CN109718861B - Alumina carrier, hydrodemetallization catalyst and preparation method thereof - Google Patents
Alumina carrier, hydrodemetallization catalyst and preparation method thereof Download PDFInfo
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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 233
- 239000003054 catalyst Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000011148 porous material Substances 0.000 claims abstract description 129
- 238000000034 method Methods 0.000 claims abstract description 27
- 238000001035 drying Methods 0.000 claims abstract description 22
- 238000010438 heat treatment Methods 0.000 claims abstract description 20
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 16
- 238000009826 distribution Methods 0.000 claims abstract description 16
- 238000007789 sealing Methods 0.000 claims abstract description 16
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims abstract description 15
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 5
- 230000002902 bimodal effect Effects 0.000 claims abstract description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 24
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 238000004898 kneading Methods 0.000 claims description 9
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 7
- 229910044991 metal oxide Inorganic materials 0.000 claims description 7
- 150000004706 metal oxides Chemical class 0.000 claims description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 239000002023 wood Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- 239000000295 fuel oil Substances 0.000 abstract description 10
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 6
- 239000000243 solution Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 230000000694 effects Effects 0.000 description 9
- 238000005470 impregnation Methods 0.000 description 7
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 7
- 229910052753 mercury Inorganic materials 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000006229 carbon black Substances 0.000 description 4
- 239000000693 micelle Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000000969 carrier Substances 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000006477 desulfuration reaction Methods 0.000 description 3
- 230000023556 desulfurization Effects 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 241000219782 Sesbania Species 0.000 description 2
- -1 VIB group metals Chemical class 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 238000005899 aromatization reaction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
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- 239000012153 distilled water Substances 0.000 description 1
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- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
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- 239000003381 stabilizer Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
Images
Abstract
The invention discloses an alumina carrier, a hydrodemetallization catalyst and a preparation method thereof. The alumina carrier comprises main alumina and rod-shaped alumina, at least part of the rod-shaped alumina is distributed on the outer surface of the main alumina and in the micron-sized pore channels, and the alumina carrier is in bimodal pore distribution at the pore diameter of 15-35nm and at the pore diameter of 100-800 nm. The alumina carrier is prepared by the following method, including: (1) preparing an alumina carrier intermediate; (2) and (3) immersing the intermediate of the alumina carrier into an ammonium bicarbonate solution, then carrying out sealing heat treatment, drying and roasting the heat-treated material to obtain the alumina carrier. The alumina carrier can give consideration to both large aperture and higher specific surface area and mechanical strength, and is suitable for heavy oil hydrogenation demetalization catalyst.
Description
Technical Field
The invention relates to an alumina carrier and a preparation method thereof, in particular to an alumina carrier for a heavy oil hydrodemetallization catalyst, a preparation method thereof and a hydrodemetallization catalyst prepared by adopting the alumina carrier.
Background
In the production process of heavy oil hydrodemetallization, because a large amount of sulfur and nitrogen in heavy oil exist in asphaltene micelles, the diameter of asphaltene molecules is 4-5nm, and the formed asphaltene micelles exist in heavy oil under the action of colloid serving as a stabilizer and have the diameter of 10nm to hundreds of nm. In heavy oil hydrogenation series catalysts, even if a hydrodemetallization catalyst is arranged in front of a heavy oil hydrodesulfurization, denitrification and carbon residue removal catalyst, macromolecular asphaltene is partially crushed to form small asphaltene micelles, but the small asphaltene micelles cannot enter the catalyst and can react on the outer surface of the denitrification and carbon residue removal catalyst to block the pores on the outer surface by impurities such as metal and the like due to the fact that the pores of the hydrodemetallization and carbon residue removal catalyst are not suitable and are concentrated at about 10nm, so that the catalyst is inactivated, and industrial application is influenced.
In order to realize the long-period operation of the desulfurization, denitrification and carbon residue removal catalyst, the metal capacity of the catalyst must be improved and the pore channel proportion of 30nm to micron order must be improved while the desulfurization, denitrification and carbon residue removal of the catalyst are ensured. The existing hole expanding method is mainly a physical hole forming method, and can obtain 30nm to micron-sized macroporous channels, but the channels are discontinuously penetrated, the channels are in a dispersed state, and the orifices are of an ink bottle type, so that the diffusion effect on reactants is limited.
