CN117942962A - Alumina carrier and preparation method thereof - Google Patents
Alumina carrier and preparation method thereof Download PDFInfo
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- CN117942962A CN117942962A CN202211306918.XA CN202211306918A CN117942962A CN 117942962 A CN117942962 A CN 117942962A CN 202211306918 A CN202211306918 A CN 202211306918A CN 117942962 A CN117942962 A CN 117942962A
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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 154
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000011148 porous material Substances 0.000 claims abstract description 51
- 239000013078 crystal Substances 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 29
- 238000007789 sealing Methods 0.000 claims abstract description 25
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- 239000002243 precursor Substances 0.000 claims abstract description 18
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 13
- 239000007864 aqueous solution Substances 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 238000011065 in-situ storage Methods 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims abstract description 4
- 239000011343 solid material Substances 0.000 claims abstract description 4
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 3
- 239000007787 solid Substances 0.000 claims abstract description 3
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 241000219793 Trifolium Species 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims 5
- 239000000295 fuel oil Substances 0.000 claims 3
- 238000005984 hydrogenation reaction Methods 0.000 claims 3
- 239000000463 material Substances 0.000 abstract description 14
- 230000000052 comparative effect Effects 0.000 description 17
- 239000000243 solution Substances 0.000 description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 239000002245 particle Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 238000010335 hydrothermal treatment Methods 0.000 description 6
- 241000219782 Sesbania Species 0.000 description 5
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- -1 unsaturated aluminum ions Chemical class 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 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
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 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
- 238000003917 TEM image Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 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
- 238000005504 petroleum refining Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000007493 shaping process 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
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 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
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Abstract
The invention discloses an alumina carrier and a preparation method thereof. The alumina carrier comprises a main body alumina and flaky alumina grains on the outer surface of the main body alumina, wherein the flaky alumina grains have a parallelepiped structure, and the exposed surfaces are a (110) crystal face, (100) crystal face and a (111) crystal face; wherein the (110) crystal face area accounts for 60% -70% of the total area of the crystal grain, the (100) crystal face area accounts for 10% -25% of the total area of the crystal grain, and the (111) crystal face area accounts for 10% -25% of the total area of the crystal grain. A method for preparing an alumina carrier, comprising: immersing the alumina carrier precursor into propylene oxide aqueous solution for sealing heat treatment, separating solid from liquid after treatment, and drying and roasting the solid material to obtain the alumina material. The external surface of the alumina material prepared by the method is in-situ grown flaky alumina grains, open pore channels are formed among the flaky alumina grains, the combination is firm, and the alumina carrier is rich in pore channels of 10-30nm, can be used for preparing a catalyst for heterogeneous catalytic reaction, and is particularly suitable for the field of heavy residue hydrotreatment.
Description
Technical Field
The invention belongs to the field of material synthesis, and particularly relates to an alumina carrier and a preparation method thereof.
Background
Activated alumina is widely used as a porous material as a catalyst or a carrier because of its excellent physical and chemical properties. The pore structure and surface properties of the alumina carrier not only affect the dispersity of the supported active components, but also are closely related to the activity, selectivity, catalyst life and the like of the catalyst. With the increasing severity of crude oil heaviness, traditional small pore alumina cannot meet the production requirements, and people pay more attention to the production of mesoporous and macroporous activated alumina.
CN107913691a discloses a macroporous alumina carrier and a preparation method thereof, firstly, pseudo-boehmite powder and sesbania powder are added into a kneader to be mixed uniformly, then styrene-butadiene rubber emulsion with the particle size of 10-500nm is prepared, and organic acid or inorganic acid is added 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.
CN109718860a discloses an alumina carrier and a method for preparing the same. The alumina carrier prepared by the method comprises main alumina and rod-shaped structural alumina, wherein at least part of the rod-shaped structural alumina is distributed on the outer surface of the main alumina carrier, the length of the rod-shaped structural alumina is 1-12 mu m, and the diameter of the rod-shaped structural alumina is 100-300nm. The preparation method of the alumina carrier comprises the steps of mixing the alumina carrier, ammonium bicarbonate and water, then carrying out sealing heat treatment, and drying and roasting the heat treated materials to obtain the alumina carrier. According to the method, the pore channel structure of the carrier is regulated by growing the alumina with the rod-shaped structure on the surface of the alumina carrier, but the rod-shaped alumina growing on the surface is easy to fall off, and the firmness of the combination with the main alumina is required to be further improved.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides an alumina carrier and a preparation method thereof, wherein the outer surface of the alumina carrier prepared by the method is in-situ grown flaky alumina grains, open pore channels are formed among the flaky alumina grains, the combination is firm, and the alumina carrier is rich in 10-20nm pore channels, can be used for preparing a catalyst for heterogeneous catalytic reaction, and is particularly suitable for the field of heavy residue hydrotreatment.
