CN110354837A - Alpha-alumina supports and the preparation method and application thereof - Google Patents
Alpha-alumina supports and the preparation method and application thereof Download PDFInfo
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- CN110354837A CN110354837A CN201810254401.8A CN201810254401A CN110354837A CN 110354837 A CN110354837 A CN 110354837A CN 201810254401 A CN201810254401 A CN 201810254401A CN 110354837 A CN110354837 A CN 110354837A
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- China
- Prior art keywords
- component
- alpha
- preparation
- alumina supports
- praseodymium
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 229910001679 gibbsite Inorganic materials 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 229910001593 boehmite Inorganic materials 0.000 claims abstract description 14
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 150000003114 praseodymium compounds Chemical class 0.000 claims abstract description 13
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 11
- 239000007787 solid Substances 0.000 claims abstract description 10
- 239000011230 binding agent Substances 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 6
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 6
- 239000011737 fluorine Substances 0.000 claims abstract description 6
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 6
- 239000010703 silicon Substances 0.000 claims abstract description 6
- 230000001404 mediated effect Effects 0.000 claims abstract description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 11
- 229910017604 nitric acid Inorganic materials 0.000 claims description 11
- 239000004411 aluminium Substances 0.000 claims description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 8
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 7
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 7
- 239000004575 stone Substances 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 230000007704 transition Effects 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 239000000470 constituent Substances 0.000 claims description 3
- 239000000428 dust Substances 0.000 claims description 3
- 238000006735 epoxidation reaction Methods 0.000 claims description 3
- 239000002006 petroleum coke Substances 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- -1 polyethylene Polymers 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229940099259 vaseline Drugs 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims 2
- 150000001213 Praseodymium Chemical class 0.000 claims 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims 1
- 229920002678 cellulose Polymers 0.000 claims 1
- 239000001913 cellulose Substances 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 13
- 239000002994 raw material Substances 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 13
- 238000000034 method Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- JJINAFAVLDNKFU-UHFFFAOYSA-N praseodymium(3+) trinitrate hydrate Chemical compound O.[Pr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JJINAFAVLDNKFU-UHFFFAOYSA-N 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000002210 silicon-based material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 2
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 2
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 description 2
- 238000005453 pelletization Methods 0.000 description 2
- 238000004375 physisorption Methods 0.000 description 2
- 229910003447 praseodymium oxide Inorganic materials 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052915 alkaline earth metal silicate Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- 229910052916 barium silicate Inorganic materials 0.000 description 1
- HMOQPOVBDRFNIU-UHFFFAOYSA-N barium(2+);dioxido(oxo)silane Chemical compound [Ba+2].[O-][Si]([O-])=O HMOQPOVBDRFNIU-UHFFFAOYSA-N 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 235000012241 calcium silicate Nutrition 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229910001506 inorganic fluoride Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- YWECOPREQNXXBZ-UHFFFAOYSA-N praseodymium(3+);trinitrate Chemical compound [Pr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YWECOPREQNXXBZ-UHFFFAOYSA-N 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 229910052917 strontium silicate Inorganic materials 0.000 description 1
- QSQXISIULMTHLV-UHFFFAOYSA-N strontium;dioxido(oxo)silane Chemical compound [Sr+2].[O-][Si]([O-])=O QSQXISIULMTHLV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- 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
- B01J35/612—Surface area less than 10 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
- B01J35/61—Surface area
- B01J35/613—10-100 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to industrial catalyst field, a kind of alpha-alumina supports and the preparation method and application thereof are provided.The preparation method includes the following steps: I) total mixture of the preparation comprising following component: component a crosses α-gibbsite of 100 mesh；Component b crosses the boehmite of 200 mesh；Component c, praseodymium compound；Component d, solid carbon-containing material；Component e, binder；Also, fluorine element, alkali earth metal and element silicon are free of in the total mixture；II) total mixture obtained in step I) is mediated uniformly and formed, obtains formed body；III) formed body obtained in step II) is dried, is roasted, the alpha-alumina supports are made；The maximum temperature of the roasting is 1000-1350 DEG C.The raw materials used inexpensive of the preparation method of alpha-alumina supports provided by the invention, alpha-alumina supports obtained have biggish specific surface area, have broad application prospects.
