CN111822057A - Preparation method of spherical alumina carrier - Google Patents
Preparation method of spherical alumina carrier Download PDFInfo
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- CN111822057A CN111822057A CN201910326570.2A CN201910326570A CN111822057A CN 111822057 A CN111822057 A CN 111822057A CN 201910326570 A CN201910326570 A CN 201910326570A CN 111822057 A CN111822057 A CN 111822057A
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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 35
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 69
- 238000000034 method Methods 0.000 claims abstract description 43
- 239000011148 porous material Substances 0.000 claims abstract description 27
- 238000002156 mixing Methods 0.000 claims abstract description 25
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical class O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000001035 drying Methods 0.000 claims abstract description 16
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 14
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims abstract description 13
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims abstract description 13
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000465 moulding Methods 0.000 claims abstract description 11
- 238000005096 rolling process Methods 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 238000007789 sealing Methods 0.000 claims abstract description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- 239000005995 Aluminium silicate Substances 0.000 claims description 10
- 235000012211 aluminium silicate Nutrition 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 239000002131 composite material Substances 0.000 claims description 8
- 229920002472 Starch Polymers 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 7
- 239000008107 starch Substances 0.000 claims description 7
- 235000019698 starch Nutrition 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 238000005507 spraying Methods 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 239000003292 glue Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 238000010907 mechanical stirring Methods 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 18
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 7
- 239000000295 fuel oil Substances 0.000 abstract description 2
- 239000003921 oil Substances 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000012535 impurity Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 239000002608 ionic liquid Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- 238000010561 standard procedure Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 101150116295 CAT2 gene Proteins 0.000 description 1
- 101100392078 Caenorhabditis elegans cat-4 gene Proteins 0.000 description 1
- 101100326920 Caenorhabditis elegans ctl-1 gene Proteins 0.000 description 1
- 101100494773 Caenorhabditis elegans ctl-2 gene Proteins 0.000 description 1
- 101100112369 Fasciola hepatica Cat-1 gene Proteins 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 101100005271 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-1 gene Proteins 0.000 description 1
- 101100005280 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-3 gene Proteins 0.000 description 1
- 101100126846 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) katG gene Proteins 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- PQLVXDKIJBQVDF-UHFFFAOYSA-N acetic acid;hydrate Chemical compound O.CC(O)=O PQLVXDKIJBQVDF-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- -1 aluminum alkoxide Chemical class 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- KKTCWAXMXADOBB-UHFFFAOYSA-N azanium;hydrogen carbonate;hydrate Chemical compound [NH4+].O.OC([O-])=O KKTCWAXMXADOBB-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/651—50-500 nm
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Thermal Sciences (AREA)
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Abstract
The invention discloses a preparation method of a spherical alumina carrier, which comprises the following steps: (1) mixing pseudo-boehmite with a physical pore-enlarging agent to obtain a material W1(ii) a (2) Mixing activated kaolin, ammonium bicarbonate and water, sealing, heat treating, drying, roasting and desiliconizing the heat treated material to obtain material W2(ii) a (3) Mixing the materials W1Forming by rolling balls to obtain a spherical precursor I; (4) mixing the materials W2Mixing with the spherical precursor I, carrying out rolling ball molding, and then drying and roasting to obtain the spherical alumina carrier. The alumina prepared by the method of the inventionThe carrier has a pore passage structure from the surface to the inside, and is very suitable for being used as a carrier of an inferior heavy oil hydrogenation catalyst.
Description
Technical Field
The invention belongs to the field of catalyst material preparation, and particularly relates to a preparation method of a spherical alumina carrier.
Background
Crude oil and distillate oil obtained from crude oil contain impurities such as sulfur, nitrogen, oxygen and metals. The presence of these impurities not only affects the stability of the oil, but also discharges SO during useX、NOXAnd the environment is polluted by harmful gases. During the secondary processing of oil products, the presence of impurities such as sulfur, nitrogen, oxygen, and metals can poison the catalyst. Therefore, the removal of the above impurities is an important process in oil processing. The distillate oil hydrotreating refers to a process of contacting raw oil and hydrogen with a catalyst at a certain temperature and pressure to remove impurities and saturate aromatic hydrocarbons.
