CN102463135B - EU-1/MOR composite molecular sieve and preparation method thereof - Google Patents
EU-1/MOR composite molecular sieve and preparation method thereof Download PDFInfo
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- CN102463135B CN102463135B CN2010105361972A CN201010536197A CN102463135B CN 102463135 B CN102463135 B CN 102463135B CN 2010105361972 A CN2010105361972 A CN 2010105361972A CN 201010536197 A CN201010536197 A CN 201010536197A CN 102463135 B CN102463135 B CN 102463135B
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Abstract
The invention discloses an EU-1/MOR composite molecular sieve and its preparation method. The composite molecular sieve simultaneously has EU-1 molecular sieve crystal phase and MOR zeolite crystal phase. The pore volume of the composite molecular sieve's mesopore accounts for 30-75% of the total pore volume. The mesopore aperture ranges from 30nm to 70nm. A synthetic method of the composite molecular sieve provided by the invention comprises the following steps of: fully and uniformly mixing the EU-1 molecular sieve, a silicon source, alkali, water and a template, carrying out hydrothermal crystallization at the temperature of 140-170 DEG C for 1-4 days, and recovering to obtain the EU-1/MOR composite molecular sieve. The composite molecular sieve provided by the invention has two molecular sieve crystal phases, namely the EU-1 and MOR molecular sieve crystal phases, and simultaneously has large-aperture pore channels. According to the invention, application problems of the microporous molecular sieve are solved.
Description
Technical field
The present invention relates to a kind of double-micropore composite molecular sieve and preparation method thereof, specifically a kind of preparation method of EU-1/MOR double-micropore composite molecular sieve.
Background technology
Modenite (MOR) is one of human knowledge's zeolite the earliest.1948, the use sodium carbonate such as HOW were mineralizer, used silicic acid gel and sodium aluminate aqueous solution to make the raw water thermal crystallisation, manually synthesized first modenite.Heat-resisting, the acidproof and water resistant vapour function admirable of modenite.Modenite has good xylene isomerization performance, is the main acidic components of industrial xylene isomerization catalyst at present.Chinese patent CN1044053, CN1110630 and CN1156642 have embodied the performance of modenite on xylene isomerization.
The EU-1 molecular sieve is a kind of mesopore high-silica zeolite, have-the netted micropore canals structure of Wei, contain the straight-through duct of ten-ring (orifice diameter be 0.58 * 0.41nm) and with it the twelve-ring side pocket of vertical UNICOM (being of a size of 0.68 * 0.58 * 0.81nm) structure, is that a class has the molecular sieve of characteristics very much on pore passage structure.The EU-1 molecular sieve is applied to xylene isomerization as the catalyst of acid constituent element, has good catalytic performance.Adopting EUO topological structure molecular sieve under identical condition is that the xylene isomerization catalyst of acid constituent element has higher activity and selectivity, has good prospects for commercial application.Chinese patent CN01121423.6, CN01121442.2 and CN200610112735.9 have embodied the performance of EU-1 molecular sieve on the dimethylbenzene isomery.
The above-mentioned EU-1 of showing molecular sieve and MOR zeolite have important purposes at petrochemical industry, are the important acidic components of xylene isomerization catalyst.Characteristics due to EU-1 type zeolite molecular sieve and MOR zeolite molecular sieve, EU-1 type zeolite molecular sieve and MOR zeolite molecular sieve are combined with each other, both learn from other's strong points to offset one's weaknesses to make it, mutually supplement, synthetic a kind of composite zeolite molecular sieve with dual structure and acidity can be regulated both structure and sour the distribution, better meets the demand of commercial Application.
Two kinds of molecular sieves are all micro porous molecular sieves, and the micropore canals significant adverse is in the diffusion of absorption, reaction and the product of reactant, and the pore properties of molecular sieve has limited the carrying out of reaction.Exist larger duct, aperture effectively to address the above problem.And existing composite molecular screen, as Industrial Catalysis 10 phases in 2008 " preset crystal seed synthesizes the EU-1/MOR composite molecular screen " introduced a kind of take C6 (HMBr2) as template, modenite (MOR) is as crystal seed, adopt preset crystal seed method synthetic composite molecular screen EU-1/MOR in the dense system of height, the composite molecular screen product that it obtains does not have the duct of larger aperture.