The alumina carrier comprises main alumina and flaky alumina grains which grow on the outer surface of the main alumina in situ, wherein the flaky alumina grains are of a parallelepiped structure, and the exposed surfaces are a (110) crystal face, (100) crystal face and a (111) crystal face; (110) The long side of the crystal surface is 240-350nm, the wide side is 180-300nm, and the included angle between the long side and the wide side is 60-85.; the crystal surface of (100) has a long side of 240-350nm and a wide side of 50-80nm; (111) the crystal surface has a long side of 180-300nm and a wide side of 50-80nm; wherein the (110) crystal face area accounts for 60% -70% of the total area of the crystal grain, the (100) crystal face area accounts for 10% -25% of the total area of the crystal grain, and the (111) crystal face area accounts for 10% -25% of the total area of the crystal grain.
In the alumina carrier of the invention, flaky alumina grains are piled up on the outer surface of main alumina to form 40-300nm pore canal. The coverage rate of the flaky alumina grains on the outer surface of the main body alumina is 85% -100%, wherein the coverage rate refers to the percentage of the surface occupied by the flaky alumina grains on the outer surface of the main body alumina to the outer surface of the main body alumina.
The specific surface area of the alumina carrier is 180-300m 2/g, the pore volume is 0.6-1.1mL/g, the most probable pore diameter is 10-30nm, and the pore canal of 10-30nm accounts for 45% -65% of the total pore volume.
The preparation method of the alumina carrier comprises the following steps: immersing the alumina carrier precursor into propylene oxide aqueous solution for sealing heat treatment, separating solid from liquid after treatment, and drying and roasting the solid material to obtain the alumina carrier.
In the method of the invention, the alumina carrier precursor is gamma-phase alumina, and can be purchased or self-made. The alumina carrier precursor may be in the shape of a conventional alumina carrier, such as a sphere, having a particle size of generally 2-8.0mm, such as a cylindrical bar, clover, etc., having a diameter of about 0.2-3.0mm and a length of about 3-8.0mm. The specific surface area of the gamma-phase alumina is 150-300m 2/g, and the pore volume is 0.6-1.1mL/g. The pore volume of the pores with the diameter smaller than 10nm accounts for less than 50% of the total pore volume, and the pore volume of the pores with the diameter of 10-30nm accounts for 30% -50% of the total pore volume.
The gamma-phase alumina is generally prepared by the following method: kneading, shaping, drying and roasting the pseudo-boehmite to obtain the product. The kneading molding is carried out by a conventional method in the field, and an extrusion aid and a peptizer can be added according to the requirement in the molding process. The extrusion aid is sesbania powder, and the addition amount of the extrusion aid is 0.1-0.5 wt% of the weight of the alumina carrier. The peptizing agent is one or more of hydrochloric acid, nitric acid, sulfuric acid, acetic acid, oxalic acid and the like, and the addition amount of the peptizing agent is 0.5-1.5 wt% of the weight of the alumina carrier. The drying temperature is 100-160 ℃, and the drying time is 6-10 hours; the roasting temperature is 450-700 ℃ and the roasting time is 4-6 hours; the calcination is carried out in an oxygen-containing atmosphere, preferably in an air atmosphere.
In the method of the invention, the mass percentage concentration of the propylene oxide aqueous solution is 2.5% -12%, preferably 4% -8%, and the mass ratio of the dosage of the propylene oxide aqueous solution to the alumina carrier is 3:1-10:1, preferably 4:1-8:1.
In the process of the present invention, the sealing heat treatment is carried out in a closed vessel, preferably an autoclave, and the sealing heat treatment is preferably a two-step sealing heat treatment, namely, firstly, a low-temperature sealing heat treatment at 60-100 ℃ for 1-4 hours, and then a sealing heat treatment at 110-180 ℃, preferably 120-160 ℃ for 14-20 hours.
