CN108212134A - Siliceous boehmite catalyst carrier and preparation method thereof - Google Patents
Siliceous boehmite catalyst carrier and preparation method thereof Download PDFInfo
- Publication number
- CN108212134A CN108212134A CN201711274711.8A CN201711274711A CN108212134A CN 108212134 A CN108212134 A CN 108212134A CN 201711274711 A CN201711274711 A CN 201711274711A CN 108212134 A CN108212134 A CN 108212134A
- Authority
- CN
- China
- Prior art keywords
- catalyst carrier
- aluminum sulfate
- preparation
- crystallization
- silica
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 title claims abstract description 51
- 229910001593 boehmite Inorganic materials 0.000 title claims abstract description 50
- 239000003054 catalyst Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 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 85
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000011148 porous material Substances 0.000 claims abstract description 50
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims abstract description 45
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 30
- 235000019353 potassium silicate Nutrition 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000011734 sodium Substances 0.000 claims abstract description 25
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002135 nanosheet Substances 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 13
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 27
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 27
- 238000002425 crystallisation Methods 0.000 claims description 24
- 230000008025 crystallization Effects 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000013019 agitation Methods 0.000 claims description 8
- 229910001679 gibbsite Inorganic materials 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 3
- 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 abstract description 17
- 229910052708 sodium Inorganic materials 0.000 abstract description 17
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 230000001276 controlling effect Effects 0.000 abstract 1
- 230000001681 protective effect Effects 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 49
- 239000000047 product Substances 0.000 description 14
- 238000002156 mixing Methods 0.000 description 6
- 239000002002 slurry Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 241000190022 Pilea cadierei Species 0.000 description 1
- WAKTWVHWRCNIKU-UHFFFAOYSA-N S(=O)(=O)(O)O.[AlH3] Chemical compound S(=O)(=O)(O)O.[AlH3] WAKTWVHWRCNIKU-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 229910001648 diaspore Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- -1 wherein Substances 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/12—Silica and alumina
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/618—Surface area more than 1000 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/638—Pore volume more than 1.0 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The present invention relates to catalyst carrier preparing technical fields, and in particular to siliceous boehmite catalyst carrier and preparation method thereof.Wherein, which is porous material, and the porous material is porous silica-alumina material, and the porous sial is nano-sheet, and silica content is 1 20wt.%, and specific surface area is 800 1000m2/ g, pore volume are 1.7 4.0cm3/ g, most probable pore size are 2 30nm.The present invention controls reaction end by regulating and controlling the mass ratio of sodium metaaluminate, aluminum sulfate and waterglass based on aluminium oxide and silica content, can prepare bigger serface, macropore volume nano-sheet siliceous boehmite catalyst carrier, and this method is simple for process, it is environmentally protective, it is easy to industrialize.
Description
Technical field
The present invention relates to catalyst carrier preparing technical fields, and in particular to siliceous boehmite catalyst carrier and its system
Preparation Method.
Background technology
Boehmite (boehmite) has larger specific surface area and pore volume, available for preparing as adsorbent and urging
The aluminium oxide of agent carrier.Siliceous boehmite destroys the hexa-coordinate structure of part aluminium due to the introducing of silicon, has and more optimizes
Acidity, it is preferably be used as catalyst carrier.
The mixed solution of sodium metaaluminate and waterglass is added drop-wise in aluminum sulfate solution in patent CN102663409A, is prepared
Obtain the siliceous boehmite of threadiness that silicone content is 0.05-3wt%, fibre diameter 6-15nm.
In siliceous boehmite preparation process, acid-base neutralization method is a kind of common method.Neutralization reaction is that heat release is anti-
Should, with the mixing of acid ＆ alkali liquid, the temperature of system is gradually increasing, and the pH numerical value measured for pH meter has a significant impact, although warm
The method of degree compensation can eliminate a part of influence, but be difficult all to eliminate.And the concentration of acid ＆ alkali liquid can also produce terminal pH
It is raw to influence, it is therefore desirable to avoid using the method for measuring pH determining that terminal is added dropwise.
In addition, fibrous boehmite makes it with bigger serface and big hole body due to its special appearance structure
Long-pending characteristic, this is all incomparable for common boehmite and boehmite.But fibrous boehmite is for example
Boehmite is greater than 400m2/g although the specific surface area with super large, but due to its appearance structure, hole
Volume is generally less than 1.5ml/g or so.