Summary of the invention
The purpose of this invention is to provide a kind of EU-1 molecular sieve of combination and composite molecular screen of MOR zeolite and preparation method thereof, composite molecular screen of the present invention is when having above-mentioned two kinds of molecular sieve crystalline phases, duct with larger aperture, solved micro porous molecular sieve runs in application problem.
EU-1/MOR composite molecular screen of the present invention has EU-1 molecular sieve crystalline phase and MOR zeolite crystalline phase simultaneously, and the mesoporous pore volume of composite molecular screen accounts for 30%～75% of total pore volume, and mesoporous aperture (bore dia) concentrates on 30～70nm.
EU-1/MOR composite molecular screen of the present invention has the XRD feature spectrogram of EU-1 molecular sieve and MOR zeolite simultaneously.The analysis showed that by ESEM (SEM) and X-ray diffraction (XRD), the structure of this composite molecular screen is that EU-1 molecular sieve and MOR zeolite closely are embedded in composite molecular screen particle together, and the particle size of composite molecular screen is generally 1～4 μ m.The weight content of EU-1 molecular sieve in composite molecular screen is 25%～70%.The SiO of EU-1/MOR composite molecular screen
2/ Al
2O
3Mol ratio is 30～60.
Significantly different from conventional MOR zeolite and EU-1 molecular sieve, the diffraction maximum at 2 θ=9.7 ± 0.5 places that belongs to the MOR phase in the present invention significantly strengthens.The diffraction maximum in 2 θ=27 ± 0.5 that belongs to the EU-1 molecular sieve significantly strengthens, and belongs in 2 θ=22 ± 0.5 place's diffraction maximum d values, enlarging markedly of EU-1 molecular sieve.The two micro porous molecular sieves that make all increase at aspects such as acid strength, heat and hydrothermal stabilities.
The preparation method of EU-1/MOR composite molecular screen provided by the invention comprises the steps:
(1) EU-1 molecular sieve, silicon source, alkali, water and template are fully mixed, in gel, each component is as follows by the ratio of its oxide, wherein SiO
2For SiO in the silicon source
2Content, do not comprise the silicon in the EU-1 molecular sieve:
EU-1/SiO
2(gram/gram)=1～10
R/SiO
2(moles/mole)=0.06～0.38
Na
2O/SiO
2(moles/mole)=0.69～4.6
H
2O/SiO
2(moles/mole)=33～166
Be preferably:
EU-1/SiO
2(gram/gram)=1.2～7.5
R/SiO
2(moles/mole)=0.07～0.28
Na
2O/SiO
2(moles/mole)=0.86～3.45
H
2O/SiO
2(moles/mole)=40～95
R represents template
(2) crystallization: the reaction mixture gel of step (1) preparation is warming up to 140 ℃～170 ℃, and hydrothermal crystallizing 1～4 day;
(3) after crystallization is completed, after filtration, washing, drying and roasting make the EU-1/MOR composite molecular screen.
Wherein said template is selected from tetraethyl ammonium hydroxide or tetraethylammonium bromide.Be preferably tetraethylammonium bromide.
Described silicon source can be White Carbon black, Ludox, waterglass, silicic acid or ethyl orthosilicate, preferred White Carbon black.
Described crystal seed is the EU-1 molecular sieve.The EU-1 molecular sieve can be the sodium type molecular sieve of roasting or the molecular sieve of roasting not, is preferably the sodium type EU-1 molecular sieve of roasting.
Hydrothermal crystallizing described in step (2) is that the reaction mixture gel that will be mixed with is placed in pressure vessel and carries out under temperature constant state, i.e. thermostatic crystallization.Hydrothermal crystallizing can be static crystallization or dynamic crystallization.
