CN107159314A - A kind of magnesia alumina spinel-zirconia aluminium complex carrier and preparation method thereof - Google Patents
A kind of magnesia alumina spinel-zirconia aluminium complex carrier and preparation method thereof Download PDFInfo
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- CN107159314A CN107159314A CN201610130100.5A CN201610130100A CN107159314A CN 107159314 A CN107159314 A CN 107159314A CN 201610130100 A CN201610130100 A CN 201610130100A CN 107159314 A CN107159314 A CN 107159314A
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- magnesium
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- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 title claims abstract description 138
- 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 83
- 239000000395 magnesium oxide Substances 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229910052782 aluminium Inorganic materials 0.000 title claims description 20
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims description 20
- 239000004411 aluminium Substances 0.000 title claims description 20
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims description 18
- 238000000034 method Methods 0.000 claims abstract description 58
- 239000011777 magnesium Substances 0.000 claims abstract description 33
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 33
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 19
- 239000010703 silicon Substances 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- 238000007598 dipping method Methods 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 23
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 22
- 239000012535 impurity Substances 0.000 claims description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 16
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 14
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 14
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 12
- 150000001412 amines Chemical class 0.000 claims description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- 229910021529 ammonia Inorganic materials 0.000 claims description 8
- 239000004202 carbamide Substances 0.000 claims description 8
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 8
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 8
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 8
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 3
- 239000001095 magnesium carbonate Substances 0.000 claims description 3
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 3
- 239000000347 magnesium hydroxide Substances 0.000 claims description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 125000003916 ethylene diamine group Chemical group 0.000 claims 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims 2
- 229910001648 diaspore Inorganic materials 0.000 claims 1
- 239000011148 porous material Substances 0.000 abstract description 69
- 229910052593 corundum Inorganic materials 0.000 abstract description 48
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract description 48
- 229910052596 spinel Inorganic materials 0.000 abstract description 45
- -1 magnesium aluminate Chemical class 0.000 abstract description 15
- 239000011029 spinel Substances 0.000 abstract description 14
- 239000003054 catalyst Substances 0.000 abstract description 10
- 239000002131 composite material Substances 0.000 abstract description 4
- 229910026161 MgAl2O4 Inorganic materials 0.000 description 31
- 238000002441 X-ray diffraction Methods 0.000 description 26
- 238000002156 mixing Methods 0.000 description 19
- 235000012254 magnesium hydroxide Nutrition 0.000 description 11
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 238000000465 moulding Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000005470 impregnation Methods 0.000 description 6
- 229910020068 MgAl Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910001593 boehmite Inorganic materials 0.000 description 4
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 150000002171 ethylene diamines Chemical class 0.000 description 3
- 238000010335 hydrothermal treatment Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000007493 shaping process Methods 0.000 description 3
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 3
- 229910001051 Magnalium Inorganic materials 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- HODPISPVTPCXIU-UHFFFAOYSA-N ethane-1,2-diamine;nitric acid Chemical compound NCCN.O[N+]([O-])=O HODPISPVTPCXIU-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000006253 efflorescence Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- LFETXMWECUPHJA-UHFFFAOYSA-N methanamine;hydrate Chemical compound O.NC LFETXMWECUPHJA-UHFFFAOYSA-N 0.000 description 1
- 238000010327 methods by industry Methods 0.000 description 1
- 150000003956 methylamines Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000001935 peptisation Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 206010037844 rash Diseases 0.000 description 1
- 238000006057 reforming reaction Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003836 solid-state method Methods 0.000 description 1
- 238000013112 stability test Methods 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
- B01J23/005—Spinels
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/10—Magnesium; Oxides or hydroxides thereof
-
- B01J35/61—
-
- B01J35/647—
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0205—Impregnation in several steps
Abstract
The present invention relates to catalyst carrier preparation field, a kind of magnesium aluminate spinel alumina composite carrier and preparation method thereof is disclosed, this method includes：(1) silicon source, magnesium source and alkaline peptizing agent are mixed in the presence of water, then mixture is dried and is calcined successively, obtain just grade carrier；(2) with the aqueous slkali dipping just grade carrier, then it is dried and is calcined successively.The magnesium aluminate spinel alumina composite carrier that the method for the present invention is obtained, is constituted as magnesium aluminate spinel and activated alumina (γ Al2O3) two kinds of thing phases, not magnesia thing phase, and the carrier specific surface area is high, pore volume and aperture are big, is suitable as catalyst carrier and uses.
Description
Technical field
The present invention relates to catalyst carrier preparation field, in particular it relates to a kind of magnesia alumina spinel-zirconia
Aluminium complex carrier and preparation method thereof, it is more particularly to a kind of to be without MgO impurity, specific surface area
200-260m2/ g, pore volume are 0.3-0.5cm3/ g magnesia alumina spinel-zirconia aluminium complex carrier.
