CN107413321A - A kind of preparation method of hud typed carrier - Google Patents
A kind of preparation method of hud typed carrier Download PDFInfo
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- CN107413321A CN107413321A CN201710400659.XA CN201710400659A CN107413321A CN 107413321 A CN107413321 A CN 107413321A CN 201710400659 A CN201710400659 A CN 201710400659A CN 107413321 A CN107413321 A CN 107413321A
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- glue
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- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 239000000463 material Substances 0.000 claims abstract description 66
- 239000003292 glue Substances 0.000 claims abstract description 60
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 37
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 36
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000010936 titanium Substances 0.000 claims abstract description 30
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000002243 precursor Substances 0.000 claims abstract description 24
- 239000001768 carboxy methyl cellulose Substances 0.000 claims abstract description 9
- 239000002002 slurry Substances 0.000 claims abstract description 8
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims abstract description 7
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims abstract description 7
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims abstract description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 22
- 241000219782 Sesbania Species 0.000 claims description 18
- 229910052593 corundum Inorganic materials 0.000 claims description 14
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 14
- 229910052681 coesite Inorganic materials 0.000 claims description 13
- 229910052906 cristobalite Inorganic materials 0.000 claims description 13
- 239000000377 silicon dioxide Substances 0.000 claims description 13
- 229910052682 stishovite Inorganic materials 0.000 claims description 13
- 229910052905 tridymite Inorganic materials 0.000 claims description 13
- 229910052594 sapphire Inorganic materials 0.000 claims description 2
- 239000011257 shell material Substances 0.000 abstract description 19
- 239000000758 substrate Substances 0.000 abstract description 11
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 239000013078 crystal Substances 0.000 abstract description 5
- 238000002156 mixing Methods 0.000 abstract description 3
- 238000005245 sintering Methods 0.000 abstract description 2
- 244000275012 Sesbania cannabina Species 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 20
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 16
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 16
- 238000009495 sugar coating Methods 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 11
- 238000000034 method Methods 0.000 description 9
- 229910000510 noble metal Inorganic materials 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 6
- 238000006356 dehydrogenation reaction Methods 0.000 description 6
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 235000007926 Craterellus fallax Nutrition 0.000 description 1
- 240000007175 Datura inoxia Species 0.000 description 1
- 239000004287 Dehydroacetic acid Substances 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- 229910010062 TiCl3 Inorganic materials 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 229910001648 diaspore Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- -1 spinelle Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910006415 θ-Al2O3 Inorganic materials 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
-
- 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
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention provides a kind of preparation method of hud typed carrier, including：Ludox, Alumina gel, titanium colloidal sol, sesbania gum, sodium carboxymethylcellulose and water mixing, obtain glue；The glue is sprayed on base material, in 100 200 DEG C of roastings, obtains carrier precursor；Shell slurries are coated on outside the support precursor, are then calcined at 300 500 DEG C of temperature.One layer of glue-line is first prepared on base material, the roughness of substrate surface is added, avoids the phenomenon that Shell Materials easily come off from base material；From the glue for limiting proportioning, the duct on base material not only can be effectively blocked, and increase mechanical strength to a certain extent；Sintering temperature is controlled to be effectively guaranteed the crystal formation of shell at 300 500 DEG C, increase the specific surface area of carrier.
Description
Technical field
The present invention relates to catalyst carrier field, and in particular to a kind of preparation method of hud typed carrier.
Background technology
As chemical industry constantly develops towards environmental protection, energy-conservation and efficient direction.To the performance requirements of catalyst
Improve constantly.Loaded catalyst is so that its catalytic activity is high and selective good and is widely used.Wherein using noble metal as activity
The loaded catalyst of component is most widely used, and particularly in petrochemical industry, noble metal carrier catalyst is excellent with its
The catalytic performance of effect is widely applied in the techniques such as purification for gas, raw material hydrogenation, cracking.The most frequently used prepares noble-metal-supported
The method of type catalyst is, by noble metal active component by the mode such as impregnating, spraying, is directly loaded in the load more larger than surface
On body, then by roasting, noble metal carrier catalyst is finally given.In above-mentioned preparation method, compare surface due to having selected
The larger carrier of product, and larger its duct of carrier of specific surface area so allows for during load, had compared with horn of plenty
The noble metal of sizable part penetrates into carrier inside, and carrier inside noble metal in catalytic process utilization rate it is very low,
The waste of noble metal is thus caused, and noble metal is expensive, greatly adds the cost of production.