Composite molecular screen provided by the present invention can be used for the reactions such as especially polymerization, aromatisation, isomerization in different hydrocarbon conversion reactions, for example to C
8The aromatics isomerization reaction table reveals very high reactivity.
Description of drawings
Fig. 1 is X-ray diffraction (XRD) spectrogram of the composite molecular screen of the embodiment of the present invention 1 preparation.
Fig. 2 is the stereoscan photograph of the composite molecular screen of the embodiment of the present invention 1 preparation.
The specific embodiment
The x-ray diffractometer that the phase mensuration of EU-1/MOR composite molecular screen of the present invention and the mensuration of degree of crystallinity adopt is the D/max-2500 type full-automatic rotating target x-ray diffractometer that Rigaku Co., Ltd. produces.During experiment, sample is ground to the 300 above compressing tablets of order, the machine of then going up characterizes.Experiment condition: the Cu target, K α radiation source, graphite monochromator, operating voltage 40kV, tube current 80mA, sweep limits is 5-40 °, and sweep speed is 8 °/min, and step-length is 0.01 °.
Below in conjunction with embodiment, the present invention is further detailed.
Embodiment 1
Successively add 2.0g NaOH, 1.55g tetraethylammonium bromide, 50ml distilled water in beaker, stir, then add 7.5gEU-1 molecular sieve crystal seed, stir 10min, add finally the 1.75g White Carbon black, the synthesis reactor of packing into after stirring 30min.170 ℃ of heating 96h, filter resulting product in baking oven, is washed with distilled water to neutrality, and drying, namely obtain the EU-1/MOR composite molecular screen at 550 ℃ of lower roasting 5h.
The XRD spectra of this EU-1/MOR composite molecular screen and stereoscan photograph are as shown in Figure 1, 2.As can be seen from Figure 1, in this composite molecular screen, the characteristic peak of EU-1 molecular sieve and MOR zeolite is quite obvious.As can be seen from Figure 2, the structure of this composite molecular screen is that EU-1 molecular sieve and MOR zeolite closely are embedded in composite molecular screen particle together, and the size of composite molecular screen integral particle is at 1～2 μ m.The silica alumina ratio of this composite molecular screen is 42.In composite molecular screen, EU-1 molecular sieve weight content is 25%.Mesoporous pore volume accounts for 43% of total pore volume, and mesoporous aperture concentrates on 55nm.
Embodiment 2
Successively add 1.8g NaOH, 1.55g tetraethylammonium bromide, 50ml distilled water in beaker, stir, then add 7.5gEU-1 molecular sieve crystal seed, stir 10min, add finally the 1.75g White Carbon black, the synthesis reactor of packing into after stirring 30min.170 ℃ of heating 48h, filter resulting product in baking oven, is washed with distilled water to neutrality, and drying, namely obtain the EU-1/MOR composite molecular screen at 550 ℃ of lower roasting 5h.
The silica alumina ratio of this composite molecular screen is 42.In composite molecular screen, EU-1 molecular sieve weight content is 60%.Mesoporous pore volume accounts for 64% of total pore volume, and mesoporous aperture concentrates on 50nm.
Embodiment 3
Successively add 1.35g NaOH, 1.55g tetraethylammonium bromide, 50ml distilled water in beaker, stir, then add 2gEU-1 molecular sieve crystal seed, stir 10min, add finally the 1.75g White Carbon black, the synthesis reactor of packing into after stirring 30min.170 ℃ of heating 48h, filter resulting product in baking oven, is washed with distilled water to neutrality, and drying, namely obtain the EU-1/MOR composite molecular screen at 550 ℃ of lower roasting 5h.
The silica alumina ratio of this composite molecular screen is 60.In composite molecular screen, EU-1 molecular sieve weight content is 50%.Mesoporous pore volume accounts for 57% of total pore volume, and mesoporous aperture concentrates on 50nm.
