CN117942963A - Preparation method of double-pore distribution alumina carrier - Google Patents
Preparation method of double-pore distribution alumina carrier Download PDFInfo
- Publication number
- CN117942963A CN117942963A CN202211306919.4A CN202211306919A CN117942963A CN 117942963 A CN117942963 A CN 117942963A CN 202211306919 A CN202211306919 A CN 202211306919A CN 117942963 A CN117942963 A CN 117942963A
- Authority
- CN
- China
- Prior art keywords
- pore
- boehmite
- pseudo
- alumina carrier
- roasting
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000011148 porous material Substances 0.000 title claims abstract description 59
- 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 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000009826 distribution Methods 0.000 title claims description 11
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 31
- 239000000463 material Substances 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 20
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 16
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims abstract description 9
- 238000004898 kneading Methods 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 238000007789 sealing Methods 0.000 claims abstract description 4
- 238000012216 screening Methods 0.000 claims abstract description 3
- 238000010335 hydrothermal treatment Methods 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 239000000295 fuel oil Substances 0.000 claims description 5
- 238000005984 hydrogenation reaction Methods 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 230000009977 dual effect Effects 0.000 claims 2
- 239000003054 catalyst Substances 0.000 abstract description 7
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 12
- 239000000843 powder Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 241000219782 Sesbania Species 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920002538 Polyethylene Glycol 20000 Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- -1 aluminum alkoxide Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000009740 moulding (composite fabrication) Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 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 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- 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
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of a double-pore alumina carrier, which comprises the following steps: (1) Roasting aluminum nitrate, and then crushing and screening to obtain powdery materials; (2) Immersing the powdery material in the step (1) into propylene oxide solution for sealing and heat treatment, and drying the treated material to obtain sheet-like pseudo-boehmite P1; (3) And (3) kneading the sheet pseudo-boehmite P1 and the pseudo-boehmite P2 in the step (2) to form a formed product, and drying and roasting the formed product to obtain the double-pore alumina carrier. The method can directionally regulate and control the pore canal structure of the alumina carrier, and the preparation process is simple, and the prepared alumina carrier is suitable for preparing a catalyst for heterogeneous catalytic reaction, and is particularly suitable for the field of heavy residual oil hydrotreatment.
Description
Technical Field
The invention belongs to the field of material synthesis, and particularly relates to a preparation method of a double-pore distribution alumina carrier.
Background
With the increasing strictness of environmental regulations and the increasing degree of crude oil heaviness, the efficient conversion of heavy oil becomes an important trend in the development of oil refining technology. The fixed bed hydrogenation technology of residual oil is an effective means for realizing high-efficiency conversion of heavy oil, and the residual oil contains a large amount of metal impurities such as nickel, vanadium and the like, and mainly exists in the form of macromolecular micelles such as colloid, asphaltene and the like, and has the advantages of complex structure, large molecular size and difficult diffusion. The traditional small-pore alumina can not meet the production requirement, and a carrier material with reasonable pore distribution and capable of effectively improving mass transfer diffusion, reaction and metal deposition of macromolecular reactants needs to be developed. The carrier is used as a framework of the catalyst, and can promote the high dispersion of active metal while providing reaction pore channels and surfaces, so that the pore channel structure of the carrier has an important influence on the activity and stability of the catalyst. In recent years, according to the requirements of different catalytic reactions, the pore structure modulation of alumina carriers has been studied in various ways.
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.
CN107913691A discloses an alumina carrier containing macropores and a preparation method thereof, wherein the method comprises the steps of firstly, adding pseudo-boehmite powder and sesbania powder into a kneader for uniform mixing, then, preparing styrene-butadiene rubber emulsion with the particle size of 10-500nm, and adding organic acid or inorganic acid into the emulsion; then adding acid liquor containing styrene-butadiene rubber emulsion into pseudo-boehmite powder and sesbania powder, kneading uniformly, extruding strips, forming, drying and roasting to obtain the alumina carrier containing macropores. The pore size of the alumina carrier prepared by the method is distributed at 60-400nm. However, the preparation process of the hole expanding agent styrene-butadiene rubber emulsion is complex.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a preparation method of a double-pore alumina carrier, which can directionally regulate and control the pore canal structure of the alumina carrier, has simple preparation process, and is suitable for preparing catalysts for heterogeneous catalytic reactions, in particular for the field of heavy residual oil hydrotreatment.