Background technology
Magnesium aluminate spinel (MgAl2O4) with fusing point is high, thermal coefficient of expansion is low, thermal conductivity is good, water resistant
Property it is good and the advantages of act on strong.Simultaneously because magnesium aluminate spinel has surface acidity and alkalescence simultaneously, as
Carrier material is widely used in strong exothermal reaction, such as methanation reaction, transformationreation, methane reforming
Reaction etc..Activated alumina is with its larger specific surface area, surface acidity, nanoscale aperture, as good
Good catalyst carrier material.Complex carrier is prepared with reference to the characteristics of magnesium aluminate spinel and activated alumina,
Intensity and specific surface area can be taken into account, the performance of catalyst is lifted.Patent application CN102936022A is situated between
Continued a kind of preparation method of magnesium aluminate spinel, is synthesized using high temperature solid-state method, and technique is simple, but made
Powder granularity is larger, and pollution is easily formed in preparation process.Li Yang etc. proposes a kind of chemical precipitation method
Prepare method (the process engineering journal, 2009, (S1) of magnesium aluminate spinel:177-180).This method work
Skill is relatively easy, cost is relatively low, but Mg ions are difficult precipitation in precipitation process, and process conditions are more difficult
Control.Activated alumina is typically prepared using roasting boehmite method, the precipitation method.
When preparing the carrier containing magnesium aluminate spinel and activated alumina, in the carrier that existing method is obtained
Often contain magnesium aluminate spinel, aluminum oxide and magnesia, if containing magnesia, there is CO2The gas of participation
In solid catalysis reaction, magnesia can be with CO2Reaction generation MgCO3, cause carrier phase-change, it is long
Catalyst strength declines during periodic reaction, or even causes the efflorescence of catalyst.According to high-temperature roasting
Magnesia and Al can also be made2O3Reaction generation MgAl completely2O4, so as to eliminate magnesia phase.Typically
Afore-said hot sintering temperature needs to be higher than 700 DEG C, and still, high temperature can cause carrier specific surface area significantly to drop
It is low, so as to reduce the activity of made catalyst.
Therefore, research and develop it is a kind of without MgO impurity, be made up of completely magnesium aluminate spinel and activated alumina,
The preparation method for the carrier that specific surface area is big, performance is good, has important practical significance.
The content of the invention
The invention aims to overcome the drawbacks described above of prior art there is provided a kind of magnesium aluminate spinel-
Alumina composite carrier and preparation method thereof.
The present inventor is had found in surprise under study for action, and silicon source, magnesium source and alkaline peptizing agent are deposited in water
In lower mixing, then mixture is dried successively and is once calcined, obtain just grade carrier；And use alkali
The solution dipping just grade carrier, then be dried successively and after baking, can obtain being free of magnesia
Impurities phase, composition be magnesium aluminate spinel and activated alumina (γ-Al2O3) two kinds of thing phases magnalium point
Spar-alumina composite carrier, and by using double-steeping roasting technique, in lower temperature (400-600
DEG C, preferably 450-550 DEG C) under, you can the thorough removal of MgO thing phases is realized, carrier can be retained
Large specific surface area.
To achieve these goals, in a first aspect, the invention provides a kind of magnesia alumina spinel-zirconia aluminium
Complex carrier (MgAl2O4-Al2O3Complex carrier) preparation method, this method includes：
(1) silicon source, magnesium source and alkaline peptizing agent are mixed in the presence of water, then by mixture successively
It is dried and is calcined, obtains just grade carrier；
(2) with the aqueous slkali dipping just grade carrier, then it is dried and is calcined successively.
Second aspect, is combined the invention provides the magnesia alumina spinel-zirconia aluminium that the above method is prepared
Carrier.
The magnesia alumina spinel-zirconia aluminium complex carrier that the method for the present invention is obtained, is constituted as magnesium aluminate spinel
With activated alumina (γ-Al2O3) two kinds of thing phases, not magnesia thing phase.This method uses carrier
Double-steeping roasting technique, at lower temperature (400-600 DEG C, preferably 450-550 DEG C), can be achieved
The thorough removal of MgO thing phases, remains the large specific surface area of carrier.Because carrier is completely by magnalium
Spinelle and activated alumina composition, it shows good hydration-resisting in the reaction for having water vapour to participate in
Stability.And the carrier specific surface area is high, pore volume and aperture (0-200nm average pore size) greatly,
Catalyst carrier is suitable as to use.
Other features and advantages of the present invention will be described in detail in subsequent embodiment part.
Brief description of the drawings
Fig. 1 is the XRD spectra for the carrier that embodiment 1 is obtained.
Fig. 2 is the graph of pore diameter distribution for the carrier that embodiment 1 is obtained.
Fig. 3 is the XRD spectra for the carrier that comparative example 1 is obtained.
Fig. 4 is the graph of pore diameter distribution for the carrier that comparative example 1 is obtained.
Fig. 5 be the carrier that embodiment 1 is obtained and activated alumina (German Sasol companies) through hydro-thermal at
XRD comparison diagrams after reason.
Embodiment
The embodiment to the present invention is described in detail below.It should be appreciated that this place is retouched
The embodiment stated is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The end points and any value of disclosed scope are not limited to the accurate scope or value herein, this
A little scopes or value should be understood to comprising the value close to these scopes or value.For number range, respectively
Between the endpoint value of individual scope, between the endpoint value of each scope and single point value, and individually point
Can be combined with each other between value and obtain one or more new number ranges, these number ranges should by regarding
For specific disclosure herein.