Embodiment 4
Successively add 2.3g NaOH, 1g tetraethylammonium bromide, 50ml distilled water in beaker, stir, then add 7.5gEU-1 molecular sieve crystal seed, stir 10min, add finally the 1.5g White Carbon black, the synthesis reactor of packing into after stirring 30min.140 ℃ of heating 48h, filter resulting product in baking oven, is washed with distilled water to neutrality, and drying, namely obtain the EU-1/MOR composite molecular screen at 550 ℃ of lower roasting 5h.
The silica alumina ratio of this composite molecular screen is 41.In composite molecular screen, EU-1 molecular sieve weight content is 25%.Mesoporous pore volume accounts for 36% of total pore volume, and mesoporous aperture concentrates on 50nm.
Embodiment 5
Successively add 1.8g NaOH, 1.55g tetraethylammonium bromide, 50ml distilled water in beaker, stir, then add 7.5gEU-1 molecular sieve crystal seed, stir 10min, add finally the 1.75g White Carbon black, the synthesis reactor of packing into after stirring 30min.170 ℃ of heating 72h, filter resulting product in baking oven, is washed with distilled water to neutrality, and drying, namely obtain the EU-1/MOR composite molecular screen at 550 ℃ of lower roasting 5h.
The silica alumina ratio of this composite molecular screen is 42.In composite molecular screen, EU-1 molecular sieve weight content is 65%.Mesoporous pore volume accounts for 67% of total pore volume, and mesoporous aperture concentrates on 48nm.
Embodiment 6
Successively add 1.35g NaOH, 1.55g tetraethylammonium bromide, 50ml distilled water in beaker, stir, then add 7.5gEU-1 molecular sieve crystal seed, stir 10min, add finally and contain 1.75g SiO
2Ludox, stir after 30min the synthesis reactor of packing into.170 ℃ of heating 24h, filter resulting product in baking oven, is washed with distilled water to neutrality, and drying, namely obtain the EU-1/MOR composite molecular screen at 550 ℃ of lower roasting 5h.
The silica alumina ratio of this composite molecular screen is 42.In composite molecular screen, EU-1 molecular sieve weight content is 70%.Mesoporous pore volume accounts for 66% of total pore volume, and mesoporous aperture concentrates on 50nm.
Comparative example
Prepare composite molecular screen by existing method, 2g MOR zeolite is joined NaOH (1.2mol/L) aqueous solution of 10ml, stirring at room 30min, then add successively 2g C6 (HMBr
2), 5g White Carbon black and 2g silicon aluminium microsphere (silica alumina ratio is 10), continue to be stirred to evenly.The colloidal solution that forms is transferred to the stainless steel still, in 175 ℃ of static crystallization, took out afterwards in 2 days, quenching washes with water to neutrality to room temperature, and drying namely obtains the EU-1/MOR composite molecular screen at 550 ℃ of lower roasting 5h.
The silica alumina ratio of this composite molecular screen is 24.In composite molecular screen, EU-1 molecular sieve weight content is 55%.Micropore volume accounts for 92% of total pore volume.
Claims (10)
1. EU-1/MOR composite molecular screen, composite molecular screen has EU-1 molecular sieve crystalline phase and MOR zeolite crystalline phase simultaneously, it is characterized in that: the mesoporous pore volume of composite molecular screen accounts for 30%～75% of total pore volume, and mesoporous aperture concentrates on 30～70nm.
2., according to composite molecular screen claimed in claim 1, it is characterized in that: the structure of composite molecular screen is that EU-1 molecular sieve and MOR zeolite closely are embedded in composite molecular screen particle together, and the particle size of composite molecular screen is 1～4 μ m.
3., according to the described composite molecular screen of claim 1 or 2, it is characterized in that: the weight content of EU-1 molecular sieve in composite molecular screen is 25%～70%.
4., according to the described composite molecular screen of claim 1 or 2, it is characterized in that: the SiO of EU-1/MOR composite molecular screen
2/ Al
2O
3Mol ratio is 30～60.