Therefore, it is necessary to study develop while have bigger serface and a nano-sheet boehmite of macropore volume.
Invention content
The purpose of the invention is to overcome the above problem of the existing technology, a kind of siliceous boehmite catalysis is provided
Agent carrier and preparation method thereof, this method by regulate and control sodium metaaluminate, aluminum sulfate and waterglass mass ratio (by aluminium oxide and
Silica content meter) control reaction end, can prepare bigger serface, macropore volume white powder it is siliceous thin
Diaspore catalyst carrier.
To achieve these goals, in a first aspect, the present invention provides a kind of siliceous boehmite catalyst carrier,
In, the siliceous boehmite catalyst carrier be porous material, the porous material be porous silica-alumina material, the porous sial
Material is nano-sheet, silica content 1-20wt.%, specific surface area 800-1000m2/ g, pore volume 1.7-
4.0cm3/ g, most probable pore size 2-30nm.
Second aspect, the present invention provides a kind of preparation method of siliceous boehmite catalyst carrier, wherein, this method
Include the following steps：
(1) gibbsite with sodium hydroxide is contacted, obtains sodium aluminate solution；
(2) sodium aluminate solution is added drop-wise in aluminum sulfate solution under agitation；
(3) sodium aluminate solution, aluminum sulfate solution and waterglass are added drop-wise to simultaneously under agitation obtained by step (2)
In suspension；
(4) by step (3) products therefrom under crystallization condition crystallization；
(5) crystallization product obtained by step (4) is filtered, and filtering obtained solid is washed with deionized, is dried.
The third aspect, the present invention provides the siliceous boehmite catalyst loads by preparation method preparation described above
Body.
Through the above technical solutions, the present invention is controlled using sodium metaaluminate, aluminum sulfate and waterglass as raw material in mixed process
The mass ratio (based on aluminium oxide and silica content) of two kinds of raw materials, using pH monitoring as supplementary means, then to obtaining in
Between product carry out hydro-thermal process, last filtration washing is dried to obtain powdered siliceous boehmite.
Description of the drawings
Fig. 1 is the high-resolution-ration transmission electric-lens photo of the nano-sheet boehmite prepared in the embodiment of the present invention 1.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood to comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It between the endpoint value of a range and individual point value and can be individually combined with each other between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
In a first aspect, the present invention provides a kind of siliceous boehmite catalyst carrier, wherein, which urges
Agent carrier is porous material, and the porous material is porous silica-alumina material, and the porous silica-alumina material is nano-sheet, is aoxidized
Silicone content is 1-20wt.%, and specific surface area can be 800-1000m2/ g, pore volume can be 1.7-4.0cm3/ g, most probable hole
Diameter can be 2-30nm.
In accordance with the present invention it is preferred that the porous silica-alumina material is nano-sheet, silica content 2-18wt.%, than
Surface area is 810-980m2/ g, pore volume 2.5-3.8cm3/ g, most probable pore size 5-25nm.
According to the present invention, it is further preferred that the porous silica-alumina material is nano-sheet, silica content 3-
15wt.%, specific surface area 820-950m2/ g, pore volume 3.0-3.7cm3/ g, most probable pore size 7-20nm.
According to the present invention, it is further preferred that the porous silica-alumina material specific surface area is 825-890m2/g。
In invention, the property of the carrier of catalyst is controlled in above range, can be supported on catalytic active component
On the carrier, that is, the carrier can be used in supporting active component, and then can prepare the catalyst with special properties.
According to the present invention, the porous material is siliceous boehmite and/or the dehydration product of siliceous boehmite.
Second aspect, the present invention provides a kind of preparation method of siliceous boehmite catalyst carrier, wherein, this method
Include the following steps：
(1) gibbsite with sodium hydroxide is contacted, obtains sodium aluminate solution；
(2) sodium aluminate solution is added drop-wise in aluminum sulfate solution under agitation；
(3) sodium aluminate solution, aluminum sulfate solution and waterglass are added drop-wise to simultaneously under agitation obtained by step (2)
In suspension；
(4) by step (3) products therefrom under crystallization condition crystallization；
(5) crystallization product obtained by step (4) is filtered, and filtering obtained solid is washed with deionized, is dried.
