CN104402020A - Micro-mesoporous beta molecular sieve and preparation method and application thereof - Google Patents
Micro-mesoporous beta molecular sieve and preparation method and application thereof Download PDFInfo
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- CN104402020A CN104402020A CN201410386943.2A CN201410386943A CN104402020A CN 104402020 A CN104402020 A CN 104402020A CN 201410386943 A CN201410386943 A CN 201410386943A CN 104402020 A CN104402020 A CN 104402020A
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Abstract
The invention belongs to the field of inorganic materials and discloses a micro-mesoporous beta molecular sieve and its preparation method and application. According to the method, sodium metaaluminate is used as the optimum aluminium source, ethyl orthosilicate is used as the optimum silicon source, and a 8-amino Bola-type quaternary ammonium surfactant with different carbon chain lengths is used as a template. A beta hierarchical zeolite molecular sieve which simultaneously has mesoporous and microporous structures is prepared by a hydrothermal method under the alkaline condition. By using the 8-amino Bola-type quaternary ammonium surfactant as a structure-directing agent of the beta molecular sieve, the microporous structure is generated; and by aggregation of hydrophobic long chain end radicals of the template, micelle is generated such that the mesoporous structure of the molecular sieve is formed. The prepared hierarchical molecular sieve has mesoporous and crystalline microporous structures. According to the molecular sieve with the microporous structure and the mesoporous structure, defects caused by a single pore structure can be avoided. The prepared molecular sieve can better adapt to reactions of molecules of different sizes and also can better be applied in fields of adsorption separation and the like.
Description
Technical field
The invention belongs to field of inorganic materials, particularly micro-diplopore beta molecular sieve and its preparation method and application in one.
Background technology
Beta molecular sieve is that a kind of due to its high specific surface area, aperture is adjustable, high thermostability and chemical stability, strong acidity, and is widely used in the fields such as fractionation by adsorption, ion-exchange, catalysis.But be generally present in its duct or basket structure due to acid sites, be subject to the restriction of micropore canals size (<1nm), make it there is huge resistance to mass transfer relating in macromolecular catalyzed reaction, its catalytic performance is declined.This resistance to mass transfer problem can be overcome by the thickness reducing molecular sieve crystal, the particle diameter reducing molecular sieve can make its evolving path reduce, improve rate of diffusion, and well improve the specific surface area of molecular sieve, outer surface acidity, surfactivity, thus its catalytic activity is strengthened.The method of solution diffusional limitation conventional at present has: prepare the molecular sieve of larger aperture, prepare nano particle molecular sieve, prepare lamella molecular sieve etc.The shortcomings such as it is wayward that nano particle molecular sieve exists particle diameter, difficult separation; The synthesis of lamella molecular sieve is comparatively complicated; Therefore there is strong catalysis novel micro-mesoporous molecular sieve that is acid and high effective diffusion coefficient and become a recent studies on focus.
Therefore, in order to solve diffusional limitation problem, multi-stage porous molecular sieve, the especially preparation of micro-mesoporous molecular sieve, become the study hotspot in molecular sieve art.What prepare that micro-mesoporous molecular sieve adopts at first is the method for aftertreatment dealuminzation, desiliconization.Groen [P é rez ?Ram í rez J, Abello S, Bonilla A, et al.Tailored mesoporosity development in zeolite crystals by partial detemplation and desilication [J] .Advanced Functional Materials, 2009,19 (1): 164-172.] etc. by the change of roasting condition, remove the segment template agent in Beta molecular sieve, then desiliconization under alkaline alkaline condition, finally obtains the Beta molecular sieve with grade pore structure.Although