In a first aspect, the invention provides a kind of preparation method of magnesia alumina spinel-zirconia aluminium complex carrier,
This method includes：
(1) silicon source, magnesium source and alkaline peptizing agent are mixed in the presence of water, then by mixture successively
It is dried and is calcined, obtains just grade carrier；
(2) with the aqueous slkali dipping just grade carrier, then it is dried and is calcined successively.
Process of the present invention it is preferred in the case of, in step (1), silicon source is boehmite.
Process of the present invention it is preferred in the case of, in step (1), magnesium source is magnesium hydroxide, nitric acid
At least one of magnesium and magnesium carbonate, more preferably magnesium hydroxide.
In the method for the present invention, for alkaline peptizing agent, there is no particular limitation, can be energy in this area
Enough promote under the various alkaline matters of boehmite peptization, preferable case, in step (1), alkalescence
Peptizing agent is at least one of ammoniacal liquor, organic amine and urea, it is further preferred that organic amine is second two
At least one of amine, triethylamine, hexamethylenetetramine, diethylamine and methylamine.
In the method for the present invention, in order to adjust specific surface area, pore volume and the aperture of carrier, preferable case
Under, in step (1), magnesium source and silicon source are respectively in terms of magnesia and aluminum oxide, the weight of magnesium source and silicon source
Amount is than being 0.05-0.4：1, more preferably 0.1-0.3：1.Those skilled in the art should understand that
It is that silicon source is in excessive state.
It is excellent in order to further improve specific surface area, pore volume and the aperture of carrier in the method for the present invention
In the case of choosing, in step (1), the mol ratio of alkaline peptizing agent and the silicon source in terms of aluminum oxide is
0.005-0.1：1, more preferably 0.01-0.05：1.
In the method for the present invention, in step (1), for by silicon source, magnesium source and alkaline peptizing agent in water
In the presence of the method that mixes there is no particular limitation, can for example may be used in various methods commonly used in the art
To use kneading method, first silicon source and magnesium source are mixed, then alkali is added into the mixture in silicon source and magnesium source
The aqueous solution of property peptizing agent, is sufficiently stirred for.
In the method for the present invention, in step (1), first mixture can also be carried out before being dried
Shaping, for the specific method of shaping, there is no particular limitation, can in various methods commonly used in the art,
Can be for example extruded moulding, the diameter of the sample of shaping can be 1-3mm.
Process of the present invention it is preferred in the case of, in step (2), aqueous slkali is ammonia spirit, had
At least one of machine amine aqueous solution and urea liquid, more preferably ammonia spirit.
Wherein it is preferred to, the concentration of aqueous slkali is 1-5wt%.
Preferably, the mode of dipping is equi-volume impregnating.
Preferably, organic amine is in ethylenediamine, triethylamine, hexamethylenetetramine, diethylamine and methylamine
It is at least one.
Process of the present invention it is preferred in the case of, in step (1) and step (2), the drying
Condition includes：Temperature is 100-200 DEG C, and the time is 2-5h.
In the method for the present invention, in order to further improve the specific surface area of carrier and obtain suitable pore volume
And aperture, under preferable case, in step (1) and step (2), the condition of roasting includes：Temperature is
400-600 DEG C, more preferably 450-550 DEG C；Time is 1-6h, more preferably 2-4h.
Second aspect, is combined the invention provides the magnesia alumina spinel-zirconia aluminium that the above method is prepared
Carrier.
The carrier that the present invention is obtained is not contained under MgO impurity, preferable case, and specific surface area is
200-260m2/ g, pore volume is 0.3-0.5cm3/g。
Under the carrier that the present invention is obtained, preferable case, 0-200nm average pore size (can be straight by instrument
Connect reading) it is 3-10nm.
According to the present invention it is possible to determine to contain MgAl in carrier by XRD spectra analysis2O4With
Al2O3, it is to have MgAl at 19 °, 31 °, 36 ° in 2 θ in the XRD spectra of the catalyst2O4's
Characteristic peak, is to have Al at 45 °, 60 °, 66 ° in 2 θ2O3Characteristic peak.
Embodiment
The present invention will be described in detail by way of examples below.In following examples and comparative example, such as
Without special instruction, each material can be by commercially available, and each method is method commonly used in the art.
Boehmite is purchased from Chalco Shandong branch company, Al2O3Content be 70wt%.
The XRD spectra of carrier is determined by X-ray diffractometer, X-ray diffractometer is purchased from Japan Rigaku
Company, model D/max-2600/pc.
The specific surface area of carrier, pore volume, aperture are measured by nitrogen adsorption methods, nitrogen adsorption instrument
Purchased from Micromeritics companies, model tristarII 3020-M.
Embodiment 1
The present embodiment is used for the preparation method for illustrating the magnesia alumina spinel-zirconia aluminium complex carrier of the present invention.
(1) by 200g boehmites and 20g magnesium hydroxides (w/w, MgO/Al2O3=0.1) squeezing
It is well mixed in the batch mixing hopper of bar machine.
(2) 4g ethylenediamines (mol/mol, ethylenediamine/Al are weighed2O3=0.05) be dissolved in 100g water and stirring
30min is mixed, ethylenediamine solution is configured to.