CN1160602A discloses a macroporous alumina carrier suitable for use as a hydrodemetallization catalyst carrier and a preparation method thereof. The preparation method of the macroporous alumina carrier comprises the steps of mixing the pseudo-boehmite dry glue powder with water or aqueous solution, kneading into a plastic body, extruding the obtained plastic body into a strip-shaped object on a strip extruding machine, drying and roasting to obtain a product; in the above-mentioned process also the carbon black powder is added as physical pore-expanding agent and chemical pore-expanding agent containing phosphorus, silicon or boron compound which can produce chemical action with pseudo-boehmite or alumina. Wherein the amount of the carbon black powder is 3-10% (based on the weight of the alumina). The prepared alumina carrier can be used for preparing heavy oil, in particular a heavy oil hydrodemetallization and/or hydrodesulfurization catalyst.
US4448896 proposes the use of carbon black as a pore-enlarging agent. Uniformly mixing a pore-expanding agent and pseudo-boehmite dry rubber powder, adding a nitric acid aqueous solution with the mass fraction of 4.3% into the mixture, kneading for 30 minutes, then adding an ammonia aqueous solution with the mass fraction of 2.1%, kneading for 25 minutes, extruding into strips and forming after uniform kneading, and roasting the formed carrier to obtain the final alumina carrier. Wherein the addition amount of the carbon black powder is preferably more than 20% of the weight of the activated alumina or the precursor thereof.
CN102441436A discloses a preparation method of an alumina carrier. The method for preparing the alumina carrier comprises the following steps: the pseudo-boehmite dry glue powder and the extrusion aid are mixed uniformly, then the aqueous solution in which the physical pore-enlarging agent and the chemical pore-enlarging agent are dissolved is added, the mixture is mixed uniformly, the mixture is extruded on a strip extruder to be formed, and the alumina carrier is prepared after drying and roasting.
The physical pore-expanding agent can increase the proportion of macropores, but in the case of industrial catalysts, certain specific surface area and mechanical strength are required in order to improve the activity of the catalyst. However, the specific surface area and the mechanical strength are reduced while the macropores are increased, so that the physical pore-expanding agent is limited by other performance requirements of the catalyst when being used for pore expansion, and the physical pore-expanding agent cannot be taken into consideration.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides an alumina carrier, a hydrodemetallization catalyst and a preparation method thereof. The alumina carrier can give consideration to large aperture, higher specific surface area and mechanical strength, so that when the alumina carrier is used for a heavy oil hydrodemetallization catalyst, the alumina carrier not only has higher activity, but also has good activity stability, and the running period of the device is prolonged.
The invention provides an alumina carrier, which comprises main alumina and rod-shaped alumina, wherein the main alumina is alumina with micron-sized pore channels, at least part of the rod-shaped alumina is distributed on the outer surface of the main alumina and in the micron-sized pore channels with the pore diameter D of 5-10 mu m, the length of the rod-shaped alumina is 1-12 mu m, and the diameter of the rod-shaped alumina is 100-300 nm; the pores of the alumina carrier are distributed in a bimodal pore distribution, and the specific distribution is as follows: the pore volume occupied by the pores with the pore diameter of 15-35nm is 40% -60% of the total pore volume, and the pore volume occupied by the pores with the pore diameter of 100-800nm is 15% -26% of the total pore volume.
The micron-sized pore canal in the invention refers to a micron-sized pore canal with the pore diameter D of 5-10 μm.
In the alumina carrier, the rod-shaped alumina is basically distributed on the outer surface of the main alumina and in the micron-sized pore channel. The rod-shaped alumina distributed on the outer surface of the main alumina and in the micron-sized pore channels accounts for more than 95 percent of the total weight of all the rod-shaped alumina, and preferably more than 97 percent.
In the alumina carrier, the length of the rod-shaped alumina in the micron-sized pore channels is mainly 0.3D-0.9D (which is 0.3-0.9 time of the diameter of the micron-sized pore channels), namely the length of more than 85 percent of the rod-shaped alumina in the micron-sized pore channels by weight is 0.3D-0.9D; the length of the rod-shaped alumina on the outer surface is mainly 3-8 μm, that is, the length of more than 85% of the rod-shaped alumina on the outer surface is 3-8 μm.
Wherein, in the micron-scale pore channels of the main alumina, the rod-shaped alumina is distributed in a disordered and mutually staggered state.
Wherein at least one end of at least part of the rod-shaped alumina is attached to the micron-sized pore channel wall of the main body, and preferably at least one end of at least part of the rod-shaped alumina is bonded to the micron-sized pore channel wall and is integrated with the main body alumina. Further preferably, at least one end of the rod-shaped alumina in the micron-sized pore channel is bonded to the wall of the micron-sized pore channel, and is integrated with the main alumina.
Wherein the rod-like aluminas are distributed on the outer surface of the main alumina in a disordered and staggered state.
