CN107398263A - A kind of pillared layered sial composite oxides and preparation method thereof - Google Patents
A kind of pillared layered sial composite oxides and preparation method thereof Download PDFInfo
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- CN107398263A CN107398263A CN201710855990.0A CN201710855990A CN107398263A CN 107398263 A CN107398263 A CN 107398263A CN 201710855990 A CN201710855990 A CN 201710855990A CN 107398263 A CN107398263 A CN 107398263A
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- 239000002131 composite material Substances 0.000 title claims abstract description 87
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 100
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 50
- 239000011148 porous material Substances 0.000 claims abstract description 17
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 5
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims abstract description 5
- -1 polyoxyethylene groups Polymers 0.000 claims abstract description 5
- XQSBLCWFZRTIEO-UHFFFAOYSA-N hexadecan-1-amine;hydrobromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[NH3+] XQSBLCWFZRTIEO-UHFFFAOYSA-N 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 84
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 34
- 229910052681 coesite Inorganic materials 0.000 claims description 33
- 229910052906 cristobalite Inorganic materials 0.000 claims description 33
- 229910052682 stishovite Inorganic materials 0.000 claims description 33
- 229910052905 tridymite Inorganic materials 0.000 claims description 33
- 238000003756 stirring Methods 0.000 claims description 27
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 235000012239 silicon dioxide Nutrition 0.000 claims description 17
- 239000000499 gel Substances 0.000 claims description 13
- 229910001868 water Inorganic materials 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 238000010792 warming Methods 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 239000004411 aluminium Substances 0.000 claims description 8
- 229910052593 corundum Inorganic materials 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000008279 sol Substances 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 238000005245 sintering Methods 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 230000031709 bromination Effects 0.000 claims 1
- 238000005893 bromination reaction Methods 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- 230000008014 freezing Effects 0.000 claims 1
- 238000007710 freezing Methods 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 12
- 238000009826 distribution Methods 0.000 abstract description 10
- 230000015572 biosynthetic process Effects 0.000 abstract description 9
- 238000003786 synthesis reaction Methods 0.000 abstract description 8
- 239000011229 interlayer Substances 0.000 abstract description 3
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 9
- 238000001354 calcination Methods 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910021417 amorphous silicon Inorganic materials 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 241000446313 Lamella Species 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910021426 porous silicon Inorganic materials 0.000 description 1
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- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
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- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28064—Surface area, e.g. B.E.T specific surface area being in the range 500-1000 m2/g
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- 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
- B01J35/617—500-1000 m2/g
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Abstract
The invention discloses a kind of pillared layered sial composite oxides and preparation method thereof, this method comprises the following steps：Stratiform sial composite oxides are synthesized by structure directing agent of cetyl polyoxyethylene groups cetyl ammonium bromide, then silica " post " presoma tetraethyl orthosilicate is introduced into sial composite oxides interlayer, pillared layered sial composite oxides is obtained after hydrolyzing, dry, be calcined.The pillared layered sial composite oxides have the characteristics of micro- mesoporous hierarchical porous structure, pore size distribution are narrower and specific surface area is big, and this method has the advantages that technique is simple, synthesis condition is gentle, synthesis cycle is short.
Description
Technical field
The invention belongs to inorganic porous material preparation field, and in particular to a kind of pillared layered sial composite oxides and its
Preparation method.
Background technology
The catalyst important as petrochemical industry or catalyst carrier, porous silicon aluminium composite oxide are widely used in being catalyzed
The courses of reaction such as cracking, alkylation and isomerization.But due to the aperture of amorphous silicon aluminium composite oxides is smaller and distribution compared with
Width, the shortcomings of aperture control is difficult, and duct does not connect be present.Meanwhile the development that becomes more meticulous of petrochemical industry is to sial combined oxidation
The structure of thing catalyst proposes new requirement, it is necessary to which sial composite oxides have high surface area and pore volume and narrower
Pore-size distribution.