Currently, in the industrial hydroprocessing catalyst, alumina or alumina containing a small amount of auxiliary agent is usually used as a carrier, and the preparation method of the spherical particle catalyst mainly comprises the following steps: spray drying molding, rolling molding, molding in oil, ball finishing, and the like. The rotary forming is that powder and proper amount of water (or other adhesive) are fed into a container rotating at low speed, the powder particles are agglomerated together under the action of liquid bridge and capillary tube force to form micro-nuclei, and the micro-nuclei continuously rotate and grow in the powder layer under the action of friction force and rolling impact generated by the rotation of the container, finally become spherical particles with certain size and leave the container. The rotary forming treatment capacity is large, the equipment investment is low, and the operation rate is high.
CN106669851A discloses a spherical alumina carrier and a preparation method thereof, the method comprises the steps of firstly preparing ionic liquid I, II, then preparing pseudo-boehmite I, II and III, finally placing the pseudo-boehmite I in a turntable molding machine for fully mixing, spraying the aqueous solution of the ionic liquid I on alumina in a turntable through a sprayer, and obtaining a spherical precursor I after mixing and contacting; fully mixing the pseudoboehmite II and the spherical precursor I in a turntable forming machine, and mixing and contacting a medium-volume ionic liquid II aqueous solution through a sprayer to obtain a spherical precursor II; and then fully mixing the pseudoboehmite III and the spherical precursor II in a turntable forming machine, mixing and contacting a small amount of ionic liquid II aqueous solution by a sprayer to obtain a spherical precursor III, drying and roasting to obtain the spherical alumina carrier. The content of macropores of the alumina carrier prepared by the method, especially the content of macropores on the surface of the carrier is relatively low, so that macromolecular reactants are not favorably introduced.
CN103041868A discloses a method for preparing a spherical catalyst carrier, which improves the physical properties of the surface of an alumina carrier, adjusts the adhesion and rheological property of materials in the carrier forming process, reduces the plasticity of the carrier after forming and greatly improves the yield of the spherical carrier by adding an anionic surfactant and a cationic surfactant into an alumina precursor respectively. The alumina carrier prepared by the method has small aperture and is not suitable for hydrogenation reaction of heavy residual oil.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of a spherical alumina carrier. The alumina carrier prepared by the method has a pore passage structure from large to small from the surface to the inside, and is very suitable for serving as a carrier of an inferior heavy oil hydrogenation catalyst.
The preparation method of the spherical alumina carrier comprises the following steps:
(1) mixing pseudo-boehmite with a physical pore-enlarging agent to obtain a material W1；
(2) Mixing activated kaolin, ammonium bicarbonate and water, sealing, heat treating, drying, roasting and desiliconizing the heat treated material to obtain material W2；
(3) Mixing the materials W1Forming by rolling balls to obtain a spherical precursor I;
(4) mixing the materials W2Mixing with the spherical precursor I, carrying out rolling ball molding, and then drying and roasting to obtain the spherical alumina carrier.
In the method of the present invention, the pseudoboehmite described in the step (1) may be a pseudoboehmite prepared by any method, for example, prepared by a precipitation method, an aluminum alkoxide hydrolysis method, an inorganic salt sol-gel method, a hydrothermal method, a vapor deposition method, and the like. The physical pore-enlarging agent can be one or more of graphite, activated carbon, starch and cellulose, preferably starch, and the mass ratio of the physical pore-enlarging agent to the pseudo-boehmite is 1:100-1: 20.
In the method of the present invention, the activated kaolin in the step (2) is kaolin subjected to high temperature roasting treatment, wherein the roasting temperature is generally 750-.
In the method, the mass ratio of the amount of the ammonium bicarbonate in the step (2) to the activated kaolin is 1.5:1-5.0:1, and the mass ratio of the amount of the water to the sum of the activated kaolin and the ammonium bicarbonate is 2:1-4: 1; the kaolin, the ammonium bicarbonate and the water can be added and mixed in any sequence, for example, the water can be added into the mixture of the kaolin and the ammonium bicarbonate, or the kaolin is immersed into the ammonium bicarbonate water solution.
In the method of the present invention, the sealing heat treatment conditions in step (2) are as follows: the temperature is 120-160 ℃, and the treatment time is 4-8 hours. The drying temperature is 100-160 ℃, the drying time is 6-10 hours, the roasting temperature is 600-850 ℃, and the roasting time is 4-8 hours.
In the method of the present invention, the desiliconization treatment in step (2) may be a desiliconization treatment method well known in the art, preferably an alkali desiliconization treatment is adopted, wherein an alkali solution used in the alkali desiliconization treatment process is a sodium hydroxide, potassium hydroxide or ammonia water solution, the mass percentage concentration of the solution is 10% -20%, the liquid-solid mass ratio is 5:1-10:1, the treatment time is 30-90 minutes, the treatment temperature is 70-90 ℃, and the treatment process is generally performed under mechanical stirring or ultrasonic conditions. And after the alkali desiliconization treatment is finished, drying at the drying temperature of 100-160 ℃ for 6-10 hours.
In the method of the present invention, the material W obtained in the step (2)2Has the following properties: the silicon-aluminum composite oxide has a micron-scale columnar structure, the length of the columnar structure is 1-5 mu m, the diameter of the columnar structure is 100-500nm, the silicon-aluminum ratio is 0.75:1-1.1:1, the silicon-aluminum ratio refers to the mass ratio of silicon oxide to aluminum oxide, the total amount of acid is 0.03-0.1mmol/g, and the specific surface area is 0.03-0.1mmol/g60-150m2The pore volume is 0.1-0.5mL/g, and the diameter of each pore is 10-20 nm.
In the method, the rolling ball forming is carried out in a turntable forming machine, and the rotation operating conditions of the turntable forming machine are as follows: the inclination angle of the rotary table is 40-70 degrees, and the rotating speed of the rotary table is 10-30 rpm; the molding time of the material in the turntable is 5-30 min. Spraying aqueous solution containing a glue solvent into the material in the forming process; the aqueous solution of the glue-containing solvent is one or a mixture of several of aqueous solutions of nitric acid, phosphoric acid, oxalic acid and acetic acid, the mass concentration of the solution is 1-3%, and the aqueous solution of the acetic acid is preferred.
In the method, the drying time in the step (4) is 1-5 hours, preferably 2-4 hours, the drying temperature is 60-180 ℃, and preferably 80-150 ℃; the roasting temperature is 350-800 ℃, preferably 500-700 ℃, and the roasting time is 2-6 hours, preferably 2-4 hours.
Compared with the prior art, the spherical alumina carrier provided by the invention has the following advantages:
1. the kaolin after high-temperature activation is subjected to ammonium bicarbonate heat treatment to obtain a micron-sized columnar silicon-aluminum composite oxide, the composite oxide is subjected to desiliconization in an alkaline solution, and due to the removal of silicon, a proper amount of mesoporous structure is formed on the surface of the composite oxide, so that the content of mesoporous channels of the final carrier is increased.
2. When the carrier rolling ball is molded, different types of molding materials are sequentially added, so that the pore channel of the prepared spherical alumina carrier has a pore channel structure from large to small from the surface to the inside, namely the pore channel on the surface of the spherical alumina carrier is formed by interweaving columnar silicon-aluminum composite oxides, and the pore channel is large; the inner pore canal is formed by stacking pseudo-boehmite particles, and a proper amount of physical pore expanding agent is added for expanding pores, so that the pore structure is moderate. When the alumina is used as a carrier to prepare the hydrodemetallization catalyst, due to the unique pore channel structure, macromolecular reactants can easily enter the interior of the catalyst, so that the surface and the interior of the catalyst have high catalytic activity, and the surface pore channel of the catalyst is large and is not easy to block, thereby improving the activity stability of the corresponding catalyst.
Drawings
FIG. 1 shows a material W2-1SEM image of (d).
FIG. 2 shows a material W2-2SEM image of (d).
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. The pseudo-boehmite adopted in the embodiment and the comparative example of the invention is self-made by a method of using aluminum sulfate and sodium metaaluminate.
Application N2Physical adsorption-desorption characterization of pore structures of samples of examples and 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 50nm is obtained according to a BJH model.
Acid property test: a self-made vacuumizing system (comprising a vacuumizing system, a temperature control system, a quartz infrared absorption pool and the like) is applied, and the acid property of the surface of the sample is measured by adopting a quartz spring weight adsorption method. During measurement, 200 mg of the sample was added into a beaker at the lower end of the quartz spring. The vacuum system is pumped to 1 x 10-2Pa, heating to 500 ℃, keeping the temperature for one hour, purifying the sample, removing adsorbate, water and the like covered on the surface of the sample, then continuously vacuumizing, reducing the temperature to room temperature, introducing pyridine for adsorption, then heating to 160 ℃, keeping the temperature for 1 hour, desorbing the physical adsorption pyridine, and calculating the acid amount of the sample.
The scanning electron microscope is used for representing the microstructure of a sample, 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.
The method adopts NB/SH/T0704-.
The sulfur content in the oil product is determined by adopting an SH/T0689-.
The content of the asphaltene in the oil product is determined by adopting the NB/SH/T0509-2010 standard method.
And the contents of Ni and V in the oil product are determined by adopting a GB/T34099-2017 standard method.
Material W2The preparation of (1):
(1) material W2-1Preparation of
200 g of kaolin are activated at a high temperature of 800 ℃ for 4 hours in a high-temperature muffle furnace. Weighing 100g of the activated kaolin and 300 g of ammonium bicarbonate, adding 1600 g of distilled water into the materials, stirring for 20 minutes, transferring the mixed materials into a high-pressure kettle, sealing, heating to 80 ℃ at a speed of 10 ℃/min, keeping the temperature for 3 hours, heating to 130 ℃ at a speed of 5 ℃/min, keeping the temperature for 6 hours, drying the materials at 110 ℃ for 6 hours, and roasting at 750 ℃ for 5 hours.
Weighing 50 g of the materials, placing the materials into a beaker, adding 350 g of 13.5 mass percent sodium hydroxide solution into the beaker, placing the beaker into an ultrasonic container for ultrasonic treatment at the treatment temperature of 75 ℃ for 60 minutes, and drying the treated materials at the temperature of 110 ℃ for 6 hours after liquid-solid separation to obtain a material W2-1. The material has a micron-sized columnar structure, the length of the material is 3-5 mu m, the diameter of the material is 150-300nm, the silicon-aluminum ratio is 0.86:1, the total amount of acid is 0.06mmol/g, and the specific surface area is 92m2The pore volume is 0.35mL/g, and the diameter of several pores is 15 nm.
(2) Material W2-2Preparation of
Same material W2-1The preparation was carried out except that the activation temperature of kaolin was 850 ℃, the amount of ammonium hydrogencarbonate added was 400 g, the amount of distilled water added was 1200 g, the sealing heat treatment temperature was 140 ℃ and the treatment time was 5 hours. The mass concentration of the sodium hydroxide is 16.5 percent, the adding amount is 450 g, the processing temperature is 80 ℃, the processing time is 45 minutes, and a material W is prepared2-2. The material has a micron-sized columnar structure, the length of the material is 2-4 mu m, the diameter of the material is 120-250nm, the silicon-aluminum ratio is 0.94:1, the total amount of acid is 0.07mmol/g, and the specific surface area is 105m2The pore volume is 0.4mL/g, and the diameter of several pores is 12.5 nm.
(2) Material W2-3Preparation of
Same material W2-1Except that the activation temperature of kaolin was 750 deg.C, the amount of ammonium bicarbonate added was 450 g, the amount of distilled water added was 1100 g, the sealing heat treatment temperature was 120 deg.C, and the treatment time was 7 hours. The sodium hydroxide with the mass concentration of 10.5 percent is added in 300 g, the treatment temperature is 85 ℃, the treatment time is 30 minutes, and the material W is prepared2-3. The material has a micron-sized columnar structure, the length of the material is 1-3 mu m, the diameter of the material is 150-300nm, the silicon-aluminum ratio is 0.81:1, the total amount of acid is 0.05mmol/g, and the specific surface area is 75m2The pore volume is 0.25mL/g, and the diameter of several pores is 12.5 nm.
Example 1
(1) Mixing 6 g of starch and 200 g of pseudo-boehmite uniformly to obtain a material W1。
(2) 100g of material W1Placing the mixture in a rotary table forming machine for full mixing, and adjusting the inclination angle of a rotary table to be 40 degrees and the rotating speed of the rotary table to be 10 rpm; spraying acetic acid water solution with the mass concentration of 2% to the alumina forming material W in the rotary disc by a sprayer-1After the materials are mixed and contacted, the forming time of the materials in a turntable is 30min, and a spherical precursor I with the diameter of 1.0-1.5 mm is obtained;
(3) 100g of material W2-1And (3) placing the spherical precursor I prepared in the step (2) in a turntable molding machine for fully mixing, adjusting the inclination angle of the turntable to 40 degrees, rotating the turntable at 10rpm, spraying an acetic acid aqueous solution with the mass concentration of 2% onto the materials in the turntable through a sprayer, mixing and contacting, wherein the molding time of the materials in the turntable is 10min to obtain spherical materials with the diameter of 1.5-2.0 mm, drying the obtained spherical materials at 120 ℃ for 3h, and roasting at 650 ℃ for 4h to obtain a spherical alumina carrier S-1, wherein the carrier properties are shown in Table 1.
Example 2
Same as example 1 except that Material W1The addition amount of the medium starch is 8 g, and the material W2-1Changed into material W2-3To obtain the spherical alumina carrier S-2, the carrier properties are shown in Table 1.
Example 3
Same as example 1 except that Material W1The addition of medium starch is 4 g, and the spherical alumina carrier S-3 is obtainedThe properties are shown in Table 1.
Example 4
Same as example 1 except that Material W1The addition amount of the medium starch is 9 g, and the material W2-1Changed into material W2-2To obtain the spherical alumina carrier S-4, the carrier property is shown in Table 1.
Comparative example 1
Same as example 1 except that the material W was used in the ball formation2Comparative spherical alumina support S-5 was prepared without desilication treatment, and the support properties are shown in Table 1.
Comparative example 2
Same as example 1 except that the material W was used in the ball formation2The kaolin was activated at high temperature, and the activated kaolin was not subjected to hydrothermal treatment and desilication treatment to prepare comparative spherical alumina support S-6, the properties of which are shown in Table 1.
Table 1 properties of the vector.
Activity evaluation experiment:
after the alumina carriers of examples 1-4 and comparative examples 1-2 were loaded with the hydrogenation active metal component by impregnation (active metal content in the catalyst was about MoO)3: 10.2wt%, NiO: 3.9 wt%) to obtain hydrogenation catalysts, which are numbered Cat-1, Cat-2, Cat-3, Cat-4, Cat-5 and Cat-6 respectively. The catalytic performance is evaluated on a fixed bed residual oil hydrogenation reaction device, 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 is 1000, the content of each impurity in the produced oil is measured after 3000 hours of reaction, the impurity removal rate is calculated, the properties of the residual oil are shown in table 2, and the evaluation results are shown in table 3.
TABLE 2 Properties of the feed oils
TABLE 3 comparison of catalyst hydrogenation performance
As can be seen from the data in tables 1 and 3, due to the special pore structure of the spherical alumina carrier prepared by the method, the catalyst prepared by taking the alumina as the carrier is particularly suitable for the hydrotreating process of the inferior residual oil with high metal impurity content, and the catalyst has high metal and asphaltene removal rate and high activity stability.
Claims (10)
1. A method for preparing a spherical alumina carrier is characterized by comprising the following steps: (2) mixing pseudo-boehmite with a physical pore-enlarging agent to obtain a material W1(ii) a (2) Mixing activated kaolin, ammonium bicarbonate and water, sealing, heat treating, drying, roasting and desiliconizing the heat treated material to obtain material W2(ii) a (3) Mixing the materials W1Forming by rolling balls to obtain a spherical precursor I; (4) mixing the materials W2Mixing with the spherical precursor I, carrying out rolling ball molding, and then drying and roasting to obtain the spherical alumina carrier.
2. The method of claim 1, wherein: the physical pore-enlarging agent is one or more of graphite, activated carbon, starch or cellulose; the mass ratio of the physical pore-expanding agent to the pseudo-boehmite is 1:100-1: 20.
3. The method of claim 1, wherein: the activated kaolin in the step (2) is kaolin subjected to high-temperature roasting treatment, wherein the roasting temperature is 750-.
4. The method of claim 1, wherein: the mass ratio of the amount of the ammonium bicarbonate to the activated kaolin in the step (2) is 1.5:1-5.0:1, and the mass ratio of the amount of the water to the total amount of the activated kaolin and the ammonium bicarbonate is 2:1-4: 1.
5. The method of claim 1, wherein: the sealing heat treatment conditions in the step (2) are as follows: the temperature is 120-160 ℃, and the treatment time is 4-8 hours.
6. The method of claim 1, wherein: and (3) carrying out alkali desiliconization treatment in the step (2), wherein alkali liquor used in the alkali desiliconization treatment process is sodium hydroxide, potassium hydroxide or ammonia water solution, the mass percent concentration of the solution is 10% -20%, the liquid-solid mass ratio is 5:1-10:1, the treatment time is 30-90 minutes, the treatment temperature is 70-90 ℃, and the treatment process is carried out under the condition of mechanical stirring or ultrasound.
7. The method of claim 1, wherein: the material W obtained in the step (2)2Has the following properties: the silicon-aluminum composite oxide is of a micron-scale columnar structure, the length of the silicon-aluminum composite oxide is 1-5 mu m, the diameter of the silicon-aluminum composite oxide is 100-500nm, the silicon-aluminum ratio is 0.75:1-1.1:1, the silicon-aluminum ratio is the mass ratio of silicon oxide to aluminum oxide, and the total amount of acid is 0.03-0.1 mmol/g.
8. The method according to claim 1 or 7, characterized in that: the material W obtained in the step (2)2Has the following properties: the specific surface area is 60-150m2The pore volume is 0.1-0.5mL/g, and the diameter of each pore is 10-20 nm.
9. The method of claim 1, wherein: the rolling ball forming is carried out in a turntable forming machine, and the rotation operating conditions of the turntable forming machine are as follows: the inclination angle of the rotary table is 40-70 degrees, and the rotating speed of the rotary table is 10-30 rpm; the molding time of the material in the turntable is 5-30 min.
10. The method of claim 1, wherein: in the forming process, spraying an aqueous solution containing a glue solvent into the material; the aqueous solution of the glue-containing solvent is one or a mixture of several of aqueous solutions of nitric acid, phosphoric acid, oxalic acid and acetic acid, and the mass concentration of the solution is 1-3%.
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Effective date of registration: 20231017 Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Patentee after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd. Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee before: CHINA PETROLEUM & CHEMICAL Corp. Patentee before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp. |