Wherein one end of at least part of the rod-shaped alumina is attached to the outer surface of the main alumina, and preferably, one end of at least part of the rod-shaped alumina is combined on the outer surface of the main alumina, and the other end of the rod-shaped alumina extends outwards and is integrated with the main alumina. Further preferably, one end of the rod-shaped alumina on the outer surface of the main body alumina is bonded to the outer surface of the main body alumina, and the other end thereof is protruded outward to be integrated with the main body.
According to the alumina carrier, the coverage rate of the rod-shaped alumina in the micron-sized pore channels of the main alumina is 70-95%, wherein the coverage rate refers to the percentage of the surface of the inner surface of the micron-sized pore channels of the main alumina, which is occupied by the rod-shaped alumina, in the inner surface of the micron-sized pore channels of the main alumina. The coverage rate of the rod-shaped alumina on the outer surface of the main body alumina is 70-95%, wherein the coverage rate refers to the percentage of the surface of the outer surface of the main body alumina, which is occupied by the rod-shaped alumina, on the outer surface of the main body alumina.
The alumina carrier of the invention has the following properties: specific surface areaThe volume is 160-300m2(iv)/g, pore volume of 0.6-1.5mL/g, crush strength of 10-20N/mm.
In the alumina carrier, the pores formed by the rod-shaped alumina in a disordered and staggered way are concentrated between 100 and 800 nm.
In a second aspect, the present invention provides a method for preparing an alumina carrier, comprising:
(1) preparing an alumina carrier intermediate;
(2) and (3) immersing the intermediate of the alumina carrier into an ammonium bicarbonate solution, then carrying out sealing heat treatment, drying and roasting the heat-treated material to obtain the alumina carrier.
In the preparation method of the alumina carrier, the properties of the alumina carrier intermediate in the step (1) are as follows: the specific surface area is 120-290m2The pore volume is 0.7-1.1mL/g, and the pore distribution is as follows: the pore volume occupied by the pores with the pore diameters of 15-35nm is 35% -55% of the total pore volume, the pore volume occupied by the pores with the pore diameters of 100-800nm is 5% -10% of the total pore volume, and the pore volume occupied by the pores with the pore diameters of more than 5 mu m (preferably the pores with the pore diameters of 5-10 mu m) is 3% -10% of the total pore volume.
In the preparation method of the alumina carrier, the alumina carrier intermediate in the step (1) can be prepared by a conventional method, such as a physical pore-enlarging agent method, and the specific process is as follows: kneading and molding the pseudo-boehmite and a physical pore-enlarging agent, and drying and roasting the molded product to obtain the alumina carrier intermediate. The physical pore-enlarging agent can be one or more of activated carbon, sawdust and polyvinyl alcohol, the particle size of the physical pore-enlarging agent is selected according to the micron-sized pore canal of the alumina carrier intermediate, the particle size of the physical pore-enlarging agent is preferably about 5-10 mu m, and the addition amount of the physical pore-enlarging agent is 10wt% -20wt% of the weight of the alumina carrier intermediate. The kneading molding can be carried out by adopting a conventional method in the field, and in the molding process, conventional molding aids, such as one or more of peptizing agents, extrusion aids and the like can be added according to needs. The peptizing agent is one or more of hydrochloric acid, nitric acid, sulfuric acid, acetic acid, oxalic acid and the like, and the extrusion assistant agent is a substance which is beneficial to extrusion forming, such as sesbania powder and the like. The drying and roasting conditions of the formed product are as follows: the drying temperature is 100-160 ℃, the drying time is 6-10 hours, the roasting temperature is 600-750 ℃, the roasting time is 4-6 hours, and the roasting is carried out in an oxygen-containing atmosphere, preferably an air atmosphere.
In the preparation method of the alumina carrier, the mass ratio of the using amount of the ammonium bicarbonate solution in the step (2) to the alumina carrier intermediate obtained in the step (1) is 4:1-8:1, and the mass concentration of the ammonium bicarbonate solution is 15-20%.
In the preparation method of the alumina carrier, the sealing heat treatment temperature in the step (2) is 120-160 ℃, the constant temperature treatment time is 4-8 hours, the heating rate is 5-20 ℃/min, and the sealing heat treatment is generally carried out in a high-pressure reaction kettle.
In the preparation method of the alumina carrier, the step (2) is preferred, sealing pretreatment is carried out before sealing heat treatment, the pretreatment temperature is 60-100 ℃, the constant temperature treatment time is 2-4 hours, the temperature rise rate before the pretreatment is 10-20 ℃/min, the temperature rise rate after the pretreatment is 5-10 ℃/min, and the temperature rise rate after the pretreatment is at least 3 ℃/min, preferably at least 5 ℃/min lower than that before the pretreatment.