Patent CN 105056928A disclose a kind of side that controllable hole structure sial composite oxides are prepared by hydro-thermal reaction
Method.Silicon source and silicon source are mainly subjected to neutralization plastic at ambient pressure, 100~200 DEG C of high pressure water heating kettle is then transferred to and enters water-filling
Thermal response, by controlling hydrothermal temperature and time, realize aperture and the distribution of final sial composite oxides.Although the party
Method can obtain a series of different pore sizes (5-20nm) and the sial composite oxides of specific surface area, but need in high temperature hydro-thermal
Under the conditions of carry out, method is relatively complicated, and energy consumption is higher.The B of patent CN 103769070 disclose one kind and use polymer
The method that microballoon colloid crystal templating prepares the ordered big hole sial composite oxides that hole wall is thicker, specific surface area is higher, but its
Specific surface area is relatively small, only 150-250m2/g；Aperture is larger, in 100-600nm scopes, and preparation process be related to it is poly-
The brilliant preparation of compound microballoon glue, process are more complicated.
The pillared of stratified material can form new meso-hole structure between stratified material lamella, so as to obtain pore-size distribution
Concentrate, specific surface area is big and porous material with high thermal stability.But not pillared layered sial composite oxides
Open report.
The content of the invention
It is an object of the invention to solve the above problems, and supply a kind of pillared layered sial composite oxides；It is prepared
Pillared layered sial composite oxides there is big, Stability Analysis of Structures of micro- mesoporous hierarchical porous structure, pore distribution concentration, specific surface area etc.
Advantage.Meanwhile this method has the advantages that technique is simple, synthesis condition is gentle, synthesis cycle is short.
Technical scheme provided by the invention is：
Stratiform sial combined oxidation is made in a kind of preparation method of pillared layered sial composite oxides, including following raw material
Thing presoma：Alumina sol, sodium hydroxide, silicon dioxide gel, CPAB, then add column-supporting agent tetraethyl orthosilicate and be made pillared
Stratiform sial composite oxides intermediate, finally it is sintered to obtain the pillared layered sial composite oxides.
Preferably, following steps are specifically included：
(1) according to mol ratio SiO2∶Al2O3=30-200, NaOH: SiO2=0.1-0.4, CPAB: SiO2=0.05-0.2,
H2O∶SiO2=40-60, raw alumina colloidal sol, sodium hydroxide, silicon dioxide gel, CPAB and deionized water are weighed, wherein
CPAB is cetyl polyoxyethylene groups cetyl ammonium bromide；
(2) sodium hydroxide is dissolved in deionized water and is configured to solution, to sodium hydrate aqueous solution under stirring
Middle addition alumina sol, 20-40 minutes are stirred, silicon dioxide gel is added dropwise, 20-60 minutes are stirred under normal temperature condition；
(3) CPAB of respective amount, 40-60 DEG C of condition is added dropwise into mixed liquor obtained by step (2) under stirring
Lower stirring reaction 20-240 minutes, after reaction terminates, reaction solution is centrifuged, is washed to neutrality, is dried to obtain stratiform sial
Composite oxides；
(4) the dried stratiform sial composite oxides of step (3) are mixed for 1: 5 in mass ratio with tetraethyl orthosilicate
It is even, in a nitrogen atmosphere, 30-90 DEG C of stirring 3-8 hour, centrifuge, be dried to obtain in pillared layered sial composite oxides
Mesosome；
(5) the dried pillared layered sial composite oxides intermediate of step (4) is placed in sintering furnace and be warming up to
400-600 DEG C, 5-8 hours are calcined, obtain pillared layered sial composite oxides.
Preferably, step (1) is according to mol ratio SiO2∶Al2O3=100, NaOH: SiO2=0.32, CPAB: SiO2=
0.12、H2O∶SiO2=45, raw alumina colloidal sol, sodium hydroxide, silicon dioxide gel, CPAB and deionized water are weighed, wherein
CPAB is cetyl polyoxyethylene groups cetyl ammonium bromide.
Preferably, in step (3), stirring reaction 60 minutes under the conditions of 50 DEG C.
Preferably, in step 5, sintering furnace is warming up to 550 DEG C with 2 DEG C/min of heating rate.
Pillared layered sial composite oxides made from the preparation method of the invention also provided described in a kind of use.
Preferably, the pillared layered sial composite oxides：Interlamellar spacing 2.9-3.3nm, specific surface area 500-
600m2/ g, average pore size 2.1-2.5nm.