5. the synthetic method of the described EU-1/MOR composite molecular screen of claim 1, is characterized in that comprising the steps:
(1) EU-1 molecular sieve, silicon source, alkali, water and template are fully mixed, in gel, each component is as follows by the ratio of its oxide, wherein SiO
2For SiO in the silicon source
2Content, do not comprise the silicon in the EU-1 molecular sieve:
In gram/gram, EU-1/SiO
2=1～10
In moles/mole, R/SiO
2=0.06～0.38, R represents template
In moles/mole, Na
2O/SiO
2=0.69～4.6
In moles/mole, H
2O/SiO
2=33～166
(2) crystallization: the reaction mixture gel of step (1) preparation is warming up to 140 ℃～170 ℃, and hydrothermal crystallizing 1～4 day;
(3) after crystallization is completed, after filtration, washing, drying and roasting make the EU-1/MOR composite molecular screen.
6. in accordance with the method for claim 5, it is characterized in that each component in gel by the ratio of its oxide is:
In gram/gram, EU-1/SiO
2=1.2～7.5
In moles/mole, R/SiO
2=0.07～0.28
In moles/mole, Na
2O/SiO
2=0.86～3.45
In moles/mole, H
2O/SiO
2=40～95
R represents template.
7., according to the described method of claim 5 or 6, it is characterized in that: template is selected from tetraethyl ammonium hydroxide or tetraethylammonium bromide.
8. want 5 described methods according to right, it is characterized in that: the silicon source is White Carbon black, Ludox, waterglass, silicic acid or ethyl orthosilicate.
9. it is characterized in that in accordance with the method for claim 5: the EU-1 molecular sieve is the sodium type molecular sieve of roasting or the molecular sieve of roasting not.
10. in accordance with the method for claim 5, it is characterized in that: the hydrothermal crystallizing in step (2) is that the reaction mixture gel that will be mixed with is placed in pressure vessel and carries out under temperature constant state, and hydrothermal crystallizing is static crystallization or dynamic crystallization.
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| CN103803575B (en) * | 2012-11-08 | 2015-09-02 | 中国石油化工股份有限公司 | A kind of synthetic method of EU-1/MOR coexisting molecular sieve |
| CN103803574B (en) * | 2012-11-08 | 2016-01-06 | 中国石油化工股份有限公司 | A kind of preparation method of EU-1/MOR coexisting molecular sieve |
| CN104556095B (en) * | 2013-10-22 | 2016-08-17 | 中国石油化工股份有限公司 | A kind of preparation method of Y/Silicalite-1 composite molecular screen |
| CN104556094B (en) * | 2013-10-22 | 2016-06-22 | 中国石油化工股份有限公司 | A kind of Y/Silicalite-1 composite molecular screen and preparation method thereof |
Citations (3)
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|---|---|---|---|---|
| US6342200B1 (en) * | 1998-11-02 | 2002-01-29 | Institut Francais Du Petrole | Process for preparing a zeolite with structure type EUO |
| CN1772611A (en) * | 2005-09-28 | 2006-05-17 | 中国科学院大连化学物理研究所 | Composite molecular sieve in ten-element cyclic structure and its synthesis process |
| CN101340976A (en) * | 2005-12-22 | 2009-01-07 | 法国石油公司 | Dual zeolite catalyst comprising a group VIII metal and a group IIIV metal and its use in isomerization of aromatic C8 compounds |
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2010
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6342200B1 (en) * | 1998-11-02 | 2002-01-29 | Institut Francais Du Petrole | Process for preparing a zeolite with structure type EUO |
| CN1772611A (en) * | 2005-09-28 | 2006-05-17 | 中国科学院大连化学物理研究所 | Composite molecular sieve in ten-element cyclic structure and its synthesis process |
| CN101340976A (en) * | 2005-12-22 | 2009-01-07 | 法国石油公司 | Dual zeolite catalyst comprising a group VIII metal and a group IIIV metal and its use in isomerization of aromatic C8 compounds |
Non-Patent Citations (2)
| Title |
|---|
| 周朋燕等.预置晶种合成EU-1/MOR复合分子筛.《工业催化》.2008,第16卷(第10期), |
| 预置晶种合成EU-1/MOR复合分子筛;周朋燕等;《工业催化》;20081031;第16卷(第10期);80-83 * |
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