CN117816141A - Preparation method of alumina carrier - Google Patents
Preparation method of alumina carrier Download PDFInfo
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- CN117816141A CN117816141A CN202311751811.0A CN202311751811A CN117816141A CN 117816141 A CN117816141 A CN 117816141A CN 202311751811 A CN202311751811 A CN 202311751811A CN 117816141 A CN117816141 A CN 117816141A
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- boehmite
- pseudo
- alumina carrier
- alumina
- organic alkali
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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 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims abstract description 41
- 239000011148 porous material Substances 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims description 27
- 239000003513 alkali Substances 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 17
- 238000010335 hydrothermal treatment Methods 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 10
- 238000007789 sealing Methods 0.000 claims description 8
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 6
- 238000004898 kneading Methods 0.000 claims description 5
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 238000007796 conventional method Methods 0.000 claims description 3
- 238000003916 acid precipitation Methods 0.000 claims description 2
- -1 aluminum alkoxide Chemical class 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 239000011343 solid material Substances 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 12
- 230000001105 regulatory effect Effects 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 16
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 13
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000012071 phase Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000012876 carrier material Substances 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000000306 component Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- GJPYYNMJTJNYTO-UHFFFAOYSA-J sodium aluminium sulfate Chemical compound [Na+].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GJPYYNMJTJNYTO-UHFFFAOYSA-J 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 244000275012 Sesbania cannabina Species 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000009740 moulding (composite fabrication) Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007670 refining Methods 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
- 239000007790 solid phase Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- 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)
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention aims to provide a preparation method of an alumina carrier, which belongs to the field of material synthesis, and when the alumina carrier is prepared, pseudo-boehmite with an elliptic sheet shape is selected as a part of raw materials, and the elliptic sheet pseudo-boehmite is piled to form a large number of macroporous pore channels, so that the pore channel structure of the carrier can be flexibly regulated and controlled by regulating the addition amount of the elliptic sheet pseudo-boehmite, and the requirements of different reactions on the catalyst pore channel structure can be met.
Description
Technical Field
The invention belongs to the field of material synthesis, and particularly relates to a preparation method of an alumina carrier.
Background
As a traditional catalyst carrier material, the alumina has the characteristics of mature preparation technology, adjustable pore structure, low use cost and easy processing and forming, and is widely used for preparing the oil refining chemical catalyst. The carrier is used as an important component of the catalyst, so that on one hand, the dispersing effect of the active component can be improved, and on the other hand, the pore channel structure of the carrier provides a diffusion channel of reactant molecules and product molecules, and the utilization efficiency of metal is improved. The macroporous carrier material has the characteristics of small mass transfer resistance and high efficiency, and in recent years, the carrier is widely researched as a core component of the catalyst, such as alumina, molecular sieve, active carbon and the like with a macroporous structure, so as to improve the service efficiency of the catalyst. Macroporous materials can be divided into two categories according to the synthesis process: one is to directly synthesize a new carrier material with a macroporous structure in the synthesis process, and the other is to obtain a carrier material with a macroporous structure by modifying the material.
CN201510191156.7 discloses a heavy oil hydrogenation catalyst and a preparation method thereof. The catalyst comprises an alumina carrier consisting of flaky polycrystalline gamma-alumina and hydrogenation active metals. The preparation method of the catalyst comprises the following steps: adding the flaky gamma-polycrystalline alumina raw powder into a binder and an extrusion aid, kneading, forming, drying and roasting to obtain an alumina carrier, and loading active metals on the obtained alumina carrier by adopting a conventional method. The preparation method of the flaky polycrystalline gamma-alumina comprises the following steps: (1) Inorganic aluminum salt, low-carbon alcohol and/or water and low-carbon oxyalkane are uniformly mixed to form gel, and then the gel is aged; (2) Soaking the gel obtained in the step (1) with low-carbon alcohol, and then drying and roasting; (3) And (3) immersing the material obtained in the step (2) into ammonia water for closed hydrothermal treatment, carrying out solid-liquid separation, and drying to obtain flaky gamma-polycrystalline alumina raw powder. The invention adjusts the pore canal structure of the carrier by adding flaky polycrystalline gamma-alumina into the alumina carrier, but the preparation process of the flaky polycrystalline gamma-alumina is more complex.
