CN102092739B - Method for preparing molecular sieve compound by assembling with bridging silane - Google Patents

Method for preparing molecular sieve compound by assembling with bridging silane Download PDF

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CN102092739B
CN102092739B CN 201010600586 CN201010600586A CN102092739B CN 102092739 B CN102092739 B CN 102092739B CN 201010600586 CN201010600586 CN 201010600586 CN 201010600586 A CN201010600586 A CN 201010600586A CN 102092739 B CN102092739 B CN 102092739B
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molecular sieve
mother liquor
bridged silane
molecular
silane
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CN102092739A (en
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王一萌
王海曼
陈丽
张颖
张坤
何鸣元
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East China Normal University
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Abstract

The invention discloses a method for preparing a molecular sieve compound by assembling with bridging silane, which comprises the following steps: (1) selecting a prepared nano molecular sieve as the required molecular sieve mother liquor; (2) adding a bridging silane reagent into the molecular sieve mother liquor, and stirring under reflux at 100-150 DEG C until the hydrolysis completely finishes; and (3) directly filtering the slurry or sending the slurry into a kettle, crystallizing at 25-200 DEG C for 2-5 days, cooling, carrying out vacuum filtering, washing with water, and drying at 100 DEG C to obtain the molecular sieve compound. After being modified and treated, the crystallized nano microporous molecular sieve can be assembled into the compound with the granularity of greater than tens of micrometers. The invention solves the problem of difficulty in filtering of the nano molecular sieve; and meanwhile, intergranular mesopores are formed, thereby reducing the diffusional resistance and having high reaction activities.

