CN100344537C - Prepn process of high-silicon mordenite - Google Patents
Prepn process of high-silicon mordenite Download PDFInfo
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- CN100344537C CN100344537C CNB2005100238025A CN200510023802A CN100344537C CN 100344537 C CN100344537 C CN 100344537C CN B2005100238025 A CNB2005100238025 A CN B2005100238025A CN 200510023802 A CN200510023802 A CN 200510023802A CN 100344537 C CN100344537 C CN 100344537C
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Abstract
The present invention provides a method for preparing high silicon mordenite (MOR) by means of a vapor phase autorotation crystal (a vapor phase transmitting method, which is VPT.) in a complete inorganic system. In the method, a mixture prepared from an oxide source containing an alkali metal (M) source and a trivalent element (X), an oxide source containing a quadrivalent element (Y) and water is made into gelatin which is dehydrated, and dry gelatin is obtained. The autorotation crystal reaction is carried out in the vapor phase, and a product is obtained after an MOR zeolite crystal is cooled, washed, sucked, filtered and dried with the product SiO2/ Al2O3 = 20 to 40.
Description
Technical field
The invention belongs to field of material synthesis technology, be specifically related to the brilliant method of high silicon mordenite (being MOR) for preparing of vapor phase rotation in a kind of full-inorganic system.
Background technology
Zeolite molecular sieve is a kind of inorganic silicon aluminate crystal, contain in its skeleton regular and ordered arrangement, molecular dimension duct or cage (ca.3～15 ), have effects such as shape selective catalysis, ion-exchange and molecular sieving, be widely used in crude refining, petroleum catalytic cracking and field of petrochemical industry.
Tetra-atomic ring that is connected by the 5-3 structural unit in the mordenite and five-ring (five-ring is preponderated) constitute oval 12 yuan of ring main channels, have the octatomic ring passage to link up between the main channel.12 yuan of straight cylindrical channel size 0.695 * 0.581nm of ring, the octatomic ring arrangement of passages is irregular, aperture 0.28nm, general molecule is difficult for turnover.Because synthetic mordenite purity height, pore structure can be regulated, and has good heat-resisting, acidproof and anti-steam performance, industrial gas or the isolating sorbent material of liquid mixture and hydrocarbon polymer cracking, isomerization, alkylation, the catalyzer such as disproportionation of being widely used as.
That the MOR zeolite synthesis removes is traditional, at Na
2O-SiO
2-Al
2O
3-H
2Hydrothermal synthesis method in the O reaction mixture system (Bajpai P K.Zeolites, 1986,6 (1), 2 have summarized this), after this brilliant synthesis method of non-aqueous system synthesis method (Xu Wenyang etc., CN 88 100228.1988) and vapor phase rotation etc. is arranged again.But resulting product silica alumina ratio is all about 10, do not obtain the more MOR zeolite of high silica alumina ratio, and mordenite with high silicon aluminum ratio has the characteristics of high heat (more than 1000 ℃) stability, and in transalkylation reaction, catalytic activity, selectivity and stability all improve with the increase of silica alumina ratio.In high silicon mordenite synthetic, generally all need add a large amount of organic amine template, thereby cost improves, also may cause environmental pollution simultaneously.Method (the Qi Xiaolan etc. that add fluorochemical in the inorganic body system are arranged again in recent years, CN 1198404.1998) and method (the Hitoshi Sasaki of organic ammonium positively charged ion and fluorochemical coexistence, etc.J.Mater.Chem.2003,13,1173), significantly improve the silica alumina ratio of synthetic MOR zeolite, but had problems such as expensive, seriously polluted equally.
Summary of the invention
The objective of the invention is to propose a kind ofly not use organic formwork agent and fluorochemical, temperature of reaction is low, the time is short, pollution-free, full-inorganic reactant system that product degree of crystallinity is high is at H
2The brilliant method for preparing the MOR zeolite of rotation in the O vapor phase.
The prepared MOR zeolite crystal of the present invention is with Na
2O-SiO
2-Al
2O
3-H
2O reaction-ure mixture gelling system is after dried glue is made in dehydration, at H
2Obtain by autogiration crystal reaction in the O vapor phase.