CN110467206a discloses a macroporous alumina carrier and a preparation method thereof, and the preparation method of macroporous alumina of the present invention comprises the following contents: (1) preparing aluminum sol; (2) Uniformly mixing inorganic aluminum salt, polyethylene glycol, the aluminum sol obtained in the step (1) and an organic compound containing amide groups with a low-carbon alcohol aqueous solution; (3) Adding propylene oxide and/or pyridine into the mixture obtained in the step (2), uniformly mixing to obtain gel, and aging to obtain an aging product; (4) Soaking the aging product by using a low-carbon alcohol aqueous solution, then carrying out solid-liquid separation, and drying and roasting the solid phase to obtain the macroporous alumina. The method for preparing the alumina carrier has complicated process and is not beneficial to industrial production.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a preparation method of an alumina carrier, which has simple process for preparing the alumina carrier and adjustable macroporous pore channel content in the alumina carrier, and is suitable for preparing catalysts for heterogeneous catalytic reactions, in particular to the field of heavy residual oil hydrotreatment.
The invention adopts the following technical scheme:
a method for preparing an alumina carrier, comprising the following steps:
firstly, roasting hydrated alumina to obtain gamma-phase alumina powder;
secondly, immersing the gamma-phase alumina powder obtained in the first step into an organic alkali solution I for sealing and preheating treatment, and carrying out liquid-solid separation on the treated material;
thirdly, immersing the solid material separated in the second step into an organic alkali solution II again for sealing hydrothermal treatment, and carrying out liquid-solid separation and drying on the treated material to obtain elliptic sheet pseudo-boehmite F1;
and fourthly, kneading the elliptic sheet pseudo-boehmite F1 and the pseudo-boehmite F2 obtained in the third step to form, and drying and roasting the formed product to obtain the alumina carrier.
Further, the hydrated alumina in the first step is pseudo-boehmite, which can be prepared or purchased by the existing method, and is more preferably pseudo-boehmite prepared by an aluminum sulfate-sodium metaaluminate method, wherein the roasting temperature is 450-650 ℃ and the roasting time is 4-8 hours.
Further, the organic alkali solution I in the second step comprises one of tetramethyl ammonium hydroxide, tetraethyl aluminum hydroxide and tetrapropyl ammonium hydroxide, preferably tetraethyl ammonium hydroxide, and the mass concentration of the organic alkali in the organic alkali solution I is 0.8% -2.0%.
Further, the sealed preheating treatment in the second step is performed in a sealed container, preferably a high-pressure reaction kettle, at a pretreatment temperature of 80-120 ℃ for 1-4 hours.
Further, the organic alkali solution II in the third step comprises one of tetramethyl ammonium hydroxide, tetraethyl aluminum hydroxide and tetrapropyl ammonium hydroxide, preferably tetraethyl ammonium hydroxide. The organic alkali solution II and the organic alkali solution I may be the same or different, and are preferably the same. The mass concentration of the organic alkali in the organic alkali solution II is 3.5% -12.5%.
Further, the sealed hydro-thermal treatment in the third step is performed in a sealed container, the sealed container is preferably a high-pressure reaction kettle, the hydro-thermal treatment temperature is 140-180 ℃, the hydro-thermal treatment time is 4-10 hours, the drying temperature is 100-160 ℃, and the drying time is 6-10 hours.
Further, the pseudo-boehmite F2 in the fourth step may be pseudo-boehmite prepared by any method, such as acid precipitation, alkali precipitation, aluminum alkoxide hydrolysis, etc., preferably pseudo-boehmite with a pore size of 10-20nm, more preferably pseudo-boehmite with a pore size of 10-20nm accounting for more than 50% of the total pore volume.
Further, the mass ratio of the elliptic sheet pseudo-boehmite F1 to the pseudo-boehmite F2 in the fourth step is 1:4-2:3.
further, the kneading molding in the fourth step is carried out by a conventional method in the field, the drying temperature is 100-160 ℃, and the drying time is 6-10 hours; the roasting temperature is 550-750 ℃ and the roasting time is 4-6 hours.
The beneficial effects of the invention are as follows:
1. when the alumina carrier is prepared by the method, the pseudo-boehmite with the shape of an elliptic sheet is selected as part of raw materials, and a large number of macroporous pore canals are formed by stacking the elliptic sheet pseudo-boehmite, so that the pore canal structure of the carrier can be flexibly regulated and controlled by regulating the addition amount of the elliptic sheet pseudo-boehmite, and the requirements of different reactions on the catalyst pore canal structure can be met.
2. The preparation process of the elliptic sheet pseudo-boehmite is simple, raw materials are easy to obtain, the prepared elliptic sheet pseudo-boehmite is uniform in form, and pore channels formed by cross stacking of sheet particles are wide.
3. According to the invention, two pseudo-boehmite with different forms are used as raw materials to prepare the alumina carrier, so that the pore channel structure of the carrier is effectively regulated, the surface chemical property of the carrier is regulated, and the catalytic activity of the corresponding catalyst is improved.