In the method of the invention, the drying temperature is 100-160 ℃, the drying time is 2-8 hours, the roasting temperature is 450-750 ℃, the roasting time is 4-6 hours, and the roasting is carried out in an oxygen-containing atmosphere, preferably in an air atmosphere.
Compared with the prior art, the invention has the following advantages: the pore canal on the outer surface of the alumina carrier prepared by the invention is formed by stacking flaky grain alumina, the pore canal structure is wide, the diffusion of macromolecular reactants into the carrier is facilitated, meanwhile, the flaky alumina has uniform grain structure and strong binding force with the surface of the carrier, and the formed pore canal is firm; the preparation method of the alumina carrier is that the precursor of the alumina carrier is immersed into the epoxypropane aqueous solution for sealing hydrothermal treatment. In the low-temperature sealing heat treatment, propylene oxide is hydrolyzed to form an alcohol solution, and the solution is made to be alkalescent. During high-temperature sealing hydrothermal treatment, the grains on the surface of the alumina carrier are grown outwards in situ under the alkaline and alcohol solution environment to form flaky alumina grains, so that 40-300nm open pore canal is formed on the surface of the carrier. The particles in the carrier grow secondarily at the same time, so that the stacking state of the particles is changed, and the content of pore channels of 10-30nm in the carrier is increased. The coordination state of unsaturated aluminum ions and oxygen ions on the surface of the carrier can be effectively regulated during the hydrothermal treatment, so that the surface property of the carrier can be regulated; the preparation process of the alumina carrier is simple and is easy for industrial production.
Drawings
FIG. 1 is a low-magnification SEM image of an alumina carrier prepared in example 3.
FIG. 2 is a high-magnification SEM image of an alumina carrier prepared in example 3.
FIG. 3 is a TEM image of flaky alumina grains on the surface of the alumina support prepared in example 3.
Fig. 4 is an SEM image of the alumina carrier prepared in comparative example 2.
Fig. 5 is an SEM image of the alumina carrier prepared in comparative example 2.
Fig. 6 is a simulated view of flaky alumina grains.
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.
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.
Crystal face type of flaky alumina crystal grains and area ratio of each crystal face are measured: and (3) stripping flaky alumina grains grown on the outer surface of the main body alumina in situ from the main body alumina, and measuring the crystal face types and the area occupation ratios of the crystal faces of the flaky alumina grains according to the method of literature 'the relation between the surface acid property and the microstructure of an industrial application gamma-Al 2O3 carrier' (petroleum refining and chemical industry, 2015, (46) 10:17-21).
Preparation of alumina support precursor:
Example 1
500 G of pseudo-boehmite (an aluminum alkoxide method) is weighed, 2.5 g of sesbania powder is added and mixed uniformly, then a proper amount of acetic acid solution with the mass concentration of 0.5% is added into the mixed material to be mixed and kneaded uniformly, the mixture is extruded and molded, the molded material is dried at 120 ℃ for 8 hours, and the molded material is roasted at 500 ℃ for 5 hours, so that an alumina carrier precursor A is prepared, and the properties of the alumina carrier precursor are shown in table 1.
Example 2
500 G of pseudo-boehmite (prepared by an aluminum sulfate-sodium metaaluminate method) is weighed, 2.5 g of sesbania powder is added and mixed uniformly, then an appropriate amount of acetic acid solution with the mass concentration of 0.5% is added into the mixed material, the mixture is kneaded uniformly, extruded into strips, the formed material is dried at 120 ℃ for 8 hours, and the formed material is roasted at 500 ℃ for 5 hours, so that an alumina carrier precursor B is prepared, and the properties of the alumina carrier precursor are shown in table 1.