Description
Technical field
The present invention relates to industrial catalyst fields, more particularly, to a kind of alpha-alumina supports, the alpha-alumina supports
The application in a variety of reactions of preparation method and the alpha-alumina supports.
Background technique
Aluminium oxide as adsorbent, catalyst and catalyst carrier chemical industry, environmental protection, in terms of
It is used widely, is widely applied on chemical industry especially as catalyst carrier.
In chemical industry, common alumina material is mainly gama-alumina, η-aluminium oxide and Alpha-alumina.Wherein α-
Because specific surface area is lower, surface inertness and heat resistance are mostly used as the carrier of load type metal catalyst, such as ethylene aluminium oxide
Epoxidation silver catalyst, two/carbon of carbon, three selective hydrogenation precious metals palladium catalyst, nickel catalyst used for steam reforming.
Be typically used by the industrial catalyst or carrier of alumina support preparation in continuously flow gas-solid, liquid-solid or
In gas-liquid-solid heterogeneous system.To meet certain requirement, alumina support is generally increased by work as spherical, cylinder, three
The bar shaped of leaf grass-like, Rasching ring, porous honeycomb or gear shape, and require certain mechanical strength, specific surface area and hole
Structure.
All aqua oxidation aluminum feedstocks, such as common boehmite, boehmite, α-gibbsite, β-gibbsite,
Stable hexagonal phase Alpha-alumina can be converted by high-temperature process.Consider from economy, using α-gibbsite system
Standby Alpha-alumina has great cost advantage, but the usual specific surface area of Alpha-alumina prepared therefrom is lower, is being used as load
When metallic catalyst carrier, catalytic activity is lower, this is the big disadvantage of one.
Therefore, how to play the cheap advantage of α-gibbsite, there is high specific surface area using it as primary raw material preparation
Alpha-alumina be an important technical problem.
Summary of the invention
The purpose of the present invention is in view of the above shortcomings of the prior art, provide a kind of alpha-alumina supports and preparation method thereof
With application.The present invention uses cheap α-gibbsite for primary raw material, by the way that less amount of praseodymium compound is added in the feed,
The alpha-alumina supports with bigger serface have been made.
The first aspect of the present invention provides a kind of preparation method of alpha-alumina supports, which includes following step
It is rapid:
I) preparation includes the total mixture of following component:
Component a, α-gibbsite of 100 mesh of mistake based on component a and component b total weight 30-85wt%, is preferably based on group
Divide α-gibbsite of 100 mesh of mistake of a and component b total weight 50-80wt%；
Component b, the boehmite of 200 mesh of mistake based on component a and component b total weight 15-70wt%, is preferably based on group
Divide the boehmite of 200 mesh of mistake of a and component b total weight 20-50wt%；
Component c, in terms of praseodymium element, the praseodymium compound based on component a and component b total weight 0.05-3.0wt%, preferably base
In the praseodymium compound of component a and component b total weight 0.1-2.6wt%；
Component d, the solid carbon-containing material based on component a and component b total weight 0-20wt%, is preferably based on component a and group
Divide the solid carbon-containing material of b total weight 5.0-15wt%；
Component e is preferably based on the total mixture weight based on the binder of the total mixture weight 9.0-35wt%
The binder of 10-20wt%；
Fluorine element, alkali earth metal and element silicon are free of in total mixture；
II) total mixture obtained in step I) is mediated uniformly and formed, obtains formed body；
III) formed body obtained in step II) is dried, is roasted, the alpha-alumina supports are made；The roasting
The maximum temperature of burning is 1000-1350 DEG C, preferably 1050-1250 DEG C.
The present inventor has found that praseodymium compound, which is added, can be improved the specific surface area of catalyst carrier under study for action,
But when being free of alkali earth metal and element silicon in total mixture, maturing temperature cannot be excessively high, otherwise will will greatly affect and urge
The specific surface area of agent carrier.The alkali earth metal common various alkali in alpha-alumina supports preparation field
Earth metal compound, the term meaning and scope are known to the skilled person.Specifically, the alkaline earth metal compound choosing
From at least one of the compound of magnesium, calcium, strontium and barium, including but not limited to: barium carbonate, barium sulfate, barium chloride, barium nitrate.
