CN1235798C - Prepn process of MCM-48 medium-pore molecular sieve with ternary mixed cationic, non-ionic and anionic surfactant as template agent - Google Patents
Prepn process of MCM-48 medium-pore molecular sieve with ternary mixed cationic, non-ionic and anionic surfactant as template agent Download PDFInfo
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- CN1235798C CN1235798C CN 03116140 CN03116140A CN1235798C CN 1235798 C CN1235798 C CN 1235798C CN 03116140 CN03116140 CN 03116140 CN 03116140 A CN03116140 A CN 03116140A CN 1235798 C CN1235798 C CN 1235798C
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Abstract
The present invention uses ternary mixed water solution, of hexadecyl trimethyl ammonium bromide (CTAB, a cationic surfactant), p-octyl polyethylene glycol phenyl ether (OP-10, a non-ionic surfactant) and dodecyl carboxylic acid sodium (SL, an anionic surfactant), as a template agent and uses tetraethyl orthosilicate (TEOS) as a silicon resource for preparing an MCM-48 medium-pore molecular sieve with high regulation degree, high specific surfaces and high quality under a low CTAB/SiO2 molar ratio and low concentration of a total surfactant. The prior art has the defects of high reaction requirements, complicated operation, environmental pollution, high cost, etc. A ternary mixed cationic surfactant, the non-ionic surfactant and the anionic surfactant are used as the template agent for preparing the MCM-48 medium-pore molecular sieve; an alkali source and the silicon resource are added in a ternary mixture, crystallized, dried and calcined. The process has the advantages of low cost, simple and convenient operation and environmental-friendly performance, and is favourable for large-scale production and the satisfaction of practical application requirements.
Description
Technical field
The present invention utilizes hexadecyl trimethyl ammonium bromide (CTAB, cats product), Triton X-100 (OP-10, nonionogenic tenside) and dodecyl carboxylic acid sodium (SL, anion surfactant) ternary mixed aqueous solution is a template, (TEOS) is the silicon source with tetraethoxy, prepares silica-based MCM-48 mesoporous molecular sieve.
Background technology
MCM-48 is a member in the class novel inorganic porous material M41S series that occurs the early 1990s, and the p6m structure of the MCM-41 of its Ia3d texture ratio six side's phases, one-dimensional channels system has higher structural symmetry.MCM-48 has two separate 3 D pore canal systems simultaneously, can reduce plug-hole, significantly reduce diffusional limitation, thereby be more conducive to the transmission of material, thereby on macromole absorption, separation and catalytic applications and in the various fields such as preparation of assembling, micro element, chemical sensitisation, nonlinear optical material and the nano material of functional polymer mixture, have broad application prospects.Therefore, MCM-48 has caused that people more and more pay close attention to.But, under normal conditions, use the condition of the synthetic MCM-48 of single quaternary ammonium salt cationic surfactant relatively harsher, phase region is narrow and template large usage quantity (CTAB/SiO
2=0.65), is unfavorable for scale operation and application, so people attempt utilizing other route to synthesize MCM-48.
Stucky 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 Xuewus etc. are the silicon source with tetraethoxy (TEOS), have synthesized the higher MCM-48 of hydrothermal stability in neutral amine amino dodecane (DDA) and CTAB mixed system.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 adjust pH or add salt, operate more loaded down with trivial detailsly, and the silicon source wants oneself to prepare.Zhao Wei etc. are the silicon source with water glass, have synthesized the MCM-48 of high heat and hydrothermal stability with biodegradable nonionic surfactant OP-10 and CTAB mixed system, reduce CTAB/SiO
2Mol ratio to 0.12, total surfactant concentration reduces to 4.0wt%.But the batching scope is narrow.More than these work greatly improved the composition problem of MCM-48.But further reduce CTAB/SiO
2Ratio is sought the synthetic method that cost is cheaper, environment is more friendly and is remained the required of scale operation and practical application.