dealuminzation, desiliconization method effectively can introduce central hole structure in micro porous molecular sieve, removing of silicon or aluminium, easily causes the reduction of degree of crystallinity and the destruction of skeleton structure.Nanoclusters self-assembly a kind ofly in micro porous molecular sieve, introduces the mesoporous method preparing micro-mesoporous molecular sieve.Yan Zhu [Zhu Y, Hua Z, Zhou J, et al.Hierarchical Mesoporous Zeolites:Direct Self ?Assembly Synthesis in a Conventional Surfactant Solution by Kinetic Control over the Zeolite Seed Formation [J] .Chemistry-A European Journal, 2011,17 (51): 14618-14627.] the sub-nanocrystal of ZSM-5 molecular sieve etc. is formed by aging positive silane second fat, aluminum isopropylate, tetramethyl-ammonium mixing solutions.Again the solution being full of nanocrystal is mixed with cetyl trimethylammonium bromide (CTAB) template, the mesoporous ZSM-5 molecular sieve of Hydrothermal Synthesis in ethanol/water solution.The method is different from traditional soft template method, and the synthesis of nanometer seed is particularly crucial.But the method does not finally have the molecular sieve of synthetic crystallization, is only the assembling that zeolite nanocrystal carries out according to template micella.Jian Zhou [Zhou J, Hua Z, Liu Z, et al.Direct synthetic strategy of mesoporous ZSM-5zeolites by using conventional block copolymer templates and the improved catalytic properties [J] .ACS Catalysis, 2011,1 (4): 287-291] etc. people uses F127 common on the market, and this based block copolymer of P123 directly synthesizes mesopore type ZSM 5 molecular sieve as mesopore soft template.Wookdong Kim [Kim W, Kim J-C, Kim J, Seo Y, Ryoo R.External Surface Catalytic Sites of Surfactant-Tailored Nanomorphic Zeolites for Benzene Isopropylation to Cumene [J] .ACS Catalysis.2013,3 (2): 192-5.] etc. people is by hydrothermal synthesis method, uses quaternary ammonium salt C
22h
45-N
+(CH
3)
2-C
6h
12-N
+(CH
3)
2-CH
2-(C
6h
4)-CH
2-N
+(CH
3)
2-C
6h
12-N
+(CH
3)
2-CH
2-(C
6h
4)-CH
2-N
+(CH
3)
2-C
6h
12-N
+(CH
3)
2-C
22h
45(Br
-)
2(Cl
-)
4tensio-active agent is as structure directing agent, and under the condition of different ratio, synthesize nanoparticle structure BEA, MTW and MRE molecular sieve, this molecular sieve has micropore and meso-hole structure simultaneously.
Summary of the invention
In order to solve the shortcoming and defect part of prior art, primary and foremost purpose of the present invention be to provide a kind of in the preparation method of micro-diplopore beta molecular sieve.
Another object of the present invention is to provide a kind of prepared by aforesaid method in micro-diplopore beta molecular sieve.
Another object of the present invention be to provide a kind of above-mentioned in the application of micro-diplopore beta molecular sieve.
The object of the invention is achieved through the following technical solutions:
In the preparation method of micro-diplopore beta molecular sieve, this preparation method comprises following operation steps:
(1) under 60 ~ 65 DEG C of conditions, stir 1 ~ 2h after 0.2 ~ 0.4mmol sodium metaaluminate, 2 ~ 3mmol sodium hydroxide, 0.4 ~ 0.6mmol eight ammonium head Bola type tensio-active agent and 400 ~ 500mmol deionized water being mixed, obtain mixing solutions;
(2) step (1) gained mixing solutions is cooled to room temperature under agitation, 7 ~ 8mmol tetraethoxy is dripped under the stirring velocity of 50 ~ 60rpm/s, at room temperature aging 3 ~ 5min, then continue to stir 12h at 60 ~ 65 DEG C, obtain gelating soln;
(3) by step (2) gained gelating soln crystallization 7d in 140 ~ 150 DEG C of homogeneous reactors, after crystallization, product be cooled to room temperature suction filtration and use deionized water wash, vacuum-drying, then 550 ~ 600 DEG C of roasting 6 ~ 10h in retort furnace, micro-diplopore Beta molecular sieve in obtaining.
The structural formula of the described eight ammonium head Bola type tensio-active agents of step (1) is: [CH
3(CH
2)
5(CH
3)
2n
+(CH
2)
6(CH
3)
2n
+cH
2(p-C
6h
4) CH
2n
+(CH
3)
2(CH
2)
6n
+(CH
3)
2(CH
2)
noC
6h
4c
6h
4o (CH
2)
nn
+(CH
3)
2(CH
2)
6n
+(CH
3)
2cH
2(p-C
6h
4) CH
2n
+(CH
3)
2(CH
2)
6n
+(CH
3)
2(CH
2)
5cH
3] [Br
-]
4[Cl
-]
4, wherein n is 6,10 or 12.
