CN104556131A - Microwave synthesis method of ZSM-5/Silicalite-1 core-shell molecular sieve - Google Patents
Microwave synthesis method of ZSM-5/Silicalite-1 core-shell molecular sieve Download PDFInfo
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Abstract
The invention relates to a microwave synthesis method of a ZSM-5/Silicalite-1 core-shell molecular sieve and mainly aims at solving the problem that the core-shell molecular sieve can be synthesized in situ only after a nuclear-phase molecular sieve is treated when the core-shell molecular sieve is synthesized by use of a hydrothermal method. The problem is well solved by virtue of the following technical scheme: the method comprises the following steps: a) blending a silicon source, a template agent R and water in a certain ratio to form a feed liquid A; b) adding a ZSM-5 nuclear-phase molecular sieve to the feed liquid A to obtain a feed liquid B; c) putting the feed liquid B into a reaction tube and heating to the range of 50-200 DEG C by virtue of microwave for crystallizing for 1-240 minutes; d) after finishing crystallization, separating, washing and drying to obtain the ZSM-5/Silicalite-1 core-shell molecular sieve; and e) taking the solid product obtained in the step d as the nuclear-phase molecular sieve; the microwave synthesis method of the ZSM-5/Silicalite-1 core-shell molecular sieve can be applied to the industrial production of toluene disproportionation.
Description
Technical field
The present invention relates to a kind of method of Microwave synthesize ZSM-5/Silicalite-1 core-shell molecular sieve.
Background technology
Along with the development of zeolite catalysis technology, the Shape-selective of zeolite molecular sieve more and more becomes study hotspot.Because outer surface of zeolite exists the acidic site of 3-5%, these acidic sites limit without limited space, so do not have shape selective catalysis performance.
The selectivity of usual raising zeolite catalyst often will by removing outer surface acidity position method, and general surface hydroxyl hydrogenation, alkylation or alkoxylation process, rare earth, phosphorus, metal-salt or oxide modifying method, metal surfactant modification method and chemical Vapor deposition process (CVD) or the chemical liquid deposition (CLD) etc. of adopting carries out modification to the outside surface of zeolite molecular sieve.But, use these method modifications, although improve zeolite selectivity, also can reduce even to block molecular sieve aperture or duct simultaneously, its diffusion can be affected like this, catalytic activity is declined.In addition, these method of modifying or technology difficulty are often larger.
Shape function zeolite [molecular sieve is selected in preparation more and more becomes study hotspot, because the Zeolite synthesis that this catalyzer uses is relatively easy, what have again uniqueness selects shape function.Core-shell type molecular sieve arises at the historic moment in line with this thinking exactly.In the constructional feature that nuclear phase zeolite crystal outgrowth one deck shell molecular sieve is exactly core-shell molecular sieve, shell molecular sieve can play the effect of modifying nuclear phase molecular sieve outer surface acidity and modulation duct size, the negative impact in meanwhile can not result in blockage molecular sieve aperture or duct.The catalyzer prepared by core-shell type molecular sieve at present uses in aromatic hydrocarbons reaction, shows good Shape-selective [J Catal, 2006,243:389-394; Chem Mater, 2006,18(20): 4959-4966].
In many core-shell type molecular sieves, ZSM-5/Silicalite-1 type core-shell molecular sieve methylates at methylbenzene shape-selective, it is most widely used to select shape in toluene disproportionation, its constructional feature is that ZSM-5 and Silicalite-1 molecular sieve is almost identical on crystalline structure, there is nucleocapsid interface cohesion very closely with firm, good mechanical property; Shell defect is few, and parcel compactness is high; Shell thickness is adjustable, shell is by Si0
2composition, hydrophobicity is better, can strengthen absorption and the catalytic performance of nonpolar organic molecule; Shell duct is relatively more orderly, is conducive to molecular diffusion.[Adv Mater, 2005,17(16): 1985-1988] based on these advantages, ZSM-5/Silicalite-1 type core-shell molecular sieve reaches better selects shape effect than the catalyzer of the molecular sieve with general method modification.