In view of the above-mentioned problems, people are improved carrier, a kind of hud typed carrier is designed, it is small in specific surface area
Carrier on coat the larger material of one layer of specific surface area, the depth in the larger material surface duct of specific surface area is reduced with this.
γ-Al2O3And TiO2It is big with its specific surface area, and cheap wide material sources, and be widely used on Shell Materials, at present
With γ-Al2O3Preparation method for the hud typed carrier of Shell Materials is：It will be made Alumina gel of boehmite, then by base
Material is immersed in Alumina gel, then drying and roasting, and hud typed carrier prepared by the above method is uneven there is shell thickness, and
The problem of bad mechanical strength；With TiO2Preparation method for the hud typed carrier of Shell Materials is：Titanium chloride is mixed with water, taken
The titanium colloidal sol that its upper strata is formed, carrier is placed in titanium colloidal sol and impregnated, and is calcined, in the preparation method, after meeting water due to titanium chloride,
Violent hydrolysis occurs immediately, simultaneous largely precipitates generation so that the amount of the titanium colloidal sol of generation is then considerably less, is only
5%-10% or so, so that substantial amounts of titanium material is wasted, while substantial amounts of dusty gas chlorination is also produced in hydrolytic process
Hydrogen；Simultaneously, the problem of shell carrier prepared using this kind of method equally exists bad mechanical strength.
Therefore, a kind of thin-shell type noble metal catalysts of Chinese patent CN101491778A, it is adopted using aluminum oxide as kernel
To γ-Al2O3Coating material and water, glue and surfactant are mixed and made into slurries, then by powder as coating material
Slurries are sprayed on substrate surface again, is calcined at 700-1200 DEG C, obtains lamellar composite carrier.In above-mentioned technical proposal, directly
Connect and use with γ-Al2O3The mixing of powder glue is used as Shell Materials, and for adhesion strength, it can only use very high temperature to roast
Burn, it is understood that the presence temperature of the aluminum oxide crystal formation of γ phases is at 400-600 DEG C, if temperature is too high, may result in crystal formation
Change, and at 700-1200 DEG C, the crystal formation of the aluminum oxide of γ phases can be converted into the δ phases or/and θ phases of specific surface area very little, greatly
The big specific surface area for reducing carrier；At the same time, technical scheme disclosed in above-mentioned patent does not have to the mechanical strength of carrier yet
There is improvement；
Simultaneously in technical scheme disclosed in above-mentioned patent, disclosed base material is the less α-Al of specific surface area2O3、θ-
Al2O3, spinelle, quartz etc. be used as base material, above-mentioned material surface is smooth, and during gluing, often producing glue can not
Situation about being supported on base material.
The content of the invention
Therefore, the technical problem to be solved in the present invention is to overcome shell thickness of the prior art uneven, when it is negative
When carrying active component, active component is readily permeable to the defects of on base material, mechanical strength is low, and Shell Materials are not easy to be coated on
Defect on base material, so as to provide a kind of preparation method of hud typed carrier.
A kind of preparation method of hud typed carrier, comprises the following steps：
(1) Ludox, Alumina gel, titanium colloidal sol, sesbania gum, sodium carboxymethylcellulose and water are mixed, obtains glue；
(2) glue is sprayed on base material, in 100-200 DEG C of roasting, obtains carrier precursor；
(3) shell slurries are coated on outside the support precursor, are then calcined, obtain at 300-500 DEG C of temperature
The hud typed carrier.
Preferably, in described preparation method, the shell slurries are Alumina gel or titanium colloidal sol.
Preferably, in described preparation method, in the glue, SiO2、Al2O3、TiO2, sesbania gum, carboxymethyl cellulose
The mass ratio of plain sodium and water is：(0.1-10)：(0.1-10)：(0.1-10)：(0.1-1)：(0.1-1)：100.
Preferably, in described preparation method, in the glue, SiO2、Al2O3、TiO2, sesbania gum, carboxymethyl cellulose
The mass ratio of plain sodium and water is：0.1：1：1：0.1：0.2：100.
Preferably, in described preparation method, the mass ratio of the glue and the base material is：(1-13)：25.