Drawings
FIG. 1 is a scanning electron microscope image of an elliptic sheet pseudoboehmite prepared in example 1.
FIG. 2 is a cross-sectional scanning electron microscope image of the alumina carrier prepared in example 1.
FIG. 3 is a cross-sectional scanning electron microscope image of the alumina carrier prepared in comparative example 4.
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.
Sample pore structure characterization: sample pore structure was characterized using a Micromeritics Trister 3000 nitrogen physical adsorption instrument.
Characterization of the distribution ratio of pore diameters above 100 nm: the sample well distribution was characterized using a fully automatic mercury porosimeter of the united states of america, autoPore 9500.
Sample microstructure characterization: the microstructure of the samples was characterized using a Hitachi SU8220 Scanning Electron Microscope (SEM).
Example 1
(1) Roasting a proper amount of pseudo-boehmite prepared by an aluminum sulfate-sodium metaaluminate method for 6 hours at 500 ℃ to obtain gamma-phase alumina powder;
(2) Weighing a proper amount of gamma-phase alumina powder in the step (1), adding tetraethylammonium hydroxide solution with the concentration of 0.9wt% to completely submerge the gamma-phase alumina powder, stirring the mixed material for 45 minutes, transferring the mixed material into an autoclave for sealing, preheating at 90 ℃ for 3.5 hours, and filtering the treated material to obtain a filter cake for later use;
(3) Filling the filter cake obtained in the step (2) into a reaction lining of an autoclave again, adding tetraethylammonium hydroxide solution with the concentration of 6.5wt% to completely submerge the material, stirring the mixed material for 45 minutes, sealing the autoclave, carrying out hydrothermal treatment at 165 ℃ for 6 hours, filtering the treated material, and drying the filter cake at 140 ℃ for 6 hours to obtain elliptic sheet pseudo-boehmite, wherein a scanning electron microscope diagram of a sample is shown in figure 1;
(4) 600 g of pseudo-boehmite (the pore canal of 10-20nm accounts for 56.5% of the total pore volume) is weighed, 220 g of elliptic sheet pseudo-boehmite prepared in the step (3) and 3.5 g of sesbania powder are uniformly mixed, then a proper amount of peptizing agent is added to mix and knead the mixture into a plastic body, the plastic body is extruded and molded, the bar-shaped carrier is dried at 140 ℃ for 8 hours, and baked at 700 ℃ for 6 hours, so that the alumina carrier Z1 is prepared, the properties of the carrier are shown in table 1, and a scanning electron microscope image of the cross section of the carrier is shown in figure 2.
Example 2
The same procedure as in example 1 was followed except that the tetraethylammonium hydroxide concentration in step (2) was 1.3wt%, the preheating treatment temperature was 100℃and the treatment time was 2.5 hours. The concentration of tetraethylammonium hydroxide in the step (3) is 8.5wt%, the hydrothermal treatment temperature is 155 ℃, and the treatment time is 8.5 hours. The addition amount of the elliptic sheet pseudo-boehmite in the step (4) is 300 g, and the alumina carrier Z2 of the invention is prepared, and the properties of the carrier are shown in Table 1.
Example 3
The same procedure as in example 1 was followed except that the tetraethylammonium hydroxide concentration in step (2) was 1.6wt%, the pre-heat treatment temperature was 80℃and the treatment time was 4 hours. The concentration of tetraethylammonium hydroxide in the step (3) is 10.5wt%, the hydrothermal treatment temperature is 140 ℃, and the treatment time is 10 hours. The addition amount of the elliptic sheet pseudo-boehmite in the step (4) is 170 g, and the alumina carrier Z3 of the invention is prepared, and the properties of the carrier are shown in Table 1.
Example 4
The same procedure as in example 1 was followed except that tetraethylammonium hydroxide in step (2) was changed to tetrapropylammonium hydroxide, the concentration of the solution was 1.1wt%, the preheating treatment temperature was 110℃and the treatment time was 1.5 hours. The concentration of tetraethylammonium hydroxide in the step (3) is 4.5wt%, the hydrothermal treatment temperature is 175 ℃, and the treatment time is 4.5 hours. The addition amount of the elliptic sheet pseudo-boehmite in the step (4) is 400 g, and the alumina carrier Z4 of the invention is prepared, and the properties of the carrier are shown in Table 1.
Comparative example 1
Comparative alumina support Z5 was prepared as in example 1 except that the tetraethylammonium hydroxide solutions of step (2) and step (3) were replaced with aqueous ammonia solutions of the same concentration, and the properties of the support are shown in Table 1.