In the method of the invention, the drying temperature in the step (2) is 160 ℃ for 6-10 hours, the roasting temperature is 600 ℃ for 750 ℃ for 4-6 hours.
In the method, compared with the alumina carrier intermediate in the step (1), the alumina carrier prepared in the step (2) has more concentrated distribution than the carrier intermediate for the pore diameter distribution of 15-35nm and 100-800 nm.
The third aspect of the invention provides a hydrodemetallization catalyst, which comprises a carrier and an active metal component, wherein the carrier adopts the alumina carrier.
In the hydrodemetallization catalyst, the active metal components are VIB group metals and VIII group metals. The VIB group metal is selected from one or more of W, Mo, and the VIII group metal is selected from one or more of Co and Ni. Based on the weight of the hydrodemetallization catalyst, the content of active metal oxides is 8% -18.0%, preferably 9.5% -18.0%, more preferably the content of VIB group metals is 6.5% -15% calculated by metal oxides, and the content of VIII group metals is 1.5% -3.5% calculated by metal oxides.
The hydrodemetallization catalyst of the invention can be prepared by conventional methods, such as an impregnation method, a kneading method and the like, and the impregnation method is preferably adopted. The carrier is prepared by a conventional impregnation method by adopting an impregnation method to load the active metal component, and can adopt a spray impregnation method, a saturated impregnation method or a supersaturated impregnation method. After the active metal components are impregnated, the hydrogenation protection catalyst is obtained after drying and roasting. The drying condition is that the drying is carried out for 1 to 5 hours at the temperature of 100-130 ℃; the roasting condition is roasting at 400-550 ℃ for 2-10 hours.
The alumina carrier can also be used in catalytic reactions containing macromolecular reactants or products, such as residual oil hydrotreating, macromolecular polymerization reaction, macromolecular and macromolecular hydrogenation reaction, dehydrogenation reaction, oxidation reaction, aromatization, isomerization, alkylation, reforming catalysis, etherification and other reactions.
Compared with the prior art, the invention has the following advantages:
1. the alumina carrier of the invention fully utilizes micron-scale pore channels of the alumina intermediate, and the rod-shaped alumina is distributed in the micron-scale pore channels in a staggered way in a disorder way, so that on one hand, the penetrability of the micron-scale pore channels is maintained, the specific surface area of the carrier is improved, the mechanical strength is enhanced, on the other hand, a certain hole expanding effect is performed on the nanometer-scale pore channels of the alumina carrier intermediate, and the penetrability and the uniformity of the nanometer-scale pore channels are further promoted. Therefore, the alumina carrier of the invention overcomes the problem that the large aperture, the specific surface area and the mechanical strength are not compatible caused by adopting a physical pore-expanding agent.
2. In the process of preparing the alumina carrier, the alumina carrier is pretreated at a certain temperature before sealing heat treatment, the pretreatment condition is relatively mild, and NH is slowly formed on the outer surface of the alumina carrier in a sealed and hydrothermal mixed atmosphere of carbon dioxide and ammonia gas4Al(OH)2CO3Crystal nuclei in later heatReaction temperature NH is increased4Al(OH)2CO3The crystal nucleus continues to grow evenly to make rod-shaped NH4Al(OH)2CO3Having uniform diameter and length while increasing rod-like NH4Al(OH)2CO3Coverage on the outer surface of the alumina intermediate and the inner surface of the micron-sized pore channel.
3. The alumina carrier is particularly suitable for preparing a hydrodemetallization catalyst, has higher hydrodemetallization activity and hydrodesulfurization activity when being used for residual oil hydrodemetallization reaction, has good stability, and can prolong the running period of a device.
Drawings
FIG. 1 is an SEM image of a cut surface of an alumina support obtained in example 1;
wherein the reference numbers are as follows: 1-main alumina, 2-rod-shaped alumina and 3-micron pore canal.
Detailed Description
The following examples are provided to further illustrate the technical solutions of the present invention, but the present invention is not limited to the following examples. In the present invention, wt% is a mass fraction.
Application N2Physical adsorption-desorption characterization of the pore structures of the carriers of the examples and the comparative examples, the specific operations are as follows: adopting ASAP-2420 type N2And the physical adsorption-desorption instrument is used for characterizing the pore structure of the sample. A small amount of samples are taken to be treated for 3 to 4 hours in vacuum at the temperature of 300 ℃, and finally, the product is placed under the condition of liquid nitrogen low temperature (-200 ℃) to be subjected to nitrogen absorption-desorption test. Wherein the specific surface area is obtained according to a BET equation, and the distribution rate of the pore volume and the pore diameter below 40nm is obtained according to a BJH model.