The dropping temperature of step (2) described tetraethoxy is 25 ~ 35 DEG C.
Step (3) described vacuum-drying be under 120 DEG C of conditions time of drying 12h.
A kind of prepared by above-mentioned preparation method in micro-diplopore beta molecular sieve.
The application of micro-diplopore beta molecular sieve in the aldol reaction of catalysis ethylene glycol and formaldehyde in above-mentioned.
The a series of eight ammonium head Bola type tensio-active agents of design and synthesis of the present invention are as template, and preparation had not only had meso-hole structure but also had the micro-mesoporous molecular sieve of crystal form beta type micropore.By changing the length of hydrophobic carbochain, reach the object of modulation mesoporous pore size size, thus synthesize the micro-mesoporous molecular sieve that better can be applied to the field such as catalyzed reaction, fractionation by adsorption.
Compared with prior art, the present invention has following beneficial effect:
(1) the present invention utilizes eight ammonium head Bola type tensio-active agents to be template, and the ammonium head in tensio-active agent plays structure-directing effect, forms beta microvoid structure; Then there is Supramolecular self assembly and form micella in hydrophobic chain, forms meso-hole structure, thus the multi-stage porous molecular sieve of beta of micro-diplopore in being formed;
(2) the present invention is with sodium hydroxide, sodium metaaluminate and tetraethoxy for raw material, adopts hydrothermal synthesis method, and technique is simple, and cost is low;
(3) the present invention's micro-diplopore beta molecular sieve in preparing, introduces central hole structure, greatly reduces resistance to mass transfer, improve mass-transfer efficiency in beta molecular sieve; Not only there is central hole structure but also have crystalline microporous, can be good at avoiding, due to single the caused defect in duct, having wide practical use in the field such as bulky molecular catalysis and fractionation by adsorption.
Figure of description
Fig. 1 is the X-ray diffractogram of micro-diplopore beta molecular sieve in prepared by the embodiment of the present invention 1.
Fig. 2 is the N of micro-diplopore beta molecular sieve in prepared by the embodiment of the present invention 1
2adsorption-desorption isothermal figure.
Fig. 3 is the stereoscan photograph figure of micro-diplopore beta molecular sieve in prepared by embodiment 1, and wherein a is amplification 1 × 10
4stereoscan photograph figure doubly, b is amplification 4 × 10
4stereoscan photograph figure doubly.
Fig. 4 is the transmission electron microscope sheet figure of micro-diplopore beta molecular sieve in prepared by embodiment 1.
Fig. 5 is the beta zeolite molecular sieve pore size distribution curve figure of hierarchical porous structure prepared by the embodiment 1 calculated according to BJH model.
embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Eight ammonium head Bola type tensio-active agents of the present invention are at document [Shen, S.; Garcia-Bennett, A.E.; Liu, Z.; Lu, Q.; Shi, Y.; Yan, Y.; Yu, C.; Liu, W.; Cai, Y.; Terasaki, O.; Zhao, D.:Three-dimensional low symmetry mesoporous silica structures templated from tetra-headgroup rigid bolaform quaternary ammonium surfactant.Journal of the American Chemical Society 2005,127,6780-7.] [Chen, Q.; Sakamoto, Y.; Terasaki, O.; Che, S.:Synthesis of silica mesoporous crystals with controlled structure and morphology using gemini surfactant.Microporous and Mesoporous Materials2007,105,24-33.] basis on design and synthesis, below with C