Beneficial effects of the present invention are as follows：
Firstth, the raw material that the present invention uses is cheap and easy to get, and cost of material is low, building-up process green non-pollution, synthesis step
Few, technique is simple, easy to operate, and synthesis condition is gentle, and synthesis cycle is shorter, is suitable for any large-scale production, significantly reduced life
Cost is produced, there are significant market prospects；
Secondth, pillared layered sial composite oxides stratiform sial composite oxides compared with the prior art are made in the present invention,
Stable SiO is formd between laminate2" post ", there is the pillared layered sial composite oxides knot that " post " structure causes the present invention
Structure is stable, and pillared layered sial composite oxides interlayer forms new pore structure, the ratio surface of pillared sial composite oxides
Product, pore volume are dramatically increased, and pore-size distribution is more concentrated so that pillared sial composite oxides of the invention as catalyst or are urged
Agent carrier is stablized in use, and dosage is few, and adsorptivity significantly increases, and is advantageous to reaction and carries out.
Brief description of the drawings
Fig. 1：The XRD spectrum of stratiform sial composite oxides presoma prepared by embodiment 1.
Fig. 2：Sial composite oxides and embodiment 1 prepared by comparative example 1 prepare pillared layered sial composite oxides
XRD spectrum.
Fig. 3：It is compound that sial composite oxides roasting direct and embodiment 1 prepared by comparative example 1 prepares pillared layered sial
The N2- Adsorption and desorption isotherms figures of oxide.
Fig. 4：Sial composite oxides and embodiment 1 prepared by comparative example 1 prepare pillared layered sial composite oxides hole
Footpath distribution map.
Embodiment
With reference to specific embodiment, the present invention is described in further detail, to make those skilled in the art's reference say
Bright book word can be implemented according to this.
Embodiment 1
1st, according to mol ratio SiO2/Al2O3=50, NaOH/SiO2=0.28, H2O/SiO2=45, CPAB/SiO2=
0.09, weigh raw alumina colloidal sol 0.65g, sodium hydroxide 0.31g, silicon dioxide gel 4.81g, CPAB 4.64g, go from
Sub- water 21.63mL,
2nd, 0.31g sodium hydroxides are dissolved in 21.63mL deionized waters and are configured to sodium hydrate aqueous solution, in stirring shape
0.65g alumina sols are added under state into the sodium hydrate aqueous solution prepared, stirs 30 minutes, 4.81g is then added dropwise
Silicon dioxide gel, stir 1 hour under the conditions of 35 DEG C；
3rd, 4.64g CPAB, until completely dissolved, 50 is added dropwise into mixed liquor obtained by step (2) under stirring
Stirring reaction 60 minutes under the conditions of DEG C, after reaction terminates, reaction solution is poured into centrifuge tube and centrifuged, be washed to neutrality, 60
DEG C dry 48 hours, obtain stratiform sial composite oxides presoma；
4th, the dried stratiform sial composite oxides of step (3) are mixed for 1: 5 in mass ratio with tetraethyl orthosilicate
Even, in air atmosphere, 35 DEG C are stirred 6 hours, are centrifuged, drying at room temperature 48 hours, are obtained pillared layered sial composite oxygen
Compound intermediate,
5th, the intermediate is placed in Muffle furnace and is warming up to 550 DEG C with 2 DEG C/min of heating rate, constant temperature calcining 6 is small
When, obtain pillared layered sial composite oxides.
Embodiment 2
1st, according to mol ratio SiO2/Al2O3=30, NaOH/SiO2=0.4, H2O/SiO2=40, CPAB/SiO2=0.1,
Weigh raw alumina colloidal sol 0.96g, sodium hydroxide 0.47g, silicon dioxide gel 4.27g, CPAB 5.49g, deionized water
20.46mL。
2nd, 0.47g sodium hydroxides are dissolved in 20.46mL deionized waters and are configured to sodium hydrate aqueous solution, in stirring shape
0.96g alumina sols are added under state into the sodium hydrate aqueous solution prepared, after aluminium to be oxidized is completely dissolved, are added dropwise
4.27g silicon dioxide gels, stir under normal temperature condition 30 minutes and above-mentioned mixed liquor is completely dissolved；
3rd, 5.49g CPAB, until completely dissolved, 50 is added dropwise into mixed liquor obtained by step (2) under stirring
Stirring reaction 60 minutes under the conditions of DEG C, after reaction terminates, reaction solution is poured into centrifuge tube and centrifuged, be washed to neutrality, 60
DEG C dry 48 hours, obtain stratiform sial composite oxides presoma；
4th, it is 1: 5 in mass ratio by the dried stratiform sial composite oxides presoma of step (3) and tetraethyl orthosilicate
Well mixed, in air atmosphere, 35 DEG C are stirred 5 hours, are centrifuged, drying at room temperature 48 hours, are obtained pillared layered sial
Composite oxides intermediate；
5th, the intermediate is placed in Muffle furnace and is warming up to 550 DEG C with 2 DEG C/min of heating rate, constant temperature calcining 6 is small
When, obtain pillared layered sial composite oxides.