The element silicon common various silicon-containing compounds, the term meaning and scope in alpha-alumina supports preparation field
It is known to the skilled person.The silicon-containing compound is selected from silica solution and/or alkaline-earth-metal silicate；Including but it is unlimited
In: magnesium silicate, calcium silicates, strontium silicate, barium silicate.Therefore, total mixture of the invention refers to not volume without alkali earth metal
Outer addition alkaline earth metal compound, total mixture of the invention refers to without element silicon, and silicon-containing compound is not added additionally.
The present inventor also found under study for action, when praseodymium compound is added, cannot have fluoride in reaction system,
Otherwise it will cause declining to a great extent for specific surface area.The fluorine element is common each in alpha-alumina supports preparation field
Kind inorganic fluoride, the term meaning and scope are known to the skilled person.Specifically, the fluoride includes but unlimited
In: aluminum fluoride, sodium fluoride, ammonium fluoride.Therefore, total mixture of the invention refers to without fluorine element, and fluoride is not added additionally.
According to the method for the present invention, the component a can also include transition aluminas and/or surge aluminium stone.The transition
Phase alumina and/or preferred 150 mesh of mistake of surge aluminium stone, relative to the total weight of component a and component b, the transition aluminas and/
Or the content of surge aluminium stone is preferably 50-75wt%.
Method in accordance with the invention it is preferred that the praseodymium compound is selected from nitrate, carbonate, the sulfate, oxidation of praseodymium
Object or their mixture.A kind of specific embodiment according to the present invention, the praseodymium compound are praseodymium nitrate or praseodymium oxide.
Method in accordance with the invention it is preferred that the solid carbon-containing material be selected from petroleum coke, graphite, carbon dust, polyethylene and
At least one of vaseline.
Method in accordance with the invention it is preferred that the binder is the aqueous solution of acid；The acid is preferably selected from acetic acid, salt
At least one of acid, nitric acid and sulfuric acid.The further preferably aqueous solution of nitric acid, in the aqueous solution of the nitric acid, nitric acid with
The weight ratio of water can be 1:2-5.
In the present invention, the component b and binder can be provided completely or partially in the form of Aluminum sol.
According to the method for the present invention, step II) described in molding the conventional extrusion pelletizing method of forming may be selected, can also be used
Screw rod is molded the regular carrier method of forming, preferably latter forming method.
According to the method for the present invention, step III) in, the drying needs so that the content of free water is lower than in formed body
10wt%, it is preferable that the temperature of the drying is 60-100 DEG C, preferably 65-90 DEG C；The time of the drying is that 2-24 is small
When.
Under the premise of meeting above-mentioned maturing temperature, the total time of the roasting is preferably 8-60 hours, wherein in highest
At a temperature of constant temperature calcining time be 2-9 hours.
The second aspect of the present invention provides a kind of alpha-alumina supports as made from above-mentioned preparation method.
The third aspect of the present invention provides a kind of alpha-alumina supports, and the specific surface area of the alpha-alumina supports is 2.0-
30m2/ g, praseodymium constituent content are 0.05-2.0wt%；It is preferred that the specific surface area of the alpha-alumina supports is 2.0-25m2/ g, praseodymium
Constituent content is 0.06-1.5wt%.
The fourth aspect of the present invention provides the alpha-alumina supports as made from above-mentioned preparation method and/or above-mentioned Alpha-alumina
Carrier is in epoxidation reaction of olefines, catalytic hydrogenation, catalytic dehydrogenation, methane vapor conversion or methane reforming, alcohols dehydration reaction
In application.
The raw materials used inexpensive of the preparation method of alpha-alumina supports provided by the invention, alpha-alumina supports obtained
With biggish specific surface area, have broad application prospects.
Other features and advantages of the present invention will then part of the detailed description can be specified.
Specific embodiment
To keep the present invention easier to understand, below in conjunction with embodiment, the present invention will be described in detail, these embodiments are only
Serve illustrative, it is not limited to application range of the invention.
