [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- -1 ammonium ions Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
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- 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
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- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
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- B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
- B01J20/28073—Pore volume, e.g. total pore volume, mesopore volume, micropore volume being in the range 0.5-1.0 ml/g
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- B01J20/28078—Pore diameter
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- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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- 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
- C01F7/44—Dehydration of aluminium oxide or hydroxide, i.e. all conversions of one form into another involving a loss of water
- C01F7/441—Dehydration of aluminium oxide or hydroxide, i.e. all conversions of one form into another involving a loss of water by calcination
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- 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
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- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
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Abstract
The invention discloses a preparation method of macroporous alumina. The preparation method of macroporous alumina comprises the following steps: (1) Impregnating the alumina precursor with an aqueous ammonium chloride solution of a suitable concentration; (2) Roasting the material obtained in the step (1) to obtain macroporous alumina; wherein the alumina precursor is pseudo-boehmite with peptization index lower than 85%. The method has simple operation process and obvious reaming effect, can effectively improve the pore channel content of 10-30nm in the alumina, and the obtained macroporous alumina can be applied to the fields of catalysis, adsorption and the like of macromolecules.
Description
Technical Field
The invention relates to the field of inorganic material preparation, in particular to a preparation method of macroporous alumina.
Background
Activated alumina is a porous material with excellent physical and chemical properties, and is widely used as a catalyst or a carrier. The pore structure of the alumina carrier not only affects the dispersity of the supported active components, but also is closely related to the activity, selectivity, catalyst life and the like of the catalyst. As crude oil becomes more and more heavy, traditional small pore alumina has failed to meet the production requirements, and development and production of mesoporous and macroporous activated alumina are increasingly important.
CN104340997a discloses a method for preparing large-aperture alumina, which comprises dissolving boehmite, pseudo-boehmite or a mixture of boehmite and pseudo-boehmite in any proportion in deionized water to form an aluminum hydroxide suspension; heating treatment in sections; carrying out hydrothermal aging on the treated aluminum hydroxide suspension; and drying and roasting after aging is finished, and finally obtaining the alumina product with large aperture.
CN105600810a discloses a preparation method of macroporous alumina material, which comprises mixing carbon black and alkali liquor, stirring, preparing aluminum salt solution, mixing carbon black obtained by filtering and drying with aluminum salt solution, stirring, ultrasonic treating, adding ammonium salt, drying the mixture, and finally treating in nitrogen, oxygen and nitrogen atmosphere in sequence to obtain alumina.
CN102795647a discloses a macroporous alumina and its preparation method, the alumina is prepared by two-stage aging method, the first stage aging adds alkaline compound or acid compound to the aluminium hydroxide suspension to adjust the pH value of the suspension, then aging, the second stage aging adds fatty alcohol, after aging, separating fatty alcohol, drying the slurry without fatty alcohol, roasting to obtain the alumina with large aperture, large specific surface and large pore volume.
Du Mingxian et al (Du Mingxian, xiaozhen, li Yuan, li Lindong, zhu Huaqing, tan Changyu. Preparation of high specific surface area narrow pore distribution alumina i. Influence of precipitation conditions. Catalytic journal, 2002, 23 (5): 465-468.) alumina having a higher specific surface area and a higher macropore content was prepared using a pH swing method.
The research shows that the alumina with higher macropore content can be prepared by adopting the technology, but the defects of complex preparation process and difficult industrialized production exist.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a preparation method of macroporous alumina. The method adopts a simple reaming technology, can effectively improve the pore channel content of 10-30nm in the alumina, and simultaneously reduces the pore channel content below 10nm, and the obtained macroporous alumina can be applied to the fields of catalysis, adsorption and the like of macromolecules.
The preparation method of macroporous alumina comprises the following steps:
(1) Impregnating the alumina precursor with ammonium chloride aqueous solution with proper concentration, carrying out solid-liquid separation and drying treatment;
(2) And (3) roasting the solid phase material obtained in the step (1) to obtain macroporous alumina powder or a macroporous alumina forming carrier.
In the method of the present invention, the alumina precursor in the step (1) is pseudo-boehmite powder with a peptization index of less than 85% or a molded article prepared from the above powder, preferably with a peptization index of less than 80%.
In the method, the formed product preparation in the step (1) specifically refers to a material obtained by kneading, forming and drying pseudo-boehmite powder with a peptization index lower than 85% serving as a raw material. The kneading and forming are the common technology in the field, and the kneading and forming process is to uniformly mix a proper amount of pseudo-boehmite with a proper amount of sesbania powder, then add a proper amount of peptizing agent aqueous solution, wherein the peptizing agent aqueous solution is one or more mixed aqueous solutions of nitric acid, hydrochloric acid, citric acid, acetic acid and oxalic acid, the mass concentration of the solution is 1% -3%, and the addition amount is determined according to the forming effect. The drying temperature is 80-160 ℃, and the drying time is 1-10 hours.