Mercury pressing method: the pore diameter distribution of the carriers of the examples and the comparative examples is characterized by applying a mercury porosimeter, and the specific operation is as follows: and characterizing the distribution of sample holes by using an American microphone AutoPore9500 full-automatic mercury porosimeter. The samples were dried, weighed into an dilatometer, degassed for 30 minutes while maintaining the vacuum conditions given by the instrument, and filled with mercury. The dilatometer was then placed in the autoclave and vented. And then carrying out a voltage boosting and reducing test. The mercury contact angle is 130 degrees, and the mercury interfacial tension is 0.485N.cm-1The distribution ratio of pore diameter of 100nm or more is measured by mercury intrusion method.
A scanning electron microscope is used for representing the microstructure of the alumina carrier, and the specific operation is as follows: and a JSM-7500F scanning electron microscope is adopted to represent the microstructure of the carrier, the accelerating voltage is 5KV, the accelerating current is 20 muA, and the working distance is 8 mm.
Example 1
Weighing 260 g of pseudo-boehmite dry glue powder (produced by Wenzhou refined crystal alumina Co., Ltd.), 30 g of active carbon with the particle size of 10 microns and 8 g of sesbania powder, uniformly mixing the materials physically, adding an appropriate amount of acetic acid aqueous solution with the mass concentration of 1.5%, kneading, extruding into strips, forming, drying the formed product at 100 ℃ for 6 hours, and roasting the dried product at 700 ℃ for 5 hours in an air atmosphere to obtain an alumina carrier intermediate ZA 1.
Weighing 1100 g of the alumina carrier intermediate ZA, placing the alumina carrier intermediate ZA in 600 g of ammonium bicarbonate solution, sealing the mixed material in a high-pressure kettle, heating to 100 ℃ at a speed of 15 ℃/min, keeping the temperature for 3 hours, heating to 140 ℃ at a speed of 10 ℃/min, keeping the temperature for 6 hours, drying the carrier at 100 ℃ for 6 hours, and roasting at 700 ℃ for 5 hours to obtain the alumina carrier A1, wherein the properties of the carrier are shown in Table 1. In the alumina carrier A1, the length of the rod-shaped alumina in the micron-sized pore channel is mainly 3-9 μm, the length of the rod-shaped alumina on the outer surface of the main alumina is mainly 3-8 μm, the coverage rate of the rod-shaped alumina on the outer surface of the main alumina is about 82%, and the coverage rate of the rod-shaped alumina in the micron-sized pore channel of the main alumina is about 79%; the pores formed by the rod-shaped alumina staggered with each other in a random order are concentrated at 300-500 nm.
Example 2
In the same manner as in example 1 except that the activated carbon was changed to polyvinyl alcohol having a particle size of 8 μm, the amount of polyvinyl alcohol added was 36 g, to obtain an alumina support intermediate ZA 2. The mass of the ammonium bicarbonate solution is 800 g, and the mass concentration of the ammonium bicarbonate solution is 17.5%. The sealing pretreatment temperature is 90 ℃, the treatment time is 2 hours, the heat treatment temperature is 120 ℃, and the treatment time is 8 hours, so that the alumina carrier A2 is prepared, and the properties of the carrier are shown in Table 1. In the alumina carrier A2, the length of the rod-shaped alumina in the micron-sized pore channel is mainly 2.5-7.0 μm, the length of the rod-shaped alumina on the outer surface of the main alumina is mainly 3-8 μm, the coverage rate of the rod-shaped alumina on the outer surface of the main alumina is about 74%, and the coverage rate of the rod-shaped alumina in the micron-sized pore channel of the main alumina is about 78%; the pores formed by the rod-shaped alumina staggered with each other in a random order are concentrated at 400-600 nm.
Example 3
In the same manner as in example 1 except that the activated carbon was changed to wood chips having a particle size of 5 μm, 40 g of the wood chips were added to obtain an alumina support intermediate ZA 3. The mass of the ammonium bicarbonate solution is 800 g, and the mass concentration of the ammonium bicarbonate solution is 20%. The heating rate before the sealing pretreatment is 11 ℃/min, the heating rate after the sealing pretreatment is 5 ℃/min, the heat treatment temperature is 150 ℃, and the treatment time is 4 hours, so that the alumina carrier A3 is prepared, wherein the properties of the carrier are shown in Table 1. In the alumina carrier A3, the length of the rod-shaped alumina in the micron-sized pore channel is mainly 1.5-4.5 μm, the length of the rod-shaped alumina on the outer surface of the main alumina is mainly 3-8 μm, the coverage rate of the rod-shaped alumina on the outer surface of the main alumina is about 85%, and the coverage rate of the rod-shaped alumina in the micron-sized pore channel of the main pore is about 80%; the pores formed by the rod-shaped alumina crossing each other in a random order were concentrated at 500-800 nm.