Current synthesis ZSM-5/Silicalite-1 type core-shell molecular sieve mainly adopts Hydrothermal Synthesis mode.Fabricated in situ is the method that synthesis ZSM-5/Silicalite-1 type core-shell molecular sieve adopts at first, according to bibliographical information, making to synthesize MFI/MFI isomorphism core-shell molecular sieve in this way only has through suitable nuclear phase treatment step, nuclear phase molecular sieve just has the effect of nucleation induction, thus shell phase molecule is sieved in its surface growth, nuclear phase molecular sieve is not treated, or processing mode is improper, all can not synthesize core-shell molecular sieve.[Acta PhySico-Chimica Sinica, 2009,2(9): 1921-1927]
The Rollmann of Mobil company etc. are the reported first synthesis of ZSM-5/silicalite-1 in patent US 4088605, also have in synthesis in position and ZSM-5 core is processed, then fabricated in situ [Appl Catal A is carried out, 2007,325:316], or improve shell [catalysis journal, 30 (9): 885-890] coverage by repeatedly fabricated in situ.Regulate shell crystallization system also can be conducive to the shell that original position epitaxy goes out no acidic position, Chu etc. [US 4788374] add NH in shell crystallization system
4the fluorochemicalss such as F demonstrate this point.Except fabricated in situ core-shell molecular sieve, secondary growth method more can obtain the core-shell molecular sieve of certain thickness and higher coverage, [the Chem. Mater such as Bouizi, 18,4959] after nuclear phase ZSM-5 outside surface absorption Silicalite-1 nanosized seeds, carry out the diauxic growth of Silicalite-1 shell again, obtain the core-shell molecular sieve that shell thickness is respectively 200 ~ 1000 nm.Chinese patent CN101723401A discloses a kind of with SiO
2/ Al
2o
3mol ratio be 15 ~ 100 ZSM-5 be nuclear phase molecular sieve, with SiO
2/ Al
2o
3mol ratio be 60 ~≤100 ZSM-5 be shell phase molecule sieve, the periphery that water heat transfer goes out nuclear phase ZSM-5 is wrapped in ZSM-5 shell, shell thickness is 20 ~ 800nm, and the weight ratio between nuclear phase and shell phase is the ZSM-5/ZSM-5 core-shell type zeolite molecular sieve of 10/90 ~ 98/2.The mixture that Chinese patent CN101723402A discloses at least one in a kind of organic amine selecting ethamine, quadrol, propylamine, butylamine or itself and inorganic ammonia is the method for template Hydrothermal Synthesis ZSM-5/ZSM-5 core-shell type zeolite molecular sieve.
Generally speaking, Hydrothermal Synthesis system is just limited at present to ZSM-5/Silicalite-1 core-shell type zeolite molecular sieve, although now by repeatedly fabricated in situ, regulate shell crystallization system or adhering to the nanocrystalline diauxic growth that carries out can obtain the higher ZSM-5/Silicalite-1 core-shell type zeolite molecular sieve of coverage, the shortcoming such as all there is generated time long (general need 1 to 5 days), nuclear phase molecular sieve needs suitably process, reaction process is complicated, step is various.Microwave technology is introduced in zeolite nucleocapsid Zeolite synthesis, will effectively solve appeal problem.
Microwave heating effect is since the middle of last century is found, although just reported to some extent about being added hot preparation polymkeric substance by microwave method as far back as 1967, but until 1981 to aqueous phase system about in the research of hydration and Decomposition, microwave method just obtains first Application as a new heat-supplying mode in chemical reaction.Subsequently, microwave method is just in the news to the reaction that molecular sieve 13X dewaters, and also obtains probing into report successively subsequently by microwave method to the synthesis preparation of molecular sieve 13X and the research of regeneration.The eighties, the experimental science men of Mobil Corp. have delivered the patent being prepared molecular sieve by microwave method first, and synthesis obtains Na-A and ZSM-5 molecular sieve.[U.S. 4 778 666 (1988), Eur.Pat. Appl. 0 358 827 (1990)]。
Also be gradually seen in report with Microwave synthesize MFI molecular screen membrane, Koegler etc. [Sci.Catal.105 (1997) 2163 – 2170] are by the Silica-1 molecular screen membrane of method fabricated in situ 100nm thickness on silicon wafer of microwave fast heating and cooling.Comparatively speaking, Motuzas etc. [Microporous Mesoporous Mater.92 (2006)] the Silica-1 molecular screen membrane that microwave secondary growth method take TPAOH as template synthesis more obviously has (101) and (001) orientation.Xianming li [Chem. Res. 2010,49,5933 – 5938] think that the feature of microwave rapid and uniform heating may help the temperature in controlling crystallizing process, molecular sieve nucleation and process of growth can separately be controlled, he by shorten colloid digestion time, improve aging temperature and shorten crystallization time and synthesized the MFI structure molecular screen membrane with b orientation on stainless steel.