In the process of the present invention, the concentration of the ammonium chloride solution in the step (1) is 2 to 7.5mol/L, preferably 3 to 6mol/L, and the amount of the solution is such that the pseudo-boehmite powder or the pseudo-boehmite molding is completely immersed, and the immersion time is 0.5 to 3 hours, preferably 2 to 3 hours.
In the method of the invention, the solid-liquid separation in the step (1) generally adopts modes of filtration, centrifugation and the like, and the separated liquid phase can be recycled after concentration adjustment.
In the method of the invention, the drying conditions in the step (1) are as follows: the drying temperature is 80-200deg.C, preferably 100-160deg.C, and the drying time is 1-10 hr, preferably 4-8 hr.
In the method of the invention, the roasting conditions in the step (2) are as follows: the calcination temperature is 500-850 ℃, preferably 650-800 ℃, and the calcination time is 1-10 hours, preferably 4-8 hours. The roasting process has no special requirements on roasting atmosphere, and the roasting process is generally carried out under an air atmosphere, or can be carried out under an inert atmosphere and/or an oxygen atmosphere.
The invention also provides a hydrogenation catalyst, which comprises the macroporous alumina forming carrier prepared by the method or the alumina carrier prepared by macroporous alumina powder.
The application of the hydrogenation catalyst in the heavy oil hydrogenation process is particularly suitable for hydrogenation processes such as hydrodemetallization, desulfurization, denitrification and the like of heavy oil.
Compared with the prior art, the invention has the following advantages:
(1) The invention uses ammonium chloride aqueous solution to impregnate pseudo-boehmite, and the impregnated pseudo-boehmite is dried and roasted to prepare the alumina. During impregnation, substances such as chloride ions, ammonium ions, water molecules and the like are uniformly distributed on the surface of the pseudo-boehmite crystal grain and in the lamellar structure. The ammonium chloride solution is heated and decomposed during high-temperature roasting of the impregnated pseudo-boehmite to generate ammonia gas, hydrogen chloride and water vapor, and the generated gas can play a role in punching on one hand; on the other hand, because the alumina is an amphoteric oxide, the generated ammonia gas and hydrogen chloride gas can act with alumina grains to change the grain size and stacking morphology, thereby improving the pore canal structure of the alumina material and increasing the macropore content in the carrier.
(2) The method has simple process, easily obtained raw materials and easy industrialized production.
Detailed Description
The technical scheme and effect of the present invention will be further described with reference to the following examples, but is not limited thereto.
BET method: application N 2 Physical adsorption-desorption characterization examples and comparative examples the pore structure of the carriers were as follows: using ASAP-2420 type N 2 The physical adsorption-desorption instrument characterizes the structure of the sample hole. And (3) taking a small amount of sample, vacuum-treating for 3-4 hours at 300 ℃, and finally placing the product under the condition of low temperature (-200 ℃) of liquid nitrogen for nitrogen adsorption-desorption test. Wherein the specific surface area is obtained according to BET equation, and the distribution ratio of pore volume and pore diameter below 100nm is obtained according to BJH model.
The determination method of the peptization index DI of pseudo-boehmite in the method of the invention is determined according to the following method: 5g of pseudo-boehmite (dry basis) which is sieved and smaller than 200 meshes is weighed and placed in a 250mL conical flask, a proper amount of distilled water is added, electromagnetic stirring is started, a proper amount of hydrochloric acid is added, the mixture is kept stand and settled for 24 hours after being continuously stirred for a certain time, the upper suspension is poured out, and then the mixture is dried and roasted, and the mass of the rest sample is weighed to be w, and DI= (5-w)/5 multiplied by 100%.
The peptization index DI of pseudo-boehmite A1 used in the method of the invention is 82% and the peptization index DI of pseudo-boehmite A2 is 78%.
Example 1
Weighing a proper amount of pseudo-boehmite A1, adding a proper amount of ammonium chloride solution with the molar concentration of 4.5mol/L to enable the pseudo-boehmite to be completely immersed, immersing the immersed material for 2 hours, then carrying out liquid-solid separation, drying the solid material at 120 ℃ for 6 hours, placing the dried material in a muffle furnace, roasting at 700 ℃ for 6 hours in an air atmosphere, and obtaining the alumina S1, wherein the carrier properties are shown in Table 1.
