CN107021493B - A method of synthesis MCM-48 mesoporous silicon oxide - Google Patents
A method of synthesis MCM-48 mesoporous silicon oxide Download PDFInfo
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- CN107021493B CN107021493B CN201710176370.4A CN201710176370A CN107021493B CN 107021493 B CN107021493 B CN 107021493B CN 201710176370 A CN201710176370 A CN 201710176370A CN 107021493 B CN107021493 B CN 107021493B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
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Abstract
The invention discloses a kind of methods for synthesizing MCM-48 mesoporous silica molecular sieve.This method uses tetradecyltrimethylammonium bromide (C14TAB) and 2- hydroxyl -3- naphthoic acid (NaHN) is template, sodium metasilicate (Na2SiO3·9H2It O) is silicon source.Synthesis step is as follows: by C14TAB is completely soluble in water, NaHN；Separately take Na2SiO3·9H2O is completely soluble in water；Then two kinds of solution are quickly mixed, stirs 20 minutes at room temperature, 2mol/L sulfuric acid is then added dropwise；Mixture is transferred in autoclave 100 DEG C after hydro-thermal 48 hours, is filtered, washing is placed in air drying.Then 6 hours removing organic matters are calcined in 560 DEG C of Muffle furnaces, obtain product.Raw material proportioning: C14TAB/NaHN/Na2SiO3·9H2O/H2SO4/H2O=1:0.15~0.27:30:30:900.The C that the present invention uses14TAB、NaHN、Na2SiO3·9H2O raw material is easy to get, and significantly reduces production cost.Fluorochemical additive is prevented in production process, environmental-friendly, the product degree of order is high, aperture is uniform, is conducive to large-scale industrial production.
Description
Technical field
The present invention relates to a kind of preparation method of porous silica si molecular sieves, specifically a kind of low cost synthesis silicon
The preparation method of the mesoporous MCM-48 of base.
Background technique
MCM-48 mesoporous silicon oxide belongs to one of the serial Metaporous silicon dioxide material of Mobil company exploitation.Such Jie
Porous materials are different from MCM-41, MCM-50 series place and are: possessing three crossings on different level ducts, symmetry with higher.
For one-dimensional channels, 3 D pore canal is more advantageous to the transmission of reactant and product, is not easy to plug.Therefore, MCM-48 is situated between
Porous materials have more good application prospect in fields such as selective catalysis, absorption, separation.But the synthesis condition of MCM-48 series
Harshness, poor repeatability, synthesis cost is high, therefore research paper, patent about MCM-48 etc. is relatively fewer.
Qisheng Huo et al. uses novel surfactant C16-12-16(C16H33N
(CH3) 2 (CH2) 12N (CH3), 2 C16H332Br) it is template, TEOS is silicon source, is made in 100 hydro-thermals
MCM-48(Chem.Mater., 1996,8,1147).Although the program can under lower table surfactant concentration be made MCM-48,
It is the Gemini surface active agent synthesis step complexity used in this method, it is with high costs.Chinese patent " yin-yang blending surface activity
The method that agent prepares MCM-48 mesoporous molecular sieve for template " (Authorization Notice No. CN1062836C) is using cetyl front three
Base ammonium bromide and undecyl carboxylic acid sodium mixed surfactant are template, and MCM-48 mesoporous molecular sieve has been made.It is Chinese special
Sharp " a kind of preparation method of MCM-48 mesopore molecular sieve " (Authorization Notice No. CN 102259886B) is disclosed using cation form
Face lammonium tosilate (CTATos) is template, and silica solution is successfully made as silicon source
MCM-48 mesopore molecular sieve.It is mesoporous that Chinese patent (Authorization Notice No. CN 102423685B) describes a kind of amino functional
The synthetic method of MCM-48.Crystallization agent sodium fluoride (NaF) is used in this method, wherein a large amount of fluorine ion is easy to make environment
At pollution.It finds lower synthesis cost and environmental-friendly MCM-48 mesoporous silicon oxide is the direction that material scholar explores.
Summary of the invention
The problem to be solved in the present invention explores a kind of synthesis high-sequential MCM-48 mesoporous silicon oxide at low cost
Method.