The specific surface area of carrier is measured according to international test standards ISO-9277 using nitrogen physisorption BET method.Example
Such as, the specific surface area of U.S. Kang Ta company NOVA2000e type nitrogen physisorption instrument measurement carrier can be used.
Comparative example 1
α-gibbsite 491g of 100 mesh will be crossed, cross the boehmite 110g of 200 mesh, blender is put into and is uniformly mixed；
It is transferred in kneader, the dilute nitric acid solution of 95mL 18wt% is added, sufficiently mediates；Extrusion molding is outer diameter about 8.0mm, length
The Raschig ring shape body of 7.2mm, internal diameter 3mm；The dry 10h at 90 DEG C makes free water content be reduced to 10wt% hereinafter, oxygen is made
Change alumina supporter green compact；It is then placed in high-temperature electric resistance furnace, is increased to 1400 DEG C from room temperature through 20h, constant temperature 4h obtains white alpha-oxidation
Alumina supporter D1.Measuring its specific surface area is 1.91m2/g.Through XRD analysis, Alpha-alumina crystal phase is only detected.
Comparative example 2
α-gibbsite 480g of 100 mesh will be crossed, cross boehmite 123g, the praseodymium nitrate hydrate 8.0g of 200 mesh, put
Enter blender to be uniformly mixed；Then it is transferred in kneader, the nitric acid solution of 95mL 16wt% is added, sufficiently mediates；Then it uses
Screw rod is molded the Raschig ring shape body that regular carrier molding machine is shaped to outer diameter about 8.0mm, long 7.2mm, internal diameter 3mm；At 90 DEG C
Dry 10h makes free water content be reduced to 10wt% hereinafter, alumina support green compact are made；It is then placed in high-temperature electric resistance furnace, passes through
20h is increased to 1400 DEG C, constant temperature 3h from room temperature, obtains white alpha-alumina supports D2.Measuring its specific surface area is 1.5m2/g。
Through XRD analysis, principal crystalline phase is Alpha-alumina, phase content about 97%.
Comparative example 3
α-gibbsite 490g of 100 mesh will be crossed, cross boehmite 112g, the praseodymium nitrate hydrate 8.0g, fluorine of 200 mesh
Change aluminium 7.0g, is put into blender and is uniformly mixed；Then it is transferred in kneader, the dilute nitric acid solution of 100mL 16wt% is added, fills
Divide and mediates；Then the Raschig ring shape body that pelletizing is shaped to outer diameter about 8.0mm, long 7.2mm, internal diameter 3mm is squeezed out；It is dry at 90 DEG C
10h makes free water content be reduced to 10wt% hereinafter, alumina support green compact are made；It is then placed in high-temperature electric resistance furnace, through 20h
1300 DEG C, constant temperature 3h are increased to from room temperature, obtains white alpha-alumina supports D3.Measuring its specific surface area is 0.6m2/g.Through
XRD analysis, principal crystalline phase are Alpha-alumina, phase content about 97%.
Embodiment 1
Preparation process is with comparative example 2, the difference is that being increased to 1100 DEG C from room temperature through 20h, constant temperature in high-temperature electric resistance furnace
4h obtains white alpha-alumina supports S1.Measuring its specific surface area is 18.8m2/ g, principal crystalline phase are that (phase content is about for Alpha-alumina
For 85%).
Comparative example 4
Preparation process with embodiment 1, unlike: by the α-gibbsite 490g for crossing 100 mesh, cross 200 purposes and intend thin water
Aluminium stone 113g is put into blender and is uniformly mixed.Finally obtain white alpha-alumina supports D4.Measuring its specific surface area is 8.0m2/
g.Principal crystalline phase is Alpha-alumina (phase content is about 95%).
Comparative example 5
Preparation process with embodiment 1, unlike: by the α-gibbsite 490g for crossing 100 mesh, cross 200 purposes and intend thin water
Aluminium stone 113g, praseodymium nitrate hydrate 8.0g, aluminum fluoride 7.0g are put into blender and are uniformly mixed.Finally obtain white Alpha-alumina
Carrier D5.Measuring its specific surface area is 1.20m2/g.Principal crystalline phase is Alpha-alumina (phase content is about 97%).