The preparation method of the double-pore distribution alumina carrier comprises the following steps: (1) Roasting aluminum nitrate, and then crushing and screening to obtain powdery materials; (2) Immersing the powdery material in the step (1) into propylene oxide solution for sealing and heat treatment, and drying the treated material to obtain sheet-like pseudo-boehmite P1; (3) And (3) kneading the sheet pseudo-boehmite P1 and the pseudo-boehmite P2 in the step (2) to form a formed product, and drying and roasting the formed product to obtain the double-pore alumina carrier.
In the method, the roasting temperature in the step (1) is 450-650 ℃ and the roasting time is 4-8 hours.
In the process of the present invention, the particle size of the powdery material in step (1) is greater than 100 mesh, preferably greater than 200 mesh.
In the method of the invention, the mass concentration of the propylene oxide solution in the step (2) is 2.5% -12%, preferably 4% -8%, and the mass ratio of the using amount of the propylene oxide solution to the aluminum-containing oxide is 3:1-10:1, preferably 4:1-8:1. more preferably, polyethylene glycol 2000-20000 is added simultaneously in propylene oxide solution, and the mass ratio of the addition amount of the polyethylene glycol 2000-20000 to the aluminum-containing oxide is 0.01:1-0.05:1.
In the method of the invention, the hydrothermal treatment in the step (2) is carried out in a closed container, the closed container is preferably an autoclave, the hydrothermal treatment temperature is 110-180 ℃, preferably 120-160 ℃, the treatment time is 4-8 hours, and the pressure in the closed container is autogenous pressure during the hydrothermal treatment.
In the method, the drying temperature in the step (2) is 100-160 ℃, and the drying time is 2-8 hours.
In the method of the present invention, the pseudo-boehmite P2 in the step (3) may be pseudo-boehmite prepared by any method, such as acid precipitation, alkali precipitation, aluminum alkoxide hydrolysis, etc., preferably pseudo-boehmite with a pore diameter of 10-20nm, more preferably pseudo-boehmite with a pore channel content of 10-20nm accounting for more than 65% of the total pore volume.
In the method of the invention, the mass ratio of the pseudo-boehmite P1 to the pseudo-boehmite P2 in the step (3) is 3:7-3:2.
In the method of the invention, the kneading molding in the step (3) is carried out by adopting a conventional method in the field, and in the molding process, one or more conventional molding aids such as a peptizing agent, an extrusion aid and the like can be added according to requirements. The peptizing agent is one or more of hydrochloric acid, nitric acid, sulfuric acid, acetic acid, oxalic acid and the like, the mass concentration of the peptizing agent is 0.5% -2%, and the dosage of the peptizing agent is determined according to the molding effect; the extrusion aid is sesbania powder, and the addition amount of the extrusion aid is 1-3% of the weight of the final alumina carrier. 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 calcination is carried out in an oxygen-containing atmosphere, preferably in an air atmosphere.
The invention can also carry out modification treatment on the carrier according to the requirement, wherein the modification elements can be elements such as phosphorus, silicon, zirconium, titanium, alkali metal, alkaline earth metal and the like, and the modification elements can be immersed into the pseudo-boehmite material, can be added during forming by kneading, and can also be added into the carrier after roasting by an immersion method. The content of the modifying element is generally 0.1% -10% by weight of the carrier.
The double-pore distribution alumina carrier prepared by the invention has the following properties: the specific surface area is 160-260m 2/g, the pore volume is 0.7-1.2mL/g, the most probable pore diameter is 10-20nm and 50-100nm, the pore canal of 10-20nm accounts for 50% -70% of the total pore volume, and the pore canal of 50-100nm accounts for 15% -35% of the total pore volume.
The double-pore alumina carrier can be applied to the heavy oil hydrogenation field.