Embodiment 3
1st, according to mol ratio SiO2/Al2O3=100, NaOH/SiO2=0.32, H2O/SiO2=45, CPAB/SiO2=
0.12, weigh raw alumina colloidal sol 0.26g, sodium hydroxide 0.34g, silicon dioxide gel 3.79g, CPAB 5.85g, go from
Sub- water 20.43mL.
2nd, 0.34g sodium hydroxides are dissolved in 20.43mL deionized waters and are configured to sodium hydrate aqueous solution, in stirring shape
0.26g alumina sols are added under state into the sodium hydrate aqueous solution prepared, after aluminium to be oxidized is completely dissolved, are added dropwise
3.79g silicon dioxide gels, stir under normal temperature condition 30 minutes and above-mentioned mixed liquor is completely dissolved；
3rd, 5.85g CPAB, until completely dissolved, 50 is added dropwise into mixed liquor obtained by step (2) under stirring
Stirring reaction 60 minutes under the conditions of DEG C, after reaction terminates, reaction solution is poured into centrifuge tube and centrifuged, be washed to neutrality, 60
DEG C dry 48 hours, obtain stratiform sial composite oxides presoma；
4th, it is 1: 5 in mass ratio by the dried stratiform sial composite oxides presoma of step (3) and tetraethyl orthosilicate
Well mixed, in air atmosphere, 35 DEG C are stirred 6 hours, are centrifuged, drying at room temperature 48 hours, are obtained pillared layered sial
Composite oxides intermediate,
5th, the intermediate is placed in Muffle furnace and is warming up to 550 DEG C with 2 DEG C/min of heating rate, constant temperature calcining 6 is small
When, obtain pillared layered sial composite oxides.
Embodiment 4
1st, according to mol ratio SiO2/Al2O3=200, NaOH/SiO2=0.2, H2O/SiO2=45, CPAB/SiO2=
0.18, weigh raw alumina colloidal sol 0.12g, sodium hydroxide 0.19g, silicon dioxide gel 3.41g, CPAB 7.90g, go from
Sub- water 18.39mL；
2nd, 0.19g sodium hydroxides are dissolved in 18.39mL deionized waters and are configured to sodium hydrate aqueous solution, in stirring shape
0.12g alumina sols are added under state into the sodium hydrate aqueous solution prepared, after aluminium to be oxidized is completely dissolved, are added dropwise
3.41g silicon dioxide gels, stir under normal temperature condition 30 minutes and above-mentioned mixed liquor is completely dissolved；
3rd, 7.90g CPAB, until completely dissolved, 50 is added dropwise into mixed liquor obtained by step (2) under stirring
Stirring reaction 60 minutes under the conditions of DEG C, after reaction terminates, reaction solution is poured into centrifuge tube and centrifuged, be washed to neutrality, 60
DEG C dry 48 hours, obtain stratiform sial composite oxides presoma；
4th, it is 1: 5 in mass ratio by the dried stratiform sial composite oxides presoma of step (3) and tetraethyl orthosilicate
Well mixed, in air atmosphere, 35 DEG C are stirred 6 hours, are centrifuged, drying at room temperature 48 hours, are obtained pillared layered sial
Composite oxides intermediate；
5th, the intermediate is placed in Muffle furnace and is warming up to 550 DEG C with 2 DEG C/min of heating rate, constant temperature calcining 6 is small
When, obtain pillared layered sial composite oxides.
Comparative example 1
The stratiform sial composite oxides presoma that embodiment 1 is prepared, by stratiform sial composite oxides presoma
It is placed in Muffle furnace and is warming up to 550 DEG C with 2 DEG C/min of heating rate, constant temperature calcining 6 hours, obtains sial composite oxides.