Summary of the invention
The objective of the invention is to seek low, the easy and simple to handle and eco-friendly method of a kind of cost and prepare the MCM-48 mesoporous molecular sieve, to satisfy the needs of scale operation and application.
The synthesis step of this method is as follows: be dissolved in a certain amount of Triton X-100, cetyl trimethylammonium bromide and dodecyl carboxylic acid sodium in the appropriate amount of deionized water respectively, mix and stir, add a certain amount of NaOH solution then, after stirring under 20～40 ℃, drip silicon source tetraethoxy, this mixture is continued to stir 1～1.5h form and have the mixture that certain mole is formed, move into then and have in the teflon-lined stainless steel cauldron in 80～130 ℃ of crystallization 3～6 days.Product takes out postcooling, through suction filtration, washing, and oven dry, oven dry promptly obtains the former powder of synthesis type generally at 80 ℃.The former powder of this synthesis type is warming up to 400～800 ℃ of roastings 0.5～3 hour under nitrogen gas stream, then in air under 400～800 ℃ roasting 3～8h again, obtain roasting type sample.
Material ratio in above-mentioned synthesizing is:
(1) the reaction mass mol ratio is:
1.0SiO
2: xCTAB: yOP-10: zSL: 0.28Na
2O: 58H
2O, wherein 0.03＜x＜0.12,0.003＜y＜0.024,0＜z＜0.01;
(2) concentration of CTAB is 1.0～3.0wt%;
(3) concentration of total surfactant (CTAB+OP-10+SL) is 1.6～4.0wt%;
(4) concentration of sodium hydroxide solution is 0.4～1.6mol/L;
Synthesis condition of the present invention is better in following ranges:
(1) CTAB with SiO
2The mol ratio 0.04～0.1 in the silicon source of meter;
(2) concentration of CTAB is 1.4～2.4wt%;
(3) concentration of sodium hydroxide solution is 0.7～1.2mol/L;
(4) crystallization temperature is 90～120 ℃, and crystallization time is 3～5 days;
(5) be warming up to 500～600 ℃ of roasting 1～2h under the nitrogen gas stream, then in air in 500～600 ℃ of following roasting 4-6h.
The product of the present invention's preparation can be at low especially (CTAB+OP-10+SL)/SiO
2(as ≈ 1.74wt%) is synthetic under mol ratio (as ≈ 0.05: 1) and the low especially total surfactant concentration, significantly reduces CTAB/SiO
2Mol ratio, also significantly reduce the concentration of CTAB.Owing to use biodegradable nonionic surfactant OP-10 and pollute little anion surfactant, greatly reduce in the preparation process pollution to environment.Low, the easy and simple to handle and environmental friendliness of present method cost is very beneficial for mass production.Simultaneously, institute's synthetic MCM-48 mesoporous molecular sieve has typical Ia3d cubic structure, and characterization result shows with this method synthetic sample to have very high regularity, pore size distribution homogeneous.The mesopore aperture of synthetic MCM-48 is 2.4nm, and pore volume is 0.9cm
3/ g, BET surface-area are 1016m
2/ g.
Description of drawings:
The prepared MCM-48 of the present invention has the characterization result of typical Fig. 1-6.
Fig. 1 is at (CTAB+OP-10+SL)/SiO
2The X-ray diffractogram (XRD) of synthetic MCM-48 mesoporous molecular sieve under=0.07 condition, feature XRD figure for typical MCM-48 sample, locate to demonstrate stronger cube mesopore phase character diffraction peak in (211), (220), and the characteristic diffraction peak of the more weak representative cube mesopore phase fine structure of (321), (400), (420), (322), (421), (431) equal strength is also high-visible, demonstrates sample and has very high regularity and very high quality.
Fig. 2 is the XRD figure spectrum of the MCM-48 mesoporous molecular sieve sample after the roasting, demonstrates the several characteristic diffraction peak of typical cube of mesopore phase among the figure, i.e. (211), (220), (321), (400), (420) and (322).