Embodiment 2
α-gibbsite 210g of 100 mesh will be crossed, cross the boehmite 380g of 200 mesh, praseodymium nitrate hydrate 8.2g is put
Enter blender to be uniformly mixed；It is transferred in kneader, the dilute nitric acid solution of 98mL 18wt% is added, sufficiently mediates；Extrusion molding is
The Raschig ring shape body of outer diameter about 8.0mm, long 7.2mm, internal diameter 3mm；The dry 10h at 90 DEG C, is reduced to free water content
10wt% is hereinafter, be made alumina support green compact；It is then placed in high-temperature electric resistance furnace, is increased to 1300 DEG C from room temperature through 20h, constant temperature
2h obtains white alpha-alumina supports S2.Measuring its specific surface area is 3.5m2/g.Through XRD analysis, Alpha-alumina crystal content
About 97%.
Embodiment 3
α-gibbsite 365g of 100 mesh will be crossed, cross boehmite 234g, the praseodymium nitrate hydrate 13.2g of 200 mesh,
Blender is put into be uniformly mixed；It is transferred in kneader, the dilute nitric acid solution of 98mL 18wt% is added, sufficiently mediates；Extrusion molding
For the Raschig ring shape body of outer diameter about 8.0mm, long 7.2mm, internal diameter 3mm；The dry 10h at 90 DEG C, is reduced to free water content
10wt% is hereinafter, be made alumina support green compact；It is then placed in high-temperature electric resistance furnace, is increased to 1200 DEG C from room temperature through 20h, constant temperature
3h obtains white alpha-alumina supports S3.Measuring its specific surface area is 12.1m2/g.Through XRD analysis, Alpha-alumina crystal content
About 92%.
Embodiment 4
By the α-gibbsite 50g for crossing 100 mesh, the boehmite 239g for crossing the surge aluminium stone 310g of 200 purposes, crossing 200 mesh,
Praseodymium nitrate hydrate 4.2g is put into blender and is uniformly mixed；It is transferred in kneader, the dust technology that 100mL 18wt% is added is molten
Liquid is sufficiently mediated；Extrusion molding is the Raschig ring shape body of outer diameter about 8.0mm, long 7.2mm, internal diameter 3mm；It is dry at 90 DEG C
10h makes free water content be reduced to 10wt% hereinafter, alumina support green compact are made；It is then placed in high-temperature electric resistance furnace, through 20h
1200 DEG C, constant temperature 2h are increased to from room temperature, obtains white alpha-alumina supports S4.Measuring its specific surface area is 21.1m2/g.Through
XRD analysis, Alpha-alumina crystal content are about 87%.
Embodiment 5
Preparation process with embodiment 2, unlike: the additional petroleum coke 60g that 60-80 mesh is added is put into blender mixing
Uniformly.Finally obtain white alpha-alumina supports S5.Measuring its specific surface area is 3.20m2/ g, principal crystalline phase are Alpha-alumina (phase
97%) content is about.
Embodiment 6
By boehmite 200g, the praseodymium oxide of α-gibbsite 402.0g, 200 mesh excessively that granularity is 200-250 mesh
9.0g is put into blender and is uniformly mixed；It is transferred in kneader, the dilute nitric acid solution of 98mL 18wt% is added, sufficiently mediates；It squeezes
It is shaped to the Raschig ring shape body of outer diameter about 8.0mm, long 7.2mm, internal diameter 3mm out；The dry 10h at 90 DEG C, makes free water content
10wt% is reduced to hereinafter, alumina support green compact are made；It is then placed in high-temperature electric resistance furnace, is increased to 1200 from room temperature through 20h
DEG C, constant temperature 3h obtains white alpha-alumina supports S6.Measuring its specific surface area is 14.8m2/g.Through XRD analysis, Alpha-alumina
Crystal content is about 94%.
By energy containing praseodymium compound it can be seen from the measurement result of comparative example 1 and comparative example 2 and comparative example 4 and embodiment 1
Enough significantly improve the specific surface area of catalyst carrier.
If being added simultaneously it can be seen from comparative example 3 and comparative example 2 and embodiment 1 and the measurement result of comparative example 4-5
Containing praseodymium compound and fluoride, the specific surface area of catalyst carrier can decline to a great extent.
