CN1155518C - Proess for preparing mesoporous molecular sieve MCM-48 by using mixture of cationic surfactant and non-ionic surfactant as template agent - Google Patents
Proess for preparing mesoporous molecular sieve MCM-48 by using mixture of cationic surfactant and non-ionic surfactant as template agent Download PDFInfo
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- CN1155518C CN1155518C CNB021363005A CN02136300A CN1155518C CN 1155518 C CN1155518 C CN 1155518C CN B021363005 A CNB021363005 A CN B021363005A CN 02136300 A CN02136300 A CN 02136300A CN 1155518 C CN1155518 C CN 1155518C
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Abstract
The present invention uses industrial grade water glass as a silicon resource, uses hexadecyl trimethyl ammonium bromide, CTAB for short, as a cationic surfactant, and uses p-octyl polyethylene glycol phenyl ether, OP-10 for short, as a non-ionic surfactant; the mixture of the cationic surfactant and the non-ionic surfactant is used as a template agent for preparing an MCM-48 mesoporous molecular sieve with high thermal stability and hydrothermal stability. Although the current problem of synthesizing the MCM-48 mesoporous molecular sieve is largely improved, the defect of poor hydrothermal stability is still a main hindrance not practically applied. The MCM-48 mesoporous molecular sieve with high adjusting degree and good hydrothermal stability can be obtained by adjusting the molar ratio of the CTAB and the OP-10 and the molar ratio of the CTAB and silicon and changing a calcining condition. The process of the present invention has the advantages of simple operation and low cost, and can reduce pollution.
Description
Technical field
The present invention utilizes hexadecyl trimethyl ammonium bromide (CTAB, cats product) and Triton X-100 (OP-10, nonionogenic tenside) mixed aqueous solution is a template, is the silicon source with the industrial-grade sodium silicate, has prepared the MCM-48 mesoporous molecular sieve of high heat, hydrothermally stable.
Background technology
M41s series mesoporous molecular sieve is a class novel inorganic porous material that occurs the early 1990s, comprises the MCM-41 of hexagonal phase, the MCM-48 of cube phase and three kinds of mesoporous molecular sieves of MCM-50 of lamellar phase.The MCM-50 thermally labile of lamellar phase wherein, the MCM-41 of hexagonal phase are synthetic easily, and the MCM-48 complex structure of cube phase, the synthesis condition harshness.Yet, because the p6m structure of the Ia3d texture ratio MCM-41 of MCM-48 has higher structural symmetry, its two separate 3 D pore canal systems significantly reduce its plug-hole situation simultaneously, be more conducive to the transmission of material, thereby on macromole absorption, separation and catalytic applications, have more wide application prospect.Therefore, MCM-48 is just causing that people more and more pay close attention to.Owing to use the synthetic MCM-48 synthesis condition harshness of single cats product, template large usage quantity (CTAB/SiO
2=0.65), simultaneously, hydrothermal stability is relatively poor, is unfavorable for scale operation and application.Therefore, people attempt utilizing other route to synthesize MCM-48.
Stuck in 1996 etc. are with two kinds of divalent cation tensio-active agent C
16-12-16And C
16-3-1For mixed templates successfully synthesizes MCM-48.But above two kinds of divalent cation tensio-active agents drop into commercialization far away.Subsequently, Chen Fengxi etc. utilize cats product CTAB and anion surfactant dodecyl carboxylic acid sodium (SL) for hybrid template than low surfactant/SiO
2Also synthesized MCM-48 under (0.168: 1) condition.The MCM-48 mean pore size that synthesizes with this method is bigger, and the skeleton wall is thinner.Yan Xuewu] etc. be the silicon source with tetraethoxy (TEOS), in neutral amine amino dodecane (DDA) and CTAB mixed system, synthesized the higher MCM-48 of hydrothermal stability.But neutral amine has pollution to environment in this synthetic route.Ryoo etc. utilize mixed-cation Surfactant CTAB and nonionogenic tenside C
12(EO)
3Synthesized hydrothermal stability MCM-48 preferably, but its building-up process need repeatedly be adjusted pH or adding salt, thus more loaded down with trivial details, and oneself preparation is wanted in the silicon source.More than these work greatly improved the composition problem of MCM-48, but the relatively poor shortcoming of its hydrothermal stability not be improved significantly, and to adopt cheap silicon source also be the needs of reality.
Summary of the invention
The objective of the invention is to seek the MCM-48 that a kind of cost is low, method that pollution is little, synthesis condition is easy prepares high heat and hydrothermally stable.
The synthesis step of this method is as follows: be dissolved in a certain amount of Triton X-100 and cetyl trimethylammonium bromide in the distilled water respectively, mix and stir, after stirring under 20-40 ℃, drip technical grade silicon source water glass and form mixture with certain mole composition, with this mixture continue to stir the back move in the stainless steel cauldron that has teflon gasket 80-120 ℃ crystallization 1-4 days, take out the back suction filtration, product is through washing, filter the back oven dry, promptly obtain the former powder of synthesis type.Should former powder directly in air behind 500-700 ℃ of following roasting 4-7h, the 700-850 ℃ of roasting 1-5h that heat up again promptly obtains product.