Preparation in accordance with the present invention, wherein, in step (1), the condition of the contact can be：Temperature is 120-
160 DEG C, time 8-20h；Preferably, temperature is 130-150 DEG C, time 10-15h.
Preferably, the molar ratio of the sodium hydroxide and the Na/Al of the gibbsite can be (2-5)：1, more preferably
For (4.1-4.9)：1, it is still more preferably (4.2-4.8：1).
A concentration of 0.1-1mol/kg of the aluminum sulfate solution, more preferably 0.3-0.9mol/kg, further preferably
0.5-0.8mol/kg；
Preferably, the quality of the aluminum sulfate solution is calculated as 1.0-10.2wt%, more preferably 3-9wt% by aluminium oxide,
Still more preferably it is 5.0-8.0wt%, most preferably 6.5-7.5wt%.
In the present invention, the concentration for adjusting sodium aluminate solution and aluminum sulfate solution can control gained boehmite specific surface
Product and pore volume.
Preferably, the mass ratio of the sodium aluminate solution and the aluminum sulfate solution is calculated as (5-10) by aluminium oxide：10,
More preferably (6-8)：10, it is still more preferably (6.5-8.0)：10；
Preferably, pH 9.1-9.9, more preferably 9.2-9.8.
Preferably, the mass ratio of the sodium aluminate solution, the aluminum sulfate solution and the waterglass by aluminium oxide and
Silica meter can be for (5-10)：10：(0.15-5.0), preferably (6-8)：10：(0.16-4.5), still more preferably for
(7-8)：10：0.17-4.5)；
Preferably, pH 9.1-9.9, more preferably 9.2-9.8.
In the present invention, first sodium aluminate solution is added drop-wise in aluminum sulfate solution under agitation, as bottom liquid；
Then, in step (3), by the way that sodium aluminate solution, aluminum sulfate solution and waterglass are added drop-wise to simultaneously under agitation
In suspension obtained by step (2)；Present inventors discovered unexpectedly that by by sodium aluminate solution, aluminum sulfate solution and
Waterglass cocurrent is fed, the advantage of doing so is that：Obtained product is uniform, and property is stablized, and is suitble to industrial production.
Preparation in accordance with the present invention, wherein, in step (4), the condition of the crystallization is：Crystallization temperature is 50-
140 DEG C, crystallization time 2-48h；
Preferably, crystallization temperature is 80-120 DEG C, crystallization time 2.5-24h.
In invention, the crystallization can carry out in autoclave.
Preparation in accordance with the present invention, wherein, it, will be in step (4) after the completion of reaction, by high pressure in step (5)
Reaction kettle is cooled to room temperature, and then, obtained white depositions are washed with deionized, dry, wherein, the item of the drying
Part can be：Drying temperature is 60-170 DEG C, preferably 90-140 DEG C, more preferably 90-110 DEG C；The equipment of the drying does not have
There is specific restriction, for example, can be baking oven.
In the present invention, in preparation process, by controlling the sodium aluminate solution, the aluminum sulfate solution and described
The mass ratio (based on aluminium oxide and silica content) of waterglass, using pH monitoring as supplementary means, the then centre to obtaining
Product carries out hydro-thermal process, can prepare nano-sheet, and with bigger serface and macropore volume and with specific
The boehmite of most probable pore size.
The third aspect, the present invention provides a kind of siliceous boehmite catalyst prepared by preparation method described above
Carrier.The property that the carrier has is with described above consistent, and details are not described herein.
The present invention will be described in detail by way of examples below.
In following embodiment, specific surface area and pore volume parameter are measured by BET method of testing methods；
Most probable pore size parameter is measured by BJH test methods；
Sodium hydroxide, analysis is pure, purchased from Beijing Chemical Plant；Gibbsite is purchased from the commercially available product of Shanxi Aluminium Plant industry.
Waterglass is purchased from Peking University (sodium oxide molybdena 8.76wt.%, silica 27.42wt.%).
HRTEM is by being purchased from JEOL companies of Jeol Ltd., the scanning high-resolution transmission of model JEM 2100
Electronic Speculum.