6-
6-ph-
6-
10-OBr
4cl
4for example, concrete steps are as follows:
(1) first by 1g4,4 ˊ-bigeminy phenol (5.38mmol) and 8.1g (27mmol) 1,10-Dibromododecane [Br (CH
2)
10br] be dissolved in containing 0.64g potassium hydroxide 40ml hot ethanol, 80 DEG C of backflow 20h under nitrogen protection; Filtered while hot, by solid sample with diethyl ether solution repetitive scrubbing repeatedly, 50 DEG C of vacuum-drying 10h, namely obtain purer intermediate product 1, solid is denoted as: Br (CH
2)
10– O-(p-C
6h
4)
2-O-(CH
2)
10br;
(2) by 2g Br (CH
2)
10-O-(p-C
6h
4)
2-O-(CH
2)
10br and 11g N, N, N ', it is in the acetonitrile of 1:1 and the mixing solutions of toluene that N '-tetramethyl--1,6-hexanediamine is dissolved in 100ml volume ratio, (N at 75 DEG C
2protection) reflux 10h; Product is added ether sedimentation to separate out and be placed in ice-water bath and cool, filter and use washed with diethylether, being placed on dry 10h in the vacuum drying oven of 50 DEG C after filtration, can obtain purer intermediate product 2, solid is denoted as: [N (CH
3)
2-C
6h
12-N
+(CH
3)
2-(CH
2)
10-O-(p-C
6h
4)
2-O-(CH
2)
10-N
+(CH
3)
2-C
6h
12-N (CH
3)
2] [Br
-]
2;
(3) by 0.976g [N (CH
3)
2-C
6h
12-N
+(CH
3)
2-(CH
2)
10-O-(p-C
6h
4)
2-O-(CH
2)
10-N
+(CH
3)
2-C
6h
12-N (CH
3)
2] [Br
-]
2be dissolved in 60mL toluene/acetonitrile (v/v=1:1) mixed solution with the chloro-p-Xylol of 17.5g α, α '-two, under nitrogen protection, under 75 DEG C of conditions, stir 10h.Product is added ether chromatography to be placed in ice-water bath and to cool, and filter with washed with diethylether, by its dry 12h in the vacuum drying oven of 50 DEG C after filtration, intermediate product 3 can be obtained, [ClCH
2(p-C
6h
4) CH
2-N
+(CH
3)
2-C
6h
12-N
+(CH
3)
2c
10h
20-O-C
6h
4-C
6h
4-O-C
10h
20-N
+(CH
3)
2-C
6h
12-N
+(CH
3)
2-CH
2-(p-C
6h
4)-CH
2cl] [Br
-]
2[Cl
-]
2.
(4) by 1.328g [ClCH
2(p-C
6h
4) CH
2-N
+(CH
3)
2-C
6h
12-N
+(CH
3)
2c
nh
2n-O-C
6h
4-C
6h
4-O-C
nh
2n-N
+(CH
3)
2-C
6h
12-N
+(CH
3)
2-CH
2-(p-C
6h
4)-CH
2cl] [Br
-]
2[Cl
-]
2with 17.2gN, N, N ', N '-tetramethyl--1,6-hexanediamine is dissolved in 80ml body toluene/acetonitrile (v/v=1:1) mixed solution, stirs 10h in nitrogen atmosphere under 80 DEG C of conditions.Product is added ether chromatography to be placed in frozen water and to cool, and filter with washed with diethylether, cross filtered product dry 12h in the vacuum drying oven of 50 DEG C, intermediate product 4 can be obtained, [N (CH
3)
2-C
6h
12-N
+(CH
3)
2-CH
2(p-C
6h
4) CH
2-N
+(CH
3)
2-C
6h
12-N
+(CH
3)
2c
10h
20-O-C
6h
4-C
6h
4-O-C
10h
20-N
+(CH
3)
2-C
6h
12-N
+(CH
3)
2-CH
2-(p-C
6h
4)-CH
2-N
+(CH
3)
2-C
6h
12-N (CH
3)
2] [Br
-]
2[Cl
-]
4.
(5) by 1.670g [N (CH
3)
2-C
6h
12-N
+(CH
3)
2-CH
2(p-C
6h
4) CH
2-N
+(CH
3)
2-C
6h
12-N
+(CH
3)
2c
10h
20-O-C
6h
4-C
6h
4-O-C
10h
20-N
+(CH
3)
2-C
6h
12-N
+(CH
3)
2-CH
2-(p-C
6h
4)-CH
2-N
+(CH
3)
2-C
6h
12-N (CH
3)
2] [Br
-]
2[Cl
-]
4with 3.3g1-bromo n-hexane dissolution in 80ml body toluene/acetonitrile (v/v=1:1) mixed solution, in nitrogen atmosphere, under 88 DEG C of conditions, stir 10h.Product is added ether chromatography to be placed in frozen water and to cool, and filter with washed with diethylether, cross filtered product dry 12h in the vacuum drying oven of 50 DEG C, can final product be obtained, [C
6h
13-N
+(CH
3)
2-C
6h
12-N
+(CH
3)
2-CH
2(p-C
6h
4) CH
2-N
+(CH
3)
2-C
6h
12-N
+(CH
3)
2c
10h
20-O-C
6h
4-C
6h
4-O-C
10h
20-N
+(CH
3)
2-C
6h
12-N
+(CH
3)
2-CH
2-(p-C
6h
4)-CH
2-N
+(CH
3)
2-C
6h
12-N
+(CH
3)
2– C
6h
13] [Br
-]
4[Cl
-]
4.
Embodiment 1
(1) by 0.092g sodium hydroxide, 0.029g sodium metaaluminate, 1g eight ammonium head surface promoting agent (C
6-
6-ph-
6-12-OBr
4cl
4) and 7.920g deionized water under 65 DEG C of conditions, stir 1h;
(2) solution that step (1) obtains is cooled to room temperature, then stir on rotating speed 50rmp/s limit and obtain gelating soln for limit drips 1.528g tetraethoxy to it, aged at room temperature 5min, then stirs 12h by gelating soln under 65 DEG C of conditions;
(3) colloidal solution that step (2) is obtained is transferred in the stainless steel cauldron of sealing, 168h under 150 DEG C of conditions, after crystallization completes, cool and use deionized water wash suction filtration, solid sample is vacuum-drying 12h under 120 DEG C of conditions, in retort furnace, 600 DEG C of roasting 6h remove template, the beta multi-stage porous molecular sieve of micro-double-pore structure in obtaining again.
Embodiment 2
(1) by 0.095g sodium hydroxide, 0.030g sodium metaaluminate, 1g eight ammonium head surface promoting agent (C
6-
6-ph-
6-10-OBr
4cl
4) and 8.143g deionized water under 65 DEG C of conditions, stir 1h;
(2) solution that step (1) obtains is cooled to room temperature, then stir 50rmp/s limit on rotating speed 50rmp/s limit and obtain gelating soln to its dropping 1.571g tetraethoxy, aged at room temperature 5min, then stirs 12h by gelating soln under 65 DEG C of conditions;
(3) colloidal solution that step (2) is obtained is transferred in the stainless steel cauldron of sealing, 168h under 150 DEG C of conditions, after crystallization completes, cool and use deionized water wash suction filtration, solid sample is vacuum-drying 12h under 120 DEG C of conditions, in retort furnace, 600 DEG C of roasting 6h remove template, the beta multi-stage porous molecular sieve of micro-double-pore structure in obtaining again.
Embodiment 3
(1) by 0.095g sodium hydroxide, 0.030g sodium metaaluminate, 1g eight ammonium head surface promoting agent (C
6-
6-ph-
6-10-OBr
4cl
4) and 8.143g deionized water under 63 DEG C of conditions, stirring 1h;
(2) solution that step (1) obtains is cooled to room temperature, then drips 1.571g tetraethoxy to it while stirring at rotating speed 50rmp/s and obtain gelating soln, aged at room temperature 5min, then gelating soln is stirred 12h under 63 DEG C of conditions;
(3) colloidal solution that step (2) is obtained is transferred in the stainless steel cauldron of sealing, 168h under 150 DEG C of conditions, after crystallization completes, cool and use deionized water wash suction filtration, solid sample is vacuum-drying 12h under 120 DEG C of conditions, in retort furnace, 600 DEG C of roasting 6h remove template, the beta multi-stage porous molecular sieve of micro-double-pore structure in obtaining again.
Embodiment 4
(1) by 0.095g sodium hydroxide, 0.030g sodium metaaluminate, 1g eight ammonium head surface promoting agent (C
6-
6-ph-
6-10-OBr
4cl
4) and 8.143g deionized water under 60 DEG C of conditions, stirring 1h;
(2) solution that step (1) obtains is cooled to room temperature, then drips 1.571g tetraethoxy to it while stirring at rotating speed 50rmp/s and obtain gelating soln, aged at room temperature 5min, then gelating soln is stirred 12h under 60 DEG C of conditions;
(3) colloidal solution that step (2) is obtained is transferred in the stainless steel cauldron of sealing, 168h under 150 DEG C of conditions, after crystallization completes, cool and use deionized water wash suction filtration, solid sample is vacuum-drying 12h under 120 DEG C of conditions, in retort furnace, 600 DEG C of roasting 6h remove template, the beta multi-stage porous molecular sieve of micro-double-pore structure in obtaining again.
Embodiment 5
(1) by 0.095g sodium hydroxide, 0.030g sodium metaaluminate, 1g eight ammonium head surface promoting agent (C
6-
6-ph-
6-10-OBr
4cl
4) and 8.143g deionized water under 65 DEG C of conditions, stir 2h;
(2) solution that step (1) obtains is cooled to room temperature, then drips 1.571g tetraethoxy to it while stirring at rotating speed 50rmp/s and obtain gelating soln, aged at room temperature 5min, then gelating soln is stirred 12h under 65 DEG C of conditions;
(3) colloidal solution that step (2) is obtained is transferred in the stainless steel cauldron of sealing, 168h under 150 DEG C of conditions, after crystallization completes, cool and use deionized water wash suction filtration, solid sample is vacuum-drying 12h under 120 DEG C of conditions, in retort furnace, 600 DEG C of roasting 6h remove template, the beta multi-stage porous molecular sieve of micro-double-pore structure in obtaining again.
Embodiment 6
(1) by 0.0.101g sodium hydroxide, 0.031g sodium metaaluminate, 1g eight ammonium head surface promoting agent (C
6-
6-ph-
6-6-OBr
4cl
4) and 8.628g deionized water under 65 DEG C of conditions, stir 1h;
(2) solution that step (1) obtains is cooled to room temperature, then drips 1.664g tetraethoxy to it while stirring at rotating speed 50rmp/s and obtain gelating soln, aged at room temperature 5min, then gelating soln is stirred 12h under 65 DEG C of conditions;
(3) colloidal solution that step (2) is obtained is transferred in the stainless steel cauldron of sealing, 168h under 150 DEG C of conditions, after crystallization completes, cool and use deionized water wash suction filtration, solid sample is vacuum-drying 12h under 120 DEG C of conditions, in retort furnace, 550 DEG C of roasting 6h remove template, the beta multi-stage porous molecular sieve of micro-double-pore structure in obtaining again.
Embodiment 7
(1) by 0.095g sodium hydroxide, 0.030g sodium metaaluminate, 1g eight ammonium head surface promoting agent (C
6-
6-ph-
6-10-OBr
4cl
4) and 8.143g deionized water under 65 DEG C of conditions, stir 1h;
(2) solution that step (1) obtains is cooled to room temperature, then drips 1.571g tetraethoxy to it while stirring at rotating speed 55rmp/s and obtain gelating soln, aged at room temperature 5min, then gelating soln is stirred 12h under 65 DEG C of conditions;
(3) colloidal solution that step (2) is obtained is transferred in the stainless steel cauldron of sealing, 168h under 150 DEG C of conditions, after crystallization completes, cool and use deionized water wash suction filtration, solid sample is vacuum-drying 12h under 120 DEG C of conditions, in retort furnace, 600 DEG C of roasting 10h remove template, the beta multi-stage porous molecular sieve of micro-double-pore structure in obtaining again.
Embodiment 8
(1) by 0.095g sodium hydroxide, 0.030g sodium metaaluminate, 1g eight ammonium head surface promoting agent (C
6-
6-ph-
6-10-OBr
4cl
4) and 8.143g deionized water under 65 DEG C of conditions, stir 1h;
(2) solution that step (1) obtains is cooled to room temperature, then limit is stirred 60rmp/s limit and is obtained gelating soln, aged at room temperature 5min to its dropping 1.571g tetraethoxy, then gelating soln is stirred 12h under 65 DEG C of conditions;
(3) colloidal solution that step (2) is obtained is transferred in the stainless steel cauldron of sealing, 168h under 150 DEG C of conditions, after crystallization completes, cool and use deionized water wash suction filtration, solid sample is vacuum-drying 12h under 120 DEG C of conditions, in retort furnace, 600 DEG C of roasting 6h remove template, the beta multi-stage porous molecular sieve of micro-double-pore structure in obtaining again.