Example 2
Weighing a proper amount of pseudo-boehmite A2, adding a proper amount of ammonium chloride solution with the molar concentration of 3.5mol/L to enable the pseudo-boehmite to be completely immersed, immersing the immersed material for 2 hours, then carrying out liquid-solid separation, drying the solid material at 140 ℃ for 5 hours, placing the dried material in a muffle furnace, and roasting the dried material at 750 ℃ for 4 hours under nitrogen atmosphere to obtain the alumina S2, wherein the carrier properties are shown in Table 1.
Example 3
Weighing a proper amount of pseudo-boehmite A1, adding a proper amount of ammonium chloride solution with the molar concentration of 2.5mol/L to enable the pseudo-boehmite to be completely immersed, immersing the immersed material for 2 hours, then carrying out liquid-solid separation, drying the solid material at 160 ℃ for 4 hours, placing the dried material in a muffle furnace, roasting at 800 ℃ for 6 hours under an oxygen atmosphere to obtain alumina S3, wherein the carrier properties are shown in table 1.
Example 4
Weighing a proper amount of pseudo-boehmite A1, adding a proper amount of ammonium chloride solution with the molar concentration of 5.5mol/L to enable the pseudo-boehmite to be completely immersed, immersing the immersed material for 2 hours, then carrying out liquid-solid separation, drying the solid material at 100 ℃ for 7 hours, placing the dried material in a muffle furnace, and roasting the dried material at 650 ℃ for 7 hours under an air atmosphere to obtain alumina S4, wherein the carrier properties are shown in Table 1.
Example 5
Weighing a proper amount of pseudo-boehmite A1, adding a proper amount of ammonium chloride solution with the molar concentration of 2.5mol/L to enable the pseudo-boehmite to be completely immersed, immersing the immersed material for 2 hours, then carrying out liquid-solid separation, drying the solid material at 180 ℃ for 3 hours, placing the dried material in a muffle furnace, roasting at 700 ℃ for 6 hours in an air atmosphere, and obtaining alumina S5, wherein the carrier properties are shown in table 1.
Example 6
Weighing a proper amount of pseudo-boehmite A1, adding a proper amount of sesbania powder, controlling the mass of the sesbania powder to be 1% of the mass of the pseudo-boehmite A1, uniformly mixing the materials, adding a proper amount of nitric acid aqueous solution with the mass concentration of 1%, uniformly kneading, extruding strips for molding, and drying the molded strips at 120 ℃ for 6 hours to obtain the pseudo-boehmite molded product.
Weighing a proper amount of the pseudo-boehmite forming object, adding a proper amount of ammonium chloride solution with the molar concentration of 4.5mol/L to enable the pseudo-boehmite forming object to be completely immersed, immersing the immersed material for 2 hours, then carrying out liquid-solid separation, drying the solid material at 120 ℃ for 6 hours, placing the dried material in a muffle furnace, and roasting the dried material at 700 ℃ for 6 hours in an air atmosphere to obtain the alumina carrier S6, wherein the properties of the carrier are shown in table 1.
Example 7
Weighing a proper amount of pseudo-boehmite A2, adding a proper amount of sesbania powder, controlling the mass of the sesbania powder to be 1% of the mass of the pseudo-boehmite A1, uniformly mixing the materials, adding a proper amount of nitric acid aqueous solution with the mass concentration of 1%, uniformly kneading, extruding strips for molding, and drying the molded strips at 120 ℃ for 6 hours to obtain the pseudo-boehmite molded product.
Weighing a proper amount of the pseudo-boehmite forming object, adding a proper amount of ammonium chloride solution with the molar concentration of 4.5mol/L to enable the pseudo-boehmite forming object to be completely immersed, immersing the immersed material for 2 hours, then carrying out liquid-solid separation, drying the solid material at 120 ℃ for 6 hours, placing the dried material in a muffle furnace, and roasting the dried material at 700 ℃ for 6 hours in an air atmosphere to obtain the alumina carrier S7, wherein the properties of the carrier are shown in table 1.
Comparative example 1
Comparative alumina S8 was obtained by directly firing pseudo-boehmite A1 without adding ammonium chloride as in example 1, and the support properties are shown in Table 1.
Comparative example 2
Comparative alumina S9 was obtained by directly firing pseudo-boehmite A2 without adding ammonium chloride as in example 1, and the support properties are shown in Table 1.
Comparative example 3
Comparative alumina S10 was prepared as in example 1 except that ammonium chloride was replaced with ammonium fluoride at the same molar concentration, and the carrier properties are shown in table 1.
Comparative example 4
Comparative alumina S11 was prepared as in example 1 except that ammonium chloride was replaced with ammonium citrate at the same molar concentration and the support properties are shown in table 1.