Preferably, in described preparation method, the base material is α-Al2O3、δ-Al2O3、θ-Al2O3Or α-SiO2。
Preferably, in described preparation method, the base material is spherical, a diameter of 2-5mm.
Preferably, in described preparation method,
In the step 2, roasting time 0.5-1h；
In the step 3, roasting time 0.5-3h.
Technical solution of the present invention, have the following advantages that：
The invention provides a kind of preparation method of hud typed carrier, including：Ludox, Alumina gel, titanium colloidal sol, sesbania
Glue, sodium carboxymethylcellulose and water mixing, obtain glue；The glue is sprayed on base material, in 100-200 DEG C of roasting, obtained
To carrier precursor；Shell slurries are coated on outside the support precursor, is then calcined, obtains at 300-500 DEG C of temperature
To the hud typed carrier.First, one layer of glue-line is first prepared on base material, the roughness of substrate surface is added, avoids shell
Layer material comes off from base material；Secondth, from the glue for limiting proportioning, the duct on base material not only can be effectively blocked, and
And increase mechanical strength to a certain extent, tests prove that, mechanical strength can reach 170N/ grains；3rd, control sintering temperature
Degree is effectively guaranteed the crystal formation of shell, increases the specific surface area of carrier at 300-500 DEG C.
Simultaneously, the catalyst that the hud typed carrier prepared with method disclosed by the invention is prepared also has higher
Catalytic activity.
Embodiment
Technical scheme will be clearly and completely described below, it is clear that described embodiment is this hair
Bright part of the embodiment, rather than whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art are not having
There is the every other embodiment made and obtained under the premise of creative work, belong to the scope of protection of the invention.In addition, below
As long as it is mutual not form conflict can each other for involved technical characteristic in described different embodiments of the present invention
With reference to.
Heretofore described Alumina gel and titanium colloidal sol can use any method preparation for preparing it in the prior art
Obtain, finished product on the market can also be bought, for the ease of comparing, the preparation method of Alumina gel is in embodiment 1-3：It will intend thin
After diaspore powder is well mixed with water, at 80 DEG C, such as salpeter solution is added dropwise while stirring, is cooled to room temperature, admittedly contained
Measure the Alumina gel for 10%；The preparation method of titanium colloidal sol is in embodiment 4-6：By TiCl3Mixed with water, it is quiet after stirring
5-10min is put, takes upper strata glue, as solid content is 10% titanium colloidal sol.
Embodiment 1
A kind of preparation method of hud typed carrier, including：
(1) at room temperature, Ludox, Alumina gel, titanium colloidal sol, sesbania gum, CMC (sodium carboxymethylcellulose) and water are mixed
Close, stir, obtain glue, wherein, in the glue, SiO2、Al2O3、TiO2, sesbania gum, the mass ratio of CMC and water be
0.1:0.1:10:1:0.1:100；
(2) a diameter of 2mm spherical α-Al are chosen2O3It is placed in as base material in sugar coating machine, with glue and the mass ratio of base material
For 1:25 amount, glue is sprayed onto on base material, and 0.5h is then rolled in sugar coating machine, glue is uniformly coated on outside base material
Portion, 0.5h is calcined at being 100 DEG C in temperature, obtains carrier precursor；
(3) it is 1 by Alumina gel and substrate mass ratio:25 amount, Alumina gel is sprayed on to obtain on carrier precursor,
At 300 DEG C, 3h is calcined, that is, obtains carrier A；
Embodiment 2
A kind of preparation method of hud typed carrier, including：
(1) at room temperature, Ludox, Alumina gel, titanium colloidal sol, sesbania gum, CMC and water are mixed, stirs, obtain glue
Liquid, wherein, in the glue, SiO2、Al2O3、TiO2, sesbania gum, the mass ratio of CMC and water be 10:10:0.1:0.1:1:100；
(2) a diameter of 5mm spherical δ-Al are chosen2O3It is placed in as base material in sugar coating machine, with glue and the mass ratio of base material
For 13:25 amount, glue is sprayed onto on base material, and 1h is then rolled in sugar coating machine, glue is uniformly coated on outside base material
Portion, 1h is calcined at being 150 DEG C in temperature, obtains carrier precursor；
(3) it is 13 by Alumina gel and substrate mass ratio:25 amount, Alumina gel is sprayed on to obtain on carrier precursor,
At 500 DEG C, 0.5h is calcined, that is, obtains carrier B；
Embodiment 3
A kind of preparation method of hud typed carrier, including：
(1) at room temperature, Ludox, Alumina gel, titanium colloidal sol, sesbania gum, CMC and water are mixed, stirs, obtain glue
Liquid, wherein, in the glue, SiO2、Al2O3、TiO2, sesbania gum, the mass ratio of CMC and water be 1:1:1:1:1:100；
(2) a diameter of 3mm spherical θ-Al are chosen2O3It is placed in as base material in sugar coating machine, with glue and the mass ratio of base material
For 7:25 amount, glue is sprayed onto on base material, and 1h is then rolled in sugar coating machine, glue is uniformly coated on outside base material
Portion, 1h is calcined at being 200 DEG C in temperature, obtains carrier precursor；
(3) it is 7 by Alumina gel and substrate mass ratio:25 amount, Alumina gel is sprayed on to obtain on carrier precursor,
At 400 DEG C, 2h is calcined, that is, obtains support C.