Example 4
As in example 1, the temperature was raised to 140 ℃ at a rate of 15 ℃/min and the heat treatment was carried out without any pretreatment before the heat treatment. The alumina carrier A4 of the present invention was prepared, and the properties of the carrier are shown in Table 1. In the alumina carrier A4, the length of the rod-shaped alumina in the micron-sized pore channel is mainly 3-9 μm, the length of the rod-shaped alumina on the outer surface of the main alumina is mainly 3-8 μm, the coverage rate of the rod-shaped alumina on the outer surface of the main alumina is about 73%, and the coverage rate of the rod-shaped alumina in the micron-sized pore channel of the main alumina is about 75%; the pores formed by the rod-shaped alumina staggered with each other in a random order are concentrated at 300-600 nm.
Comparative example 1
A comparative alumina support a5 was prepared as in example 1 except that the alumina support intermediate ZA1 was not heat treated in aqueous ammonium bicarbonate solution, but in distilled water, and the same mass of ammonium bicarbonate was added as the alumina support was shaped, the properties of the support being shown in table 1.
Comparative example 2
A comparative alumina support A6 was prepared as in example 1 except that the ammonium bicarbonate was changed to ammonium carbonate of the same mass, and the properties of the support are shown in Table 1.
TABLE 1 Properties of the alumina support intermediate and the alumina support
| Example 1 | Example 1 | Example 2 | Example 2 | Example 3 | Example 3 | |
| Numbering | ZA1 | A1 | ZA2 | A2 | ZA3 | A3 |
| Specific surface area, m2/g | 181 | 193 | 183 | 192 | 190 | 213 |
| Pore volume, mL/g | 0.92 | 1.07 | 0.89 | 1.04 | 0.93 | 1.03 |
| Pore distribution:, v% | ||||||
| 15-35nm | 39 | 48 | 36 | 47 | 44 | 53 |
| 100-800nm | 6 | 24 | 8 | 21 | 9 | 20 |
| Over 5 mu m | 6 | Is free of | 5 | Is free of | 9 | Is free of |
| Crush strength, N/mm | 11.1 | 13.1 | 11.6 | 13.6 | 11.4 | 12.4 |
TABLE 1 Properties of the alumina support intermediate and the alumina support
| Example 4 | Comparative example 1 | Comparative example 2 | |
| Numbering | A4 | A5 | A6 |
| Specific surface area, m2/g | 184 | 171 | 176 |
| Pore volume, mL/g | 1.06 | 0.74 | 0.70 |
| Pore distribution:, v% | |||
| 15-35nm | 46 | 31 | 33 |
| 100-800nm | 18 | 10 | 9 |
| Over 5 mu m | - | 6 | 7 |
| Crush strength, N/mm | 12.3 | 9.4 | 9.7 |
Note: pore distribution refers to the percentage of the pore volume of pores within a certain diameter range in the support to the total pore volume.
Example 5
This example uses the aluminas obtained in the above examples and comparative examples as supports to prepare hydrodemetallization catalysts.
Weighing the alumina carrier intermediate ZA 1100 g of example 1, adding 150mL of Mo-Ni-NH3Solution (according to MoO content in the final catalyst)39.0wt% and NiO3.0 wt%) for 2 hours, filtering off the excess solution, drying at 120 ℃ for 3 hours, and calcining at 550 ℃ for 5 hours to obtain the hydrodemetallization catalyst C0.
Catalysts C1-C6 were prepared in the same manner as catalyst C0 except that the intermediate ZA1 of the alumina carrier was replaced with the alumina carriers A1-A6 prepared in examples 1-4 and comparative examples 1-2, respectively, to obtain hydrodemetallization catalysts C1-C6.
Example 6
The following examples illustrate the catalytic performance of hydrodemetallization catalysts C0-C6.
Raw oil listed in Table 2 is used as a raw material, the catalytic performance of C0-C6 is evaluated on a fixed bed residual oil hydrogenation reaction device, the catalyst is a strip with the length of 2-3 mm, the reaction temperature is 380 ℃, the hydrogen partial pressure is 13MPa, and the liquid hourly volume space velocity is 1.0 hour-1The volume ratio of hydrogen to oil was 1000, the content of each impurity in the produced oil was measured after 3000 hours of reaction, the impurity removal rate was calculated, and the evaluation results are shown in table 3.