Comparative example 5
Comparative alumina support S12 was prepared by baking the pseudo-boehmite molding without immersing the pseudo-boehmite molding in an ammonium chloride solution as in example 6, and the support properties are shown in Table 1.
Comparative example 6
Comparative alumina support S13 was prepared as in example 6 except that ammonium chloride was replaced with ammonium fluoride at the same molar concentration and the support properties are shown in Table 1.
Comparative example 7
Comparative alumina support S14 was prepared by baking the pseudo-boehmite molding without immersing the pseudo-boehmite molding in an ammonium chloride solution as in example 7, and the support properties are shown in Table 1.
Table 1 alumina properties.
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 | |
| Alumina carrier | S1 | S2 | S3 | S4 | S5 | S6 | S7 |
| Specific surface area, m 2 /g | 212 | 230 | 204 | 221 | 213 | 181 | 209 |
| Pore volume, mL/g | 0.80 | 0.86 | 0.79 | 0.79 | 0.81 | 0.73 | 0.83 |
| Pore distribution, v% | |||||||
| <10nm，% | 34.8 | 32.4 | 36.2 | 35.7 | 38.5 | 41.1 | 37.8 |
| 10-30nm，% | 56.4 | 62.8 | 55.7 | 55.3 | 53.6 | 54.6 | 58.6 |
| >30nm，% | 8.8 | 4.8 | 8.1 | 8.0 | 7.9 | 4.3 | 3.6 |
Table 1 (follow) alumina properties.
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 | Comparative example 7 | |
| Alumina carrier | S8 | S9 | S10 | S11 | S12 | S13 | S14 |
| Specific surface area, m 2 /g | 217 | 241 | 146 | 228 | 183 | 151 | 215 |
| Pore volume, mL/g | 0.81 | 0.86 | 0.61 | 0.81 | 0.72 | 0.60 | 0.82 |
| Pore distribution, v% | |||||||
| <10nm，% | 45.7 | 41.2 | 39.6 | 50.1 | 48.3 | 44.2 | 45.8 |
| 10-30nm，% | 48.6 | 55.6 | 52.5 | 45.8 | 47.6 | 50.1 | 51.6 |
| >30nm，% | 5.7 | 3.2 | 7.9 | 4.1 | 4.1 | 5.7 | 2.6 |
As can be seen from Table 1, the alumina prepared by the method of the present invention after the impregnation treatment of pseudo-boehmite with ammonium chloride solution has a reduced pore channel content of less than 10nm and an increased pore channel content of 10-30nm and more than 30nm compared with untreated alumina, which indicates that the treatment method has the effect of improving the pore diameter of alumina. And when the ammonium fluoride solution is added, the pore volume and specific surface area of the carrier are seriously damaged. The pore size of the support was reduced upon addition of ammonium citrate solution.
Claims (8)
1. A preparation method of macroporous alumina is characterized in that: the method comprises the following steps: (1) Impregnating an alumina precursor with an aqueous ammonium chloride solution with the concentration of 2-7.5mol/L, carrying out solid-liquid separation, and carrying out drying treatment; (2) Roasting the solid phase material obtained in the step (1) to obtain macroporous alumina powder or a macroporous alumina forming carrier; the alumina precursor is pseudo-boehmite powder with peptization index of 78% or a formed product prepared from the pseudo-boehmite powder; the ammonium chloride solution in the step (1) is used for completely immersing the pseudo-boehmite powder or the pseudo-boehmite molding for 0.5-3 hours.
2. The method according to claim 1, characterized in that: the formed product in the step (1) is specifically a material obtained by kneading, forming and drying pseudo-boehmite powder with a peptization index of 78% serving as a raw material.
3. The method according to claim 1, characterized in that: the concentration of the ammonium chloride solution in the step (1) is 3-6mol/L.
4. The method according to claim 1, characterized in that: the drying conditions in the step (1) are as follows: the drying temperature is 80-200deg.C, and the drying time is 1-10 hours.
5. The method according to claim 1, characterized in that: the roasting conditions in the step (2) are as follows: the roasting temperature is 500-850 ℃ and the roasting time is 1-10 hours.
6. The method according to claim 1, characterized in that: the roasting conditions in the step (2) are as follows: the roasting temperature is 650-800 ℃ and the roasting time is 4-8 hours.
7. A hydrogenation catalyst characterized by: the catalyst comprises a macroporous alumina forming support or macroporous alumina powder prepared by the method of any one of claims 1-6.
8. Use of the hydrogenation catalyst of claim 7 in a heavy oil hydrogenation process.
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