Compared with the prior art, the invention has the following advantages: according to the invention, aluminum nitrate is used as a raw material, the material obtained by roasting is subjected to propylene oxide hydrothermal treatment to prepare the sheet-like pseudo-boehmite, the process for preparing the sheet-like pseudo-boehmite is simple, and the acid-base neutralization gel forming process in the conventional technology is omitted. The prepared pseudo-boehmite has regular structure and uniform morphology, and the pseudo-boehmite flaky grains are piled to form a large number of pore structures of 50-150nm, so that the pore structures are firm and not easy to collapse, and the pseudo-boehmite can be used as a raw material to effectively ensure the macroporous content of the alumina carrier in the later stage. The preparation process of the alumina carrier takes two pseudo-boehmite as raw materials, the pore channel structure of the carrier can be regulated by regulating the addition amount of the two pseudo-boehmite, and the directional design and control preparation of the pore channel of the alumina carrier can be realized according to the requirements of different reactions on the pore channel structure of the alumina carrier; on the other hand, the two pseudo-boehmite can effectively regulate the pore channel structure of the carrier and simultaneously realize the regulation of the surface acidity, hydroxyl and other surface characters of the carrier, so that the final carrier has excellent physicochemical properties.
Drawings
FIG. 1 is a low-magnification SEM image of a first pseudo-boehmite P-1-1 prepared in example 1.
FIG. 2 is a high-magnification SEM image of the first pseudo-boehmite P-1-1 prepared in example 1.
FIG. 3 is an XRD spectrum of the first pseudo-boehmite P-1-1 prepared in example 1.
FIG. 4 is an SEM image of comparative pseudo-boehmite P-1-6 prepared in comparative example 2.
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. Wherein, in the invention, wt% represents mass fraction.
BET method: the pore structure of the carrier of the examples and the comparative examples is characterized by physical adsorption-desorption by using N 2, and the specific operation is as follows: and (3) characterizing the structure of the sample hole by adopting an ASAP-2420 type N 2 physical absorption-desorption instrument. 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 30nm is obtained according to BJH model.
The microstructure of the alumina carrier is characterized by applying a scanning electron microscope, and the specific operation is as follows: the JSM-7500F scanning electron microscope is adopted to characterize the microstructure of the carrier, the accelerating voltage is 5KV, the accelerating current is 20 mu A, and the working distance is 8mm.
X-ray diffraction (XRD) analysis was performed on a D/max-2500 type full-automatic rotary target X-ray diffractometer manufactured by Japanese Kabushiki Kaisha. The Cu target, the K alpha radiation source, the graphite monochromator and the tube voltage of 40kV and the tube current of 80mA are adopted.
The most probable pore size measurement: and taking the pore diameter of the material as an abscissa, taking the change rate of pore volume along with the pore diameter as an ordinate to obtain a pore diameter differential distribution curve, wherein the peak value in the curve is the most probable pore diameter.
Example 1
(1) Weighing a proper amount of aluminum nitrate, placing the aluminum nitrate into a crucible, roasting for 5.5 hours at 500 ℃, and carrying out powder treatment on the roasted material
Crushing, and sieving out particles with the size of more than 200 meshes;
(2) Weighing 100 g of the sieved particles, and adding an aqueous solution of propylene oxide with the mass concentration of 5.5 percent
610 G, magnetically stirring for 30min, transferring the mixed material into an autoclave, sealing, heating at 145 ℃ for 5.3 h, cooling, filtering, washing, drying at 120 ℃ for 4h to obtain pseudo-boehmite P1-1, observing the microstructure of the sample by a scanning electron microscope to form stacked flaky grains, wherein a scanning electron microscope image is shown in fig. 1 and 2, and an XRD image is shown in fig. 3.
(3) Weighing 50 g of pseudo-boehmite P1-1 in the step (2), 110 g of pseudo-boehmite P2 (prepared by an aluminum sulfate-sodium metaaluminate method, wherein a pore channel of 10-20nm accounts for 68% of the total pore volume) in mass, 1.5g of sesbania powder, uniformly mixing the materials, kneading a proper amount of acetic acid solution with the mass concentration of 1%, extruding the mixture into strips, forming, drying the formed product at 120 ℃ for 8 hours, and roasting at 650 ℃ for 5 hours to obtain the aluminum oxide carrier S1, wherein the properties of the carrier are shown in table 1.