Embodiment 4
A kind of preparation method of hud typed carrier, including：
(1) at room temperature, Ludox, Alumina gel, titanium colloidal sol, sesbania gum, CMC and water are mixed, stirs, obtain glue
Liquid, wherein, in the glue, SiO2、Al2O3、TiO2, sesbania gum, the mass ratio of CMC and water be 0.1:1:1:0.1:0.2:100；
(2) a diameter of 4mm spherical α-Al are chosen2O3It is placed in as base material in sugar coating machine, with glue and the mass ratio of base material
For 9:25 amount, glue is sprayed onto on base material, and 1h is then rolled in sugar coating machine, glue is uniformly coated on outside base material
Portion, 1h is calcined at being 130 DEG C in temperature, obtains carrier precursor；
(3) it is 9 by titanium colloidal sol and substrate mass ratio:25 amount, titanium colloidal sol is sprayed on to obtain on carrier precursor,
At 400 DEG C, 2h is calcined, that is, obtains carrier D.
Embodiment 5
A kind of preparation method of hud typed carrier, including：
(1) at room temperature, Ludox, Alumina gel, titanium colloidal sol, sesbania gum, CMC and water are mixed, stirs, obtain glue
Liquid, wherein, in the glue, SiO2、Al2O3、TiO2, sesbania gum, the mass ratio of CMC and water be 5:4:6:0.5:0.7:100；
(2) a diameter of 4mm spherical α-SiO are chosen2It is placed in as base material in sugar coating machine, with glue and the mass ratio of base material
For 10:25 amount, glue is sprayed onto on base material, and 1h is then rolled in sugar coating machine, glue is uniformly coated on outside base material
Portion, 1h is calcined at being 180 DEG C in temperature, obtains carrier precursor；
(3) it is 10 by titanium colloidal sol and substrate mass ratio:25 amount, titanium colloidal sol is sprayed on to obtain on carrier precursor,
At 500 DEG C, 3h is calcined, that is, obtains carrier E.
Embodiment 6
One kind is with γ-Al2O3For the preparation method of the hud typed carrier of shell, including：
(1) at room temperature, Ludox, Alumina gel, titanium colloidal sol, sesbania gum, CMC and water are mixed, stirs, obtain glue
Liquid, wherein, in the glue, SiO2、Al2O3、TiO2, sesbania gum, the mass ratio of CMC and water be 9:8:10:0.7:0.3:100；
(2) a diameter of 5mm spherical θ-Al are chosen2O3It is placed in as base material in sugar coating machine, with glue and the mass ratio of base material
For 12:25 amount, glue is sprayed onto on base material, and 2h is then rolled in sugar coating machine, glue is uniformly coated on outside base material
Portion, 1h is calcined at being 110 DEG C in temperature, obtains carrier precursor；
(3) it is 12 by titanium colloidal sol and substrate mass ratio:25 amount, titanium colloidal sol is sprayed on to obtain on carrier precursor,
At 500 DEG C, 3h is calcined, that is, obtains carrier F.