(3) ethylenediamine solution for obtaining step (2) is added in the mixture obtained to step (1),
And 1h is stirred in banded extruder batch mixing hopper with well mixed.
(4) material for obtaining step (3) extruded moulding on banded extruder, obtains a diameter of 3mm
Molded samples.
(5) molded samples for obtaining step (4) dry 2h at 120 DEG C, then at 500 DEG C
4h is calcined, just grade carrier is obtained.
(6) primary obtained by equi-volume impregnating with 5wt% ammonia spirit impregnation steps (5)
Carrier, and 2h is dried at 120 DEG C, 4h then is calcined at 500 DEG C, carrier is obtained.
The XRD spectra of obtained carrier is determined as shown in figure 1, being compared with standard spectrogram, the load is determined
Body is MgAl2O4And Al2O3Mixed phase (2 θ be 19 °, 31 °, 36 ° at have MgAl2O4Spy
Peak is levied, is to have Al at 45 °, 60 °, 66 ° in 2 θ2O3Characteristic peak), i.e., the carrier be MgAl2O4-Al2O3
Complex carrier, without MgO phase impurity.
The pore structure of carrier, the graph of pore diameter distribution of carrier are determined as shown in Fig. 2 after measured, specific surface area
For 252m2/ g, pore volume is 0.43cm3/ g, 0-200nm average pore size are 5.7nm.
Embodiment 2
The present embodiment is used for the preparation method for illustrating the magnesia alumina spinel-zirconia aluminium complex carrier of the present invention.
(1) by 200g boehmites and 40g magnesium hydroxides (w/w, MgO/Al2O3=0.2) squeezing
It is well mixed in the batch mixing hopper of bar machine.
(2) 1.24g diethylamine (mol/mol, diethylamine/Al are weighed2O3=0.0124) it is dissolved in 100g
30min is stirred in water, diethylamine solution is configured to.
(3) diethylamine solution for obtaining step (2) is added in the mixture obtained to step (1),
And 1h is stirred in banded extruder batch mixing hopper with well mixed.
(4) material for obtaining step (3) extruded moulding on banded extruder, obtains a diameter of 3mm
Molded samples.
(5) molded samples for obtaining step (4) dry 5h at 100 DEG C, then at 450 DEG C
2h is calcined, just grade carrier is obtained.
(6) primary obtained by equi-volume impregnating with 4wt% ammonia spirit impregnation steps (5)
Carrier, and 5h is dried at 100 DEG C, 2h then is calcined at 450 DEG C, carrier is obtained.
The XRD spectra for determining obtained carrier is consistent with Fig. 1, is compared with standard spectrogram, determines the load
Body is MgAl2O4And Al2O3Mixed phase (2 θ be 19 °, 31 °, 36 ° at have MgAl2O4Spy
Peak is levied, is to have Al at 45 °, 60 °, 66 ° in 2 θ2O3Characteristic peak), i.e., the carrier be MgAl2O4-Al2O3
Complex carrier, without MgO phase impurity.
The pore structure of carrier is determined, after measured, specific surface area is 242m2/ g, pore volume is 0.40cm3/ g,
0-200nm average pore size is 6.0nm.
Embodiment 3
The present embodiment is used for the preparation method for illustrating the magnesia alumina spinel-zirconia aluminium complex carrier of the present invention.
(1) by 200g boehmites and 60g magnesium hydroxides (w/w, MgO/Al2O3=0.3) squeezing
It is well mixed in the batch mixing hopper of bar machine.
(2) 1.37g triethylamines (mol/mol, triethylamine/Al are weighed2O3=0.01) it is dissolved in 100g water
Middle stirring 30min, is configured to triethylamine solution.
(3) triethylamine solution for obtaining step (2) is added in the mixture obtained to step (1),
And 1h is stirred in banded extruder batch mixing hopper with well mixed.
(4) material for obtaining step (3) extruded moulding on banded extruder, obtains a diameter of 3mm
Molded samples.
(5) molded samples for obtaining step (4) dry 3h at 180 DEG C, then at 550 DEG C
3h is calcined, just grade carrier is obtained.
(6) by equi-volume impregnating obtained with 2wt% methylamine water solution impregnation steps (5) just
Grade carrier, and 3h is dried at 180 DEG C, 3h then is calcined at 550 DEG C, carrier is obtained.
The XRD spectra for determining obtained carrier is consistent with Fig. 1, is compared with standard spectrogram, determines the load
Body is MgAl2O4And Al2O3Mixed phase (2 θ be 19 °, 31 °, 36 ° at have MgAl2O4Spy
Peak is levied, is to have Al at 45 °, 60 °, 66 ° in 2 θ2O3Characteristic peak), i.e., the carrier be MgAl2O4-Al2O3
Complex carrier, without MgO phase impurity.
The pore structure of carrier is determined, after measured, specific surface area is 246m2/ g, pore volume is 0.42cm3/ g,
0-200nm average pore size is 5.8nm.
Embodiment 4
The present embodiment is used for the preparation method for illustrating the magnesia alumina spinel-zirconia aluminium complex carrier of the present invention.
(1) by 200g boehmites and 20g magnesium hydroxides (w/w, MgO/Al2O3=0.1) squeezing
It is well mixed in the batch mixing hopper of bar machine.