Description

A kind of method for preparing molecular screen composite with the bridged silane assembling
Technical field
The present invention relates to the preparation of molecular sieve, specifically a kind of method of utilizing bridged silane reagent synthesis of molecular sieve mixture is namely utilized bridged silane that molecular sieve is piled up assembling and is formed mixture.
Background technology
Molecular sieve is as most important family in the inorganic microporous crystalline material, with its superior ion exchangeable, and adsorptivity, shape selectivity and catalytic activity etc. has been brought into play important effect in every field.Wherein representational micro porous molecular sieve is TS-1, ZSM-5, Silicalite-1, Beta equimolecular sieve.If the size of these micro porous molecular sieves all at nanometer scale (less than 200 nm), can greatly reduce diffusional limitation in catalyzed reaction; But molecular sieve is undersized, also can cause separation difficulty, uses simple filtration can not directly reclaim the sieve sample of nano-scale.For overcoming the problem of micro porous molecular sieve separation difficulty, people wish in sieve synthesis procedure can moulding and keep simultaneously the advantage of nano molecular sieve.Silylating reagent is used in catalyst surface modification and coating and the mould material usually.Bridged silane by hydrolysis after formed silicon hydroxyl can with the silicon hydroxyl condensation on molecular sieve surface, form chemical bond, both firmly can be coupled together, the molecular sieve surface is modified, form intergranular pore, construct multistage pore canal.
The people such as Kenneth J. Shea as far back as 1999 with regard to systematic research the character of bridged silane reagent hydrolytic condensation, obtain the composite organic-inorganic material of different performance by the process of control bridged silane sol-gel polymerization, can realize by the abutment of selecting different chain length such as the size in material duct.What but the author obtained is aerosol and the dried glue of the porous of monomer autohemagglutination mostly, bridged silane is not incorporated into the Zeolite synthesis system.（Douglas?A.?Loy,?James?V.?Beach,?Kenneth?J.?Shea;? Chem.?Mater.?1999,?11,3333;?K.?J.?Shea,?D.?A.?Loy;? Chem.?Mater.?2001,?13 ,?3306-3319）。
The people such as Corma are incorporated into organic group the mesoporous zone of USY first, and before this, most people just utilizes the organic reagents such as silylating reagent that other solid materials such as mesopore molecular sieve and amorphous silicon are carried out organic functional.Few people carry out functionalization with silylating reagent to poromerics.The people such as Mark E. Davis are incorporated into the micro porous molecular sieve synthetic system with γ-aminopropylsilane, successfully synthesize to have the organic functional molecular sieve of BEA topological framework.（Katsuyuki?Tsuji,?Christopher?W.?Jones,?Mark?E.?Davis；Microporous?and?Mesoporous?Materials?29?(1999)?339–349）。
Takashi Tatsumi etc. utilizes bridged silane to successfully synthesize the hybrid inorganic-organic molecular sieve.Sauerstoffatom part in the framework of molecular sieve is replaced by the methylene radical of bridged silane, successful change the backbone element of molecular sieve, amazing is that molecular sieve has higher hydrothermal stability and shape selectivity after changing, this proves absolutely that also it is the combination of traditional molecular sieve and amorphous material that synthetic material has more than, but a kind of novel hybrid inorganic-organic materials.The people such as Corma are incorporated into more organic composition in the framework of molecular sieve on this basis, in kept on the hydrothermal stability basis of traditional molecular sieve systematic research framework of molecular sieve type and degree of crystallinity on introducing the impact of organosilane molecular amounts.Though the synthetic hybrid material of this kind method has good catalytic performance, the required crystallization time of molecular sieve is long especially, generally needs tens days, and the size of molecular sieve is less, separates still cumbersome.（Katsutoshi?Yamamoto，Takashi?Tatsumi； Chem.?Mater.?2005,17 ,?3913;?Katsutoshi?Yamamoto，Takashi?Tatsumi； Science?2003,?300,?470;?Urbano?Diaz,?Jos?A.?Vidal-Moya,?Avelino?Corma,?Microporous?and?Mesoporous?Materials?2006,?93,?180.）。
David P. Serrano adds silylating reagent and controls the molecular sieve that further accumulation degree of molecular sieve obtains having multistage pore canal in the ZSM-5 molecular sieve crystal seed.Building-up process is as follows: the synthetic colloidal sol of ZSM-5 was descended pre-crystallization 20 hours at 40 ℃, obtain crystal seed, its composition and ratio is 1 Al 2O 3: 60SiO 2: 11TPAOH:1500H 2O.Add N-phenyl-3-TSL 8330 (PHAPTMS) in the crystal seed 90 ℃ of lower stirrings 6 hours, 170 ℃ of crystallization 7 days, obtain sieve sample behind the centrifugal washing and drying at last.Utilizing the synthetic about 200nm of molecular sieve assembly of this method, is to form by piling up less than the crystal seed of 10nm, has simultaneously micropore and mesoporous.Because sieve particle still is in nano level, brings a lot of difficulties to separation.In addition, the adding of silylating reagent has also further stoped the crystallization of molecular sieve, has reduced degree of crystallinity.（D.?P.?Serrano,?J.?Aguado,?G.?Morales,?J.?M.?Rodriguez； Chem.?Mater.?2009,21,?641.）。