Test result：
Embodiment 1 is made stratiform sial composite oxides presoma, pillared layered sial composite oxides and comparative example 1 and made
Stratiform sial composite oxides be respectively adopted D8Advance types x-ray diffractometer (by German Brooker company produce),
BelSorp-Max types physical adsorption appearance (being produced by Japanese Bayer AG) is characterized, and as a result sees Fig. 1 and Fig. 2.Fig. 1 is implementation
The XRD spectrum of stratiform sial composite oxides presoma prepared by example 1, from Fig. 1 XRD characterization results, it is apparent that reality
There is the feature diffraction for corresponding respectively to 001 crystal face, 002 crystal face in the synthesis stratiform sial composite oxides presoma for applying example 1
Peak, show the formation of layer structure；Fig. 2 is that sial composite oxides prepared by comparative example 1 and embodiment 1 prepare pillared layered silicon
The XRD spectrum of aluminium composite oxide, from Fig. 2：The XRD spectrum of stratiform sial composite oxides can be seen that made from comparative example 1
001st, 002 characteristic diffraction peak disappears, and layer structure collapses, and forms the amorphous silicon aluminium composite oxides of disordered structure；And implement
Pillared layered sial composite oxides XRD has been effectively maintained 001 characteristic diffraction peak made from example 1, illustrates the shape between laminate
Into stable SiO2" post ", so as to form constitutionally stable pillared layered sial composite oxides.Can from Fig. 3, Fig. 4 and table 1
To find out, the aperture of sial composite oxides made from comparative example 1 is 1.6nm, and its total pore volume is 0.24cm3/ g, and pillared layer
Shape sial composite oxides interlayer forms new pore structure, and its aperture integrated distribution increases in 1.9nm or so, pore volume
0.33em3/g；Secondly, specific surface area dramatically increases, and increases to 589m by 3392/g.In summary, pillared sial composite oxides
Specific surface area, pore volume dramatically increase, pore-size distribution is more concentrated.
The pore property of 1 different samples of table
| Sample name | Specific surface area (m2/g) | Pore volume (cm3/g) | Average pore size (nm) |
| Comparative example 1 | 339 | 0.24 | 2.7 |
| Embodiment 1 | 589 | 0.33 | 2.2 |
| Embodiment 2 | 532 | 0.31 | 2.3 |
| Embodiment 3 | 595 | 0.35 | 2.2 |
| Embodiment 4 | 575 | 0.32 | 2.2 |
Although embodiment of the present invention is disclosed as above, it is not restricted in specification and embodiment listed
With it can be applied to various suitable the field of the invention completely, can be easily for those skilled in the art
Other modification is realized, therefore under the universal limited without departing substantially from claim and equivalency range, it is of the invention and unlimited
In specific details and shown here as the embodiment with description.
Claims (7)
1. a kind of preparation method of pillared layered sial composite oxides, it is characterised in that stratiform silicon is made including following raw material
Aluminium composite oxide presoma：Alumina sol, sodium hydroxide, silicon dioxide gel, CPAB, then add the positive silicic acid second of column-supporting agent
Pillared layered sial composite oxides intermediate is made in ester, is finally sintered to obtain the pillared layered sial combined oxidation
Thing.
2. the preparation method of pillared layered sial composite oxides as claimed in claim 1, it is characterised in that specifically include with
Lower step：
(1) according to mol ratio SiO2∶Al2O3=30-200, NaOH: SiO2=0.1-0.4, CPAB: SiO2=0.05-0.2, H2O∶
SiO2=40-60, weigh raw alumina colloidal sol, sodium hydroxide, silicon dioxide gel, CPAB and deionized water, wherein CPAB
For cetyl polyoxyethylene groups cetyl ammonium bromide；
(2) sodium hydroxide is dissolved in deionized water and is configured to solution, added under stirring into sodium hydrate aqueous solution
Enter alumina sol, stir 20-40 minutes, silicon dioxide gel is added dropwise, 20-60 minutes are stirred under normal temperature condition；
(3) CPAB of respective amount is added dropwise into mixed liquor obtained by step (2) under stirring, is stirred under the conditions of 40-60 DEG C
Mix reaction 20-240 minutes, after reaction terminates, reaction solution is centrifuged, is washed to neutrality, it is compound to be dried to obtain stratiform sial
Oxide；
(4) the dried stratiform sial composite oxides of step (3) are well mixed for 1: 5 in mass ratio with tetraethyl orthosilicate,
In a nitrogen atmosphere, 30-90 DEG C of stirring 3-8 hour, centrifuge, be dried to obtain among pillared layered sial composite oxides
Body；
(5) the dried pillared layered sial composite oxides intermediate of step (4) is placed in sintering furnace and is warming up to 400-600
DEG C, 5-8 hours are calcined, obtain pillared layered sial composite oxides.