Comparative example 1
A kind of preparation method of hud typed carrier, including：
(1) at room temperature, Ludox, CMC and water are mixed, stirs, obtain glue, wherein, in the glue,
SiO2, CMC and water mass ratio be 0.5：0.5：100；
(2) a diameter of 4mm spherical α-Al are chosen2O3It is placed in as base material in sugar coating machine, with glue and the mass ratio of base material
For 9:25 amount, glue is sprayed onto on base material, and 1h is then rolled in sugar coating machine, glue is uniformly coated on outside base material
Portion, 1h is calcined at being 130 DEG C in temperature, obtains carrier precursor；
(3) it is 9 by titanium colloidal sol and substrate mass ratio:25 amount, titanium colloidal sol is sprayed on to obtain on carrier precursor,
At 400 DEG C, 2h is calcined, that is, obtains carrier G.
Comparative example 2
A kind of preparation method of the hud typed carrier of shell, including：
(1) a diameter of 4mm spherical α-Al are chosen2O3It is placed in as base material in sugar coating machine, with glue and the mass ratio of base material
For 9:25 amount, glue is sprayed onto on base material, and 1h is then rolled in sugar coating machine, glue is uniformly coated on outside base material
Portion, 1h is calcined at being 130 DEG C in temperature, obtains carrier precursor；
(2) it is 9 by titanium colloidal sol and substrate mass ratio:25 amount, titanium colloidal sol is sprayed on to obtain on carrier precursor,
At 400 DEG C, 2h is calcined, that is, obtains carrier H.
Compliance test result：
The present invention, which prepares hud typed carrier, to be prepared into any one catalysis according to preparation method of the prior art
Agent, for the ease of comparing, carrier A-H prepared by embodiment 1-6 and comparative example 1-2 is prepared into deoxidation by the following method
Catalyst A-H.
The preparation method of dehydrogenation catalyst, including：
The chloroplatinic acid aqueous solution that weight/mass percentage composition is 10% is prepared, it is water-soluble in 100mL chloroplatinic acids according to 1g carrier impregnations
The amount of liquid, by carrier impregnation in chloroplatinic acid aqueous solution 1.5h, 2h is dried at 70 DEG C, at 500 DEG C, be calcined 2h, obtain deoxidation
Catalyst.
1. the Liquid penetrant testing of active component platinum
The evaluation of metal active constituent load capacity is carried out to catalyst A-H using electron probe, tests catalyst A-H carriers
Base material on the amount of platinum that loads, as a result as shown in table 1.
The tenor of the hud typed carrier inside base material of table 1
As it can be seen from table 1 the dehydrogenation catalyst A-F prepared with embodiment 1-6 carrier A-F, on its base material (core portion)
Substantially platinum is not detected；And the dehydrogenation catalyst G and H prepared with comparative example 1-2 carrier G and H, detect on its base material
To there is platinum active component.
2. deoxidation effectiveness detects
Dehydrogenation catalyst A-H is used for the deoxidation of unstripped gas, the unstripped gas to be nitrogen, and in normal temperature and pressure, air speed is
5000h-1Under conditions of, hydrogen is added using mass flowmenter control system, determines the deoxy performance of catalyst, it the results are shown in Table
Shown in 2.
The deoxy performance of the catalyst of table 2
From table 2 it can be seen that the deoxy performance that dehydrogenation catalyst is prepared with embodiment 1-8 carrier is substantially better than with contrast
The deoxy performance of dehydrogenation catalyst prepared by example 1-2 carrier.
3. carrier A-H mechanical strengths detect
The embodiment 1-6 and comparative example 1-2 carrier A-H prepared mechanical strength is carried out using pressure particle testing machine
Detection, test result are shown in Table 3.
The carrier mechanical strength of table 3
| Mechanical strength (N/ grains) | ||
| Embodiment 1 | Carrier A | 150 |
| Embodiment 2 | Carrier B | 152 |
| Embodiment 3 | Support C | 162 |
| Embodiment 4 | Carrier D | 170 |
| Embodiment 5 | Carrier E | 159 |
| Embodiment 6 | Carrier F | 155 |
| Comparative example 1 | Carrier G | 113 |
| Comparative example 2 | Carrier H | 94 |
From table 3 it is observed that carrier A-F prepared by embodiment 1-6 mechanical strength is substantially better than comparative example 1-2 preparations
Carrier G-H mechanical strength.
4. carrier A-K specific surface areas detect
Using BET specific surface area detection method, detection carrier A-H specific surface area, testing result is shown in Table 4.