Visible, the molecular sieve of MFI structure can be synthesized with microwave heating.Synthesizing molecular sieve film to communicate part with the technology of synthesis core-shell molecular sieve itself, and its growth in situ is identical with the principle of diauxic growth in a broad sense, can synthesize MFI molecular screen membrane with microwave, so, also should be feasible with Microwave synthesize core-shell molecular sieve.When the special thermal induction performance of microwave can also make to synthesize core-shell molecular sieve in position, nuclear phase molecular sieve does not need through suitable process.
Summary of the invention
Technical problem solved by the invention be existing hydrothermal method when not processing nuclear phase molecular sieve, can not the problem of fabricated in situ core-shell molecular sieve.The invention provides a kind of method of Microwave synthesize ZSM-5/Silicalite-1 core-shell molecular sieve, the method has the advantages such as quick, easy and simple to handle.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of ZSM-5/Silicalite-1 core-shell type zeolite molecular sieve synthetic method, comprises the following steps:
A) silicon source, template R and water are mixed with feed liquid A by a certain percentage;
B) added in feed liquid A by ZSM-5 nuclear phase molecular sieve and obtain feed liquid B, the solvent and solute weight ratio of feed liquid A and nuclear phase molecular sieve is 2 ~ 30;
C) feed liquid B is put into reaction tubes, with microwave heating to 50 DEG C of-200 DEG C of crystallization 1-240 minute;
D), after crystallization terminates, ZSM-5/Silicalite-1 core-shell molecular sieve is obtained through separation, washing, drying;
E) solid product that obtains of steps d is as nuclear phase molecular sieve, according to a) ~ d) step repeat 1 ~ 3 time.
Silicon source wherein used in (a) step is selected from least one in silicon sol, white carbon black, tetraethoxy (TEOS).Template is selected from least one in silicon tetrafluoride, ammonium silicofluoride, Neutral ammonium fluoride, TPAOH (TPAOH) or 4-propyl bromide (TPABr).
In such scheme, the silica alumina ratio SiO of ZSM-5 nuclear phase molecular sieve
2/ Al
2o
3be 15 ~ 300.Feed liquid A mole consists of: mould silicon compares R/Si0
2be 0.01 ~ 1, water silicon compares H
2o/Si0
2be 20 ~ 200.Step c) microwave heating can be divided into two sections, first paragraph is crystallization 1-60 minute at temperature is 50 DEG C-150 DEG C, and second segment is crystallization 10-180 minute at temperature is 120 DEG C-200 DEG C.Step b) in liquid-solid ratio preferable range be 4 ~ 25.The particle diameter of ZSM-5 nuclear phase molecular sieve is 0.1 micron ~ 20 microns.When controlling second segment crystallization in step c), system pressure is 20-50psi, and the method for control is in feed liquid B, drip the organic volatiles such as alcohols within five carbon atoms and acetone.
The present invention adopts the mode of microwave heating, utilizes microwave fast without the feature of gradient-heated, by microwave vibrations, by SiO in shell mother liquor
2be induced on nuclear phase molecular sieve, rapid nucleating growth, synthesis core-shell molecular sieve, utilizes technological method of the present invention, can obtain ZSM-5/Silicalite-1 core-shell molecular sieve at short notice.
Accompanying drawing explanation
Fig. 1 is the SEM figure of ZSM-5 nuclear phase molecular sieve.
Fig. 2 is that Hydrothermal Synthesis core-shell molecular sieve center phase molecule sieve is untreated, and crystallization once obtains the SEM figure of result.
Fig. 3 is that Microwave synthesize core-shell molecular sieve center phase molecule sieve is untreated, and crystallization once obtains the SEM figure of result.
Fig. 4 is that Microwave synthesize core-shell molecular sieve center phase molecule sieve is untreated, and crystallization secondary obtains the SEM figure of result.
Fig. 5 is the XRD figure of Microwave synthesize core-shell molecular sieve.
Below by embodiment, the present invention is further elaborated.