Embodiment 1
The present embodiment indicates that siliceous boehmite catalyst carrier prepared by method using the present invention.
(1) aluminum sulfate solution (alumina content 10.2wt.%) of a concentration of 1mol/kg of 10kg is weighed, is fully being stirred
It is added under conditions of mixing in molar ratio Na/Al=4.5 sodium aluminate solutions (alumina content 6.6wt.%), sodium metaaluminate is molten
The mass ratio of liquid and aluminum sulfate solution is calculated as 0.65 by aluminium oxide, and system pH is 9.5, as bottom liquid.
(2) cocurrent charging is carried out for bottom liquid with step (1)：It is molten that sodium aluminate solution, aluminum sulfate are added in into bottom liquid simultaneously
Liquid and waterglass should keep sodium metaaluminate, aluminum sulfate and waterglass mass ratio to be calculated as (by aluminium oxide and silica) in the process
6.5：10：0.19, system pH are 9.5.
(3) obtained slurry is transferred in autoclave, in 110 DEG C of baking oven crystallization 2 hours.
(4) products therefrom filters, 4 hours dry in 140 DEG C after being washed with deionized.
Prepared siliceous boehmite is understood as nano-sheet by the HRTEM electromicroscopic photographs of Fig. 1, silica content is
1.0wt.%, specific surface area 843.6m2/ g, pore volume 3.44cm3/ g, most probable pore size are 20 nanometers.
Embodiment 2
The present embodiment indicates that siliceous boehmite catalyst carrier prepared by method using the present invention.
(1) aluminum sulfate solution (alumina content 10.2wt.%) of a concentration of 0.9mol/kg of 1kg is weighed, is fully being stirred
Molar ratio is added under conditions of mixing as (alumina content 7.14wt.%) and meta-aluminic acid in Na/Al=4.5 sodium aluminate solutions
The mass ratio of sodium solution and aluminum sulfate solution is calculated as 0.70 by aluminium oxide, and system pH is 9.2, as bottom liquid.
(2) cocurrent charging is carried out for bottom liquid with step (1)：It is molten that sodium aluminate solution, aluminum sulfate are added in into bottom liquid simultaneously
Liquid and waterglass should keep sodium metaaluminate, aluminum sulfate and waterglass mass ratio to be calculated as 7 (by aluminium oxide and silica) in the process：
10：1.54, system pH are 9.2.
(3) obtained slurry is transferred in autoclave, in 110 DEG C of baking oven crystallization 2 hours.
(4) products therefrom filters, 4 hours dry in 140 DEG C after being washed with deionized.
As a result silicon boehmite is obtained as nano-sheet, silica content 8.3wt.%, specific surface area 864.6m2/
G, pore volume 3.75cm3/ g, most probable pore size are 25 nanometers.
Embodiment 3
The present embodiment indicates that siliceous boehmite catalyst carrier prepared by method using the present invention.
(1) aluminum sulfate solution (alumina content 5.0wt.%) of a concentration of 0.5mol/kg of 1kg is weighed, is fully being stirred
Molar ratio is added under conditions of mixing as (alumina content 5.0wt.%) in Na/Al=4.5 sodium aluminate solutions, sodium metaaluminate
The mass ratio of solution and aluminum sulfate solution is calculated as 1 by aluminium oxide, and system pH is 9.6, as bottom liquid.
(2) cocurrent charging is carried out for bottom liquid with step (1)：It is molten that sodium aluminate solution, aluminum sulfate are added in into bottom liquid simultaneously
Liquid and waterglass should keep the mass ratio of sodium metaaluminate, aluminum sulfate and waterglass to be calculated as (by aluminium oxide and silica) in the process
10:10:2.5, system pH are 9.6.
(3) obtained slurry is transferred in autoclave, in 110 DEG C of baking oven crystallization 2 hours.
(4) products therefrom filters, 4 hours dry in 140 DEG C after being washed with deionized.
As a result siliceous boehmite is obtained as nano-sheet, wherein, silica content 13.1wt.%, specific surface area is
886.3m2/ g, pore volume 3.41cm3/ g, most probable pore size are 25 nanometers.
Embodiment 4
The present embodiment indicates that siliceous boehmite catalyst carrier prepared by method using the present invention.
