CN102259012B - Method for preparing encapsulated pure silicon mesoporous MSU-1 (molecular sieve unit-1) molecular sieve membrane core-shell catalyst - Google Patents
Method for preparing encapsulated pure silicon mesoporous MSU-1 (molecular sieve unit-1) molecular sieve membrane core-shell catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 74
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 41
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical group [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 239000012528 membrane Substances 0.000 title claims abstract description 37
- 239000011258 core-shell material Substances 0.000 title claims abstract description 22
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 18
- 239000010703 silicon Substances 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 title claims abstract description 17
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- 239000013078 crystal Substances 0.000 claims abstract description 33
- 230000008569 process Effects 0.000 claims abstract description 8
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- 238000001354 calcination Methods 0.000 claims description 5
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- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
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- 239000001569 carbon dioxide Substances 0.000 claims description 3
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical class CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims description 3
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- IEQAICDLOKRSRL-UHFFFAOYSA-N 2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-(2-dodecoxyethoxy)ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethanol Chemical compound CCCCCCCCCCCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO IEQAICDLOKRSRL-UHFFFAOYSA-N 0.000 description 4
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- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 3
- GFLJTEHFZZNCTR-UHFFFAOYSA-N 3-prop-2-enoyloxypropyl prop-2-enoate Chemical class C=CC(=O)OCCCOC(=O)C=C GFLJTEHFZZNCTR-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention belongs to the field of catalysis and inorganic membrane application and relates to a method for preparing an encapsulated pure silicon mesoporous MSU-1 molecular sieve membrane core-shell catalyst. An MSU-1/Ni-Al2O3 core-shell catalyst with continuous and uniform membrane layer is synthesized under the coactions of a rotating synthesizing process and an ion diffusion process, the stability and heat resistance of the MSU-1 molecular sieve membrane loaded on the surface of the carrier are increased by a seed crystal induction process, and the mechanical strength of the MSU-1/Ni-Al2O3 core-shell catalyst is increased. In the invention, when the MSU-1/Ni-Al2O3 core-shell catalyst is synthesized, the catalytic reaction of macromolecular substances can be catalyzed selectively under the sieving action of the MSU-1 molecular sieve membrane; meanwhile, the MSU-1 molecular sieve membrane can serve as a protective layer to prevent materials that can affect the activity of the catalyst in a reaction system from poisoning a core catalyst.
Description
Technical field
The invention belongs to catalysis and inoranic membrane application, be specifically related to the preparation method of the mesoporous MSU-1 molecular screen membrane of a kind of coated pure silicon core-shell catalyst.
Background technology
Recent years, design and the controlled preparation with the composite of nucleocapsid structure have become a focus in material science.Nucleocapsid structure material has centronucleus and shell, and its character is controlled by the characteristic such as kind, character of different core, shell material.Compound due to its special structure and differing material properties, make the composite of nucleocapsid structure show the outstanding advantages that many other materials do not have, there is the characteristics such as special optical, electrical, magnetic, chemistry, be widely used in fields such as nano material, biology, medicine, machinery, catalysis.Wherein, to form the catalyst with nucleocapsid structure be organic zeolite membrane field and the new study hotspot of catalytic field in recent years to molecular sieve coated catalysts.Molecular screen membrane is except having the advantage of general inoranic membrane, as high temperature resistant, chemical stability good, mechanical strength is large, anti-microbe ability is strong etc., also has its exclusive feature:
(1) homogeneous and the microchannel structure of rule, pore size approaches molecular dimension, can realize molecule screening, and separation selectivity is high.
(2) molecular sieve silica alumina ratio can modulation, and cation can be realized exchange, and its crystal Coulombian field is regulated, alternative absorption polarity or the different molecule of polarizable degree.
(3) there is acid site in molecular sieve surface, and itself can be used as catalyst, not only can bring into play the effect of molecular separation after film forming, also can realize catalysis, reaches separation catalytic integration.
The core-shell catalyst that coated traditional porous catalyst forms, has realized the compound of the function of molecular screen membrane and catalyst function, has given the many new functions of traditional catalyst and characteristic, has realized the performance optimization of traditional catalyst.Have the catalyst of the coated nucleocapsid structure of molecular screen membrane, can bring into play the catalytic action of shell separation and stratum nucleare, this biphase cooperative acts on catalytic field and has good application prospect.At present, micro porous molecular sieve is as ZSM-5, the core-shell catalyst that Silicalite-1 coated catalysts forms is due to the maturation of its synthetic technology, the advantages such as pore size and guest molecule approach receive publicity day by day at catalytic field, but the core-shell catalyst forming for mesopore molecular sieve coated catalysts also rarely has report.