Material ratio and reaction conditions in above-mentioned synthesizing are:
(1) mol ratio of CTAB and OP-10 is 11～4;
(2) the reaction mass mol ratio is:
1.0SiO
2: xCTAB: yOP-10: 0.282Na
2O: 58H
2O, wherein 0.09＜x＜0.31,0.015＜y＜0.03;
(3) concentration of CTAB is 3-8wt%.
Synthesis condition of the present invention is better in following ranges:
(1) mol ratio of CTAB and OP-10 is 8～5, because the interface assembling process coupling in this mol ratio and the building-up process better
(2) mol ratio 0.12～0.18 of CTAB and silicon
(3) concentration of CTAB is 4-6wt%
(4) crystallization temperature 80-110 ℃, crystallization time 1-4 days.
Post-treatment condition of the present invention is:
The former powder of synthesis type is behind roasting 4-6h between 550-700 ℃, again 750-850 ℃ of roasting 1-3 hour time.
Heat of the present invention and hydrothermal treatment consists condition are:
(1) thermal treatment: sample is placed silica tube, 1000 ℃ of static roasting 2～4h in air
(2) hydrothermal treatment consists: sample is placed silica tube, and at 600 ℃, logical 100% water vapour is handled 2～6h down
The product of the present invention preparation can keep the Ia3d cubic structure of MCM-48 under 1000 ℃ of roastings 2 hours, 600 ℃ of water vapour (100%) are handled 4 hours test condition, and its BET specific surface, pore volume change little.This compares with the MCM-48 that obtains with other synthetic route, and hydrothermal stability significantly improves.This method can further reduce the mol ratio to 0.12 of CTAB/Si simultaneously, reduces total surfactant concentration to 4wt%, and operation is easier, is beneficial to very much mass production.The characterization result of sample shows that this sample has very high regularity, pore size distribution homogeneous (the pore distribution curve halfwidth only is 2.94 ), and this may be its reason with Gao Re and hydrothermal stability.This invention lays a solid foundation for the MCM-48 mesoporous molecular sieve drops into practical application.
Description of drawings
Fig. 1 is the feature X-ray diffractogram (XRD) of MCM-48 sample after the roasting.
Fig. 2 is the feature high-resolution electron microscopy figure (TEM) of MCM-48 sample after the roasting.
Fig. 3 is the feature N of MCM-48 sample after the roasting
2Adsorption-desorption curve, illustration are corresponding pore distribution curve figure.
Fig. 4 is the hot analytical results of feature of MCM-48 sample after the roasting, and a is a weight-loss curve, and b is a differential thermal analysis curve, and illustration is the XRD figure of sample after the end of test (EOT).
Fig. 5 is the XRD figure of MCM-48 sample after heat and the hydrothermal treatment consists.
Fig. 6 is the feature N of MCM-48 sample after heat and the hydrothermal treatment consists
2Adsorption-desorption graphic representation, illustration are corresponding pore distribution curve, a untreated samples, b hydrothermal treatment consists sample, c heat treated sample
Embodiment
Further describe feature of the present invention below by example.
Example 1:
Under the constant agitation speed, a certain amount of water glass is added dropwise in the mixed aqueous solution of 4: 1 CTAB and OP-10,30 ℃ are stirred down and obtain mole after 1 hour and consist of 1.0SiO
2: 0.15CTAB: 0.03OP-10: 0.282Na
2O: 58H
2The mixture of O.This mixture is moved in the stainless steel cauldron, and 100 ℃ left standstill 2 days, and product filters the back oven dry through washing, promptly obtains synthesis type MCM-48.This sample directly in air 650 ℃ of following roastings be warming up to 850 ℃ of roasting 2h after 5 hours again, can obtain the MCM-48 mesoporous molecular sieve.Typical X RD figure, TEM photo, N
2Adsorption-desorption isothermal curve and hot analytical results are seen Fig. 1～Fig. 4 respectively.And after heat and hydrothermal treatment consists the XRD figure of sample, N
2Adsorption-desorption isothermal curve and pore structure parameter are seen Fig. 5, Fig. 6 and table one respectively.