Example 2
The same procedure as in example 1 was followed except that the aluminum nitrate in step (1) was calcined at 600℃for 4.5 hours. The concentration of the propylene oxide in the step (2) is 6.7%, the dosage of the solution is 530 g, the hydrothermal treatment temperature is 135 ℃, and the treatment time is 6.5 hours. The mass of the pseudo-boehmite P2 in the step (3) is 50 g, and the alumina carrier S2 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 aluminum nitrate in step (1) was calcined at 500℃for 6.5 hours. The concentration of the epoxypropane in the step (2) is 7.8%, the dosage of the solution is 440 g, 2.5 g of polyethylene glycol-20000 is added into the solution at the same time, the hydrothermal treatment temperature is 120 ℃, and the treatment time is 7.5 hours. The mass of the pseudo-boehmite P2 in the step (3) is 75 g, and the alumina carrier S3 is prepared, and the properties of the carrier are shown in Table 1.
Example 4
The procedure of example 1 was followed except that the aluminum nitrate was calcined at 450℃for 7.5 hours in step (1). The concentration of the propylene oxide in the step (2) is 4.3%, the dosage of the solution is 740 g, the hydrothermal treatment temperature is 155 ℃, and the treatment time is 4.2 hours. The mass of the pseudo-boehmite P2 in the step (3) is 35 g, and the alumina carrier S4 is prepared, and the properties of the carrier are shown in Table 1.
Comparative example 1
Comparative alumina support S5 was prepared as in example 1, except that step (2) was absent, but the same amount of aluminum-containing oxide powder was kneaded with the same pseudo-boehmite P2, molded, dried, and calcined, and the properties of the support were as shown in Table 1.
Comparative example 2
As in example 1, except that propylene oxide in step (2) was changed to the same amount of ethylene oxide, flaky grain formation was not seen in the microstructure of the hydrothermally treated materials P1 to 6, and the scanning electron microscope image of the sample was shown in FIG. 4, comparative alumina carrier S6 was produced, and the properties of the carrier were shown in Table 1.
Comparative example 3
Comparative alumina support S7 was prepared as in example 1 except that the propylene oxide concentration in step (2) was 1% and that no flaky grain formation was seen in the microstructure of the hydrothermally treated material P1, and the properties of the support were shown in Table 1.
Comparative example 4
Comparative alumina support S8 was prepared as in example 1 except that the heat treatment temperature in step (2) was 75deg.C, and that no flaky crystal grains were formed in the microstructure of the hydrothermally treated material P1, and the properties of the support were shown in Table 1.
TABLE 1 alumina support Properties
As can be seen from the data in Table 1, the alumina carrier prepared by the method of the present invention has a higher pore channel content of 50-100nm compared with the comparative alumina carrier.
Claims (12)
1. The preparation method of the double-pore distribution alumina carrier is characterized by comprising the following steps: (1) Roasting aluminum nitrate, and then crushing and screening to obtain powdery materials; (2) Immersing the powdery material in the step (1) into propylene oxide solution for sealing and heat treatment, and drying the treated material to obtain sheet-like pseudo-boehmite P1; (3) And (3) kneading the sheet pseudo-boehmite P1 and the pseudo-boehmite P2 in the step (2) to form a formed product, and drying and roasting the formed product to obtain the double-pore alumina carrier.
2. The method according to claim 1, characterized in that: the roasting temperature in the step (1) is 450-650 ℃, and the roasting time is 4-8 hours.
3. The method according to claim 1, characterized in that: the particle size of the powdery material in the step (1) is more than 100 meshes, preferably more than 200 meshes.
4. The method according to claim 1, characterized in that: the mass concentration of the propylene oxide solution in the step (2) is 2.5% -12%, preferably 4% -8%, and the mass ratio of the propylene oxide solution to the aluminum-containing oxide is 3:1-10:1, preferably 4:1-8:1.
5. The method according to claim 1, characterized in that: adding polyethylene glycol 2000-20000 into propylene oxide solution, wherein the mass ratio of the addition amount of the polyethylene glycol 2000-20000 to the aluminum-containing oxide is 0.01:1-0.05:1.
6. The method according to claim 1, characterized in that: the hydrothermal treatment in the step (2) is carried out in a closed container, the temperature of the hydrothermal treatment is 110-180 ℃, the treatment time is 4-8 hours, and the pressure in the closed container is autogenous pressure during the hydrothermal treatment.
7. The method according to claim 1, characterized in that: the drying temperature in the step (2) is 100-160 ℃, and the drying time is 2-8 hours.