The concrete preparation method of above-mentioned MOR zeolite is: silicon source, alkali, aluminium source, water, crystal seed are mixed into gel (A), and dehydration obtains dried glue (B), with H
2O (C) places the stainless steel cauldron bottom, and the open container that holds B is positioned on the support of reactor middle and upper part, adds H
2Dried glue was not in direct contact with it when the amount of O should be controlled at reacting by heating.Can place the baking oven heating to react after the reactor sealing.Product obtains the MOR zeolite after cooling, washing, suction filtration, drying.In the aforesaid method, temperature of reaction is 100～200 ℃, and the reaction times is 12 hours～120 hours.
In the aforesaid method, used silicon source is any of silicon sol, water glass, white carbon black, and the aluminium source is Al
2(SO
4)
3, Al (OH)
3Any.
In the aforesaid method, the system material molar ratio is: (0.30～0.50) OH
-: SiO
2: (0.005～0.05) Al
2O
3: (10～30) H
2O.
In the aforesaid method, 85-95 ℃ of dehydration obtained dried glue after reaction mixture stirred.
In the aforesaid method, every mole of SiO
2Amount of seed is 0.4-0.6g/mol.
The product S iO that the present invention obtains
2/ Al
2O
3=20-40.
The feature of MOR zeolite provided by the present invention can characterize with the following method:
1, powder x-ray diffraction (XRD).In powder x-ray diffraction, the reference standard collection of illustrative plates is to determine that product is a crystallization MOR zeolite crystal completely.
2, x-ray fluorescence analysis (XRF).The content of the elements such as sial of analysed for powder product.
3,
27The Al nucleus magnetic resonance (
27Al NMR).The framework aluminum of assay products and non-framework aluminum ratio with the product chemistry silica alumina ratio that corrected X RF measures, obtain the framework si-al ratio data of product.
4, scanning electronic microscope (SEM).Intuitive judgment crystal morphology and size.
5, cryogenic nitrogen adsorption-desorption.Judge microvoid structure, measure its Langmuir specific surface area and pore volume.
The inventive method is not used organic formwork agent and fluorochemical, and the reaction conditions gentleness is pollution-free, product degree of crystallinity height.
Accompanying drawing 2 is the stereoscan photograph of MOR crystal and dried glue.Can find out that it is the bar-like single crystal body that gas phase is changeed the MOR zeolite of brilliant back generation, size 1-5 micron.
Accompanying drawing 3 is the MOR zeolite
27The Al nuclear magnetic resonance map.Can find out that no non-framework aluminum exists.
Accompanying drawing 4 is the cryogenic nitrogen adsorption-desorption figure of MOR zeolite.Can find out that its hysteresis loop area is smaller, show that its microvoid structure is better.
Description of drawings
Fig. 1 is an XRD figure of the present invention, and wherein 1 is the MOR crystal, and 2 is dried glue.
Fig. 2 is a sem photograph of the present invention, and wherein 3,4 is dried glue, and 5,6 is the MOR crystal.
Fig. 3 is of the present invention
27Al nucleus magnetic resonance figure.
Fig. 4 is cryogenic nitrogen adsorption-desorption figure of the present invention.
Embodiment
The invention is further illustrated by the following examples:
| Embodiment | Starting raw material | Proportioning raw materials (mol ratio) | Temperature (℃) | Time (h) | Product | |
| The silicon source | The aluminium source | |||||
| 1 | Silicon sol | Al 2(SO 4) 3 | 0.50OH -∶SiO 2∶0.0125Al 2O 3∶10H 2O | 160 | 20 | MOR |
| 2 | Silicon sol | Al 2(SO 4) 3 | 0.50OH -∶SiO 2∶0.025Al 2O 3∶10H 2O | 160 | 20 | MOR |
| 2 | White carbon black | Al(OH) 3 | 0.10OH -∶SiO 2∶0.05Al 2O 3∶20H 2O | 170 | 24 | MOR |
| 3 | Water glass | Al 2(SO 4) 3 | 0.40OH -∶SiO 2∶0.05Al 2O 3∶20H 2O | 170 | 24 | MOR+MFI |
| 4 | Silicon sol | Al(OH) 3 | 0.10OH -∶SiO 2∶0.001Al 2O 3∶10H 2O | 150 | 48 | MFI+MOR |
| 5 | Water glass | Al(OH) 3 | 0.50OH -∶SiO 2∶0.01Al 2O 3∶30H 2O | 160 | 20 | MOR |
| 7 | Silicon sol | Al 2(SO 4) 3 | 0.50OH -∶SiO 2∶0.005Al 2O 3∶10H 2O | 200 | 36 | MOR+Quartz |
| 8 | Silicon sol | Al 2(SO 4) 3 | 0.40OH -∶SiO 2∶0.025Al 2O 3∶20H 2O | 180 | 48 | MOR+Quartz |
| 9 | Silicon sol | Al 2(SO 4) 3 | 0.40OH -∶SiO 2∶0.05Al 2O 3∶20H 2O | 140 | 48 | MOR |
| 10 | Silicon sol | Al 2(SO 4) 3 | 0.30OH -∶SiO 2∶0.025Al 2O 3∶20H 2O | 160 | 60 | MFI+MOR |
The used alkali of the foregoing description is NaOH, and water is distilled water, and the crystal seed amount is 0.5g/mol SiO
2
Embodiment 11, measure embodiment 1 synthetic MOR zeolite with x-ray fluorescence analysis, and its chemical ingredients silica alumina ratio is 29.