Fig. 3 is the feature N of the MCM-48 sample after the roasting
2Adsorption-desorption curve, illustration are corresponding pore size distribution curve figure.
Fig. 4 is feature high-resolution-ration transmission electric-lens figure (HRTEM) figure of edge [111] face of sample.
Fig. 5 is feature high-resolution-ration transmission electric-lens figure (HRTEM) figure of edge [311] face of sample.
Fig. 6 is the sem photograph (SEM) of the silk cocoon shape of MCM-48 sample.
Fig. 7 is the sem photograph (SEM) of the ghost shape of MCM-48 sample.
Fig. 8 is the globular sem photograph (SEM) of MCM-48 sample.
Embodiment
Further describe feature of the present invention below by example, the present invention is not limited to following example.
Example 1 and 2:
Under the constant agitation speed, be dissolved in 0.03mol cetyl trimethylammonium bromide, 0.014mol Triton X-100 and 0.008mol dodecyl carboxylic acid sodium in the appropriate amount of deionized water respectively, mix and stir, add a certain amount of NaOH solution then, after stirring, dropping is equivalent to 1molSiO
2Silicon source tetraethoxy, this mixture is continued to stir 1 hour, move into then and have in the teflon-lined stainless steel cauldron in 100 ℃ or 110 ℃ crystallization 4-4.5 days.Product is through suction filtration, washing, and 80 ℃ of oven dry down promptly obtain the former powder of synthesis type.The former powder of this synthesis type is warming up to 550 ℃ of roastings one hour under nitrogen gas stream, then in air under 550 ℃ roasting 5h again, obtain roasting type sample.Typical X RD figure, SEM and TEM photo, N
2Adsorption-desorption isothermal curve figure sees Fig. 1～Fig. 6.
Example 3:
Under the constant agitation speed, be dissolved in 0.024mol Triton X-100,0.03mol cetyl trimethylammonium bromide and 0.003mol dodecyl carboxylic acid sodium in the appropriate amount of deionized water respectively, mix and stir, add a certain amount of NaOH solution then, after stirring, dropping is equivalent to 1molSiO
2Silicon source tetraethoxy, this mixture is continued to stir 1～1.5 hour, move into then and have in the teflon-lined stainless steel cauldron in 110 ℃ of crystallization 4 days.Product is through suction filtration, washing, and 80 ℃ of oven dry down promptly obtain the former powder of synthesis type.
Example 4:
Under the constant agitation speed, be dissolved in 0.004mol Triton X-100,0.06mol cetyl trimethylammonium bromide and 0.006mol dodecyl carboxylic acid sodium in the appropriate amount of deionized water respectively, mix and stir, add a certain amount of NaOH solution then, after stirring, dropping is equivalent to 1molSiO
2Silicon source tetraethoxy, this mixture is continued to stir 1～1.5 hour, move into then and have in the teflon-lined stainless steel cauldron in 100 ℃ of crystallization 4 days.Product is through suction filtration, washing, and 80 ℃ of oven dry down promptly obtain the former powder of synthesis type.
Example 5:
Be dissolved in 0.003mol Triton X-100,0.04mol cetyl trimethylammonium bromide and 0.01mol dodecyl carboxylic acid sodium in the appropriate amount of deionized water respectively, mix under the constant speed and stir, add a certain amount of NaOH solution then, after stirring, dropping is equivalent to 1molSiO
2Silicon source tetraethoxy, this mixture is continued to stir 1～1.5 hour, mixture is moved into have in the teflon-lined stainless steel cauldron then in 100 ℃ of crystallization 4.5 days.Product is through suction filtration, washing, and 80 ℃ of oven dry down promptly obtain the former powder of synthesis type.