(2) 5g hexamethylenetetramines (mol/mol, hexamethylenetetramine/Al are weighed2O3=0.026) molten
30min is stirred in 100g water, hexamethylenetetramine solution is configured to.
(3) the hexamethylenetetramine solution for obtaining step (2) is added to mixing that step (1) is obtained
In compound, and 1h is stirred with well mixed in banded extruder batch mixing hopper.
(4) material for obtaining step (3) extruded moulding on banded extruder, obtains a diameter of 3mm
Molded samples.
(5) molded samples for obtaining step (4) dry 5h at 120 DEG C, then at 500 DEG C
5h is calcined, just grade carrier is obtained.
(6) obtained by equi-volume impregnating with 2wt% ethylenediamine solution impregnation steps (5)
First grade carrier, and 5h is dried at 120 DEG C, 5h then is calcined at 500 DEG C, carrier is obtained.
The XRD spectra for determining obtained carrier is consistent with Fig. 1, is compared with standard spectrogram, determines the load
Body is MgAl2O4And Al2O3Mixed phase (2 θ be 19 °, 31 °, 36 ° at have MgAl2O4Spy
Peak is levied, is to have Al at 45 °, 60 °, 66 ° in 2 θ2O3Characteristic peak), i.e., the carrier be MgAl2O4-Al2O3
Complex carrier, without MgO phase impurity.
The pore structure of carrier is determined, after measured, specific surface area is 245m2/ g, pore volume is 0.39cm3/ g,
0-200nm average pore size is 4.2nm.
Embodiment 5
The present embodiment is used for the preparation method for illustrating the magnesia alumina spinel-zirconia aluminium complex carrier of the present invention.
(1) by 200g boehmites and 40g magnesium hydroxides (w/w, MgO/Al2O3=0.2) squeezing
It is well mixed in the batch mixing hopper of bar machine.
(2) 2g methylamines (mol/mol, methylamine/Al are weighed2O3=0.047) be dissolved in 100g water and stirring
30min, is configured to methylamine solution.
(3) methylamine solution for obtaining step (2) is added in the mixture obtained to step (1),
And 1h is stirred in banded extruder batch mixing hopper with well mixed.
(4) material for obtaining step (3) extruded moulding on banded extruder, obtains a diameter of 2mm
Molded samples.
(5) molded samples for obtaining step (4) dry 2h at 200 DEG C, then at 450 DEG C
5h is calcined, just grade carrier is obtained.
(6) obtained by equi-volume impregnating with 2wt% triethylamine aqueous solution impregnation steps (5)
First grade carrier, and 2h is dried at 120 DEG C, 5h then is calcined at 450 DEG C, carrier is obtained.
The XRD spectra for determining obtained carrier is consistent with Fig. 1, is compared with standard spectrogram, determines the load
Body is MgAl2O4And Al2O3Mixed phase (2 θ be 19 °, 31 °, 36 ° at have MgAl2O4Spy
Peak is levied, is to have Al at 45 °, 60 °, 66 ° in 2 θ2O3Characteristic peak), i.e., the carrier be MgAl2O4-Al2O3
Complex carrier, without MgO phase impurity.
The pore structure of carrier is determined, after measured, specific surface area is 246m2/ g, pore volume is 0.42cm3/ g,
0-200nm average pore size is 5.5nm.
Embodiment 6
The present embodiment is used for the preparation method for illustrating the magnesia alumina spinel-zirconia aluminium complex carrier of the present invention.
(1) by 200g boehmites and 40g magnesium hydroxides (w/w, MgO/Al2O3=0.2) squeezing
It is well mixed in the batch mixing hopper of bar machine.
(2) 2.4g urea (mol/mol, urea/Al are weighed2O3=0.03) be dissolved in 100g water and stirring
30min, is configured to urea liquid.
(3) urea liquid for obtaining step (2) is added in the mixture obtained to step (1),
And 1h is stirred in banded extruder batch mixing hopper with well mixed.
(4) material for obtaining step (3) extruded moulding on banded extruder, obtains a diameter of 2mm
Molded samples.
(5) molded samples for obtaining step (4) dry 3h at 160 DEG C, then at 450 DEG C
3h is calcined, just grade carrier is obtained.
(6) obtained by equi-volume impregnating with 2wt% ethylenediamine solution impregnation steps (5)
First grade carrier, and 2h is dried at 120 DEG C, 5h then is calcined at 450 DEG C, carrier is obtained.
The XRD spectra for determining obtained carrier is consistent with Fig. 1, is compared with standard spectrogram, determines the load
Body is MgAl2O4And Al2O3Mixed phase (2 θ be 19 °, 31 °, 36 ° at have MgAl2O4Spy
Peak is levied, is to have Al at 45 °, 60 °, 66 ° in 2 θ2O3Characteristic peak), i.e., the carrier be MgAl2O4-Al2O3
Complex carrier, without MgO phase impurity.
The pore structure of carrier is determined, after measured, specific surface area is 241m2/ g, pore volume is 0.45cm3/ g,
0-200nm average pore size is 6.2nm.