(1) aluminum sulfate solution (alumina content 1.0wt.%) of a concentration of 0.3mol/kg of 1kg is weighed, is fully being stirred
Molar ratio is added under conditions of mixing as (alumina content 0.8wt.%) in Na/Al=4.5 sodium aluminate solutions, sodium metaaluminate
The mass ratio of solution and aluminum sulfate solution is calculated as 0.80 by aluminium oxide, and system pH is 9.8, as bottom liquid.
(2) cocurrent charging is carried out for bottom liquid with step (1)：It is molten that sodium aluminate solution, aluminum sulfate are added in into bottom liquid simultaneously
Liquid and waterglass should keep the mass ratio of sodium metaaluminate, aluminum sulfate and waterglass to be calculated as (by aluminium oxide and silica) in the process
8:10:4.0, system pH are 9.8.
(3) obtained slurry is transferred in autoclave, in 110 DEG C of baking oven crystallization 2 hours.
(4) products therefrom filters, 4 hours dry in 140 DEG C after being washed with deionized.
As a result siliceous boehmite is obtained as nano-sheet, silica content 20wt.%, specific surface area 842.2m2/
G, pore volume 2.74cm3/ g, most probable pore size are 16 nanometers.
Embodiment 5
The present embodiment indicates that control sodium metaaluminate concentration can control the pore structure of prepared boehmite.
Catalyst carrier is prepared according to the method for embodiment 1, the difference is that Na/Al=5.0.
As a result siliceous boehmite is obtained as nano-sheet, and silica content 2.0wt.%, specific surface area is
801.4m2/ g, pore volume 3.47cm3/ g, most probable pore size 19nm.
Embodiment 6
The present embodiment indicates that control sulfuric acid aluminum concentration can control the pore structure of prepared boehmite.
Catalyst carrier is prepared according to the method for embodiment 2, the difference is that the concentration of aluminum sulfate is changed to 0.1mol/
kg。
As a result it obtains as nano-sheet, silica content 8.0wt.%, specific surface area 815.9m2/ g, pore volume are
3.75m3/ g, most probable pore size 28nm.
Embodiment 7
The present embodiment indicates that the hole for controlling the ratio of sodium metaaluminate and aluminum sulfate that can control prepared boehmite
Structure.
Catalyst carrier is prepared according to the method for embodiment 3, the difference is that by sodium metaaluminate and the mass ratio of aluminum sulfate
0.5 is calculated as by aluminium oxide.
As a result it obtains as nano-sheet, silica content 13.5wt.%, specific surface area 808.5m2/ g, pore volume are
3.76m3/ g, most probable pore size 24nm.
Comparative example 1
Catalyst carrier is prepared according to the method for embodiment 1, the difference is that Na/Al=6.0.
As a result siliceous boehmite is obtained as nano-sheet, and silica content 0.9wt.%, specific surface area is
752.3m2/ g, pore volume 1.5cm3/ g, most probable pore size 31nm.
Comparative example 2
Catalyst carrier is prepared according to the method for embodiment 1, the difference is that sodium metaaluminate, aluminum sulfate and waterglass matter
Amount is 3 than (based on aluminium oxide and silica)：10：0.1.
As a result siliceous boehmite is obtained as nano-sheet, and silica content 0.5wt.%, specific surface area is
682.3m2/ g, pore volume 1.3cm3/ g, most probable pore size 1.5nm.
Comparative example 3
Catalyst carrier is prepared according to the method for embodiment 1, the difference is that the mixing of sodium metaaluminate and waterglass is molten
Drop is added in aluminum sulfate solution.
As a result prepared siliceous boehmite is fibrous, silica content 0.8wt.%, and fibre diameter is received for 12
Rice.
As a result as can be seen that in preparation process, the present invention is by controlling the sodium aluminate solution, the aluminum sulfate molten
The mass ratio of liquid and the waterglass (based on aluminium oxide and silica content), using pH monitoring as supplementary means, then to obtaining
The intermediate product arrived carries out hydro-thermal process, can prepare nano-sheet, and with bigger serface and macropore volume and tool
There is the specifically siliceous boehmite containing silicone content and most probable pore size.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In the skill of the present invention
In art conception range, a variety of simple variants can be carried out to technical scheme of the present invention, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, belongs to
Protection scope of the present invention.