TABLE 2 Properties of the feed oils
| Item | |
| Density (20 ℃ C.), g/cm3 | 0.97 |
| S，wt% | 4.29 |
| N，wt% | 0.35 |
| Ni，µg/g | 20.4 |
| V，µg/g | 80.6 |
| CCR，wt% | 19 |
TABLE 3 comparison of catalyst hydrogenation performance
| Catalyst numbering | C0 | C1 | C2 | C3 | C4 | C5 | C6 |
| Ni + V removal rate wt% | 35.2 | 68.4 | 70.2 | 67.7 | 65.9 | 49.2 | 45.5 |
| Desulfurization degree, wt% | 20.1 | 45.3 | 43.3 | 42.2 | 40.8 | 33.6 | 31.4 |
As can be seen from the data in Table 3, compared with the comparative alumina carrier, the catalyst prepared by using the alumina of the invention as the carrier has higher hydrodemetallization activity and activity stability.
Claims (23)
1. An alumina carrier is characterized by comprising main alumina and rod-shaped alumina, wherein the main alumina is alumina with micron-sized pore channels, at least part of the rod-shaped alumina is distributed on the outer surface of the main body and the micron-sized pore channels with the pore diameter D of 5-10 mu m, the length of the rod-shaped alumina is 1-12 mu m, and the diameter of the rod-shaped alumina is 100-300 nm; the pores of the alumina carrier are distributed in a bimodal pore distribution, and the specific distribution is as follows: the pore volume occupied by the pores with the pore diameter of 15-35nm is 40% -60% of the total pore volume, and the pore volume occupied by the pores with the pore diameter of 100-800nm is 15% -26% of the total pore volume.
2. The alumina support of claim 1 wherein: the rod-shaped alumina is basically distributed on the outer surface of the main alumina and in the micron-sized pore channels.
3. The alumina support of claim 1 wherein: the length of the rod-shaped alumina in the micron-sized pore channel is mainly 0.3D-0.9D, and the length of the rod-shaped alumina on the outer surface is mainly 3-8 μm.
4. The alumina support of claim 1 wherein: in the micron-sized pore channels of the main alumina, the rod-shaped aluminas are distributed in a disordered and mutually staggered state; at least one end of at least part of the rod-shaped alumina is attached to the wall of the micron-sized pore channel.
5. The alumina support of claim 1 wherein: in the micron-sized pore channels of the main alumina, the rod-shaped aluminas are distributed in a disordered and mutually staggered state, and at least one end of at least part of the rod-shaped aluminas is combined on the wall of the micron-sized pore channels to form a whole with the main alumina.
6. The alumina support of claim 1 wherein: in the micron-sized pore channels of the main alumina, the rod-shaped alumina is distributed in a disordered and mutually staggered state, and at least one end of the rod-shaped alumina in the micron-sized pore channels is combined on the wall of the micron-sized pore channel and is integrated with the main alumina.
7. The alumina support of claim 1 wherein: on the outer surface of the main alumina, the rod-shaped aluminas are distributed in a disordered and mutually staggered state; one end of at least part of the rod-shaped alumina is attached to the outer surface of the main alumina.
8. The alumina support of claim 1 wherein: on the external surface of main body alumina, the rod-like aluminas are distributed in the disordered mutual staggered state, and one end of at least partial rod-like aluminas is combined on the external surface of main body alumina, and the other end is extended outwards and integrated with main body alumina.
9. The alumina support of claim 1 wherein: on the external surface of the main alumina, the rod-shaped aluminas are distributed in a disordered and mutually staggered state, one end of the rod-shaped alumina on the external surface of the main alumina is combined on the external surface of the main alumina, and the other end of the rod-shaped alumina extends outwards and is integrated with the main alumina.
10. The alumina carrier as recited in claim 1, wherein the coverage of rod-like alumina in said micron-sized channels is in the range of 70% to 95%; the coverage rate of the rod-shaped alumina on the outer surface of the main alumina is 70-95%.
11. The alumina carrier as claimed in claim 1, wherein the pores formed by the rod-like aluminas staggered with each other in a random order are concentrated between 100-800 nm.