Embodiment 7
According to the method for embodiment 1, unlike, in step (1), by 200g boehmites and
10g magnesium hydroxides (w/w, MgO/Al2O3=0.05) be well mixed in the batch mixing hopper of banded extruder.
The XRD spectra for determining obtained carrier is consistent with Fig. 1, is compared with standard spectrogram, determines the load
Body is MgAl2O4And Al2O3Mixed phase (2 θ be 19 °, 31 °, 36 ° at have MgAl2O4Spy
Peak is levied, is to have Al at 45 °, 60 °, 66 ° in 2 θ2O3Characteristic peak), i.e., the carrier be MgAl2O4-Al2O3
Complex carrier, without MgO phase impurity.
The pore structure of carrier is determined, after measured, specific surface area is 221m2/ g, pore volume is 0.48cm3/ g,
0-200nm average pore size is 8.2nm.
Embodiment 8
According to the method for embodiment 1, unlike, in step (1), by 200g boehmites and
80g magnesium hydroxides (w/w, MgO/Al2O3=0.4) be well mixed in the batch mixing hopper of banded extruder.
The XRD spectra for determining obtained carrier is consistent with Fig. 1, is compared with standard spectrogram, determines the load
Body is MgAl2O4And Al2O3Mixed phase (2 θ be 19 °, 31 °, 36 ° at have MgAl2O4Spy
Peak is levied, is to have Al at 45 °, 60 °, 66 ° in 2 θ2O3Characteristic peak), i.e., the carrier be MgAl2O4-Al2O3
Complex carrier, without MgO phase impurity.
The pore structure of carrier is determined, after measured, specific surface area is 212m2/ g, pore volume is 0.35cm3/ g,
0-200nm average pore size is 5.6nm.
Embodiment 9
According to the method for embodiment 1, unlike, in step (2), weigh 8.1g ethylenediamines (mol/mol,
Ethylenediamine/Al2O3=0.1) be dissolved in 100g water and stir 30min, it is configured to ethylenediamine solution.
The XRD spectra for determining obtained carrier is consistent with Fig. 1, is compared with standard spectrogram, determines the load
Body is MgAl2O4And Al2O3Mixed phase (2 θ be 19 °, 31 °, 36 ° at have MgAl2O4Spy
Peak is levied, is to have Al at 45 °, 60 °, 66 ° in 2 θ2O3Characteristic peak), i.e., the carrier be MgAl2O4-Al2O3
Complex carrier, without MgO phase impurity.
The pore structure of carrier is determined, after measured, specific surface area is 221m2/ g, pore volume is 0.40cm3/ g,
0-200nm average pore size is 7.2nm.
Embodiment 10
According to the method for embodiment 1, unlike, in step (2), weigh 0.4g ethylenediamines (mol/mol,
Ethylenediamine/Al2O3=0.005) be dissolved in 100g water and stir 30min, it is configured to ethylenediamine solution.
The XRD spectra for determining obtained carrier is consistent with Fig. 1, is compared with standard spectrogram, determines the load
Body is MgAl2O4And Al2O3Mixed phase (2 θ be 19 °, 31 °, 36 ° at have MgAl2O4Spy
Peak is levied, is to have Al at 45 °, 60 °, 66 ° in 2 θ2O3Characteristic peak), i.e., the carrier be MgAl2O4-Al2O3
Complex carrier, without MgO phase impurity.
The pore structure of carrier is determined, after measured, specific surface area is 217m2/ g, pore volume is 0.30cm3/ g,
0-200nm average pore size is 4.2nm.
Embodiment 11
According to the method for embodiment 1, unlike, in step (5) and step (6), the temperature of roasting
Degree is 600 DEG C.
The XRD spectra for determining obtained carrier is consistent with Fig. 1, is compared with standard spectrogram, determines the load
Body is MgAl2O4And Al2O3Mixed phase (2 θ be 19 °, 31 °, 36 ° at have MgAl2O4Spy
Peak is levied, is to have Al at 45 °, 60 °, 66 ° in 2 θ2O3Characteristic peak), i.e., the carrier be MgAl2O4-Al2O3
Complex carrier, without MgO phase impurity.
The pore structure of carrier is determined, after measured, specific surface area is 222m2/ g, pore volume is 0.46cm3/ g,
0-200nm average pore size is 7.5nm.
Embodiment 12
According to the method for embodiment 1, unlike, in step (5) and step (6), the temperature of roasting
Degree is 700 DEG C.
The XRD spectra for determining obtained carrier is consistent with Fig. 1, is compared with standard spectrogram, determines the load
Body is MgAl2O4And Al2O3Mixed phase (2 θ be 19 °, 31 °, 36 ° at have MgAl2O4Spy
Peak is levied, is to have Al at 45 °, 60 °, 66 ° in 2 θ2O3Characteristic peak), i.e., the carrier be MgAl2O4-Al2O3
Complex carrier, without MgO phase impurity.
The pore structure of carrier is determined, after measured, specific surface area is 175m2/ g, pore volume is 0.48cm3/ g,
0-200nm average pore size is 9.0nm.
Comparative example 1
(1) by 200g boehmites and 20g magnesium hydroxides (w/w, MgO/Al2O3=0.1) squeezing
It is well mixed in the batch mixing hopper of bar machine.