Embodiment 9
(1) by 0.080g sodium hydroxide, 0.038g sodium metaaluminate, 1g eight ammonium head surface promoting agent (C
6-
6-ph-
6-10-OBr
4cl
4) and 7.200g deionized water under 65 DEG C of conditions, stir 1h;
(2) solution that step (1) obtains is cooled to room temperature, then drips 1.458g tetraethoxy to it while stirring at rotating speed 50rmp/s and obtain gelating soln, aged at room temperature 5min, then gelating soln is stirred 12h under 65 DEG C of conditions;
(3) colloidal solution that step (2) is obtained is transferred in the stainless steel cauldron of sealing, 168h under 150 DEG C of conditions, after crystallization completes, cool and use deionized water wash suction filtration, solid sample is vacuum-drying 12h under 120 DEG C of conditions, in retort furnace, 600 DEG C of roasting 6h remove template, the beta multi-stage porous molecular sieve of micro-double-pore structure in obtaining again.
Embodiment 10
(1) by 0.120g sodium hydroxide, 0.033g sodium metaaluminate, 1g eight ammonium head surface promoting agent (C
6-
6-ph-
6-10-OBr
4cl
4) and 9g deionized water under 65 DEG C of conditions, stir 1h;
(2) solution that step (1) obtains is cooled to room temperature, then drips 1.667g tetraethoxy to it while stirring at rotating speed 50rmp/s and obtain gelating soln, aged at room temperature 5min, then gelating soln is stirred 12h under 65 DEG C of conditions;
(3) colloidal solution that step (2) is obtained is transferred in the stainless steel cauldron of sealing, 168h under 150 DEG C of conditions, after crystallization completes, cool and use deionized water wash suction filtration, solid sample is vacuum-drying 12h under 120 DEG C of conditions, in retort furnace, 600 DEG C of roasting 6h remove template, the beta multi-stage porous molecular sieve of micro-double-pore structure in obtaining again.
In preparing embodiment 1-3, the beta grade porous molecular sieve of micro-double-pore structure characterizes.
The XRD of sample characterizes, and D8Advance type X-ray diffractometer (Bruker company, Germany) carries out, and wherein operational condition is: copper target, 40KV, 40mA, step-length 0.02 degree, sweep velocity 17.7 seconds/step.As shown in Figure 1, the XRD characterization result of embodiment 1, has the characteristic diffraction peak of beta, illustrates that embodiment 1 sample all has the crystalline microporous structure of beta.
Adopt ASAP 2010 type N
2sorption Analyzer (Merck & Co., Inc, the U.S.) is analyzed the pore structure of product.As shown in Figure 2, the beta zeolite molecular sieve of hierarchical porous structure of the present invention shows IV type adsorption isothermal line to result.At 0.0 < P/P
0the low P/P of < 0.1
0district, adsorptive capacity is with P/P
0increase sharply increase, this is due to N
2in the filling in micropore district; Work as P/P
0when reaching 0.5, there is back stagnant ring in adsorption desorption curve, belongs to N
2capillary condensation phenomenon in mesoporous, illustrates in product to there is meso-hole structure.
ZEISS Ultra55 type field emission scanning electron microscope (Carl Zeiss company, Germany) is adopted to characterize the surface topography of sample.As shown in Figure 3, sample presents the surface topography of relatively homogeneous crystallization to result, does not observe the beta zeolite mixture of out of phase unbodied aluminosilicate material and pure crystalline state.
JEM-2100HR type transmission electron microscope (electronics corporation JEOL, Japan) is adopted to characterize product.As shown in Figure 4, the beta molecular sieve as can be seen from the figure synthesized has obvious meso-hole structure to result.