Example 6:
Respectively be dissolved in appropriate amount of deionized water by certain mol proportion 0.12mol cetyl trimethylammonium bromide, 0.003mol Triton X-100 and 0.001mol dodecyl carboxylic acid sodium, mix under the constant speed and stir, add a certain amount of NaOH solution then, after stirring, dropping is equivalent to 1molSiO
2Silicon source tetraethoxy, continue to stir 1～1.5 hour, then mixture is moved in the stainless steel cauldron, 110 ℃ of crystallization 4 days, product filters back 80 ℃ of oven dry down through washing, promptly obtains synthesis type MCM-48.This sample earlier in nitrogen gas stream in 550 ℃ of following roastings 1 hour, again in air under 550 ℃ roasting 5h again, can obtain roasting type sample MCM-48 mesoporous molecular sieve.
Claims (6)
1, a kind of ternary mixed-cation, nonionic and anion surfactant are the method that template prepares the MCM-48 mesoporous molecular sieve, it is characterized in that hexadecyl trimethyl ammonium bromide CTAB is a cats product, Triton X-100 OP-10 is a nonionogenic tenside, dodecyl carboxylic acid sodium SL is an anion surfactant, mixing solutions with the three is a template, tetraethoxy TEOS is the silicon source, sodium hydroxide solution is prepared into the MCM-48 mesoporous molecular sieve as alkali source; CTAB, OP-10 and SL are dissolved in the deionized water for stirring mixing respectively, add sodium hydroxide solution, back dropping TEOS stirs under 20-40 ℃, this mixture is continued to stir 1-1.5 hour one-tenth uniform mixture, this mixture is moved in the reactor, crystallization is 3～6 days under 80～130 ℃ of temperature, take out cooling back suction filtration, washing, oven dry promptly obtains the former powder of synthesis type, and the former powder of this synthesis type is warming up to 400～800 ℃ of roastings 0.5～3 hour under nitrogen gas stream, roasting 3～8 hours again under 400～800 ℃ in air then obtains roasting type sample;
Various material ratios are as follows:
(1) the reaction mass mol ratio is:
1.0SiO
2: xCTAB: yOP-10: zSL: 0.28Na
2O: 58H
2O, 0.03＜x＜0.12 wherein,
0.003＜y＜0.024，0＜z＜0.01；
(2) concentration of CTAB is 1.0～3.0wt%;
(3) concentration of total surfactant CTAB+OP-10+SL is 1.6～4.0wt%;
(4) concentration of sodium hydroxide solution is 0.4～1.6mol/L.
2. ternary mixed-cation according to claim 1, nonionic and anion surfactant are the method that template prepares the MCM-48 mesoporous molecular sieve, it is characterized in that CTAB and with SiO
2The mol ratio in the silicon source of meter is 0.04～0.1.
3, ternary mixed-cation according to claim 1, nonionic and anion surfactant are the method that template prepares the MCM-48 mesoporous molecular sieve, and the concentration that it is characterized in that CTAB is 1.4～2.4wt%.
4, ternary mixed-cation according to claim 1, nonionic and anion surfactant are the method that template prepares the MCM-48 mesoporous molecular sieve, and the concentration that it is characterized in that sodium hydroxide solution is between 0.7～1.2mol/L.
5. ternary mixed-cation according to claim 1, nonionic and anion surfactant are the method that template prepares the MCM-48 mesoporous molecular sieve, it is characterized in that crystallization temperature is 90～120 ℃, and crystallization time is 3～5 days.
6. ternary mixed-cation according to claim 1, nonionic and anion surfactant are the method that template prepares the MCM-48 mesoporous molecular sieve, it is characterized in that the former powder of synthesis type is warming up to 500～600 ℃ of roastings 1～2 hour under nitrogen gas stream, then in air under 500～600 ℃ again roasting carried out aftertreatment in 4～6 hours.
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| ES2617731T3 (en) | 2012-10-01 | 2017-06-19 | Dow Global Technologies Llc | Compositions and procedures for the synthesis of cubic mesoporous silicas that have "noodle" morphology |
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