The pore structure parameter of table .1 MCM-48 sample
Sample Unitcell BET Pore Pore FWHM/
parameter/ surface volume/ size/ ()
b
()
a area/ (cm
3g
-1) ()
(m
2g
-1)
Be untreated 82.7 1148.7 1.37 23.5 4.1
MCM-48
Hydrothermal treatment consists 78.3 (5.4%) 1037.8 1.16 21.2 4.7
MCM-48
Hot MCM-48 78.3 (5.4%) 762.8 0.68 20.9 5.3
It in a bracket structure cell shrinkage degree of handling the back sample
B is the halfwidth of sample pore size distribution curve
Example 2:
The process of producing synthesis type MCM-48 is with example 1, gets directly 650 ℃ of following roastings 5 hours in air of synthesis type MCM-48, can obtain the MCM-48 mesoporous molecular sieve
Example 3:
In the time of 20 ℃, a certain amount of water glass is added dropwise in the mixed aqueous solution of 10: 1 CTAB and OP-10 and stirred 1 hour, obtain mole and consist of 1.0SiO
2: 0.30CTAB: 0.02OP-10: 0.282Na
2O: 58H
2The mixture of O.This mixture is moved in stainless steel cauldron, 100 ℃ of crystallization 3 days, product filters the back oven dry through washing, promptly obtains synthesis type MCM-48.This sample can obtain the MCM-48 mesoporous molecular sieve in 4 hours 700 ℃ of following roastings more earlier 550 ℃ of following roastings of nitrogen 1 hour.
Example 4:
Respectively with 0.3g through and do not place silica tube through the sample of 800 ℃ of roasting aftertreatments, in air, find behind 1000 ℃ of static roasting 2h, kept the characteristic diffraction peak of MCM-48 Ia3d structure through the sample of 800 ℃ of roasting aftertreatments, then do not lost the characteristic diffraction peak of MCM-48 Ia3d structure through the sample of 800 ℃ of roasting aftertreatments.In addition, respectively with 0.3g through and do not place silica tube through the sample of 800 ℃ of roasting aftertreatments, at 600 ℃, logical 100% water vapour is handled 4h down and is found, kept the characteristic diffraction peak of MCM-48 Ia3d structure through the sample of 800 ℃ of roasting aftertreatments, then do not lost the characteristic diffraction peak of MCM-48 Ia3d structure through the sample of 800 ℃ of roasting aftertreatments.
Claims (5)
1. a mixed-cation nonionogenic tenside is the method that template prepares the MCM-48 mesoporous molecular sieve, it is characterized in that hexadecyl trimethyl ammonium bromide is that CTAB is a cats product, Triton X-100 is that OP-10 is a nonionogenic tenside, both mixing solutionss are template, industrial-grade sodium silicate is the silicon source, the MCM-48 mesoporous molecular sieve of preparation heat, hydrothermally stable; CTAB and OP-10 be dissolved in the distilled water mix, under agitation drip water glass solution again, continue to stir into uniform mixture, this mixed solution is moved in reactor, under 80-120 ℃ of temperature crystallization 1-4 days, take out the back suction filtration, washing, promptly obtain the former powder of synthesis type, directly in air between 550-700 ℃ behind the roasting 4-6h, 750-850 ℃ of roasting 1-3h carries out aftertreatment to the former powder of synthesis type in air again;
Various materials when reaction conditions are as follows:
(1) mol ratio of CTAB and OP-10 is 11～4;
(2) the reaction mass mol ratio is:
1.0SiO
2: xCTAB: yOP-10: 0.282Na
2O: 58H
2O, wherein 0.09＜x＜0.31,0.015＜y＜0.03;
(3) concentration of CTAB is 3-8wt%.
2. mixed-cation nonionogenic tenside according to claim 1 is the method that template prepares the MCM-48 mesoporous molecular sieve, and the mol ratio that it is characterized in that CTAB and OP-10 is 8～5.
3. mixed-cation nonionogenic tenside according to claim 1 is the method that template prepares the MCM-48 mesoporous molecular sieve, and the mol ratio that it is characterized in that CTAB and silicon is 0.12～0.18.
4. mixed-cation nonionogenic tenside according to claim 1 is the method that template prepares the MCM-48 mesoporous molecular sieve, and the concentration that it is characterized in that CTAB is 4-6wt%.
5. mixed-cation nonionogenic tenside according to claim 1 is the method that template prepares the MCM-48 mesoporous molecular sieve, it is characterized in that crystallization temperature is 80-110 ℃, and crystallization time is 1-4 days.
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| CN101186311B (en) * | 2007-11-22 | 2012-02-22 | 复旦大学 | Y/MCM-48 composite molecular screen and preparation method thereof |
| CN102453139B (en) * | 2010-10-19 | 2013-09-25 | 中国石油化工股份有限公司 | Olefin polymerization method |
| CN104986781B (en) * | 2015-07-21 | 2017-03-01 | 哈尔滨理工大学 | A kind of method synthesizing MCM 48 mesopore molecular sieve under room temperature |
| CN105384181A (en) * | 2015-11-06 | 2016-03-09 | 中国科学院山西煤炭化学研究所 | Method for synthesizing aluminum-containing MCM-48 mesoporous molecular sieve with co-template agent |
| CN107021493B (en) * | 2017-03-23 | 2019-01-15 | 泰山医学院 | A method of synthesis MCM-48 mesoporous silicon oxide |
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