12. An alumina carrier according to claim 1, characterised in that the properties of the alumina carrier are as follows: the specific surface area is 160-300m2Per g, pore volume of 0.6-1.5mL/g, crush strength of 10-20N/mm2 。
13. A process for the preparation of an alumina support as claimed in any one of claims 1 to 12, characterised by the steps of:
(1) preparing an alumina carrier intermediate;
(2) immersing the intermediate of the alumina carrier into an ammonium bicarbonate solution, then carrying out sealing heat treatment, drying and roasting the heat-treated material to obtain the alumina carrier;
wherein, step (1)The properties of the alumina carrier intermediate are as follows: the specific surface area is 120-290m2The pore volume is 0.7-1.1mL/g, and the pore distribution is as follows: the pore volume occupied by the pores with the pore diameter of 15-35nm is 35% -55% of the total pore volume, the pore volume occupied by the pores with the pore diameter of 100-800nm is 5% -10% of the total pore volume, and the pore volume occupied by the pores with the pore diameter of more than 5 mu m is 3% -10% of the total pore volume;
the sealing heat treatment temperature in the step (2) is 120-160 ℃, the constant temperature treatment time is 4-8 hours, and the heating rate is 5-20 ℃/min.
14. The method according to claim 13, wherein the alumina support intermediate of step (1) is prepared by the steps of: kneading and molding pseudo-boehmite and a physical pore-enlarging agent, and drying and roasting a molded product to obtain an alumina carrier intermediate; the physical pore-expanding agent is one or more of activated carbon, wood chips and polyvinyl alcohol, and the addition amount of the physical pore-expanding agent is 10-20 wt% of the weight of the alumina carrier intermediate.
15. The preparation method according to claim 14, characterized in that a forming aid is added to the alumina carrier intermediate in the step (1) during the forming process, the forming aid is one or more of a peptizing agent and an extrusion aid, the peptizing agent is one or more of hydrochloric acid, nitric acid, sulfuric acid, acetic acid and oxalic acid, and the extrusion aid is sesbania powder; the drying and roasting conditions of the formed product are as follows: the drying temperature is 100-160 ℃, the drying time is 6-10 hours, the roasting temperature is 600-750 ℃, and the roasting time is 4-6 hours.
16. The method according to claim 13, wherein the mass ratio of the ammonium bicarbonate solution used in step (2) to the alumina carrier intermediate used in step (2) is 4:1 to 8:1, and the ammonium bicarbonate solution has a mass concentration of 15% to 20%.
17. The method according to claim 13, wherein the sealing heat treatment in the step (2) is carried out in an autoclave.
18. The method according to claim 13, wherein the drying temperature in step (2) is 160 ℃ and the drying time is 6-10 hours, the baking temperature is 600 ℃ and 750 ℃ and the baking time is 4-6 hours.
19. The production method according to claim 13 or 17, characterized in that the step (2) is performed a sealing pretreatment before the sealing heat treatment at a pretreatment temperature of 60 to 100 ℃ for a constant temperature treatment time of 2 to 4 hours at a temperature rise rate of 10 ℃/min to 20 ℃/min before the pretreatment, at a temperature rise rate of 5 ℃/min to 10 ℃/min after the pretreatment, and at least 3 ℃/min lower than that before the pretreatment.
20. The method of claim 19, wherein the temperature rise rate after the pretreatment is at least 5 ℃/min lower than that before the pretreatment.
21. A hydrodemetallization catalyst comprising a support and an active metal component, wherein the support is an alumina support as claimed in any one of claims 1 to 12.
22. The hydrodemetallization catalyst of claim 21, characterized in that the active metal component is a group VIB metal selected from one or more of W, Mo and a group VIII metal selected from one or more of Co and Ni; based on the weight of the hydrodemetallization catalyst, the content of active metal oxide is 8.0-18.0%.
23. The hydrodemetallization catalyst of claim 22, wherein the active metal oxide content is 9.5% to 18.0%, the group VIB metal content is 6.5% to 15.0% calculated as metal oxide, and the group VIII metal content is 1.5% to 3.5% calculated as metal oxide, based on the weight of the hydrodemetallization catalyst.
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| CN101890342A (en) * | 2009-05-19 | 2010-11-24 | 中国石油化工股份有限公司 | Titanium-contained aluminum oxide carrier and preparation method thereof |
| CN101890356A (en) * | 2009-05-19 | 2010-11-24 | 中国石油化工股份有限公司 | Phosphorus-and potassium-containing aluminum oxide carrier and preparation method thereof |
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| CN101890342A (en) * | 2009-05-19 | 2010-11-24 | 中国石油化工股份有限公司 | Titanium-contained aluminum oxide carrier and preparation method thereof |
| CN101890356A (en) * | 2009-05-19 | 2010-11-24 | 中国石油化工股份有限公司 | Phosphorus-and potassium-containing aluminum oxide carrier and preparation method thereof |
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