Fig. 5 is the pore size distribution curve calculated according to desorption BJH model, illustrates that beta molecular sieve prepared by the present invention has meso-hole structure.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (6)
1. a preparation method for micro-diplopore beta molecular sieve in, is characterized in that: this preparation method comprises following operation steps:
(1) under 60 ~ 65 DEG C of conditions, stir 1 ~ 2h after 0.2 ~ 0.4mmol sodium metaaluminate, 2 ~ 3mmol sodium hydroxide, 0.4 ~ 0.6mmol eight ammonium head Bola type tensio-active agent and 400 ~ 500mmol deionized water being mixed, obtain mixing solutions;
(2) step (1) gained mixing solutions is cooled to room temperature under agitation, 7 ~ 8mmol tetraethoxy is dripped under the stirring velocity of 50 ~ 60rpm/s, at room temperature aging 3 ~ 5min, then continue to stir 12h at 60 ~ 65 DEG C, obtain gelating soln;
(3) by step (2) gained gelating soln crystallization 7d in 140 ~ 150 DEG C of homogeneous reactors, after crystallization, product be cooled to room temperature suction filtration and use deionized water wash, vacuum-drying, then 550 ~ 600 DEG C of roasting 6 ~ 10h in retort furnace, micro-diplopore Beta molecular sieve in obtaining.
2. preparation method according to claim 1, is characterized in that: the structural formula of the described eight ammonium head Bola type tensio-active agents of step (1) is: [CH
3(CH
2)
5(CH
3)
2n
+(CH
2)
6(CH
3)
2n
+cH
2(p-C
6h
4) CH
2n
+(CH
3)
2(CH
2)
6n
+(CH
3)
2(CH
2)
noC
6h
4c
6h
4o (CH
2)
nn
+(CH
3)
2(CH
2)
6n
+(CH
3)
2cH
2(p-C
6h
4) CH
2n
+(CH
3)
2(CH
2)
6n
+(CH
3)
2(CH
2)
5cH
3] [Br
-]
4[Cl
-]
4, wherein n is 6,10 or 12.
3. preparation method according to claim 1, is characterized in that: the dropping temperature of step (2) described tetraethoxy is 25 ~ 35 DEG C.
4. preparation method according to claim 1, is characterized in that: step (3) described vacuum-drying be under 120 DEG C of conditions time of drying 12h.
5. one kind prepared by preparation method described in any one of Claims 1 to 4 in micro-diplopore beta molecular sieve.
6. the application of micro-diplopore beta molecular sieve in the aldol reaction of catalysis ethylene glycol and formaldehyde according to claim 5.
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| CN106672992A (en) * | 2015-11-11 | 2017-05-17 | 中国石油化工股份有限公司 | Beta zeolite and preparation method thereof |
| WO2017124304A1 (en) * | 2016-01-19 | 2017-07-27 | 北京大学深圳研究生院 | Amino acid-zeolite composite material, microporous-mesoporous level zeolite material converted therefrom, and preparation method therefor and use thereof |
| CN107364873A (en) * | 2017-07-31 | 2017-11-21 | 华南理工大学 | A kind of big pore volume two dimension Beta molecular sieve nanometer sheets and preparation method thereof |
| CN112409316A (en) * | 2020-11-27 | 2021-02-26 | 浙江工业大学 | Method for catalytic synthesis of benzaldehyde 1, 2-propylene glycol ketal by using hierarchical pore silicoaluminophosphate molecular sieve |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106672992A (en) * | 2015-11-11 | 2017-05-17 | 中国石油化工股份有限公司 | Beta zeolite and preparation method thereof |
| CN106672992B (en) * | 2015-11-11 | 2018-07-03 | 中国石油化工股份有限公司 | A kind of Beta zeolites and preparation method thereof |
| WO2017124304A1 (en) * | 2016-01-19 | 2017-07-27 | 北京大学深圳研究生院 | Amino acid-zeolite composite material, microporous-mesoporous level zeolite material converted therefrom, and preparation method therefor and use thereof |
| CN107364873A (en) * | 2017-07-31 | 2017-11-21 | 华南理工大学 | A kind of big pore volume two dimension Beta molecular sieve nanometer sheets and preparation method thereof |
| CN107364873B (en) * | 2017-07-31 | 2019-07-16 | 华南理工大学 | A kind of macropore holds two dimension Beta molecular sieve nanometer sheet and preparation method thereof |
| CN112409316A (en) * | 2020-11-27 | 2021-02-26 | 浙江工业大学 | Method for catalytic synthesis of benzaldehyde 1, 2-propylene glycol ketal by using hierarchical pore silicoaluminophosphate molecular sieve |
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Application publication date: 20150311 |