Since the scientist of Mobile company in 1992 finds mesoporous M41S series mesopore molecular sieve, mesopore molecular sieve is as a kind of catalysis and functional material of novel nano pore passage structure, there is high-sequential and equally distributed pore passage structure, aperture size changes wider range, high (the > 1000m of specific surface
2/ g), and its skeleton component has multifarious feature, receives the numerous areas researcher's such as catalysis, adsorbing separation, inorganic synthetic and materialogy concern.MSU-x be continue M41S series mesopore molecular sieve come out since the another kind of New Type of Mesoporous material with 3 D stereo worm type (Worm-like) cross arrangement pore passage structure of synthesized, in the vermiform pore passage structure of this 3 D stereo cross arrangement, skeleton hole with perpendicular to layer and be parallel to layer hole be cross-linked with each other, diffusion distance because of its duct shell thick very short, be conducive to guest molecule disperses and spreads in its duct, can transmit more quickly and efficiently material than MCM-41 or the SBA types of molecules sieve with one-dimensional tunnel structure, there is superior diffusion.The height skeleton in 3 D stereo worm type duct is cross-linked with relatively thick skeleton wall has superpower heat endurance and hydrothermal stability, makes MSU-x have the wider scope of application than other mesoporous material.In addition, MSU series mesoporous molecular sieve is mainly with non-ionic surface active agent as template, and the hydrogen bond action between end group and the inorganic precursor of non-ionic surface active agent is main, and its advantage has synthesis condition gentleness, and template is easy to remove and reclaim, environmentally friendly.Not only reduce preparation cost, also reduce the environmental pollution in roasting process.So in carrier and the structure nano-device etc. of the solidifying of separating biomass, organized enzyme material, the macromolecular oxidation of catalysis and hydrogenation reaction, effective catalyst, all demonstrate unique advantage, extremely researcher's favor in association area.
The core-shell catalyst preparation of the coated mesoporous MSU-1 molecular screen membrane of pure silicon, its key is the preparation of MSU-1 molecular screen membrane.Employing LBL (layer-by-layer) methods such as L.Jin are modified PDDA (PDDA) as adhesive on flake graphite electrode, the MSU molecular sieve of load hemoglobin is combined in to (J.S.Li on graphite electrode by different level, et al., Talanta, 2008,74:1692-1698).First Jerry Lin etc. has prepared MSU-1 molecular sieve, then adopt dipping-pulling method directly by molecular sieve carried MSU-1 in porous oxidation aluminum tube surfaces and pile up film forming (J.S.Li, et al., J.Membr.Sci., 2008,312:186-192).Prouzet seminar adopt two-step method directly on porous alumina ceramic pipe synthetic MSU-1 molecular screen membrane and for separating of the polyvinyl alcohol of different molecular weight (
.Prouzet, et al., Chem.Mater., 2003,15:460-463).In order to obtain uniform MSU-1 molecular screen membrane, they adopt the internal layer adhesion mineralizer NaF of polymer at porous ceramic pipe, then in the MSU-1 of flow circuit mother liquor, roll synthetic, obtained 300 nanometers left and right pipe theca interna (
.Prouzet, et al., J.Membr.Sci., 2005,251:17-28).In the method for bibliographical information, not yet there is the method at the mesoporous MSU-1 molecular screen membrane of ball type carrier surface coverage pure silicon at present; In addition as catalyst, under hot conditions, the rete of the core-shell structure catalyst of coated MSU-1 molecular screen membrane needs certain mechanical strength and heat resistance catalyst surface is coated, and synthetic method in bibliographical information cannot realize this requirement.
Summary of the invention
The technical problem to be solved in the present invention is to provide the preparation method of the mesoporous MSU-1 molecular screen membrane of a kind of coated pure silicon core-shell catalyst, adopts the synthetic MSU-1/Ni-Al with the continuous homogeneous of rete under rotating close established law and ion diffusion acting in conjunction
2o
3core-shell catalyst, and increased stability and the heat resistance of MSU-1 molecular screen membrane in carrier surface load by crystal seed revulsion, strengthen MSU-1/Ni-Al
2o
3the mechanical strength of core-shell catalyst.
In the synthetic liquid of MSU-1, utilize concentration difference to realize that MSU-1 mineralizer NaF is logical reaches surface in spheric catalyst, make MSU-1 molecular sieve on spheric catalyst surface synthetic and deposition film forming.For the even film layer that makes to obtain, adopt rotating close established law to make spheric catalyst in building-up process, keep rolling, avoid NaF in process of osmosis, to be subject to local concentration that gravity effect causes excessive and affect the thick uniformity of rete.In addition, by the design that adopts individual layer Silicalite-1 molecular sieve crystal seed to modify as the spheric catalyst surface of core, the firm sintering of Silicalite-1 molecular sieve crystal seed is on spheric catalyst surface on the one hand, on the other hand in the synthetic process of MSU-1, Silicalite-1 molecular sieve crystal seed can, with MSU-1 molecular sieve by " silicon-oxygen covalent bond " strong bonded, be realized the object that increases rete and catalyst bond strength.Silicalite-1 molecular sieve crystal seed is as " link medium ", more high temperature resistant than organic polymer, and is difficult for being corroded, and has reduced MSU-1/Ni-Al
2o
3the restriction of the service condition of core-shell catalyst.
Technical scheme of the present invention is as follows:
A preparation method for the mesoporous MSU-1 molecular screen membrane of coated pure silicon core-shell catalyst is the core-shell type catalyst in even, the continuous mesoporous MSU-1 molecular screen membrane preparation of pure silicon of the coated one deck in spherical nickel-base catalyst surface with mesoporous size duct.Catalyst carrier used is the spherical porous γ-Al of particle diameter at 0.8～5mm
2o
3,
Utilize infusion process to synthesize nickel-base catalyst.
Concrete preparation method's step is as follows:
(1) adopting aminopropyl trimethoxysilane (AP-TMS) is coupling agent, and absolute ethyl alcohol is medium, at Ni-Al
2o
3catalyst surface coupling particle size is the Silicalite-1 monomolecular sieve crystal seed layer of 160 nanometer left and right, and make Silicalite-1 molecular sieve crystal seed layer firmly be combined in catalyst outer surface by roasting, obtain the Ni-Al that Silicalite-1 molecular sieve crystal seed layer covers
2o
3catalyst precursor.
(2) in the NaF aqueous solution, put into the Ni-Al that Silicalite-1 molecular sieve crystal seed layer that step (1) obtains covers
2o
3catalyst precursor, in the baking oven of 60 DEG C, rapid steaming solid carbon dioxide solution, obtains the Ni-Al that comprises NaF crystal
2o
3catalyst.
(3) the synthetic liquid of preparation MSU-1 molecular sieve.Employing water is medium, and ethyl orthosilicate is silicon source, and ethoxylated dodecyl alcohol (Brij-35) is template, is mixed with uniform and stable emulsion type film forming liquid.
(4) Ni-Al that comprises NaF crystal step (2) being obtained
2o
3catalyst is put into the synthetic liquid of the MSU-1 molecular sieve that step 3 obtains, be sealed in special stainless steel synthesis reactor, under the rotating speed of 5～60rpm, 40～100 DEG C synthetic 6～24 hours.
(5) after synthetic by step (4), the MSU-1/Ni-Al obtaining
2o
3repeatedly rinse by deionized water, remove the non-rete MSU-1 sieve particle of unnecessary film forming liquid and surface attachment, then in deionized water, soak and remove NaF unnecessary in catalyst.The MSU-1/Ni-Al obtaining
2o
3after oven dry, then in Muffle furnace, remaining template Brij-35 is fallen in calcination.
The present invention uses Silicalite-1 molecular sieve crystal seed as connecting media, has strengthened bond strength between MSU-1 molecular screen membrane and carrier.Use the mineralizer of NaF as the mesoporous MSU-1 molecular sieve of pure silicon.Use NaF to be immersed in ball type carrier, utilize NaF to dissolving in film forming liquid and the effect of diffusion, NaF is contacted at ball type carrier outer surface with film forming liquid, realize MSU-1 molecular sieve and start crystallization film forming at spherical outer surface.NaF is to dissolving in film forming liquid and when diffusion, using rotating close established law to make the diffusion of NaF uniform dissolution, thereby realize integrality and the uniformity of the laminated one-tenth of MSU-1 molecular screen membrane.
By said method, solve the problem that forms MSU-1 sieve particle at ball type carrier surface in situ; Solve the problem of membrane uniformity, solved MSU-1 molecular screen membrane at carrier loaded stability problem.
The invention has the beneficial effects as follows by synthetic MSU-1/Ni-Al
2o
3catalyst, can make bulky molecular catalysis reaction realize shape selective catalysis by the sieving actoion of MSU-1 molecular screen membrane, and MSU-1 molecular screen membrane can be used as material that protective layer prevents from endangering in reaction system catalyst activity and poison the catalyst of core simultaneously.
Brief description of the drawings
Fig. 1 is the present invention program MSU-1/Ni-Al
2o
3the flow chart that catalyst is synthetic.
Fig. 2 is the present invention program MSU-1/Ni-Al
2o
3the poisoning measurement system diagram of catalyst alkali resistant.
Fig. 3 A is the MSU-1/Ni-Al that does not adopt crystal seed revulsion to prepare
2o
3catalyst is the photo of calcination after 6 hours in 650 DEG C.
Fig. 3 B prepares MSU-1/Ni-Al prepared by the present invention program according to the method for the invention
2o
3catalyst is the photo of roasting after 6 hours in 650 DEG C.
Detailed description of the invention
Describe specific embodiments of the invention in detail below in conjunction with technical scheme and accompanying drawing.
Embodiment 1: the preparation of resistance alkali composite current collecting plate
(1) preparation of pure silicon molecular sieve crystal seed and with the covalent coupling of carrier
According to TPAOH: SiO
2: H
2o=25: the synthetic precursor liquid of mol ratio preparation Sil-1 molecular sieve crystal seed of 100: 2700, wherein taking ethyl orthosilicate (TEOS) as silicon source, TPAOH (TPAOH) and deionized water be as raw material, stirring at room temperature 24 hours after fully mixing, in the stainless steel crystallizing kettle that injection contains polytetrafluoro liner, seal in the baking oven that is placed on 100 DEG C, after 15 hours, take out; By the mixed liquor centrifugation obtaining, it is washed till to neutrality repeatedly by deionized water, obtain with ethanolic solution displacement the Sil-1 molecular sieve crystal seed that particle diameter is 150～200nm afterwards, be made into the alcohol suspension that mass fraction is 0.05～0.5wt%, ultrasonic concussion mixes rear for subsequent use.
Then by Ni-Al
2o
3catalyst is placed in the mixed liquor (volume ratio 15～60: 1) 80～120 DEG C of self-heating coupling 1～5h of ethanol and γ-aminopropylsilane; Then coupling carrier is placed in to mass fraction and is 80～120 DEG C of self-heating coupling 1～5h of Sil-1 crystal seed dispersion liquid of 0.05～0.5%, after 450～550 DEG C of calcinations, can obtain the Ni-Al of load Sil-1 crystal seed layer
2o
3carrier.
(2) dipping of NaF and concentrated in carrier
Be 4%～7.5% at mass fraction, the NaF aqueous solution 20～35ml in put into the Ni-Al of the load Sil-1 crystal seed layer that step 1 obtains
2o
3carrier, rapid steaming solid carbon dioxide solution in the baking oven of 100 DEG C, obtains the Ni-Al of the load Sil-1 crystal seed layer that comprises NaF crystal
2o
3carrier.
(3) MSU-1 molecular screen membrane is synthetic
According to Brij-35: SiO
2: H
2o: EtOH=(10～80): (60～160): (1500～4000): the synthetic precursor liquid of mol ratio preparation film of (500～700), wherein taking ethyl orthosilicate (TEOS) as silicon source, ethoxylated dodecyl alcohol (Brij-35), absolute ethyl alcohol (EtOH) and deionized water be as raw material, stirring at room temperature 24 hours after fully mixing, in the stainless steel crystallizing kettle that injection contains polytetrafluoro liner, put into the Ni-Al of the load Sil-1 crystal seed layer that comprises NaF crystal
2o
3carrier, seals in the baking oven that is placed on 40～100 DEG C, taking rotating speed as 5～60rpm, after 6～24 hours, takes out; Product after crystallization is taken out, and deionized water is rinsed repeatedly, removes template get final product to obtain MSU-1/Ni-Al after 60～80 DEG C of oven dry in 450～650 DEG C of calcination 3～9h (0.2～1.2K/min)
2o
3core-shell type catalyst.