The people such as Ryoo also utilize amphipathic silylating reagent [(CH 3O) 3SiC 3H 6N (CH 3) 2C1 6H 33] Cl(TPHAC) come synthesising mesoporous MFI molecular sieve as mesoporous structure directing agent.Amphipathic silylating reagent water-wet side is connected with molecular sieve, and the hydrophobic side forms mesoporous, mesoporous size as mesoporous template and can regulate and control by the chain length of regulating the hydrophobic side.The advantages such as synthetic molecular sieve has large specific surface, and controlled mesoporous volume and molecular sieve intergranular are mesoporous, but this kind method and be not suitable for modification and the regulation and control of micro porous molecular sieve.（M.?Choi,?H.?S.?Cho,?R.?Srivastava,?C.?Venkatesan,?D.-H.?Choi,?R.?Ryoo,?Nature?Mater.?2006,?5,?718.）。
Summary of the invention
The purpose of this invention is to provide a kind of method for preparing molecular screen composite with the bridged silane assembling, come molecular sieve is carried out the finishing assembling with bridged silane, form multistage pore canal, make the Activation Diffusion in Zeolites that obtains good, reactive behavior is good, be easy to filtering separation, solve the molecular sieving hard problem.
The object of the present invention is achieved like this:
A kind of method for preparing molecular screen composite with the bridged silane assembling comprises following concrete steps:
(1) chooses the nano-class molecular sieve that prepared as required molecular sieve mother liquor;
(2) in the molecular sieve mother liquor of step (1), add bridged silane reagent, be stirred to hydrolysis fully 100～150 ℃ of lower backflows; Wherein: the silica molar ratios of bridged silane reagent and molecular sieve mother liquor is 0.05～0.3; The water silicon ratio of molecular sieve system is 10～1000;
(3) with step (2) slurries direct filtration or advance still, 25～200 ℃ of lower crystallization 2～5 days, 100 ℃ of lower oven dry, obtain described molecular screen composite after the washing of cooling suction filtration;
Wherein:
The described nano-class molecular sieve that has prepared is Silicalite-1, Silicalite-2, ZSM-5, ZSM-11, TS-1, TS-2, Beta or Y zeolite, and molecular sieve is of a size of 20 nm～1 um;
Described bridged silane reagent is for containing the different carbon chain lengths bridged silane;
The described different carbon chain lengths bridged silane that contains is 1,1-two (triethoxysilicane alkyl) methane, 1,2-two (triethoxysilicane alkyl) ethane, 1,6-two (Trimethoxy silane base) hexane or 1,8-two (triethoxysilicane alkyl) octane.
After the nanometer level microporous molecular sieve of the present invention after to crystallization carries out modification and processes, molecular sieve can be assembled into the mixture greater than tens microns, has solved the problem of nano molecular sieve filtration difficulty, forms simultaneously intergranular mesoporous, reduce diffusional resistance, had higher reactive behavior.
Description of drawings
Fig. 1 is the XRD figure of synthetic TS-1 sample;
Fig. 2 is the XRD figure of synthetic ZSM-5 sample;
Fig. 3 is synthetic TS-1, ZSM-5, the SEM figure of Silicalite-1 sample.
Embodiment
Describe the present invention in detail below by Comparative Examples and embodiment, but the present invention is not limited to this.
Comparative Examples 1
Synthesizing of TS-1 molecular sieve: with 63.77 gram tetraethyl orthosilicates, 73.08 gram TPAOH (TPAOH 25Wt%) solution and 53.19 gram deionized waters mix, at room temperature stir 1-2 hour to being hydrolyzed fully, then under ice-water bath, add 2.6 gram tetrabutyl titanates (being dissolved in the Virahol), stirred 2 hours, under 80 ℃, boil off ethanol 55.2 gram, obtained the molecular sieve mother liquor after the moisturizing at 175 ℃ of lower hydrothermal crystallizing 3-5 days.Its mole consists of SiO 2: 0.3TPAOH: 0.025TBOT: 20H 2O.This sample X-ray diffraction has the MFI structure, shown in Fig. 1 (a).
Comparative Examples 2
Synthesizing of ZSM-5 molecular sieve: with 63.77 gram tetraethyl orthosilicates, 85.26 gram TPAOH (TPAOH 25Wt%) solution and 44.05 gram deionized waters mix, at room temperature stir 1-2 hour to being hydrolyzed fully, under 80 ℃, boil off ethanol 55.2 grams after the hydrolysis, take out cooling after 6 hours in 175 ℃ of lower hydrothermal crystallizings, then add 2.06 gram aluminum isopropylates, stir hydrolysis fully.Then obtained the molecular sieve mother liquor in 5 days at 175 ℃ of lower hydrothermal crystallizings that continue.Its mole consists of SiO 2: 0.35TPAOH: 0.0167Al 2O 3: 20H 2O.This sample X-ray diffraction has the MFI structure, shown in Fig. 2 (a).
Comparative Examples 3