8. The method according to claim 1, characterized in that: the pore diameter of the pseudo-boehmite P2 in the step (3) is 10-20nm, and the pore channel content of 10-20nm is more than 65% of the total pore volume.
9. The method according to claim 1, characterized in that: the mass ratio of the pseudo-boehmite P1 to the pseudo-boehmite P2 in the step (3) is 3:7-3:2.
10. The method according to claim 1, characterized in that: the drying temperature in the step (3) 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; roasting in an oxygen-containing atmosphere.
11. A dual pore distribution alumina carrier prepared by the method of any one of claims 1 to 10, characterized in that: the specific surface area is 160-260m 2/g, the pore volume is 0.7-1.2mL/g, the most probable pore diameter is 10-20nm and 50-100nm, the pore canal of 10-20nm accounts for 50% -70% of the total pore volume, and the pore canal of 50-100nm accounts for 15% -35% of the total pore volume.
12. The dual pore distribution alumina carrier prepared by the method of any one of claims 1 to 10 is applied to the heavy oil hydrogenation field.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211306919.4A CN117942963A (en) | 2022-10-25 | 2022-10-25 | Preparation method of double-pore distribution alumina carrier |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211306919.4A CN117942963A (en) | 2022-10-25 | 2022-10-25 | Preparation method of double-pore distribution alumina carrier |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117942963A true CN117942963A (en) | 2024-04-30 |
Family
ID=90798466
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211306919.4A Pending CN117942963A (en) | 2022-10-25 | 2022-10-25 | Preparation method of double-pore distribution alumina carrier |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117942963A (en) |
-
2022
- 2022-10-25 CN CN202211306919.4A patent/CN117942963A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1311757A (en) | Process for mfg. molecular sieves | |
| CN106830007A (en) | With the molecular sieve catalysts of multi-stage porous SSZ 13 and its synthetic method and application | |
| CN107297209A (en) | A kind of hydrotreating catalyst and preparation method thereof | |
| CN108249458B (en) | Synthesis method of metal modified SAPO-34 molecular sieve | |
| JP3755826B2 (en) | Alumina production method and apparatus | |
| CN101024165A (en) | Novel gamma aluminium oxide catalyst and producing technology | |
| CN116528978A (en) | Silica-alumina composition comprising 1-30 wt% crystalline basic ammonium aluminum carbonate and process for preparing the same | |
| CN117942963A (en) | Preparation method of double-pore distribution alumina carrier | |
| CN111774065B (en) | Preparation method of hydrodemetallization catalyst | |
| CN111285382A (en) | Method for preparing metal modified nano-crystalline SAPO-34 molecular sieve, product and application thereof | |
| CN112439445A (en) | ZSM-48 molecular sieve, catalyst carrier, preparation methods thereof, catalyst and application thereof | |
| CN115231587B (en) | Nano ZSM-5 molecular sieve and preparation method and application thereof | |
| CN114618511B (en) | Heavy oil hydrodesulfurization catalyst and heavy oil hydrotreating method | |
| CN110496637B (en) | Isobutane dehydrogenation catalyst, preparation method thereof and method for preparing isobutene through isobutane dehydrogenation | |
| CN116037137A (en) | Hydrodemetallization catalyst and preparation method thereof | |
| CN110935465B (en) | Preparation method of demetalization catalyst | |
| CN108929393B (en) | Spherical double-mesoporous attapulgite composite carrier and preparation method and application thereof | |
| CN112456511A (en) | SAPO-34 molecular sieve, and preparation method and application thereof | |
| CN116037085A (en) | Macroporous alumina carrier and preparation method thereof | |
| CN110614107A (en) | Isobutane dehydrogenation catalyst with carrier of hollow spherical mesoporous molecular sieve silica gel composite material and preparation method and application thereof | |
| CN117942962A (en) | Alumina carrier and preparation method thereof | |
| CN110614118A (en) | Isobutane dehydrogenation catalyst with three-hole sepiolite spherical mesoporous composite material as carrier and preparation method and application thereof | |
| CN108948234B (en) | Spherical double-mesoporous montmorillonite composite carrier and preparation method and application thereof | |
| CN114590828B (en) | Alumina material and preparation method thereof | |
| CN117772167A (en) | Spherical alumina carrier and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination |