CN105983446A - Bimodal pore distribution macroporous alumina carrier and preparation method thereof - Google Patents
Bimodal pore distribution macroporous alumina carrier and preparation method thereof Download PDFInfo
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- CN105983446A CN105983446A CN201510059791.XA CN201510059791A CN105983446A CN 105983446 A CN105983446 A CN 105983446A CN 201510059791 A CN201510059791 A CN 201510059791A CN 105983446 A CN105983446 A CN 105983446A
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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 173
- 239000011148 porous material Substances 0.000 title claims abstract description 89
- 238000009826 distribution Methods 0.000 title claims abstract description 50
- 230000002902 bimodal effect Effects 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 238000000465 moulding Methods 0.000 claims abstract description 15
- 239000002243 precursor Substances 0.000 claims abstract description 13
- 238000001125 extrusion Methods 0.000 claims abstract description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 27
- 239000004793 Polystyrene Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 24
- 229920002223 polystyrene Polymers 0.000 claims description 24
- 229910001593 boehmite Inorganic materials 0.000 claims description 21
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 21
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 18
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 16
- 238000005245 sintering Methods 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical group O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 1
- 239000005977 Ethylene Substances 0.000 claims 1
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- 229920006389 polyphenyl polymer Polymers 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 abstract description 9
- 238000002156 mixing Methods 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract description 2
- 239000005416 organic matter Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 18
- 239000003054 catalyst Substances 0.000 description 15
- 241000219782 Sesbania Species 0.000 description 12
- 238000004898 kneading Methods 0.000 description 10
- 229920003023 plastic Polymers 0.000 description 10
- 239000004033 plastic Substances 0.000 description 10
- 239000006229 carbon black Substances 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- XFBXDGLHUSUNMG-UHFFFAOYSA-N alumane;hydrate Chemical compound O.[AlH3] XFBXDGLHUSUNMG-UHFFFAOYSA-N 0.000 description 3
- 239000000295 fuel oil Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- -1 nitrogen-containing compound Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000001935 peptisation Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229920000034 Plastomer Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000003701 mechanical milling Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 1
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- Catalysts (AREA)
Abstract
The macroporous alumina carrier with bimodal pore distribution has a specific surface area of 60-220 m2The pore volume is 0.8-2.4 mL/g, the pores are in bimodal distribution, wherein 5-30 nm pores account for 10-50% of the total pore volume, the most probable pore diameter is 10-20 nm, 50-800 nm pores account for 30-70% of the total pore volume, and the most probable pore diameter is 60-400 nm; the preparation method of the bimodal pore distribution large pore volume alumina carrier comprises the following steps: (1) uniformly mixing an alumina precursor, a peptizing agent, an extrusion aid and an organic matter solution, and then molding and drying; (2) roasting under certain conditions.
Description
Technical field
The present invention is a kind of alumina support and preparation method thereof, specifically, is that one has bimodal hole and divides
Alumina support of cloth and preparation method thereof.
Background technology
Aluminium oxide has multiple different crystal form and structure, and various crystal forms have different specific physical chemical
Matter, is widely used in the fields such as electronics, chemical industry, medicine, machinery, Aero-Space, metallurgy.γ-Al2O3
Also referred to as activated alumina, due to have high-specific surface area, can the aperture of modulation, good adsorptivity and
Surface acidity, and high temperature resistant, abrasion performance, antioxidation, the advantage such as cheap and easy to get, extensively used by extensive
In the catalyst carrier of the petrochemical process such as hydrogenation, dehydrogenation, desulfurization and cracking, it is that industrial use is the most general
Time one of catalyst carrier.
As the aluminium oxide of carrier, its pore passage structure suffers from pole to activity, selectivity and the life-span of catalyst
Its important impact.Aperture is that the alumina support of bimodal distribution has huge excellent in solid catalysis reacts
Gesture: macropore beneficially reactant molecule especially heavy oil macromole is fully contacted with active center, it is also possible to
Deposition for impurity accommodates the memory space providing bigger, and the quickly diffusion for product molecule simultaneously carries with abjection
For convenient, aperture portion then provides bigger specific surface area and reacting environment, is also beneficial to improve load
The dispersion of active metal.
CN1103009A discloses the preparation method of a kind of alumina support with double-hole distribution, the party
Method, using the aluminium hydrate powder of two kinds of pore-size distributions as predecessor, adds white carbon black and surfactant as reaming
Agent, kneading, extruded moulding, be dried, finally in oxygen flow roasting obtain double-hole distribution aluminium oxide
Carrier.The method is harsh to the requirement of predecessor aluminium hydroxide raw material, needs to add the surface activity of more amount
Agent (aluminium oxide: surfactant=100:5～6), and surfactant need to select unazotized linear primary
Alcohol polyethers or polyesters nonionic surfactant.Additionally, using carbon powder, organic expanding agent to prepare
During double-hole alumina support, because of the existence of temperature runaway phenomenon during high-temperature roasting, temperature controls complexity, and industry should
With relatively costly.
CN1089039C discloses the preparation method of a kind of big pore volume alumina support, and gained aluminium oxide is in suitable
When double-hole distribution.One or more of boehmite dry glue powder prepared by the method employing different material
Mix with white carbon black and surfactant, by peptization, molding, be dried and roasting obtain bore dia be 10～
20nm hole accounts for total pore volume more than 50%, the bore dia hole more than 100nm accounts for total pore volume 5～the oxidation of 30%
Alumina supporter.The method is employing peptization course compared with CN1103009A, makes boehmite and is added
The expanding agent such as white carbon black, surfactant mixes evenly, thus improves the intensity of gained alumina support, but
Still exist and raw material and surfactant materials are selected the shortcomings such as harsh, sintering temperature control is complicated.
CN1689703A discloses a kind of preparation method with double-hole aluminium oxide.Forerunner at aluminium oxide
Thing aluminium hydrate powder adds the nitrogen-containing compound beyond a kind of deacidification and a kind of halogen as expanding agent, one-tenth
Type, roasting obtain the alumina support with double-hole distribution.Expanding agent nitrogen-containing compound used by the method
Heat stability is relatively low, volatilization of being easily heated in dry run, thus affects reaming effect, makes product simultaneously
Repeatability variation.
CN101214454A discloses the preparation method of a kind of macroporous aluminium oxide with diplopore distribution, the party
Method is first by aluminium oxide, pore creating material, solid silicon mixture ball-milling treatment in ball mill, the mixture after process
After being kneaded into plastic with the aqueous solution being dissolved with cationic surfactant, extrusion aid and peptizer, it is placed on
Processing in steam, dry, roasting obtains final alumina support.Described pore creating material is white carbon black, cellulose
Mixture with one or more in starch.The method operating procedure is complicated, and mechanical milling process used is prone to
Introduce impurity, thus affect the final purity of product and to character.
EP237240A2 discloses the preparation method of a kind of hydrogenation catalyst, and the method is in aluminium oxide precursor
Middle addition carbon fiber as expanding agent, must arrive aperture and concentrate on less than 5nm with more than bimodal point of 100nm
Cloth alumina support.The method gained alumina support aperture portion accounts for total pore volume large percentage, anti-in catalysis
Coking and blocking duct it is prone in Ying, so that the activity decrease of catalyst.
USP3898322 discloses a kind of alumina preparation method with bimodal pore distribution, and the method is by alkane
The aluminium oxide serosity of the containing alcohol that pH value is 4～10 is made in the hydrolysis of epoxide aluminum, aging more than 24 hours, with
Enough organic solvent mixing, form water and the azeotropic mixture of organic solvent in aluminium oxide serosity, obtain one
The mixture of solvent-aluminum oxide suspension, described organic solvent selected from acetone, methanol, ethanol, propanol,
Isopropanol, butanol, isobutanol and the tert-butyl alcohol, drying composite obtains a hydration oxygen with double-hole distribution
Change aluminum.The method uses substantial amounts of organic solvent in dry run, and process for separating and recovering is complicated, produces into
This is higher, is unfavorable for large-scale industrial production.
Summary of the invention
It is an object of the invention to provide macropore alumina supporter of a kind of bimodal pore distribution and preparation method thereof.Should
In alumina support prepared by method, it is more that macroperforation accounts for total pore volume ratio, and the aperture of macroperforation is one
In the range of Ding adjustable, method is simple, and prepared alumina support is adapted for use as inferior heavy oil hydrogenation catalyst
Agent, is particularly adapted to as metal remover.
The present invention provides the macropore alumina supporter of a kind of bimodal pore distribution, and its specific surface area is 60～220
m2/ g, pore volume is 0.8～2.4mL/g, and hole is that the hole of bimodal distribution, wherein 5～30nm accounts for total pore volume
10～50%, most probable pore size is positioned at 10～20nm, and the hole of 50～800nm accounts for the 30～70% of total pore volume,
Most probable pore size is positioned at 60～400nm.
Present invention simultaneously provides the preparation method of the big pore volume alumina support of a kind of bimodal pore distribution, including with
Lower step:
(1) by the precursor of a kind of aluminium oxide, peptizer, extrusion aid, organic solution mix homogeneously,
Then molding, be dried；
(2) roasting is carried out under certain conditions.
The preparation method of the big pore volume alumina support of bimodal pore distribution of the present invention, wherein, step (1)
Described in aluminium oxide precursor selected from Alumina hydrate, boehmite, boehmite and amorphous hydrogen-oxygen
Change one or more among aluminum.
The preparation method of the big pore volume alumina support of bimodal pore distribution of the present invention, wherein, step (1)
Described in organic solution be containing having polystyrene spheres or the polymethyl methacrylate of high degree of monodispersity
The solution of ball, on the basis of aluminium oxide precursor, polystyrene spheres or the consumption of polymethyl methacrylate ball
It is 5～30%, polystyrene spheres or a diameter of the 60 of polymethyl methacrylate ball～400nm.
The preparation method of the big pore volume alumina support of bimodal pore distribution of the present invention, wherein, step (1)
Described in peptizer be nitric acid or acetic acid.
The preparation method of the big pore volume alumina support of bimodal pore distribution of the present invention, wherein, step (1)
Described in extrusion aid be sesbania powder.
The preparation method of the big pore volume alumina support of bimodal pore distribution of the present invention, wherein, step (2)
Described in sintering temperature be 500～1100 DEG C.
The preparation method of the big pore volume alumina support of bimodal pore distribution of the present invention, wherein, step (2)
Described in roasting time be 1～12h.
The present invention uses among Alumina hydrate, boehmite, boehmite and amorphous hydroted alumina
One or more be aluminium oxide precursor, by addition, there is the polystyrene spheres of high degree of monodispersity or poly-
The solution of methyl methacrylate ball, prepares the aluminium oxide of bimodal pore distribution, and macroperforation accounts for total hole
Appearance ratio is more, and the aperture of macroperforation is the most adjustable.The present invention is simple to operate, it is easy to advise greatly
Mould industrialized production.
Accompanying drawing explanation
Accompanying drawing 1 is the graph of pore diameter distribution of embodiment 4.
Detailed description of the invention
Hereinafter embodiments of the invention are elaborated: the present embodiment is premised on technical solution of the present invention
Under implement, give detailed embodiment and process, but protection scope of the present invention be not limited to following
Embodiment, the experimental technique of unreceipted actual conditions in the following example, generally according to normal condition.
Aluminium oxide precursor:
In the present invention, aluminium oxide precursor is not particularly limited, aoxidizes described in usual step (1)
Aluminum precursor can be enumerated among Alumina hydrate, boehmite, boehmite and amorphous hydroted alumina
One or more.
Organic solution described in step (1):
In the present invention, organic solution described in step (1) is not particularly limited, usual step (1)
Described in organic solution be containing having polystyrene spheres or the polymethyl methacrylate of high degree of monodispersity
The solution of ball, on the basis of aluminium oxide precursor, polystyrene spheres or the consumption of polymethyl methacrylate ball
It is 5～30%, polystyrene spheres or a diameter of the 60 of polymethyl methacrylate ball～400nm.
If the consumption of polystyrene spheres or polymethyl methacrylate ball is less than 5%, owing to consumption is very few,
Cause the effective hole that can not produce 50～800nm；And polystyrene spheres or polymethyl methacrylate ball
Consumption is more than 30%, owing to consumption is too much, causes waste, and produces " temperature runaway " phenomenon in roasting process,
There is no other beneficial effect.
If the diameter of polystyrene spheres or polymethyl methacrylate ball is less than 60nm, owing to diameter is too small,
Cause can not produce the macropore of 50～800nm or the hole of generation due to aperture too small and for inferior heavy oil
Hydroconversion reactions/residuum hydrogenating and metal-eliminating reaction is unfavorable；And polystyrene spheres or polymethyl methacrylate
The diameter of ball is more than 400nm, owing to diameter is excessive, causes difficult forming, there is no other beneficial effect.
Peptizer:
In the present invention, being not particularly limited peptizer, described in usual step (1), peptizer can arrange
Lift as nitric acid or acetic acid.
Extrusion aid:
In the present invention, being not particularly limited extrusion aid, usual extrusion aid can be sesbania powder.
Sintering temperature in step (2):
In the present invention, sintering temperature described in step (2) is not particularly limited, usual step (2)
Described in sintering temperature be 500～1100 DEG C.
If sintering temperature is less than 500 DEG C, owing to sintering temperature is too low, cause Impurity removal incomplete, and
Sintering temperature is more than 1100 DEG C, owing to temperature is too high, causes energy consumption too high, there is no other beneficial effect.
Roasting time described in step (2):
In the present invention, roasting time described in step (2) is not particularly limited, usual step (2)
Described in roasting time be 1～12h；
If roasting time described in step (2) is less than 1 hour, owing to the time is too short, impurity is caused to go
Except incomplete, and roasting time described in step (2) was more than 12 hours, caused the time to waste, and energy consumption
Too high, there is no other beneficial effects.
Example 1:
(Shandong Xing Dou petrochemical industry Science and Technology Co., Ltd. produces, aluminium oxide to take 100g boehmite
Content 70wt%), with the HNO of 3g 50wt%3, 3g sesbania powder mix homogeneously, add 100g 10wt%
Monodisperse polystyrene ball solution, a diameter of 80nm of polystyrene spheres, kneading becomes plastic, molding,
Being dried, at 780 DEG C, roasting 6h, obtains alumina support, and its specific surface area, pore volume, pore size distribution are shown in
Table 1.
Example 2:
(Shandong Xing Dou petrochemical industry Science and Technology Co., Ltd. produces, aluminium oxide to take 50g boehmite
Content 70wt%) and 50g boehmite (Shandong Xing Dou petrochemical industry Science and Technology Co., Ltd. produces,
Alumina content 70wt%), with the HNO of 4g 50wt%3, 3g sesbania powder mix homogeneously, add 110
The monodisperse polystyrene ball solution of g 15wt%, a diameter of 80nm of polystyrene spheres, kneading becomes plastic,
Molding, is dried, and at 780 DEG C, roasting 6h, obtains alumina support, its specific surface area, pore volume, hole
Distribution is shown in Table 1.
Example 3:
(Shandong Xing Dou petrochemical industry Science and Technology Co., Ltd. produces, oxidation to take 40g Alumina hydrate
Aluminum content 70wt%) and 60g amorphous hydroted alumina (Shandong star all limited public affairs of petrochemical industry science and technology share
Department produces, alumina content 70wt%), with the HNO of 4g 50wt%3, 4g sesbania powder mix homogeneously,
Add the monodisperse polystyrene ball solution of 120g 20wt%, a diameter of 100nm of polystyrene spheres, kneading
Becoming plastic, molding, be dried, at 860 DEG C, roasting 6h, obtains alumina support, its specific surface area,
Pore volume, pore size distribution are shown in Table 1.
Example 4:
(Shandong Xing Dou petrochemical industry Science and Technology Co., Ltd. produces, aluminium oxide to take 100g boehmite
Content 70wt%), to mix homogeneously with 5g acetic acid, 4g sesbania powder, the list adding 100g 10wt% divides
Dissipating polystyrene spheres solution, a diameter of 200nm of polystyrene spheres, kneading becomes plastic, molding, is dried,
At 780 DEG C, roasting 6h, obtains alumina support, and its specific surface area, pore volume, pore size distribution are shown in Table 1,
Its graph of pore diameter distribution is shown in accompanying drawing 1.
Example 5:
(Shandong Xing Dou petrochemical industry Science and Technology Co., Ltd. produces, aluminium oxide to take 50g boehmite
Content 70wt%) (Shandong Xing Dou petrochemical industry Science and Technology Co., Ltd. is raw with 50g Alumina hydrate
Produce, alumina content 70wt%), mix homogeneously with 4g acetic acid, 4g sesbania powder, add 100g 15wt%
Monodisperse polystyrene ball solution, a diameter of 150nm of polystyrene spheres, kneading becomes plastic, molding,
Being dried, at 860 DEG C, roasting 6h, obtains alumina support, and its specific surface area, pore volume, pore size distribution are shown in
Table 1.
Example 6:
(Shandong Xing Dou petrochemical industry Science and Technology Co., Ltd. produces, aluminium oxide to take 100g boehmite
Content 70wt%), to mix homogeneously with 5g acetic acid, 4g sesbania powder, the list adding 100g 10wt% divides
Dissipating polymethyl methacrylate ball solution, polymethyl methacrylate bulb diameter is 100nm, and kneading becomes can
Plastomer, molding, it is dried, at 540 DEG C, roasting 6h, obtains alumina support, its specific surface area, hole
Hold, pore size distribution is shown in Table 1.
Example 7:
(Shandong Xing Dou petrochemical industry Science and Technology Co., Ltd. produces, aluminium oxide to take 50g boehmite
Content 70wt%) and 50g boehmite (Shandong Xing Dou petrochemical industry Science and Technology Co., Ltd. produces,
Alumina content 70wt%), mix homogeneously with 5g acetic acid, 4g sesbania powder, add 120g 15wt%
Single dispersing polymethyl methacrylate ball solution, polymethyl methacrylate bulb diameter is 200nm, mixed
Pinching into plastic, molding, be dried, at 960 DEG C, roasting 3h, obtains alumina support, its specific surface
Long-pending, pore volume, pore size distribution are shown in Table 1.
Table 1
As shown in Table 1, the hole of aluminium oxide prepared by the present invention is distributed at 5～30nm and 50～800nm
More concentrate, present bimodal pore distribution, in the range of the most probable pore size at two peaks occurs in each peak.
Comparative example 1:
(Shandong Xing Dou petrochemical industry Science and Technology Co., Ltd. produces, aluminium oxide to take 100g boehmite
Content 70wt%), with the HNO of 3g 50wt%3, 3g sesbania powder mix homogeneously, add 100g water,
Kneading becomes plastic, molding, is dried, and at 780 DEG C, roasting 6h, obtains alumina support, and it compares table
Area, pore volume, pore size distribution are shown in Table 2.
Comparative example 2:
(Shandong Xing Dou petrochemical industry Science and Technology Co., Ltd. produces, aluminium oxide to take 50g boehmite
Content 70wt%) (Shandong Xing Dou petrochemical industry Science and Technology Co., Ltd. is raw with 50g Alumina hydrate
Produce, alumina content 70wt%), mix homogeneously with 4g acetic acid, 4g sesbania powder, add 100g water,
Kneading becomes plastic, molding, is dried, and at 860 DEG C, roasting 6h, obtains alumina support, and it compares table
Area, pore volume, pore size distribution are shown in Table 2.
Comparative example 3:
(Shandong Xing Dou petrochemical industry Science and Technology Co., Ltd. produces, aluminium oxide to take 50g boehmite
Content 70wt%) (Shandong Xing Dou petrochemical industry Science and Technology Co., Ltd. is raw with 50g Alumina hydrate
Produce, alumina content 70wt%), with 5g acetic acid, 5g sesbania powder, 4.2g high wear-resistant carbon black powder, 2.1
G polyacrylamide mix homogeneously, adds 110g water, and kneading becomes plastic, molding, is dried, at 860 DEG C
Lower roasting 6h, obtains alumina support, and its specific surface area, pore volume, pore size distribution are shown in Table 2.
Table 2
As shown in Table 2, do not use polystyrene spheres or polymethyl methacrylate ball, or use white carbon black, all
The alumina support with bimodal pore distribution can not be obtained, and the pore volume of gained alumina support is relatively small.
Carrier obtained by the present invention is as follows with the carrier application effectiveness comparison obtained by comparative example:
Measure the ammonia that 40mL concentration is 5%, add 2.65g ammonium heptamolybdate, stirring under agitation
After dissolving, adding the citric acid of 4.5g, stirring, until being completely dissolved, adds the nickel nitrate of 4.5g, uses
Deionized water adjusts liquor capacity to 50mL.Gained solution is sprayed into 50g by example 3 gained carrying alumina
Body, is dried 3.0 hours at 120 DEG C after taking-up, then 500 DEG C of roastings 3 hours, obtains catalyst A.
Measure the ammonia that 40mL concentration is 5%, add 2.65g ammonium heptamolybdate, stirring under agitation
After dissolving, adding the citric acid of 4.5g, stirring, until being completely dissolved, adds the nickel nitrate of 4.5g, uses
Deionized water adjusts liquor capacity to 50mL.Gained solution is sprayed into 50g by comparative example 3 gained aluminium oxide
Carrier, is dried 3.0 hours at 120 DEG C after taking-up, then 500 DEG C of roastings 3 hours, obtains catalyst B.
The evaluation result of catalyst A and catalyst B see table 3
When evaluating catalyst, pass through beds after hydrogen and raw oil mixing, take hydrogen
One-through design, process conditions are: reaction pressure (hydrogen dividing potential drop), 16.0MPa；Reaction temperature, 385 DEG C；
Total liquid hourly space velocity (LHSV), 0.26h-1；Hydrogen-oil ratio (v), 1000.Evaluation raw oil character is shown in Table 4.
As shown in Table 3, the catalyst having bimodal pore distribution alumina support prepared of gained of the present invention has
Higher demetalization (Ni+V) rate, comparative example gained alumina support does not the most have bimodal pore distribution,
Demetalization (Ni+V) rate of the catalyst being especially worth is the lowest.
Table 3
| Catalyst A | Catalyst B | |
| Demetalization (Ni+V) rate, wt% | 95.4 | 76.8 |
Table 4
| Character | Husky light often slag |
| Density (20 DEG C)/g cm-3 | 0.98 |
| S, wt% | 3.9 |
| (Ni+V), μ g.g-1 | 70.7 |
Claims (8)
1. a macropore alumina supporter for bimodal pore distribution, its specific surface area is 60～220m2/ g, pore volume
Being 0.8～2.4mL/g, hole is that the hole of bimodal distribution, wherein 5～30nm accounts for the 10～50% of total pore volume,
Most probable pore size is positioned at 10～20nm, and the hole of 50～800nm accounts for the 30～70% of total pore volume, most probable hole
Footpath is positioned at 60～400nm.
2. a preparation method for the big pore volume alumina support of the bimodal pore distribution described in claim 1,
Comprise the following steps:
(1) by the precursor of a kind of aluminium oxide, peptizer, extrusion aid, organic solution mix homogeneously,
Then molding, be dried；
(2) roasting is carried out under certain conditions.
3. according to the preparation method of big pore volume alumina support of the bimodal pore distribution described in claim 2,
It is characterized in that: aluminium oxide precursor described in step (1) selected from Alumina hydrate, boehmite,
One or more among boehmite and amorphous hydroted alumina.
4. according to the preparation side of big pore volume alumina support of the bimodal pore distribution described in Claims 2 or 3
Method, it is characterised in that: organic solution described in step (1) is containing the polyphenyl with high degree of monodispersity
Ethylene ball or the solution of polymethyl methacrylate ball, on the basis of aluminium oxide precursor, polystyrene spheres or
The consumption of polymethyl methacrylate ball is 5～30%, polystyrene spheres or polymethyl methacrylate ball
A diameter of 60～400nm.
5. according to the preparation side of big pore volume alumina support of the bimodal pore distribution described in Claims 2 or 3
Method, it is characterised in that: described in step (1), peptizer is nitric acid or acetic acid.
6. according to the preparation side of big pore volume alumina support of the bimodal pore distribution described in Claims 2 or 3
Method, it is characterised in that: described in step (1), extrusion aid is sesbania powder.
7. according to the preparation side of big pore volume alumina support of the bimodal pore distribution described in Claims 2 or 3
Method, it is characterised in that: described in step (2), sintering temperature is 500～1100 DEG C.
8. according to the preparation side of big pore volume alumina support of the bimodal pore distribution described in Claims 2 or 3
Method, it is characterised in that: described in step (2), roasting time is 1～12h.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4448896A (en) * | 1981-06-02 | 1984-05-15 | Mitsubishi Chemical Ind., Ltd. | Hydrogenation catalyst for desulfurization and removal of heavy metals |
| CN1782031A (en) * | 2004-11-30 | 2006-06-07 | 中国石油化工股份有限公司 | Slag oil hydro-demetallization catalyst and its preparing method |
| CN101214454A (en) * | 2007-12-28 | 2008-07-09 | 上海第二工业大学 | Preparation method of macroporous aluminum oxide with diplopore distribution |
| CN102614934A (en) * | 2011-01-30 | 2012-08-01 | 中国石油化工股份有限公司 | Alumina carrier with composite pore structure and preparation method thereof |
| CN103936399A (en) * | 2013-01-22 | 2014-07-23 | 中国石油化工股份有限公司 | Alumina forming material and its preparation method |
-
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- 2015-02-04 CN CN201510059791.XA patent/CN105983446B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4448896A (en) * | 1981-06-02 | 1984-05-15 | Mitsubishi Chemical Ind., Ltd. | Hydrogenation catalyst for desulfurization and removal of heavy metals |
| CN1782031A (en) * | 2004-11-30 | 2006-06-07 | 中国石油化工股份有限公司 | Slag oil hydro-demetallization catalyst and its preparing method |
| CN101214454A (en) * | 2007-12-28 | 2008-07-09 | 上海第二工业大学 | Preparation method of macroporous aluminum oxide with diplopore distribution |
| CN102614934A (en) * | 2011-01-30 | 2012-08-01 | 中国石油化工股份有限公司 | Alumina carrier with composite pore structure and preparation method thereof |
| CN103936399A (en) * | 2013-01-22 | 2014-07-23 | 中国石油化工股份有限公司 | Alumina forming material and its preparation method |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2022527909A (en) * | 2019-03-28 | 2022-06-07 | 中国石油化工股▲ふん▼有限公司 | Catalytic cracking catalyst and its preparation method |
| JP7437412B2 (en) | 2019-03-28 | 2024-02-22 | 中国石油化工股▲ふん▼有限公司 | Catalytic cracking catalyst and its preparation method |
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