(2) 100g water is added in the mixture obtained to step (1), and in banded extruder batch mixing material
1h is stirred in bucket with well mixed.
(3) material for obtaining step (2) extruded moulding on banded extruder, obtains a diameter of 3mm
Molded samples.
(4) molded samples for obtaining step (3) dry 2h at 120 DEG C, then at 500 DEG C
It is calcined 4h.
The XRD spectra of obtained carrier is determined as shown in figure 3, being compared with standard spectrogram, the load is determined
Body is MgAl2O4、Al2O3Mixed phase with MgO (is 42.9 °, 62.2 °, 75 °, 78.5 ° in 2 θ
There is MgO characteristic peak at place).
The pore structure of carrier, the graph of pore diameter distribution of carrier are determined as shown in figure 4, after measured, specific surface area
For 182m2/ g, pore volume is 0.18cm3/ g, 0-200nm average pore size are 4.0nm.
Comparative example 2
According to the method for embodiment 1, unlike, without step (6), step (5) is obtained
First grade carrier is final carrier.
The XRD spectra for determining obtained carrier is consistent with Fig. 3, is compared with standard spectrogram, determines the load
Body is MgAl2O4、Al2O3Mixed phase with MgO (is 42.9 °, 62.2 °, 75 °, 78.5 ° in 2 θ
There is MgO characteristic peak at place).
The pore structure of carrier is determined, after measured, specific surface area is 188m2/ g, pore volume is 0.21cm3/ g,
0-200nm average pore size is 3.6nm.
Comparative example 3
According to the method for embodiment 1, unlike, step (2) and step (3) are：By 100g
Water is added in the mixture obtained to step (1), and stirs 1h to mix in banded extruder batch mixing hopper
Uniformly.
The XRD spectra for determining obtained carrier is consistent with Fig. 3, is compared with standard spectrogram, determines the load
Body is MgAl2O4、Al2O3Mixed phase with MgO (is 42.9 °, 62.2 °, 75 °, 78.5 ° in 2 θ
There is MgO characteristic peak at place).
The pore structure of carrier is determined, after measured, specific surface area is 186m2/ g, pore volume is 0.20cm3/ g,
0-200nm average pore size is 2.8nm.
Comparative example 4
According to the method for embodiment 1, unlike, in step (2), replaced with equimolar nitric acid
Ethylenediamine, is configured to salpeter solution；In step (3), salpeter solution is added to step (1) and obtained
Mixture in.
The XRD spectra for determining obtained carrier is consistent with Fig. 3, is compared with standard spectrogram, determines the load
Body is MgAl2O4、Al2O3Mixed phase with MgO (is 42.9 °, 62.2 °, 75 °, 78.5 ° in 2 θ
There is MgO characteristic peak at place).
The pore structure of carrier is determined, after measured, specific surface area is 173m2/ g, pore volume is 0.17cm3/ g,
0-200nm average pore size is 3.5nm.
Comparative example 5
According to the method for embodiment 1, unlike, in step (2), replaced with equimolar nitric acid
Ethylenediamine, is configured to salpeter solution；In step (3), salpeter solution is added to step (1) and obtained
Mixture in；And 5wt% ammonia spirit is replaced with to 0.2mol/L salpeter solution in step (6).
The XRD spectra for determining obtained carrier is consistent with Fig. 3, is compared with standard spectrogram, determines the load
Body is MgAl2O4、Al2O3Mixed phase with MgO (is 42.9 °, 62.2 °, 75 °, 78.5 ° in 2 θ
There is MgO characteristic peak at place).
The pore structure of carrier is determined, after measured, specific surface area is 171m2/ g, pore volume is 0.16cm3/ g,
0-200nm average pore size is 3.3nm.
Comparative example 6
According to the method for embodiment 1, unlike, 5wt% ammonia spirit is replaced in step (6)
For 0.2mol/L salpeter solution.
The XRD spectra for determining obtained carrier is consistent with Fig. 3, is compared with standard spectrogram, determines the load
Body is MgAl2O4、Al2O3Mixed phase with MgO (is 42.9 °, 62.2 °, 75 °, 78.5 ° in 2 θ
There is MgO characteristic peak at place).
The pore structure of carrier is determined, after measured, specific surface area is 212m2/ g, pore volume is 0.31cm3/ g,
0-200nm average pore size is 5.6nm.
Embodiment 1 is compared with comparative example 1-6 and understood, method of the invention will be deposited in alkaline peptizing agent
The silicon source and the mixture in magnesium source obtained under obtains just grade carrier, then uses alkali soluble by being once calcined
Immersion stain just grade carrier, then carry out after baking, thus obtained magnesia alumina spinel-zirconia aluminium is compound to be carried
Body, is constituted as magnesium aluminate spinel and activated alumina (γ-Al2O3) two kinds of thing phases, not magnesia
Thing phase, and with significantly greater specific surface area, pore volume and aperture.
By embodiment 1 compared with embodiment 7-8 understand, respectively in terms of magnesia and aluminum oxide, magnesium source and
The weight ratio of silicon source is 0.1-0.3：When 1, MgAl can be further improved2O4-Al2O3The ratio of complex carrier
Surface area.