Preparation of alumina support
Example 3
Weighing 100 g of alumina carrier precursor A prepared in example 1, adding 670 g of propylene oxide aqueous solution with the mass concentration of 5.4%, transferring the mixed material into an autoclave, sealing, placing the autoclave into an oven, firstly sealing at 75 ℃ for 3 hours, then heating to 135 ℃ for 17 hours, sealing, washing and filtering the cooled material, drying the solid material at 120 ℃ for 8 hours, and roasting at 500 ℃ for 5 hours to obtain the alumina carrier S1 of the invention, wherein the properties of the carrier are shown in Table 1, the scanning electron microscopy images of the outer surface of the carrier are shown in FIG. 1 and FIG. 2, the transmission electron microscopy images of the outer surface flaky alumina are shown in FIG. 3, and the properties of the outer surface flaky alumina C1 are shown in Table 2.
Example 4
As in example 1 except that the concentration of propylene oxide was 6.3%, the amount of the solution was 550 g, and the hydrothermal treatment was carried out by sealing at 85℃for 2 hours, then heating to 145℃for 16 hours, the alumina carrier S2 of the present invention was obtained, the properties of the carrier were shown in Table 1, and the properties of the outer surface flaky alumina C2 were shown in Table 2.
Example 5
The alumina carrier S3 of the present invention was obtained by the same procedure as in example 1 except that the alumina carrier precursor A was changed to the alumina carrier precursor B prepared in example 2, the concentration of propylene oxide was 4.2%, the amount of the solution was 760 g, and in the hydrothermal treatment, the sealing treatment was carried out at 65℃for 4 hours, then the temperature was raised to 155℃for 15 hours, the properties of the carrier were shown in Table 1, and the properties of the outer surface plate-like alumina C3 were shown in Table 2.
Example 6
The alumina carrier S4 of the present invention was obtained by the same procedure as in example 1 except that the alumina carrier precursor A was changed to the alumina carrier precursor B prepared in example 2, the concentration of propylene oxide was 7.5%, the amount of the solution was 420 g, and in the hydrothermal treatment, the reaction was conducted by first sealing at 95℃for 1 hour, then heating to 125℃for 19 hours, and the properties of the carrier were shown in Table 1, and the properties of the outer surface plate-like alumina C4 were shown in Table 2.
Comparative example 1
Comparative alumina carrier S5 was prepared as in example 3 except that the aqueous propylene oxide solution was replaced with an aqueous ammonia solution of the same mass concentration, and the properties of the carrier are shown in Table 1.
Comparative example 2
Comparative alumina support S6 was prepared by replacing the propylene oxide aqueous solution with the same concentration of ethylene oxide solution in example 3, the properties of the support are shown in Table 1, and the scanning electron microscope images of the outer surfaces of the support are shown in FIGS. 4 and 5.
Comparative example 3
Comparative alumina carrier S7 was prepared as in example 3 except that the propylene oxide concentration was 1%, and the properties of the carrier are shown in Table 1.
Comparative example 4
Comparative alumina support S8 was prepared as in example 3 except that the heat treatment temperature was 80℃and the treatment time was 20 hours, and the properties of the support are shown in Table 1.
Comparative example 5
Comparative alumina carrier S9 was prepared as in example 3 except that the mixture was not transferred to an autoclave for sealing treatment, but was subjected to normal pressure reflux treatment in a condensing reflux apparatus, and the properties of the carrier were as shown in Table 1.
Comparative example 6
The same as in example 1, except that the mass ratio of the amount of the aqueous propylene oxide solution to the alumina carrier was 2:1, a comparative alumina support S10 was prepared, the properties of which are shown in Table 1.
TABLE 1 alumina support Properties
From the data in table 1 and fig. 1,2 and fig. 4 and 5, it can be seen that, compared with the alumina carrier of comparative example, the alumina carrier prepared by the method of the invention has higher pore channel content of 10-30nm, and the pore channels on the surface of the carrier are wide and larger.
Table 2 platelet alumina grain properties
As can be seen from the data in Table 1, compared with the alumina carrier of the comparative example, the alumina carrier prepared by the method of the invention has higher pore channel content of 10-30nm, and the pore channels on the surface of the carrier are wide and larger.
Example 7
This example examined how firmly the flaky alumina on the surface of the alumina carrier prepared in the present invention was bonded to the bulk alumina.