The carrier specific surface area of table 4
| Specific surface area (g/m2) | ||
| Embodiment 1 | Carrier A | 350 |
| Embodiment 2 | Carrier B | 320 |
| Embodiment 3 | Support C | 340 |
| Embodiment 4 | Carrier D | 280 |
| Embodiment 5 | Carrier E | 265 |
| Embodiment 6 | Carrier F | 249 |
| Comparative example 1 | Carrier G | 200 |
| Comparative example 2 | Carrier H | 155 |
As can be seen from Table 4, comparative example 1-2 systems are significantly greater than with the embodiment 1-6 carrier A-F prepared specific surface area
Standby carrier G-H specific surface area.
Obviously, above-described embodiment is only intended to clearly illustrate example, and is not the restriction to embodiment.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of change or
Change.There is no necessity and possibility to exhaust all the enbodiments.And the obvious change thus extended out or
Among changing still in the protection domain of the invention.
Claims (8)
1. a kind of preparation method of hud typed carrier, comprises the following steps：
(1) Ludox, Alumina gel, titanium colloidal sol, sesbania gum, sodium carboxymethylcellulose and water are mixed, obtains glue；
(2) glue is sprayed on base material, in 100-200 DEG C of roasting, obtains carrier precursor；
(3) shell slurries are coated on outside the support precursor, be then calcined at 300-500 DEG C of temperature, obtained described
Hud typed carrier.
2. preparation method according to claim 1, it is characterised in that the shell slurries are Alumina gel or titanium colloidal sol.
3. preparation method according to claim 1 or 2, it is characterised in that in the glue, SiO2、Al2O3、TiO2, Tian Qing
The mass ratio of glue, sodium carboxymethylcellulose and water is：(0.1-10)：(0.1-10)：(0.1-10)：(0.1-1)：(0.1-1)：
100。
4. according to any described preparation methods of claim 1-3, it is characterised in that in the glue, SiO2、Al2O3、TiO2、
The mass ratio of sesbania gum, sodium carboxymethylcellulose and water is：0.1：1：1：0.1：0.2：100.
5. according to any described preparation methods of claim 1-4, it is characterised in that the mass ratio of the glue and the base material
For：(1-13)：25.
6. according to the preparation method described in claim 1-5, it is characterised in that the base material is α-Al2O3、δ-Al2O3、θ-
Al2O3Or α-SiO2。
7. according to the preparation method described in claim 1-6, it is characterised in that the base material is spherical, a diameter of 2-5mm.
8. according to the preparation method described in claim 1-7, it is characterised in that
In the step 2, roasting time 0.5-1h；
In the step 3, roasting time 0.5-3h.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101143325A (en) * | 2006-09-13 | 2008-03-19 | 中国科学院大连化学物理研究所 | Method for preparing catalyst and application thereof |
| CN101485974A (en) * | 2009-02-23 | 2009-07-22 | 东南大学 | Method for supporting nano titanic oxide on surface of carrier material |
| CN101491778A (en) * | 2008-01-23 | 2009-07-29 | 中国石油化工股份有限公司 | Preparation method of thin shell shaped noble metal catalyst |
| CN101716533A (en) * | 2009-11-13 | 2010-06-02 | 北京化工大学 | Integrated catalyst carriers and method thereof for preparing catalyst |
| CN101992112A (en) * | 2009-08-27 | 2011-03-30 | 中国科学院金属研究所 | Titanium oxide coating/ceramic structural catalyst carrier and preparation method thereof |
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2017
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101143325A (en) * | 2006-09-13 | 2008-03-19 | 中国科学院大连化学物理研究所 | Method for preparing catalyst and application thereof |
| CN101491778A (en) * | 2008-01-23 | 2009-07-29 | 中国石油化工股份有限公司 | Preparation method of thin shell shaped noble metal catalyst |
| CN101485974A (en) * | 2009-02-23 | 2009-07-22 | 东南大学 | Method for supporting nano titanic oxide on surface of carrier material |
| CN101992112A (en) * | 2009-08-27 | 2011-03-30 | 中国科学院金属研究所 | Titanium oxide coating/ceramic structural catalyst carrier and preparation method thereof |
| CN101716533A (en) * | 2009-11-13 | 2010-06-02 | 北京化工大学 | Integrated catalyst carriers and method thereof for preparing catalyst |
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