Claims (10)
1. a kind of siliceous boehmite catalyst carrier, which is characterized in that the siliceous boehmite catalyst carrier is porous material
Material, the porous material be porous silica-alumina material, the porous silica-alumina material nano-sheet, silica content 1-20wt.%,
Specific surface area is 800-1000m2/ g, pore volume 1.7-4.0cm3/ g, most probable pore size 2-30nm.
2. siliceous boehmite catalyst carrier according to claim 1, wherein, the porous silica-alumina material is nanometer sheet
Shape, silica content 2-18wt.%, specific surface area 810-980m2/ g, pore volume 2.5-3.8cm3/ g, most probable pore size
For 5-25nm.
3. siliceous boehmite catalyst carrier according to claim 2, wherein, the porous silica-alumina material is nanometer sheet
Shape, silica content 3-15wt.%, specific surface area 820-950m2/ g, pore volume 3.0-3.7cm3/ g, most probable pore size
For 7-20nm.
4. a kind of preparation method of siliceous boehmite catalyst carrier, which is characterized in that this method includes the following steps：
(1) gibbsite with sodium hydroxide is contacted, obtains sodium aluminate solution；
(2) sodium aluminate solution is added drop-wise in aluminum sulfate solution under agitation；
(3) sodium aluminate solution, aluminum sulfate solution and waterglass are added drop-wise to simultaneously under agitation obtained by step (2) and suspended
In liquid；
(4) by step (3) products therefrom under crystallization condition crystallization；
(5) crystallization product obtained by step (4) is filtered, and filtering obtained solid is washed with deionized, is dried.
5. preparation method according to claim 4, wherein, in step (1), the condition of the contact is：Temperature is
120-160 DEG C, time 8-20h；
Preferably, the molar ratio of the sodium hydroxide and the Na/Al of the gibbsite are (2-5)：1, more preferably (4.1-
4.9)：1, it is still more preferably (4.2-4.8：1).
6. preparation method according to claim 4, wherein, a concentration of 0.1-1mol/kg of the aluminum sulfate solution is more excellent
It is selected as 0.3-0.9mol/kg, further preferably 0.5-0.8wt%；
Preferably, the quality of the aluminum sulfate solution is calculated as 1.0-10.2wt%, more preferably 3.0-9.0wt% by aluminium oxide,
Further preferably 5.0-8.0wt%；
Preferably, the mass ratio of the sodium aluminate solution and the aluminum sulfate solution is calculated as (5-10) by aluminium oxide：10, it is more excellent
It is selected as (6-8)：10, it is still more preferably (6.5-8.0)：10；
Preferably, the pH of system is 9.1-9.9, more preferably 9.2-9.8.
7. preparation method according to claim 6, wherein, the sodium aluminate solution, the aluminum sulfate solution with it is described
The mass ratio of waterglass is calculated as (5-10) by the mass ratio of aluminium oxide and silica：10：(0.15-5.0), more preferably (6-8)：
10：(0.16-4.5) is still more preferably (7-8)：10：(0.17-4.5).
8. preparation method according to claim 4, wherein, in step (4), the condition of the crystallization is：Crystallization temperature
It is 50-140 DEG C, crystallization time 2-48h；
Preferably, crystallization temperature is 80-120 DEG C, crystallization time 2.5-24h.
9. preparation method according to claim 4, wherein, in step (5), the condition of the drying is：Drying temperature
It is 60-170 DEG C, preferably 90-140 DEG C.