Comparative example 2
Comparative alumina support Z6 was prepared as in example 1 except that the tetraethylammonium hydroxide solutions of step (2) and step (3) were replaced with sodium hydroxide solutions of the same concentration, and the properties of the support are shown in Table 1.
Comparative example 3
Comparative alumina support Z7 was prepared as in example 1 except that the tetraethylammonium hydroxide solutions of step (2) and step (3) were replaced with distilled water, and the properties of the support are shown in Table 1.
Comparative example 4
As in example 1, but without step (1), step (2) and step (3), pseudo-boehmite (10-20 nm pore canal is 56.5% of total pore volume) is directly used as a raw material to prepare a comparative alumina carrier Z8, the properties of the carrier are shown in Table 1, and the cross section scanning electron microscope of the carrier is shown in FIG. 3.
TABLE 1 alumina support Properties
As can be seen from the properties of the alumina carrier in Table 1, the alumina carrier prepared by adopting the method of the invention and taking the elliptic sheet pseudo-boehmite as the raw material has higher pore channel content of more than 100nm compared with the alumina carrier of the comparative example.
As can be seen from fig. 1 and 2, the oval sheet-like pseudo-boehmite particles prepared by the method of the invention have uniform morphology, and the sheet-like particles are crossed to form a large number of macroporous structures. The macroporous channels formed by the cross of the elliptic sheet-like pseudo-boehmite particles are not collapsed during the forming of the carrier, so that the carrier is well maintained, and the stacking mode of the particles in the carrier is effectively regulated due to the addition of the elliptic sheet-like pseudo-boehmite particles in the carrier, so that the carrier has higher macroporous content.
Claims (9)
1. A preparation method of an alumina carrier is characterized in that: the method comprises the following steps:
firstly, roasting hydrated alumina to obtain gamma-phase alumina powder;
secondly, immersing the gamma-phase alumina powder obtained in the first step into an organic alkali solution I for sealing and preheating treatment, and carrying out liquid-solid separation on the treated material;
thirdly, immersing the solid material separated in the second step into an organic alkali solution II again for sealing hydrothermal treatment, and carrying out liquid-solid separation and drying on the treated material to obtain elliptic sheet pseudo-boehmite F1;
and fourthly, kneading the elliptic sheet pseudo-boehmite F1 and the pseudo-boehmite F2 obtained in the third step to form, and drying and roasting the formed product to obtain the alumina carrier.
2. The method for preparing an alumina carrier according to claim 1, wherein: in the first step, the hydrated alumina is pseudo-boehmite, the roasting temperature is 450-650 ℃, and the roasting time is 4-8 hours.
3. The method for preparing an alumina carrier according to claim 1, wherein: in the second step, the organic alkali solution I comprises one of tetramethyl ammonium hydroxide, tetraethyl aluminum hydroxide and tetrapropyl ammonium hydroxide, and the mass concentration of the organic alkali in the organic alkali solution I is 0.8% -2.0%.
4. The method for preparing an alumina carrier according to claim 1, wherein: and in the second step, the pretreatment temperature of the sealing preheating treatment is 80-120 ℃ and the preheating treatment time is 1-4 hours in a sealing container.
5. The method for preparing an alumina carrier according to claim 1, wherein: the organic alkali solution II in the third step comprises one of tetramethyl ammonium hydroxide, tetraethyl aluminum hydroxide and tetrapropyl ammonium hydroxide, and the organic alkali solution II is the same as or different from the organic alkali solution I. The mass concentration of the organic alkali in the organic alkali solution II is 3.5% -12.5%.
6. The method for preparing an alumina carrier according to claim 1, wherein: the third step of sealed hydrothermal treatment is carried out in a sealed container, the hydrothermal treatment temperature is 140-180 ℃, the hydrothermal treatment time is 4-10 hours, the drying temperature is 100-160 ℃, and the drying time is 6-10 hours.
7. The method for preparing an alumina carrier according to claim 1, wherein: the pseudo-boehmite F2 is prepared by an acid precipitation method, an alkali precipitation method or an aluminum alkoxide hydrolysis method, the pore diameter of the pseudo-boehmite F2 is 10-20nm, and the pore channel content of 10-20nm accounts for more than 50% of the total pore volume.
8. The method for preparing an alumina carrier according to claim 1, wherein: the mass ratio of the elliptic sheet pseudo-boehmite F1 to the pseudo-boehmite F2 in the fourth step is 1:4-2:3.
9. the method for preparing an alumina carrier according to claim 1, wherein: the fourth step of kneading molding is carried out by a conventional method in the field, wherein the drying temperature is 100-160 ℃ and the drying time is 6-10 hours; the roasting temperature is 550-750 ℃ and the roasting time is 4-6 hours.
Priority Applications (1)
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