Embodiment 2:MSU-1/Ni-Al
2o
3the test of catalyst alkali resistant poisoning performance
This test reactor adopt stainless steel tube (internal diameter 6mm, long 400mm), first ceramic inert filler is placed in to reactor bottom, after by original catalyst and MSU-1/Ni-Al
2o
3catalyst (500～1000mg) is placed in (quartzy cotton pad) on packing layer makes catalyst layer in heating furnace flat-temperature zone, by alkali (Li
2cO
3with K
2cO
3mol ratio is 62: 38) impregnated inert filler layer (mass fraction of alkali concn is 20%) is placed on beds; The front system of reaction passes into hydrogen (20ml/min) and carries out catalyst reduction 2～4h, by CH
4/ H
2o from reactor air inlet suitable for reading (25ml: 75ml), controlled 650 DEG C of reaction temperatures than 3: 1, the online sample detection H of gas-chromatography (GC7890, TCD detector)
2, CO, CO
2and CH
4constituent content.
Embodiment 3:MSU-1 molecular screen membrane is at the stability test of carrier surface load
By the MSU-1/Ni-Al that does not use crystal seed revulsion and use crystal seed revulsion to prepare
2o
3catalyst is put into crucible together, and roasting 10～15h in 650 DEG C of Muffle furnaces can judge the stability of MSU-1 molecular screen membrane in carrier surface load combination by rete dropping situations.
Claims (2)
1. the preparation method of the mesoporous MSU-1 molecular screen membrane of a coated pure silicon core-shell catalyst, it is characterized in that preparation has the core-shell type catalyst of the shell in mesoporous size duct at coated even, the continuous mesoporous MSU-1 molecular screen membrane of pure silicon of one deck in spherical nickel-base catalyst surface; Described spherical nickel-base catalyst is Ni-Al
2o
3catalyst; Concrete steps are as follows:
(1) adopting aminopropyl trimethoxysilane is coupling agent, and absolute ethyl alcohol is medium, at Ni-Al
2o
3catalyst surface coupling particle size is the Silicalite-1 molecular sieve crystal seed layer of 160 nanometer left and right, and make Silicalite-1 molecular sieve crystal seed layer firmly be combined in catalyst outer surface by roasting, obtain the Ni-Al that Silicalite-1 molecular sieve crystal seed layer covers
2o
3catalyst precursor;
(2) in the NaF aqueous solution, put into the Ni-Al that Silicalite-1 molecular sieve crystal seed layer that step 1 obtains covers
2o
3catalyst precursor, in the baking oven of 60 DEG C, rapid steaming solid carbon dioxide solution, obtains the Ni-Al that comprises NaF crystal
2o
3catalyst;
(3) the synthetic liquid of preparation MSU-1 molecular sieve: employing water is medium, and ethyl orthosilicate is silicon source, and ethoxylated dodecyl alcohol is template, is mixed with uniform and stable emulsion type film forming liquid;
(4) Ni-Al that comprises NaF crystal step 2 being obtained
2o
3catalyst is put into the synthetic liquid of the MSU-1 molecular sieve that step (3) obtains, in sealing stainless steel synthesis reactor, under the rotating speed of 5～60rpm, 40～100 DEG C synthetic 6～24 hours;
(5) after synthetic by step (4), the MSU-1/Ni-Al obtaining
2o
3repeatedly rinse by deionized water, remove the non-rete MSU-1 sieve particle of unnecessary film forming liquid and surface attachment, then in deionized water, soak and remove NaF unnecessary in catalyst; The MSU-1/Ni-Al obtaining
2o
3after oven dry, then in Muffle furnace, remaining template is fallen in calcination.
2. the preparation method of the mesoporous MSU-1 molecular screen membrane of a kind of coated pure silicon according to claim 1 core-shell catalyst, is characterized in that utilizing infusion process synthesizing spherical nickel-base catalyst.
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| Cedric Boissiere, et al..Ultrafiltration Membrane Made with Mesoporous MSU-X Silica.《Chem. Mater.》.2003, |
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