5G of the alumina carrier prepared in example 3 and 5g of the alumina carrier prepared according to the method of patent CN109718860A are respectively added into a beaker, 20 g of distilled water is added into the beaker, the beaker is subjected to ultrasonic treatment for 1 hour under the conditions of power of 240W and frequency of 40KHZ, the materials after ultrasonic treatment are filtered and dried, and a scanning electron microscope is used for observing the surface of the alumina carrier, the coverage rate of the flaky particles on the surface of the alumina carrier prepared in example 3 is 85%, and the coverage rate of the rod-shaped particles on the surface of the alumina carrier prepared according to the method of patent CN109718860A is 47%, which indicates that the flaky particles on the surface of the carrier prepared by the method of the invention are firmly combined with the main alumina.
Claims (14)
1. An alumina support, characterized in that: the aluminum oxide crystal comprises main aluminum oxide and flaky aluminum oxide crystal grains which grow on the outer surface of the main aluminum oxide in situ, wherein the flaky aluminum oxide crystal grains are of a parallelepiped structure, and the exposed surfaces are a (110) crystal face, (100) crystal face and a (111) crystal face; wherein the (110) crystal face area accounts for 60% -70% of the total area of the crystal grain, the (100) crystal face area accounts for 10% -25% of the total area of the crystal grain, and the (111) crystal face area accounts for 10% -25% of the total area of the crystal grain.
2. The alumina support of claim 1, wherein: (110) The long side of the crystal surface is 240-350nm, the wide side is 180-300nm, and the included angle between the long side and the wide side is 60-85 degrees; the crystal surface of (100) has a long side of 240-350nm and a wide side of 50-80nm; the (111) crystal surface has a long side of 180-300nm and a wide side of 50-80nm.
3. The alumina support of claim 1, wherein: the flaky alumina grains are piled up on the outer surface of the main body alumina to form pore channels of 40-300 nm; the coverage rate of the flaky alumina grains on the outer surface of the main body alumina is 85% -100%, wherein the coverage rate refers to the percentage of the surface occupied by the flaky alumina grains on the outer surface of the main body alumina to the outer surface of the main body alumina.
4. The alumina support of claim 1, wherein: the specific surface area is 180-300m 2/g, the pore volume is 0.6-1.1mL/g, the most probable pore diameter is 10-30nm, and the pore channel of 10-30nm accounts for 45% -65% of the total pore volume.
5. The preparation method of the alumina carrier is characterized by comprising the following steps: immersing the alumina carrier precursor into propylene oxide aqueous solution for sealing heat treatment, separating solid from liquid after treatment, and drying and roasting the solid material to obtain the alumina carrier.
6. The method according to claim 5, wherein: the alumina carrier precursor is gamma-phase alumina; the specific surface area of the gamma-phase alumina is 150-300m 2/g, and the pore volume is 0.6-1.1mL/g; the pore volume of the pores with the diameter smaller than 10nm accounts for less than 50% of the total pore volume, and the pore volume of the pores with the diameter of 10-30nm accounts for 30% -50% of the total pore volume.
7. The method according to claim 5, wherein: the shape of the alumina carrier precursor is the shape of a conventional alumina carrier, preferably a sphere, a cylindrical bar, clover or clover.
8. The method according to claim 5, wherein: the mass percentage concentration of the propylene oxide aqueous solution is 2.5-12%, preferably 4-8%, and the mass ratio of the dosage of the propylene oxide aqueous solution to the alumina carrier is 3:1-10:1, preferably 4:1-8:1.
9. The method according to claim 5, wherein: the sealing heat treatment is carried out in a closed container, and the closed container is a sealing pressure-resistant container.
10. The method according to claim 5, wherein: the sealing heat treatment is two-step sealing heat treatment, namely, firstly, the sealing heat treatment is carried out for 1-4 hours at the low temperature of 60-100 ℃, and then the sealing heat treatment is carried out for 14-20 hours at the temperature of 110-180 ℃.
11. The method according to claim 5, wherein: the drying temperature is 100-160 ℃, the drying time is 2-8 hours, the roasting temperature is 450-750 ℃, the roasting time is 4-6 hours, and the roasting is performed in an oxygen-containing atmosphere.
12. Use of the alumina support of any one of claims 1 to 4 in a heterogeneous catalytic reaction.
13. A heavy oil hydrogenation catalyst, characterized in that: the catalyst comprises the alumina carrier according to any one of claims 1to 4.
14. Use of the heavy oil hydrogenation catalyst of claim 13 in heavy oil hydrogenation reactions.
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