Embodiment 1 is compared with embodiment 9-10 and understood, alkaline peptizing agent and the silicon source in terms of aluminum oxide
Mol ratio be 0.01-0.05：When 1, MgAl can be further improved2O4-Al2O3The ratio table of complex carrier
Area.
Embodiment 1 is compared with embodiment 11-12 and understood, when sintering temperature is 450-500 DEG C, can be entered
One step improves MgAl2O4-Al2O3The specific surface area of complex carrier.
Hydration-resisting stability test
Weigh 10g support samples and 10g activated aluminas sample (German Sasol that embodiment 1-12 is obtained
Company), each sample is sealed in 100ml Pressure vessels respectively, 50g water is filled, in 180 DEG C of hydro-thermals
Handle 8h.Cooling is taken out after each sample, carries out XRD analysis.
As shown in figure 5, there is not hydration oxygen in XRD spectra after the sample hydrothermal treatment of embodiment 1
Change XRD spectra and reality after the diffraction maximum of aluminium (AlOOH), embodiment 2-12 sample hydrothermal treatment
Apply example 1 consistent, also do not occur hydrated alumina (AlOOH) diffraction maximum (will not be repeated here),
And occur obvious AlOOH diffraction maximums after activated alumina sample hydrothermal treatment, show embodiment
The hydration-resisting stability for the carrier that 1-12 is obtained is apparently higher than pure active aluminum oxide carrier.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited to above-mentioned reality
The detail in mode is applied, can be to technical side of the invention in the range of the technology design of the present invention
Case carries out a variety of simple variants, and these simple variants belong to protection scope of the present invention.
It is further to note that each particular technique described in above-mentioned embodiment is special
Levy, in the case of reconcilable, can be combined by any suitable means, in order to avoid need not
The repetition wanted, the present invention no longer separately illustrates to various possible combinations.
In addition, various embodiments of the present invention can be combined randomly, as long as its
Without prejudice to the thought of the present invention, it should equally be considered as content disclosed in this invention.
Claims (10)
1. a kind of preparation method of magnesia alumina spinel-zirconia aluminium complex carrier, includes successively：
(1) silicon source, magnesium source and alkaline peptizing agent are mixed in the presence of water, then by mixture successively
It is dried and is calcined, obtains just grade carrier；
(2) with the aqueous slkali dipping just grade carrier, then it is dried and is calcined successively.
2. according to the method described in claim 1, wherein, in step (1), source of aluminium for intend it is thin
Diaspore.
3. according to the method described in claim 1, wherein, in step (1), the magnesium source be hydrogen-oxygen
Change at least one of magnesium, magnesium nitrate and magnesium carbonate, preferably magnesium hydroxide.
4. according to the method described in claim 1, wherein, in step (1), the alkaline peptizing agent
For at least one of ammoniacal liquor, organic amine and urea, it is preferable that the organic amine is ethylenediamine, three second
At least one of amine, hexamethylenetetramine, diethylamine and methylamine.
5. according to the method described in claim 1, wherein, in step (1), magnesium source and silicon source difference
In terms of magnesia and aluminum oxide, the weight ratio of magnesium source and silicon source is 0.05-0.4：1, preferably 0.1-0.3：
1。
6. according to the method described in claim 1, wherein, in step (1), alkaline peptizing agent and with
The mol ratio of the silicon source of aluminum oxide meter is 0.005-0.1：1, preferably 0.01-0.05：1.
7. according to the method described in claim 1, wherein, in step (2), the aqueous slkali be ammonia
At least one of the aqueous solution, Amine Solutions and urea liquid, preferably ammonia spirit；
Preferably, the concentration of the aqueous slkali is 1-5wt%；
Preferably, the mode of the dipping is equi-volume impregnating；
Preferably, the organic amine is ethylenediamine, triethylamine, hexamethylenetetramine, diethylamine and methylamine
At least one of.
8. according to the method described in claim 1, wherein, in step (1) and step (2), institute
Stating dry condition includes：Temperature is 100-200 DEG C, and the time is 2-5h.
9. according to the method described in claim 1, wherein, in step (1) and step (2), institute
Stating the condition of roasting includes：Temperature is 400-600 DEG C, preferably 450-550 DEG C；Time is 1-6h, excellent
Elect 2-4h as.
10. the magnesia alumina spinel-zirconia aluminium that the method in claim 1-9 described in any one is prepared
Complex carrier；
Preferably, the carrier does not contain MgO impurity, and its specific surface area is 200-260m2/ g, hole body
Product is 0.3-0.5cm3/g。
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| US3751508A (en) * | 1970-02-25 | 1973-08-07 | Nippon Oil Co Ltd | Catalyst for selective hydrogenation of acetylenic hydrocarbon in the concurrent presence of diolefin |
| JPS58207946A (en) * | 1982-05-29 | 1983-12-03 | Toyota Central Res & Dev Lab Inc | Catalyst for partial oxidation of hydrocarbon and its manufacture |
| JP2006102628A (en) * | 2004-10-05 | 2006-04-20 | Toyota Central Res & Dev Lab Inc | Sulfur oxide absorber and its manufacturing method, and emission gas purifying facility |
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