Strong influence catalyst is carried by maturing temperature it can be seen from the measurement result of embodiment 1 and comparative example 2 is excessively high
The specific surface area of body.
Various embodiments of the present invention are described above, above description is exemplary, and non-exclusive, and
It is not limited to disclosed each embodiment.Without departing from the scope and spirit of illustrated each embodiment, for this skill
Many modifications and changes are obvious for the those of ordinary skill in art field.
Claims (10)
1. a kind of preparation method of alpha-alumina supports, which is characterized in that the preparation method includes the following steps:
I) preparation includes the total mixture of following component:
Component a, α-gibbsite of 100 mesh of mistake based on component a and component b total weight 30-85wt%, is preferably based on component a
With α-gibbsite of 100 mesh of mistake of component b total weight 50-80wt%；
Component b, the boehmite of 200 mesh of mistake based on component a and component b total weight 15-70wt%, is preferably based on component a
With the boehmite of 200 mesh of mistake of component b total weight 20-50wt%；
Component c, in terms of praseodymium element, the praseodymium compound based on component a and component b total weight 0.05-3.0wt% is preferably based on group
Divide the praseodymium compound of a and component b total weight 0.1-2.6wt%；
Component d, the solid carbon-containing material based on component a and component b total weight 0-20wt%, is preferably based on component a and component b is total
The solid carbon-containing material of weight 5.0-15wt%；
Component e is preferably based on the total mixture weight 10- based on the binder of the total mixture weight 9.0-35wt%
The binder of 20wt%；
Fluorine element, alkali earth metal and element silicon are free of in the total mixture；
II) total mixture obtained in step I) is mediated uniformly and formed, obtains formed body；
III) formed body obtained in step II) is dried, is roasted, the alpha-alumina supports are made；The roasting
Maximum temperature is 1000-1350 DEG C.
2. preparation method according to claim 1, which is characterized in that the component a further include transition aluminas and/or
Surge aluminium stone.
3. preparation method according to claim 1, which is characterized in that the praseodymium compound is selected from nitrate, the carbonic acid of praseodymium
Salt, sulfate, oxide or their mixture.
4. preparation method according to claim 1, which is characterized in that the solid carbon-containing material be selected from petroleum coke, graphite,
At least one of carbon dust, polyethylene and vaseline.
5. preparation method according to claim 1, which is characterized in that the binder is the aqueous solution of acid；The acid is excellent
Choosing is selected from least one of acetic acid, hydrochloric acid, nitric acid and sulfuric acid.
6. preparation method according to claim 5, which is characterized in that the component b and binder are all or part of with aluminium
The form of colloidal sol provides.
7. preparation method described in any one of -6 according to claim 1, which is characterized in that step III) in, the drying
Temperature be 60-100 DEG C, preferably 65-90 DEG C；The time of the drying is 2-24 hours；The maximum temperature of the roasting is
1050-1250℃；The total time of the roasting is 8-60 hours, wherein the time of constant temperature calcining is that 2-9 is small at the maximum temperature
When.
8. alpha-alumina supports made from the preparation method as described in any one of claim 1-7.
9. a kind of alpha-alumina supports, which is characterized in that the specific surface area of the alpha-alumina supports is 2.0-30m2/ g, praseodymium member
Cellulose content is 0.05-2.0wt%；It is preferred that the specific surface area of the alpha-alumina supports is 2.0-25m2/ g, praseodymium constituent content are
0.06-1.5wt%.
10. alpha-alumina supports and/or claim 8 or 9 made from preparation method described in any one of claim 1-7
The alpha-alumina supports are in epoxidation reaction of olefines, catalytic hydrogenation, catalytic dehydrogenation, methane vapor conversion or methane weight
Application whole, in alcohols dehydration reaction.
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| US11801488B2 (en) | 2020-06-19 | 2023-10-31 | Lg Chem, Ltd. | Method of preparing alumina catalyst, alumina catalyst prepared using same, and method of preparing propylene using alumina catalyst |
| US11975308B2 (en) | 2020-06-19 | 2024-05-07 | Lg Chem, Ltd. | Dehydration catalyst, method for preparing the same, and method of preparing alkene using the same |
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