Synthesizing of Silicalite-1 molecular sieve: with 21.25 gram tetraethyl orthosilicates, 24.36 gram TPAOH (TPAOH 25Wt%) solution and 17.73 gram deionized waters mix, at room temperature stir 1-2 hour to being hydrolyzed fully, under 80 ℃, boil off ethanol 18.4 gram, obtained the molecular sieve mother liquor after the moisturizing at 175 ℃ of lower hydrothermal crystallizing 3-5 days.Its mole consists of SiO 2: 0.3TPAOH: 20H 2O.This sample X-ray diffraction has the MFI structure.
Embodiment 1
Get molecular sieve mother liquor synthetic in the Comparative Examples 1 8.0 grams, add 1,8-two (triethoxysilicane alkyl) octane 0.8 gram (mol ratio of silicon-dioxide is 0.1), 115 ℃ of lower return stirring 4-6 hours to the silylating reagent hydrolysis fully, then 175 ℃ of lower crystallization 5 days.Obtain product molecular screen composite TS-1-1(X ray spectra shown in Fig. 1 (b) 100 ℃ of lower oven dry after the washing of cooling suction filtration, Electronic Speculum is shown in Fig. 3 (b)).
Embodiment 2
Method according to embodiment 1 prepares molecular screen composite TS-1-2, unique different be moisturizing 9.4 grams again after the silylating reagent hydrolysis, so that the water silicon ratio in the molecular sieve system is 50, obtain product molecular screen composite TS-1-2(X ray spectra shown in Fig. 1 (c), Electronic Speculum is shown in Fig. 3 (c)).
Embodiment 3
Method according to embodiment 1 prepares molecular screen composite TS-1-3, unique different be moisturizing 31.4 grams again after the silylating reagent hydrolysis, so that the water silicon ratio in the molecular sieve system is 120, obtain product molecular screen composite TS-1-3(X ray spectra shown in Fig. 1 (d), Electronic Speculum is shown in Fig. 3 (d)).
Embodiment 4
Method according to embodiment 2 prepares molecular screen composite TS-1-4, unique different be to add 1,8-two (triethoxysilicane alkyl) octane 1.6 grams (mol ratio of silicon-dioxide is 0.2), obtain product molecular screen composite TS-1-4(X ray spectra shown in Fig. 1 (e), Electronic Speculum is shown in Fig. 3 (e)).
Embodiment 5
Method according to embodiment 2 prepares molecular screen composite TS-1-5, unique different be to add 1,8-two (triethoxysilicane alkyl) octane 2.4 grams (mol ratio of silicon-dioxide is 0.3), obtain product molecular screen composite TS-1-5(X ray spectra shown in Fig. 1 (f), Electronic Speculum is shown in Fig. 3 (f)).
Embodiment 6
Get molecular sieve mother liquor synthetic in the Comparative Examples 2 8.0 grams, add 1,8-two (triethoxysilicane alkyl) octane 1.15 grams (mol ratio of silicon-dioxide is 0.15), complete to the silylating reagent hydrolysis at 115 ℃ of lower return stirring 4-6 hours, moisturizing 9.4 grams again after the silylating reagent hydrolysis are so that the water silicon ratio in the molecular sieve system is 50.Then 175 ℃ of lower crystallization 5 days, obtains product molecular screen composite ZSM-5-6(X ray spectra shown in Fig. 2 (b) 100 ℃ of lower oven dry after the washing of cooling suction filtration, Electronic Speculum is shown in Fig. 3 (a)).
Embodiment 7
Get molecular sieve mother liquor synthetic in the Comparative Examples 3 8.0 grams, add 1,8-two (triethoxysilicane alkyl) octane 0.8 gram (mol ratio of silicon-dioxide is 0.1), complete to the silylating reagent hydrolysis at 115 ℃ of lower return stirring 4-6 hours, moisturizing 9.4 grams again after the silylating reagent hydrolysis are so that the water silicon ratio in the molecular sieve system is 50.Then 175 ℃ of lower crystallization 5 days, obtains product molecular screen composite Silicalite-1-7(Electronic Speculum shown in Fig. 3 (g) 100 ℃ of lower oven dry after the washing of cooling suction filtration).
Embodiment 8
Get molecular sieve mother liquor synthetic in the Comparative Examples 1 8.0 grams, add 1,6-two (Trimethoxy silane base) hexane 0.57 gram (mol ratio of silicon-dioxide is 0.1), 115 ℃ of lower return stirring 4-6 hours to the silylating reagent hydrolysis fully, then 175 ℃ of lower crystallization 5 days.Obtain product molecular screen composite TS-1-8(Electronic Speculum shown in Fig. 3 (h) 100 ℃ of lower oven dry after the washing of cooling suction filtration).
Embodiment 9
The present embodiment explanation adopts the molecular sieve of the inventive method preparation to be used for the reaction effect of n-hexylene and tetrahydrobenzene catalyzed oxidation.
Take the molecular sieve of embodiment 2 preparation as catalyzer, in the reaction reflux, add the 50mg catalyzer, 10ml solvent (n-hexylene methyl alcohol, tetrahydrobenzene acetonitrile), 10mmol reactant (n-hexylene, tetrahydrobenzene), 10mmol H 2O 2(25%) and 0.5 gram trimethylbenzene as interior mark, 60 ℃ of lower backflows 2 hours.Distribution of reaction products is analyzed by gas-chromatography.
Warp is to product analysis, and reaction result is that the transformation efficiency of n-hexylene is 20.5%, and the selectivity of epoxide is 97.5%, and the transformation efficiency of tetrahydrobenzene is 10.1%, and the selectivity of epoxide and glycol is respectively 41.0% and 46.8%.As can be seen from the above results, the TS-1 synthetic with traditional method compares, and adopts the synthetic molecular screen composite of the inventive method to keep the high conversion of n-hexylene, and improved the selectivity of transformation efficiency and the product of tetrahydrobenzene.

Claims (1)

1. method for preparing molecular screen composite with bridged silane assembling is characterized in that preparation process is as follows:
(1) chooses the molecular sieve that prepared as required molecular sieve mother liquor;
(2) in the molecular sieve mother liquor of step (1), add bridged silane reagent, be stirred to hydrolysis fully 100～150 ℃ of lower backflows; Wherein: the silica molar ratios of bridged silane reagent and molecular sieve mother liquor is 0.05～0.3; The water silicon ratio of molecular sieve system is 10～1000;
(3) step (2) slurries are advanced still, 25～200 ℃ of lower crystallization 2～5 days, 100 ℃ of lower oven dry, obtain described molecular screen composite after the washing of cooling suction filtration;
Wherein:
The described molecular sieve that has prepared is Silicalite-1, Silicalite-2, ZSM-5, ZSM-11, TS-1, TS-2, Beta or Y zeolite, and molecular sieve is of a size of 20 nm～1 μ m;
Described bridged silane reagent is for containing the different carbon chain lengths bridged silane;
The described different carbon chain lengths bridged silane that contains is 1,1-two (triethoxysilicane alkyl) methane, 1,2-two (triethoxysilicane alkyl) ethane, 1,6-two (Trimethoxy silane base) hexane or 1,8-two (triethoxysilicane alkyl) octane.
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CN101081700A (en) * 2007-06-11 2007-12-05 大连理工大学 Preparation method of zeolite molecular sieve having ordered meso-porous structure

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CN101081700A (en) * 2007-06-11 2007-12-05 大连理工大学 Preparation method of zeolite molecular sieve having ordered meso-porous structure

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赵忠林等.FER型层状前驱体的层间硅烷化扩孔和功能化.《第十五届全国分子筛学术大会论文集》.2009,第2节. *

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