3. the preparation method of pillared layered sial composite oxides as claimed in claim 2, it is characterised in that step (1) is pressed
According to mol ratio SiO2∶Al2O3=100, NaOH: SiO2=0.32, CPAB: SiO2=0.12, H2O∶SiO2=45, weigh feed oxygen
It is cetyl polyoxyethylene groups ten to change Alumina gel, sodium hydroxide, silicon dioxide gel, CPAB and deionized water, wherein CPAB
Six alkyl bromination ammoniums.
4. the preparation method of pillared layered sial composite oxides as claimed in claim 2, it is characterised in that in step (3)
In, stirring reaction 60 minutes under the conditions of 50 DEG C.
5. the preparation method of pillared layered sial composite oxides as claimed in claim 2, it is characterised in that in step 5, burn
Freezing of a furnace is warming up to 550 DEG C with 2 DEG C/min of heating rate.
6. pillared layered sial composite oxides made from the preparation method as described in any in a kind of 1-5 such as claim.
7. pillared layered sial composite oxides made from preparation method as claimed in claim 6, it is characterised in that the post
Support stratiform sial composite oxides：Interlamellar spacing 2.9-3.3nm, specific surface area 500-600m2/ g, average pore size 2.1-2.5nm.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109248679A (en) * | 2018-09-11 | 2019-01-22 | 上海化工研究院有限公司 | A kind of VOCs room temperature degradation effective catalyst and its preparation and application |
| CN117343657A (en) * | 2023-11-13 | 2024-01-05 | 常州百佳年代薄膜科技股份有限公司 | High-permeability anti-corrosion photovoltaic packaging adhesive film and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103145163A (en) * | 2013-03-15 | 2013-06-12 | 河南工业大学 | Method for preparing aluminum-silicon composite oxide with mesoporous hollow microsphere structure |
| CN106517234A (en) * | 2016-11-07 | 2017-03-22 | 西北大学 | Dynamic hydrothermal synthesis method of exfoliated type MWW lamellar molecular sieve |
| CN106517239A (en) * | 2016-11-07 | 2017-03-22 | 西北大学 | Pillared layered mordenite, and preparation method thereof |
-
2017
- 2017-09-20 CN CN201710855990.0A patent/CN107398263A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103145163A (en) * | 2013-03-15 | 2013-06-12 | 河南工业大学 | Method for preparing aluminum-silicon composite oxide with mesoporous hollow microsphere structure |
| CN106517234A (en) * | 2016-11-07 | 2017-03-22 | 西北大学 | Dynamic hydrothermal synthesis method of exfoliated type MWW lamellar molecular sieve |
| CN106517239A (en) * | 2016-11-07 | 2017-03-22 | 西北大学 | Pillared layered mordenite, and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| JAN-OLAF BARTH等: "Control of Acid-Base Properties of New Nanocomposite", 《CHEM. MATER.》 * |
| R.皮尔斯等: "《催化及化学过程》", 30 November 1989 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109248679A (en) * | 2018-09-11 | 2019-01-22 | 上海化工研究院有限公司 | A kind of VOCs room temperature degradation effective catalyst and its preparation and application |
| CN109248679B (en) * | 2018-09-11 | 2021-04-02 | 上海化工研究院有限公司 | VOCs normal-temperature degradation efficient catalyst and preparation and application thereof |
| CN117343657A (en) * | 2023-11-13 | 2024-01-05 | 常州百佳年代薄膜科技股份有限公司 | High-permeability anti-corrosion photovoltaic packaging adhesive film and preparation method thereof |
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Inventor after: Huang Guiqiu Inventor after: Hao Qingqing Inventor after: Shi Haixin Inventor after: Zhang Haiyan Inventor before: Hao Qingqing Inventor before: Huang Guiqiu Inventor before: Shi Haixin Inventor before: Zhang Haiyan |
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Application publication date: 20171128 |