Embodiment
[comparative example 1]
TEOS, TPAOH and water are compared R/Si0 by mould silicon
2be 0.25, water silicon compares H
2o/Si0
2be 60 be mixed with feed liquid A; By silica alumina ratio (SiO
2/ Al
2o
3) be 180, particle diameter is that the ZSM-5 nuclear phase molecular sieve (SEM figure is shown in Fig. 1) of 3 microns adds in feed liquid A and obtains feed liquid B, the weight ratio (liquid-solid ratio) of feed liquid A and nuclear phase molecular sieve is 20; Feed liquid B is put into crystallizing kettle, 180 DEG C of crystallization 1 day.After crystallization terminates, obtain solid product through separation, washing, drying.
Observe solid product SEM spectrogram (see accompanying drawing 2), only there is the self-growing phenomenon of silicate-1, do not generate core-shell molecular sieve.
[comparative example 2]
Be 0.5 by mould silicon than R/Si02 by silicon sol, TPABr and water, water silicon is 200 be mixed with feed liquid A than H2O/Si02; By silica alumina ratio (SiO
2/ Al
2o
3) be 60, particle diameter is that the ZSM-5 nuclear phase molecular sieve of 0.2 micron adds in feed liquid A and obtains feed liquid B, the weight ratio (liquid-solid ratio) of feed liquid A and nuclear phase molecular sieve is 2; Feed liquid B is put into crystallizing kettle, 180 DEG C of crystallization 2 days.After crystallization terminates, obtain solid product through separation, washing, drying.This product is repeated above-mentioned steps as nuclear phase molecular sieve, observes gained solid product SEM spectrogram, only there is the self-growing phenomenon of silicate-1, do not generate core-shell molecular sieve.
[embodiment 1]
Be 0.25 by mould silicon than R/Si02 by TEOS, TPAOH and water, water silicon is 60 be mixed with feed liquid A than H2O/Si02; Be 180 by silica alumina ratio (SiO2/Al2O3), particle diameter is that the ZSM-5 nuclear phase molecular sieve (SEM figure is shown in Fig. 1) of 3 microns adds in feed liquid A and obtains feed liquid B, the weight ratio (liquid-solid ratio) of feed liquid A and nuclear phase molecular sieve is 20; Feed liquid B is put into reaction tubes, divides two sections of heating with microwave, first paragraph crystallization 5 minutes at temperature is 150 DEG C, second segment crystallization 30 minutes at temperature is 180 DEG C.Drip in feed liquid B ethanol control second segment crystallization time system pressure be 45psi.After crystallization terminates, obtain solid product through separation, washing, drying.Observe solid product SEM spectrogram (see accompanying drawing 3), do not find that silicate-1 is from growing phenomenon, shell molecular sieve obtains core-shell molecular sieve in the growth of nuclear phase molecular sieve surface.
[embodiment 2]
Be 0.25 by mould silicon than R/Si02 by TEOS, TPAOH and water, water silicon is 60 be mixed with feed liquid A than H2O/Si02; Added in feed liquid A as nuclear phase molecular sieve by embodiment 1 gained solid product and obtain feed liquid B, the weight ratio (liquid-solid ratio) of feed liquid A and nuclear phase molecular sieve is 20; Feed liquid B is put into reaction tubes, with microwave heating, crystallization 30 minutes at temperature is 180 DEG C.Drip in feed liquid B ethanol control second segment crystallization time system pressure be 42psi.After crystallization terminates, obtain solid product through separation, washing, drying.Observe solid product SEM spectrogram (see accompanying drawing 4), do not find that silicate-1 is from growing phenomenon, obtains core-shell molecular sieve, its XRD spectrum is shown in accompanying drawing 5.
[embodiment 3]
Be 0.5 by mould silicon than R/Si02 by silicon sol, TPABr and water, water silicon is 200 be mixed with feed liquid A than H2O/Si02; Be 60 by silica alumina ratio (SiO2/Al2O3), particle diameter is that the ZSM-5 nuclear phase molecular sieve of 10 microns adds in feed liquid A and obtains feed liquid B, the weight ratio (liquid-solid ratio) of feed liquid A and nuclear phase molecular sieve is 2; Feed liquid B is put into reaction tubes, divides two sections of heating with microwave, first paragraph crystallization 30 minutes at temperature is 80 DEG C, second segment crystallization 120 minutes at temperature is 165 DEG C.Drip in feed liquid B methyl alcohol control second segment crystallization time system pressure be 22psi.After crystallization terminates, obtain solid product through separation, washing, drying, XRD and SEM characterization result shows that this product is core-shell molecular sieve.
[embodiment 4]
By white carbon black, Neutral ammonium fluoride (R1), TPABr (R2) and water by mould silicon than R1/Si02 be 0.05, R2/Si02 is 0.05, water silicon is 20 be mixed with feed liquid A than H2O/Si02; Be 15 by silica alumina ratio (SiO2/Al2O3), particle diameter is that the ZSM-5 nuclear phase molecular sieve of 0.5 micron adds in feed liquid A and obtains feed liquid B, the weight ratio (liquid-solid ratio) of feed liquid A and nuclear phase molecular sieve is 4; Feed liquid B is put into reaction tubes, divides two sections of heating with microwave, first paragraph crystallization 1 minute at temperature is 50 DEG C, second segment crystallization 120 minutes at temperature is 180 DEG C.Drip in feed liquid B butanols control second segment crystallization time system pressure be 35psi.After crystallization terminates, obtain solid product through separation, washing, drying, using this product as nuclear phase molecular sieve, repeat to obtain final solid product for twice according to above-mentioned steps, XRD and SEM characterization result shows that this product is core-shell molecular sieve.
[embodiment 5]
By TEOS, TPABr(R1), ammonium silicofluoride (R2) and water by mould silicon than R1/Si02 be 0.03, R2/Si02 is 0.02, water silicon is 150 be mixed with feed liquid A than H2O/Si02; Be 120 by silica alumina ratio (SiO2/Al2O3), particle diameter is that the ZSM-5 nuclear phase molecular sieve of 10 microns adds in feed liquid A and obtains feed liquid B, the weight ratio (liquid-solid ratio) of feed liquid A and nuclear phase molecular sieve is 20; Feed liquid B is put into reaction tubes, divides two sections of heating with microwave, first paragraph crystallization 5 minutes at temperature is 150 DEG C, second segment crystallization 10 minutes at temperature is 165 DEG C.Drip in feed liquid B amylalcohol control second segment crystallization time system pressure be 30psi.After crystallization terminates, obtain solid product through separation, washing, drying, XRD and SEM characterization result shows that this product is core-shell molecular sieve.
[embodiment 6]
Be 0.5 by mould silicon than R/Si02 by silicon sol, white carbon black, TPABr and water, water silicon is 80 be mixed with feed liquid A than H2O/Si02; Be 300 by silica alumina ratio (SiO2/Al2O3), particle diameter is that the ZSM-5 nuclear phase molecular sieve of 0.1 micron adds in feed liquid A and obtains feed liquid B, the weight ratio (liquid-solid ratio) of feed liquid A and nuclear phase molecular sieve is 6; Feed liquid B is put into reaction tubes, divides two sections of heating with microwave, first paragraph crystallization 30 minutes at temperature is 120 DEG C, second segment crystallization 30 minutes at temperature is 150 DEG C.Drip in feed liquid B propyl alcohol control second segment crystallization time system pressure be 20psi.After crystallization terminates, obtain solid product through separation, washing, drying, using this product as nuclear phase molecular sieve, repeat once to obtain final solid product according to above-mentioned steps, XRD and SEM characterization result shows that this product is core-shell molecular sieve.
[embodiment 7]
Be 1 by mould silicon than R/Si02 by silicon sol, TPAOH and water, water silicon is 100 be mixed with feed liquid A than H2O/Si02; Be 70 by silica alumina ratio (SiO2/Al2O3), particle diameter is that the ZSM-5 nuclear phase molecular sieve of 0.8 micron adds in feed liquid A and obtains feed liquid B, the weight ratio (liquid-solid ratio) of feed liquid A and nuclear phase molecular sieve is 12; Feed liquid B is put into reaction tubes, divides two sections of heating with microwave, first paragraph crystallization 25 minutes at temperature is 80 DEG C, second segment crystallization 40 minutes at temperature is 120 DEG C.Drip in feed liquid B acetone control second segment crystallization time system pressure be 23psi.After crystallization terminates, obtain solid product through separation, washing, drying, using this product as nuclear phase molecular sieve, repeat to obtain final solid product for twice according to above-mentioned steps, XRD and SEM characterization result shows that this product is core-shell molecular sieve.
[embodiment 8]
Be 0.4 by mould silicon than R/Si02 by silicon sol, Neutral ammonium fluoride and water, water silicon is 120 be mixed with feed liquid A than H2O/Si02; Be 200 by silica alumina ratio (SiO2/Al2O3), particle diameter is that the ZSM-5 nuclear phase molecular sieve of 1 micron adds in feed liquid A and obtains feed liquid B, the weight ratio (liquid-solid ratio) of feed liquid A and nuclear phase molecular sieve is 30; Feed liquid B is put into reaction tubes, divides two sections of heating with microwave, first paragraph crystallization 60 minutes at temperature is 60 DEG C, second segment crystallization 45 minutes at temperature is 160 DEG C.Drip in feed liquid B ethanol control second segment crystallization time system pressure be 35psi.After crystallization terminates, obtain solid product through separation, washing, drying, using this product as nuclear phase molecular sieve, repeat once to obtain final solid product according to above-mentioned steps, XRD and SEM characterization result shows that this product is core-shell molecular sieve.
[embodiment 9]
By TEOS, TPAOH (R1), TPABr (R2) and water by mould silicon than R1/Si02 be 0.4, R1/Si02 is 0.2, water silicon is 40 be mixed with feed liquid A than H2O/Si02; Be 240 by silica alumina ratio (SiO2/Al2O3), particle diameter is that the ZSM-5 nuclear phase molecular sieve of 1 micron adds in feed liquid A and obtains feed liquid B, the weight ratio (liquid-solid ratio) of feed liquid A and nuclear phase molecular sieve is 18; Feed liquid B is put into reaction tubes, divides two sections of heating with microwave, first paragraph crystallization 10 minutes at temperature is 50 DEG C, second segment crystallization 110 minutes at temperature is 170 DEG C.Drip in feed liquid B methyl alcohol control second segment crystallization time system pressure be 40psi.After crystallization terminates, obtain solid product through separation, washing, drying, using this product as nuclear phase molecular sieve, repeat to obtain final solid product for twice according to above-mentioned steps, XRD and SEM characterization result shows that this product is core-shell molecular sieve.
[embodiment 10]
By silicon sol, TPAOH(R1), silicon tetrafluoride (R2) and water by mould silicon than R1/Si02 be 0.04, R1/Si02 is 0.01, water silicon is 30 be mixed with feed liquid A than H2O/Si02; Be 100 by silica alumina ratio (SiO2/Al2O3), particle diameter is that the ZSM-5 nuclear phase molecular sieve of 0.1 micron adds in feed liquid A and obtains feed liquid B, the weight ratio (liquid-solid ratio) of feed liquid A and nuclear phase molecular sieve is 25; Feed liquid B is put into reaction tubes, divides two sections of heating with microwave, first paragraph crystallization 5 minutes at temperature is 50 DEG C, second segment crystallization 100 minutes at temperature is 175 DEG C.Drip in feed liquid B ethanol control second segment crystallization time system pressure be 43psi.After crystallization terminates, obtain solid product through separation, washing, drying, using this product as nuclear phase molecular sieve, repeat once to obtain final solid product according to above-mentioned steps, XRD and SEM characterization result shows that this product is core-shell molecular sieve.
[embodiment 11]
By white carbon black, TPABr(R1), Neutral ammonium fluoride (R2) and water by mould silicon than R1/Si02 be 2, R2/Si02 is 0.2, water silicon is 50 be mixed with feed liquid A than H2O/Si02; Be 260 by silica alumina ratio (SiO2/Al2O3), particle diameter is that the ZSM-5 nuclear phase molecular sieve of 0.1 micron adds in feed liquid A and obtains feed liquid B, the weight ratio (liquid-solid ratio) of feed liquid A and nuclear phase molecular sieve is 30; Feed liquid B is put into reaction tubes, divides two sections of heating with microwave, first paragraph crystallization 15 minutes at temperature is 60 DEG C, second segment crystallization 80 minutes at temperature is 180 DEG C.Drip in feed liquid B acetone control second segment crystallization time system pressure be 45psi.After crystallization terminates, obtain solid product through separation, washing, drying, using this product as nuclear phase molecular sieve, repeat once to obtain final solid product according to above-mentioned steps, XRD and SEM characterization result shows that this product is core-shell molecular sieve.
[embodiment 12]
By silicon sol, TPABr(R1), Neutral ammonium fluoride (R2) and water by mould silicon than R1/Si02 be 0.6, R2/Si02 is 0.1, water silicon is 55 be mixed with feed liquid A than H2O/Si02; Be 200 by silica alumina ratio (SiO2/Al2O3), particle diameter is that the ZSM-5 nuclear phase molecular sieve of 0.1 micron adds in feed liquid A and obtains feed liquid B, the weight ratio (liquid-solid ratio) of feed liquid A and nuclear phase molecular sieve is 10; Feed liquid B is put into reaction tubes, divides two sections of heating with microwave, first paragraph crystallization 20 minutes at temperature is 80 DEG C, second segment crystallization 180 minutes at temperature is 200 DEG C.Drip in feed liquid B butanols control second segment crystallization time system pressure be 40psi.After crystallization terminates, obtain solid product through separation, washing, drying, using this product as nuclear phase molecular sieve, obtain final solid product in triplicate according to above-mentioned steps, XRD and SEM characterization result shows that this product is core-shell molecular sieve.
[embodiment 13]
By TEOS, TPABr(R1), ammonium silicofluoride (R2) and water by mould silicon than R1/Si02 be 0.1, R2/Si02 is 0.05, water silicon is 300 be mixed with feed liquid A than H2O/Si02; Be 170 by silica alumina ratio (SiO2/Al2O3), particle diameter is that the ZSM-5 nuclear phase molecular sieve of 5 microns adds in feed liquid A and obtains feed liquid B, the weight ratio (liquid-solid ratio) of feed liquid A and nuclear phase molecular sieve is 8; Feed liquid B is put into reaction tubes, divides two sections of heating with microwave, first paragraph crystallization 10 minutes at temperature is 100 DEG C, second segment crystallization 15 minutes at temperature is 175 DEG C.Drip in feed liquid B ethanol control second segment crystallization time system pressure be 46psi.After crystallization terminates, obtain solid product through separation, washing, drying, using this product as nuclear phase molecular sieve, repeat once to obtain final solid product according to above-mentioned steps, XRD and SEM characterization result shows that this product is core-shell molecular sieve.
[embodiment 14]
By silicon sol, TPAOH(R1), TPABr(R2) and water by mould silicon than R1/Si02 be 0.04, R2/Si02 is 0.04, water silicon is 10 be mixed with feed liquid A than H2O/Si02; Be 50 by silica alumina ratio (SiO2/Al2O3), particle diameter is that the ZSM-5 nuclear phase molecular sieve of 8 microns adds in feed liquid A and obtains feed liquid B, the weight ratio (liquid-solid ratio) of feed liquid A and nuclear phase molecular sieve is 12; Feed liquid B is put into reaction tubes, divides two sections of heating with microwave, first paragraph crystallization 2 minutes at temperature is 50 DEG C, second segment crystallization 20 minutes at temperature is 165 DEG C.Drip in feed liquid B amylalcohol control second segment crystallization time system pressure be 33psi.After crystallization terminates, obtain solid product through separation, washing, drying, using this product as nuclear phase molecular sieve, repeat once to obtain final solid product according to above-mentioned steps, XRD and SEM characterization result shows that this product is core-shell molecular sieve.
[embodiment 15]
Be 0.5 by mould silicon than R/Si02 by TEOS, silicon tetrafluoride and water, water silicon is 80 be mixed with feed liquid A than H2O/Si02; Be 260 by silica alumina ratio (SiO2/Al2O3), particle diameter is that the ZSM-5 nuclear phase molecular sieve of 3 microns adds in feed liquid A and obtains feed liquid B, the weight ratio (liquid-solid ratio) of feed liquid A and nuclear phase molecular sieve is 15; Feed liquid B is put into reaction tubes, divides two sections of heating with microwave, first paragraph crystallization 15 minutes at temperature is 110 DEG C, second segment crystallization 90 minutes at temperature is 150 DEG C.Drip in feed liquid B amylalcohol control second segment crystallization time system pressure be 25psi.After crystallization terminates, obtain solid product through separation, washing, drying, using this product as nuclear phase molecular sieve, repeat once to obtain final solid product according to above-mentioned steps, XRD and SEM characterization result shows that this product is core-shell molecular sieve.
[embodiment 16]
Be 0.3 by mould silicon than R/Si02 by white carbon black, TEOS, ammonium silicofluoride and water, water silicon is 140 be mixed with feed liquid A than H2O/Si02; Be 60 by silica alumina ratio (SiO2/Al2O3), particle diameter is that the ZSM-5 nuclear phase molecular sieve of 0.5 micron adds in feed liquid A and obtains feed liquid B, the weight ratio (liquid-solid ratio) of feed liquid A and nuclear phase molecular sieve is 4; Feed liquid B is put into reaction tubes, divides two sections of heating with microwave, first paragraph crystallization 20 minutes at temperature is 115 DEG C, second segment crystallization 60 minutes at temperature is 155 DEG C.Drip in feed liquid B ethanol control second segment crystallization time system pressure be 25psi.After crystallization terminates, obtain solid product through separation, washing, drying, using this product as nuclear phase molecular sieve, repeat once to obtain final solid product according to above-mentioned steps, XRD and SEM characterization result shows that this product is core-shell molecular sieve.
Claims (10)
1. a method for Microwave synthesize ZSM-5/Silicalite-1 core-shell molecular sieve, comprises the following steps:
A) silicon source, template R and water are mixed with feed liquid A by a certain percentage; Wherein, mould silicon compares R/Si0
2be 0.01 ~ 2, water silicon compares H
2o/Si0
2be 10 ~ 300;
B) added in feed liquid A by ZSM-5 nuclear phase molecular sieve and obtain feed liquid B, the solvent and solute weight ratio of feed liquid A and nuclear phase molecular sieve is 2 ~ 30;
C) feed liquid B is put into reaction tubes, with microwave heating to 50 DEG C ~ 200 DEG C crystallization 1 ~ 240 minute;
D), after crystallization terminates, ZSM-5/Silicalite-1 core-shell molecular sieve is obtained through separation, washing, drying;
E) solid product that obtains of steps d is as nuclear phase molecular sieve, according to a) ~ d) step repeat 1 ~ 3 time.
2. the method for Microwave synthesize ZSM-5/Silicalite-1 core-shell molecular sieve according to claim 1, is characterized in that described silicon source is selected from least one in silicon sol, white carbon black, tetraethoxy.
3. the method for Microwave synthesize ZSM-5/Silicalite-1 core-shell molecular sieve according to claim 1, is characterized in that described template is selected from least one in silicon tetrafluoride, ammonium silicofluoride, Neutral ammonium fluoride, TPAOH or 4-propyl bromide.
4. the method for Microwave synthesize ZSM-5/Silicalite-1 core-shell molecular sieve according to claim 1, is characterized in that mole consisting of of feed liquid A: mould silicon compares R/Si0
2be 0.01 ~ 1, water silicon compares H
2o/Si0
2be 20 ~ 200.
5. the method for Microwave synthesize ZSM-5/Silicalite-1 core-shell molecular sieve according to claim 1, it is characterized in that step c) microwave heating be divided into two sections, first paragraph crystallization 1 ~ 60 minute at temperature is 50 DEG C ~ 150 DEG C, second segment crystallization 10 ~ 180 minutes at temperature is 120 DEG C ~ 200 DEG C.
6. the method for Microwave synthesize ZSM-5/Silicalite-1 core-shell molecular sieve according to claim 1, is characterized in that step b) in liquid-solid ratio be 4 ~ 25.
7. the method for Microwave synthesize ZSM-5/Silicalite-1 core-shell molecular sieve according to claim 1, is characterized in that the particle diameter of ZSM-5 nuclear phase molecular sieve is 0.1 micron ~ 20 microns.
8. the method for Microwave synthesize ZSM-5/Silicalite-1 core-shell molecular sieve according to claim 1, is characterized in that step c) in control second segment crystallization time system pressure be 20-50psi.
9. the method for Microwave synthesize ZSM-5/Silicalite-1 core-shell molecular sieve according to claim 8, is characterized in that step c) in the method for system pressure when controlling second segment crystallization for drip volatile organic matter in feed liquid B.
10. the method for Microwave synthesize ZSM-5/Silicalite-1 core-shell molecular sieve according to claim 9, is characterized in that the volatile organic matter dripped is alcohols within five carbon atoms and acetone.
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| CN109399665A (en) * | 2018-09-29 | 2019-03-01 | 山东国瓷功能材料股份有限公司 | A kind of composite construction SSZ-13@Silicalite-1 molecular sieve and preparation method thereof, application |
| CN110668460A (en) * | 2019-11-15 | 2020-01-10 | 广西师范大学 | Method for synthesizing Silicalite-1 molecular sieve by using double templates |
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