Embodiment 12, use
27Al nuclear magnetic resonance measuring embodiment 1 synthetic MOR zeolite records no non-framework aluminum, obtains the zeolite framework silica alumina ratio and is 29.
Embodiment 13, measure embodiment 1 synthetic MOR zeolite with low-temperature nitrogen adsorption method, and its Langmuir specific surface area is 344.6m
2/ g, micropore volume are 0.14cm
3/ g.
Claims (4)
1, a kind of high silicon mordenite is a MOR prepare zeolite method, it is characterized in that at Na
2O-SiO
2-Al
2O
3-H
2O and MOR seed reaction mixture are stirred into behind the gel dehydration and make dried glue reactant, change crystalline substance mutually after cooling, washing, suction filtration, dry getting final product through water vapor; The mol ratio of above-mentioned each raw material of system is OH
-: SiO
2: Al
2O
3: H
2It is 100～200 ℃ that O=0.30～0.50: 1.0: 0.005～0.05: 10～30, water vapor are changeed brilliant temperature of reaction mutually, and the reaction times is 12 hours～120 hours.
2, the method for claim 1 is characterized in that the used aluminium source of system is Al
2(SO
4)
3, Al (OH)
3In any.
3, the method for claim 1, it is characterized in that reaction mixture stir the back 85-95 ℃ of dehydration obtain dried glue.
4, the method for claim 1 is characterized in that every mole of SiO
2Amount of seed is 0.4-0.6g/mol.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100238025A CN100344537C (en) | 2005-02-03 | 2005-02-03 | Prepn process of high-silicon mordenite |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100238025A CN100344537C (en) | 2005-02-03 | 2005-02-03 | Prepn process of high-silicon mordenite |
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| Publication Number | Publication Date |
|---|---|
| CN1673081A CN1673081A (en) | 2005-09-28 |
| CN100344537C true CN100344537C (en) | 2007-10-24 |
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|---|---|---|---|
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103657705B (en) * | 2012-08-30 | 2016-09-28 | 中国科学院大连化学物理研究所 | A kind of high intensity binder free multi-stage porous is combined the preparation method of MOR catalyst |
| CN102874828A (en) * | 2012-11-07 | 2013-01-16 | 景德镇陶瓷学院 | Method for synthesizing nanometer silicalite-2 molecular sieve with dry gum method and product prepared with same |
| CN105457667B (en) * | 2015-11-12 | 2018-04-13 | 复榆(张家港)新材料科技有限公司 | Zeolite molecular sieve catalyst of n-butene skeletal isomerization and preparation method thereof |
| CN109928404A (en) * | 2017-12-15 | 2019-06-25 | 中国石油化工股份有限公司 | A kind of synthetic method of zeolite molecular sieve |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1243100A (en) * | 1998-07-29 | 2000-02-02 | 中国科学院大连化学物理研究所 | Synthesizing method for high-silicon mordenite |
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2005
- 2005-02-03 CN CNB2005100238025A patent/CN100344537C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1243100A (en) * | 1998-07-29 | 2000-02-02 | 中国科学院大连化学物理研究所 | Synthesizing method for high-silicon mordenite |
Non-Patent Citations (1)
| Title |
|---|
| A Defect-free Mordenite Membrane synthesized byVapour-phase Transport Method Norikazu Nishiyama et al,Journal of The Chemical Society,Chemical Communications,No.19 1995 * |
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