10. catalyst carrier prepared by the preparation method in claim 4-9 described in any one.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711274711.8A CN108212134B (en) | 2017-12-06 | 2017-12-06 | Catalyst carrier containing silicon boehmite and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711274711.8A CN108212134B (en) | 2017-12-06 | 2017-12-06 | Catalyst carrier containing silicon boehmite and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108212134A true CN108212134A (en) | 2018-06-29 |
| CN108212134B CN108212134B (en) | 2020-06-05 |
Family
ID=62653305
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711274711.8A Active CN108212134B (en) | 2017-12-06 | 2017-12-06 | Catalyst carrier containing silicon boehmite and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108212134B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115611299A (en) * | 2021-07-15 | 2023-01-17 | 北京化工大学 | Nano fibrous boehmite and preparation method thereof |
| CN117019233A (en) * | 2023-08-10 | 2023-11-10 | 宿迁时代储能科技有限公司 | Preparation method and application of metal-containing nano-sheet porous silica-alumina gel catalyst |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102653409A (en) * | 2011-03-03 | 2012-09-05 | 中国石油天然气股份有限公司 | Preparation method of silicon-containing fibrous boehmite |
| CN104724742A (en) * | 2015-02-16 | 2015-06-24 | 北京化工大学 | Preparation method of silicon-containing boehmite with large specific surface area and large pore volume |
-
2017
- 2017-12-06 CN CN201711274711.8A patent/CN108212134B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102653409A (en) * | 2011-03-03 | 2012-09-05 | 中国石油天然气股份有限公司 | Preparation method of silicon-containing fibrous boehmite |
| CN104724742A (en) * | 2015-02-16 | 2015-06-24 | 北京化工大学 | Preparation method of silicon-containing boehmite with large specific surface area and large pore volume |
Non-Patent Citations (1)
| Title |
|---|
| 孙建川: "大比表面积大孔体积薄水铝石的制备与应用", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115611299A (en) * | 2021-07-15 | 2023-01-17 | 北京化工大学 | Nano fibrous boehmite and preparation method thereof |
| CN115611299B (en) * | 2021-07-15 | 2024-04-23 | 北京化工大学 | Nanofiber-shaped boehmite and preparation method thereof |
| CN117019233A (en) * | 2023-08-10 | 2023-11-10 | 宿迁时代储能科技有限公司 | Preparation method and application of metal-containing nano-sheet porous silica-alumina gel catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108212134B (en) | 2020-06-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101935877A (en) | Method for synthesizing mullite whiskers by normal pressure sintering | |
| CN102711983B (en) | Complex oxide, method for producing same and exhaust gas purifying catalyst | |
| CN104418346B (en) | It is a kind of have in, the Beta molecular sieves of micropore compound pore passage structure and its synthetic method | |
| CN102029192B (en) | Silicon-containing alumina and preparation method thereof | |
| CN105555711B (en) | The method for preparing zeolite SSZ 35 | |
| CN108212134A (en) | Siliceous boehmite catalyst carrier and preparation method thereof | |
| CN102910654B (en) | Preparation method of fibrous boehmite with large specific surface area and large pore area | |
| CN108212224A (en) | Boehmite catalyst carrier and preparation method thereof | |
| CN104692429A (en) | Controllable preparation method of large-specific-area large-pore-volume boehmite | |
| CN109748303A (en) | The preparation method of high pure spherical magnesia alumina spinel nanopowder | |
| CN106517239B (en) | A kind of pillared layered modenite and preparation method thereof | |
| CN102173867B (en) | Method for preparing zirconium iron pink pigment from electrically-melted zirconium oxide | |
| CN101745365A (en) | Preparation method of 13X molecular sieve with high adsorption property | |
| CN100467378C (en) | Prepn process of pseudoboehmite for luminescent material | |
| CN109304226A (en) | A kind of hydrocracking catalyst and its preparation method and application of fecund heavy naphtha and boat coal | |
| US20240018340A1 (en) | Iron-modified acoustic material, production method thereof, speaker and electronic device | |
| CN103058210B (en) | Preparation method of MCM-22 molecular sieve | |
| CN108097293A (en) | The synthetic method of the MFI structure zeolite molecular sieve of tin dope and application | |
| CN105347358B (en) | A kind of preparation method that there is three-dimensional through the zeolite molecular sieve material of mesoporous multi-stage artery structure | |
| CN110395745A (en) | A kind of P-A type molecular sieve and preparation method thereof prepared with self-igniting coal gangue | |
| CN105347377A (en) | Preparation method for high-purity flaky alumina | |
| CN104724742A (en) | Preparation method of silicon-containing boehmite with large specific surface area and large pore volume | |
| CN105314651B (en) | A kind of preparation method of small crystal grain NaY molecular sieve | |
| CN113479898A (en) | Method for preparing amorphous nano dicalcium silicate by hydrothermal method | |
| CN105148929A (en) | Preparation method of high-specific-surface-area mesoporous Ni-La-Si composite oxides |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |