CN105502430A - Beta/MCM-49 composite molecular sieve with core-shell structure and preparation method thereof - Google Patents

Beta/MCM-49 composite molecular sieve with core-shell structure and preparation method thereof Download PDF

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CN105502430A
CN105502430A CN201410533375.4A CN201410533375A CN105502430A CN 105502430 A CN105502430 A CN 105502430A CN 201410533375 A CN201410533375 A CN 201410533375A CN 105502430 A CN105502430 A CN 105502430A
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molecular sieve
beta
mcm
composite molecular
composite
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CN105502430B (en
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杨卫亚
凌凤香
王少军
沈智奇
季洪海
王丽华
郭长友
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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Abstract

The invention discloses a Beta/MCM-49 composite molecular sieve with a core-shell structure and a preparation method thereof. The Beta molecular sieve is taken as the core phase, and the MCM-49 molecular sieve is the shell layer. The size of the core phase is 0.3 to 3.0 [mu]m, and the preferable size is 0.7 to 2.0 [mu]m. The thickness of the shell layer is 0.1 to 6.0 [mu]m, and the preferable thickness is 0.3 to 5.0 [mu]m. The shell layer accounts for 35 to 90 % of the total weight of composite molecular sieve, and the preferable content of shell layer is 50 to 80%. The preparation method comprises the following steps: subjecting Beta molecular sieve to surface plasma modification, and then taking the modified Beta molecular sieve as the crystal nucleus to prepare the Beta/MCM-49 composite molecular sieve. The composite molecular sieve has a good core-shell cladding form and has a good application prospect in alkylation reaction between alkene and benzene.

Description

Beta/MCM-49 composite molecular screen of a kind of nucleocapsid structure and preparation method thereof
Technical field
The invention belongs to field of inorganic material preparing technology, Beta/MCM-49 composite molecular screen relating to a kind of nucleocapsid structure particularly and preparation method thereof.
Background technology
MCM-49 topology molecular sieve type is MWW, belongs to the molecular screen material of same type with MCM-22.MCM-49 and Beta molecular sieve is applied comparatively extensive in propylene and benzene alkylation preparing isopropylbenzene are produced.MCM-49 and MCM-22 molecular sieve is compared, and in propylene and benzene alkylation reaction, catalytic performance is all comparatively good generally, but also has unique reaction advantage respectively.Because MCM-49 and Beta molecular sieve has different catalysis characteristicses separately, if two kinds of molecular sieves are carried out organic composite, and give the rational acid distribution of composite crystal, good shape selectivity, learn from other's strong points to offset one's weaknesses, make the advantages such as its shape selectivity giving full play to MCM-49 molecular sieve, stability and Beta molecular sieve high reactivity, special concerted catalysis effect may be produced to propylene and benzene alkylation reaction.The form of composite molecular screen is varied, and the composite molecular screen of nucleocapsid structure is a kind of ideal structural form.At present, about the synthesis of the composite molecular screen of nucleocapsid structure, main policies is prepared by two step crystallization methods.Put into by a kind of powder of molecular sieve in the second molecular sieve gel, crystallization obtains the hud typed composite molecular screen that the latter wraps up the former.But two step crystallization method building-up processes are wayward, are difficult to obtain perfect nucleocapsid clad structure, product is the sieve particle isolated mixture existed separately often.
CN103058219A discloses a kind of preparation method of Y-MOR composite molecular sieve.The method first carries out suitable alkaline purification to prepare structure directing agent to mordenite, then after Y zeolite, mineral alkali, water being uniformly mixed, adding structure directing agent, aluminium source and silicon source successively, then obtain Y-MOR composite molecular sieve through hydrothermal crystallizing.
CN101618883A discloses a kind of synthetic method of Beta/Y composite molecular screen.1st step, preparation Y structure directing agent; 2nd step, stirs sodium hydroxide, water, aluminium source, Beta molecular sieve pulp and Y structure directing agent according to a certain ratio, carries out crystallization, obtained Beta/Y composite molecular screen.The method is with Beta molecular sieve pulp for initial feed, although decrease synthesis step, the Compound Degree of sintetics is wayward, and Beta and Y zeolite are self-existent in a large number, do not form nucleocapsid structure.
CN1583563A discloses a kind of two micropore Beta/Y composite molecular screen and preparation method thereof.It is characterized in that adopting two-step approach, the first step prepares Na-Beta molecular sieve; Second step, appropriate sodium aluminate solution is added on the basis of Na-Beta molecular sieve, regulates the basicity of material system, synthesis Beta/Y composite molecular screen.The Compound Degree of the method gained composite molecular screen is wayward, and a large amount of Beta and Y zeolite do not form nucleocapsid structure.
The preparation of above-mentioned composite molecular screen is all by the improvement of chemically treated means to two step crystallization method synthesis core-shell structure compound molecular sieve methods substantially, still there is various deficiency.
Summary of the invention
For the deficiencies in the prior art, Beta/MCM-49 composite molecular screen that the present invention proposes a kind of nucleocapsid structure and preparation method thereof.First the present invention carries out surface plasma modification to Beta molecular sieve, then with it for nucleus, prepared the hud typed composite molecular screen of Beta/MCM-49, this composite molecular screen has the coated form of good nucleocapsid.
The Beta/MCM-49 composite molecular screen of nucleocapsid structure of the present invention, with Beta molecular sieve for nuclear phase, MCM-49 molecular sieve is shell, nuclear phase is of a size of 0.3-3.0 μm, preferred 0.7-2.0 μm, and shell thickness is 0.1-6.0 μm, preferred 0.3-5.0 μm, with composite molecular screen weight for benchmark, shell content is 35%-90%, is preferably 50%-80%.
The specific surface of composite molecular screen of the present invention is 400-700m 2/ g, pore volume is 0.2-0.7ml/g.
The Beta/MCM-49 composite molecular screen preparation method of nucleocapsid structure of the present invention, comprises following content:
(1) by Beta molecular sieve powder activation treatment, cool for subsequent use;
(2) with Ar-H 2plasma atmosphere treatments B eta molecular sieve;
(3) joined in the organic formwork agent aqueous solution by the Beta molecular sieve after process, mix, molecular sieve fully adsorbs organic formwork agent, then joins in above-mentioned Beta molecular sieve suspension liquid by sodium hydroxide, aluminium source, silicon source, plastic, crystallization; Wherein organic formwork agent is HMI(U-4527);
(4) crystallization product is after washing, filtration, drying, obtains the former powder of Beta/MCM-49 nucleocapsid composite molecular screen, obtains the Beta/MCM-49 nucleocapsid composite molecular screen of stripper plate after roasting.
In the inventive method, the Beta molecular sieve described in step (1) need remove contained organic formwork through roasting, and (described silica alumina ratio is SiO to the silica alumina ratio of wherein Beta molecular sieve herein 2with Al 2o 3mol ratio) be 15-35, grain-size is 0.5-3.0 μm.
In the inventive method, the activation treatment condition described in step (1) is: activate 1-5 hour at 150-350 DEG C.Room temperature is cooled to for subsequent use after activation treatment.
In the inventive method, the plasma treatment described in step (2) is carried out in vacuum plasma producer, and plasma processing condition is: vacuum tightness 10-100mTorr, Ar and H 2total flux is that 10-60sccm(marks condition milliliter per minute), Ar/H 2(mol ratio) is 0.5-3.5, and exciting power is 50-300W, and the treatment time is 1-30min.
In the inventive method, described in step (3), silicon source is silicon sol and/or silicic acid, is preferably silicon sol; Described aluminium source is sodium metaaluminate and/or aluminum chloride, is preferably sodium metaaluminate.
In the inventive method, final material system in step (3), disregard Beta molecular sieve, other material meets mol ratio and is: SiO 2/ Al 2o 3for 20-35, OH -/ SiO 2for 0.12-0.18, H 2o/SiO 2for 20-45, HMI/SiO 2for 0.1-0.5.
In the inventive method, in step (3) with the quality of silicon oxide for benchmark, the consumption of Beta molecular sieve is the 10%-65% of siliconoxide mass, be preferably 20%-50%.
In the inventive method, the plastic process described in step (3) is generally carried out under normal temperature condition.
In the inventive method, the crystallization condition described in step (3) is: crystallization 6-60 hour under 165-185 DEG C of Dynamic Hydrothermal condition.
In the inventive method, the drying conditions described in step (4) is: 80-150 DEG C of dry 2-20 hour; Roasting condition is: 400-800 DEG C of roasting 0.5-8 hour.
The present invention is with Ar-H 2plasma body reasonable sanding Beta molecular sieve, high energy plasma bombardment molecular sieve surface, impels metastable aluminium tetrahedron in Si-O-Al to rupture in alumina key junction, forms the aluminum-oxygen tetrahedron with lone-pair electron and new Si-OH terminal hydroxy group.The electronegativity of molecular sieve surface reduces, and alumina bond rupture occurs the aluminum-oxygen tetrahedron with lone-pair electron further, produces positive polarity.Beta molecular sieve after Cement Composite Treated by Plasma is immersed in HMI solution, and HMI is adsorbed to Beta molecular sieve surface, forms the concentration gradient centered by Beta.At MCM-49 crystallization stage, because Beta molecular sieve precursor has electronegativity, and the HMI concentration that Beta surface is higher, guide electronegativity shell MCM-49 molecular sieve precursor around nucleus growth in Beta by electrical attraction effect, in crystallization process, there is hydroxyl condensation, crystallization, wrap up layer by layer in molecular sieve precursor, thus forms the good Beta/MCM-49 core-shell structure compound molecular sieve of form further.Method of the present invention adopts normal-temperature vacuum Cement Composite Treated by Plasma, only produces slight effect to molecular sieve outer surface, and less to inherent structure influence, and nucleocapsid parcel has higher success rate.Beta/MCM-49 composite molecular screen of the present invention achieves good nucleocapsid parcel effect, and the alkylated reaction of alkene and benzene has good catalytic effect.
Accompanying drawing explanation
Fig. 1 is the X ray diffracting spectrum of the Beta/MCM-49 composite molecular screen of nucleocapsid structure prepared by embodiment 1.
Fig. 2 is the stereoscan photograph of the Beta molecular sieve that embodiment 1 uses.
Fig. 3 is the stereoscan photograph of the Beta/MCM-49 composite molecular screen of nucleocapsid structure prepared by embodiment 1.
Fig. 4 is the stereoscan photograph that comparative example 1 prepares sample.
Embodiment
Below by embodiment to the inventive method detailed description in addition.The crystal formation of composite molecular screen adopts X-ray diffraction to characterize, and pattern adopts scanning electronic microscope to carry out observing and dimensional measurement.
Embodiment 1
By the silica alumina ratio of certain mass be 23 Beta molecular sieve (grain-size 1.7 μm) powder at 300 DEG C, activate 3h, vacuum plasma producer is inserted after naturally cooling, system excitation of plasma program (vacuum tightness 70mTorr, gas flow 45sccm, Ar/H are set 2be 0.8, power 50W), with Ar-H 2plasma atmosphere treatments B eta molecular sieve 5min.Beta molecular sieve after process is immersed in certain density HMI solution, stirs and make it fully to adsorb organic formwork agent.Sodium hydroxide, sodium metaaluminate, silicon sol to be joined successively in above-mentioned Beta molecular sieve suspension liquid and normal temperature plastic, final gel masses proportioning (Beta is not counted in) meets: SiO again 2/ Al 2o 3be 30, OH -/ SiO 2be 0.12, H 2o/SiO 2be 35, HMI/SiO 2be 0.35.Wherein the content of Beta is SiO 220% of quality.By gel crystallization 15h under 185 DEG C of Dynamic Hydrothermal conditions.After reaction terminates, washing, filter, 120 DEG C of dryings 12 hours and 550 DEG C of roastings are after 5 hours, namely obtain the Beta/MCM-49 nucleocapsid composite molecular screen of stripper plate.Detect through XRD, mixture has the typical diffractive peak of Beta molecular sieve and MCM-49, and occurs without stray crystal; Observe through SEM, product has good nucleocapsid complex morphological, and wherein Beta is core, size about 1.7 μm, and MCM-49 is shell, and thickness on average about 2.2 μm, shell quality accounts for 75%.Composite molecular screen pore volume is 0.54ml/g, and specific surface is 428m 2/ g.
Embodiment 2
By the silica alumina ratio of certain mass be 23 Beta molecular sieve (grain-size 1.7 μm) powder at 350 DEG C, activate 1h, vacuum plasma producer is inserted after naturally cooling, system excitation of plasma program (vacuum tightness 20mTorr, gas flow 60sccm, Ar/H are set 2be 1.3, power 100W), with Ar-H 2plasma atmosphere treatments B eta molecular sieve 10min.Beta molecular sieve after process is immersed in certain density HMI solution, stirs and make it fully to adsorb organic formwork agent.Sodium hydroxide, sodium metaaluminate, silicon sol to be joined successively in above-mentioned Beta molecular sieve suspension liquid and normal temperature plastic, final gel masses proportioning (Beta is not counted in) meets: SiO again 2/ Al 2o 3be 35, OH -/ SiO 2be 0.15, H 2o/SiO 2be 40, HMI/SiO 2be 0.25.Wherein the content of Beta is SiO 240% of quality.By gel crystallization 48h under 170 DEG C of Dynamic Hydrothermal conditions.After reaction terminates, through washing, filter, 120 DEG C of dryings 12 hours and 550 DEG C of roastings are after 7 hours, namely obtain the Beta/MCM-49 nucleocapsid composite molecular screen of stripper plate.Detect through XRD, mixture has the typical diffractive peak of Beta molecular sieve and MCM-49, and occurs without stray crystal; Observe through SEM, product has good nucleocapsid complex morphological, and wherein Beta is core, size about 1.7 μm, and MCM-49 is shell, and mean thickness about 2.1 μm, shell quality accounts for 60%.Composite molecular screen pore volume is 0.41ml/g, and specific surface is 493m 2/ g.
Embodiment 3
By the silica alumina ratio of certain mass be 34 Beta molecular sieve (grain-size 0.7 μm) powder at 200 DEG C, activate 5h, vacuum plasma producer is inserted after naturally cooling, system excitation of plasma program (vacuum tightness 50mTorr, gas flow 30sccm, Ar/H are set 2be 3.0 power 200W), with Ar-H 2plasma atmosphere treatments B eta molecular sieve 15min.Beta molecular sieve after process is immersed in certain density HMI solution, stirs and make it fully to adsorb organic formwork agent.Sodium hydroxide, sodium metaaluminate, silicon sol to be joined successively in above-mentioned Beta molecular sieve suspension liquid and normal temperature plastic, final gel masses proportioning (Beta is not counted in) meets: SiO again 2/ Al 2o 3be 20, OH -/ SiO 2be 0.18, H 2o/SiO 2be 40, HMI/SiO 2be 0.50.Wherein the content of Beta is SiO 250% of quality.
By gel crystallization 60h under 165 DEG C of Dynamic Hydrothermal conditions.After reaction terminates, through washing, filter, 120 DEG C of dryings 12 hours and 550 DEG C of roastings are after 7 hours, namely obtain the Beta/MCM-49 nucleocapsid composite molecular screen of stripper plate.Detect through XRD, mixture has the typical diffractive peak of Beta molecular sieve and MCM-49, and occurs without stray crystal; Observe through SEM, product has good nucleocapsid complex morphological, and wherein Beta is core, size about 0.8 μm, and MCM-49 is shell, and thickness about 0.6 μm, shell quality accounts for 50%.Composite molecular screen pore volume is 0.67ml/g, and specific surface is 659m 2/ g.
Comparative example 1
By the silica alumina ratio of certain mass be 23 Beta molecular sieve (grain-size on average about 1.7 μm) powder be immersed in certain density HMI solution, stir and make it fully to adsorb organic formwork agent.Sodium hydroxide, sodium metaaluminate, silicon sol to be joined successively in above-mentioned Beta molecular sieve suspension liquid and normal temperature plastic, final gel masses proportioning (Beta is not counted in) meets: SiO again 2/ Al 2o 3be 30, OH -/ SiO 2be 0.12, H 2o/SiO 2be 35, HMI/SiO 2be 0.35.Wherein the content of Beta is SiO 220% of quality.
By gel crystallization 15h under 185 DEG C of Dynamic Hydrothermal conditions.After reaction terminates, through washing, filter, 120 DEG C of dryings 12 hours and 550 DEG C of roastings are after 5 hours, namely obtain the composite sample of stripper plate.Detect through XRD, mixture has the typical diffractive peak of Beta molecular sieve and MCM-49; Observe through SEM, in product, most of MCM-49 and Beta is separated, and does not have good nucleocapsid complex morphological.

Claims (14)

1. a Beta/MCM-49 composite molecular screen for nucleocapsid structure, is characterized in that: with Beta molecular sieve for nuclear phase, MCM-49 molecular sieve is shell, nuclear phase is of a size of 0.3-3.0 μm, shell thickness is 0.1-6.0 μm, and with composite molecular screen weight for benchmark, shell content is 35%-90%.
2. according to composite molecular screen according to claim 1, it is characterized in that: nuclear phase is of a size of 0.7-2.0 μm, shell thickness is 0.3-5.0 μm, and with composite molecular screen weight for benchmark, shell content is 50%-80%.
3. according to the composite molecular screen described in claim 1 or 2, it is characterized in that: the specific surface of composite molecular screen is 400-700m 2/ g, pore volume is 0.2-0.7ml/g.
4. the composite molecular screen preparation method described in claim 1 or 2, is characterized in that comprising following content: (1), by Beta molecular sieve powder activation treatment, cools for subsequent use; (2) with Ar-H 2plasma atmosphere treatments B eta molecular sieve; (3) the Beta molecular sieve after process is joined in the organic formwork agent aqueous solution, mix, then sodium hydroxide, aluminium source, silicon source are joined in above-mentioned Beta molecular sieve suspension liquid, plastic, crystallization; Wherein organic formwork agent is HMI, U-4527; (4) crystallization product is after washing, filtration, drying, obtains the former powder of Beta/MCM-49 nucleocapsid composite molecular screen, obtains the Beta/MCM-49 nucleocapsid composite molecular screen of stripper plate after roasting.
5. in accordance with the method for claim 4, it is characterized in that: the Beta molecular sieve described in step (1) removes contained organic formwork through roasting, wherein the silica alumina ratio of Beta molecular sieve is 15-35, and grain-size is 0.5-3.0 μm.
6. in accordance with the method for claim 4, it is characterized in that: the activation treatment condition described in step (1) is: activate 1-5 hour at 150-350 DEG C.
7. in accordance with the method for claim 4, it is characterized in that: the plasma processing condition described in step (2) is: vacuum tightness 10-100mTorr, Ar and H 2total flux is 10-60sccm, Ar/H 2mol ratio be 0.5-3.5, exciting power is 50-300W, and the treatment time is 1-30min.
8. in accordance with the method for claim 4, it is characterized in that: described in step (3), silicon source is silicon sol and/or silicic acid.
9. in accordance with the method for claim 4, it is characterized in that: the aluminium source described in step (3) is sodium metaaluminate and/or aluminum chloride.
10. in accordance with the method for claim 4, it is characterized in that: final material system in step (3), disregard Beta molecular sieve, other material meets following mol ratio: SiO 2/ Al 2o 3for 20-35, OH -/ SiO 2for 0.12-0.18, H 2o/SiO 2for 20-45, HMI/SiO 2for 0.1-0.5.
11. in accordance with the method for claim 4, it is characterized in that: in step (3) with the quality of silicon oxide for benchmark, the consumption of Beta molecular sieve is the 10%-65% of siliconoxide mass.
12. in accordance with the method for claim 4, it is characterized in that: the crystallization condition described in step (3) is: crystallization 12-60 hour under 165-185 DEG C of Dynamic Hydrothermal condition.
13. in accordance with the method for claim 4, it is characterized in that: the drying conditions described in step (4) is: 80-150 DEG C of dry 2-20 hour; Roasting condition is: 400-800 DEG C of roasting 0.5-8 hour.
Composite molecular screen described in 14. 1 kinds of claims 1 or 2 is applied to the alkylated reaction of alkene and benzene.
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CN107185488A (en) * 2017-05-27 2017-09-22 华东理工大学 A kind of hud typed composite molecular screen and its purposes for separating carbon dioxide
CN107311197A (en) * 2017-05-27 2017-11-03 华东理工大学 The method of plasma technique processing synthesis core-shell structure compound molecular sieve material
CN109529922A (en) * 2018-11-30 2019-03-29 中国科学院大连化学物理研究所 A kind of Beta@Silicalite-1 type core-shell molecular sieve and its preparation method and application
CN113387370A (en) * 2020-03-11 2021-09-14 中国科学院深圳先进技术研究院 Method for adjusting crystal morphology and structure of zeolite molecular sieve by using low-temperature plasma technology

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CN103831129A (en) * 2012-11-27 2014-06-04 中国石油天然气股份有限公司 Catalyst for synthesizing ethylbenzene through ethylene and benzene liquid phase method and preparation and application of catalyst

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WO2012030440A1 (en) * 2010-08-30 2012-03-08 Exxonmobil Chemical Patents Inc. Improved alkylation process
CN102464328A (en) * 2010-11-11 2012-05-23 中国石油天然气股份有限公司 Preparation method of H beta/HMCM-49 compound molecular sieve
CN102863311A (en) * 2011-07-08 2013-01-09 中国石油天然气股份有限公司 Method for producing isopropylbenzene through transalkylation
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Publication number Priority date Publication date Assignee Title
CN107185488A (en) * 2017-05-27 2017-09-22 华东理工大学 A kind of hud typed composite molecular screen and its purposes for separating carbon dioxide
CN107311197A (en) * 2017-05-27 2017-11-03 华东理工大学 The method of plasma technique processing synthesis core-shell structure compound molecular sieve material
CN109529922A (en) * 2018-11-30 2019-03-29 中国科学院大连化学物理研究所 A kind of Beta@Silicalite-1 type core-shell molecular sieve and its preparation method and application
CN113387370A (en) * 2020-03-11 2021-09-14 中国科学院深圳先进技术研究院 Method for adjusting crystal morphology and structure of zeolite molecular sieve by using low-temperature plasma technology
CN113387370B (en) * 2020-03-11 2023-01-03 中国科学院深圳先进技术研究院 Method for adjusting crystal morphology and structure of zeolite molecular sieve by using low-temperature plasma technology

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