The technical solution of the present invention is as follows: first by tetradecyltrimethylammonium bromide (C14TAB) soluble in water, rear be added is helped
Surfactant 2- hydroxyl -3- naphthoic acid (NaHN) obtains solution A after stirring 15 minutes.Sodium metasilicate is dissolved to obtain uniform
Bright solution B.Solution A is added dropwise in solution B, after mixing evenly, adjusting pH with the sulfuric acid solution of 2mol/L is between 9-10, after
Through 100 DEG C hydro-thermal 48 hours, filtering, washing, air drying, by resulting combination product be placed in Muffle furnace with 1.5 DEG C/
The speed of min heats up in air is heated to 600 DEG C, 5 hours getting the products of constant temperature calcining.In above-mentioned synthetic method, respectively
Molar ratio between substance are as follows: C14TAB/ NaHN/ Na2SiO3·9H2O/ H2SO4/H2O=1:0.15~0.27:30:30:
900。
Wherein tetradecyltrimethylammonium bromide, 2- hydroxyl -3- naphthoic acid are from Aladdin reagent Co., Ltd；Nine water
Sodium metasilicate comes from Sinopharm Chemical Reagent Co., Ltd.；Sulfuric acid comes from Laiyang chemical reagent work.
The present invention has the advantages that as follows:
(1) using commercially available cheap surfactant, the surface of cosurfactant compounding fictitious hosts valuableness
Activating agent；Organic silicon source tetraethyl orthosilicate, quanmethyl silicate are substituted using low-cost nine water sodium metasilicate；
(2) surfactant compound system synergistic effect so that " template " assembling ability it is stronger, silicon source and surface-active
Agent ratio can be as high as 30:1, save high-cost surfactant.
(3) the product aperture that the present invention obtains is uniform, the degree of order is high.Specific surface area reaches 1104m2/g, and BJH method calculates to obtain hole
Diameter is 2.6nm.
(4) present invention is avoided using sodium fluoride, environmental-friendly.
Detailed description of the invention:
Fig. 1 is small angle X-ray diffraction (XRD) map of 1 product of embodiment；
Fig. 2 is high-resolution-ration transmission electric-lens (HRTEM) figure of 1 calcined product of embodiment；
Fig. 3 is scanning electron microscope (SEM) figure of 1 product of embodiment
Fig. 4 is nitrogen adsorption-desorption (N2 adsorption-desorption of 1 calcined product of embodiment
Isotherms) curve；
Fig. 5 is the thermogravimetric curve of the resulting honeycomb small-bore mesoporous silicon oxide without calcining of embodiment 1.
About attached drawing it should be noted that the product of embodiment 2-4 acquisition is similar with 1 result of embodiment, to avoid repeating,
Attached drawing part only provides the various test results of the product of embodiment 1.
Specific embodiment
Below by embodiment, the invention will be further described, it is therefore intended that more fully understand the contents of the present invention rather than
It limits the scope of the invention.
Embodiment 1
The feature that the invention is further illustrated by the following examples, but the present invention is not limited to the following examples.
In embodiment material electron scanning micrograph using 962 type scanning electron microscope of Zeiss company of Germany DSM into
Row measurement.
The transmission electron microscope photo of material uses FEI Co. of U.S. Tecnai G2 F20 S-Twin type in embodiment
Transmission electron microscope is measured.
The scanning electron specific surface area of material, aperture, Kong Rong use U.S. Kang Ta company Autosorb-IQ type in embodiment
Gas absorption instrument is measured.
The XRD of material is measured using Rigaku company D/max-rB type X-ray diffractometer in embodiment.
The thermogravimetric curve of material is measured using Japan's Shimadzu Corporation DTG-60AH type thermal analyzer in embodiment.
Embodiment 1
2.48g tetradecyltrimethylammonium bromide and 0.27g 2- hydroxyl -3- naphthoic acid is taken to be dissolved in 60 ml water at room temperature
In, 0.5 h of stirring obtains solution A, separately takes 63.11 g Na2SiO3·9H2O, which is dissolved in 60 ml water, obtains B solution；By solution A and B
Solution quickly mixes, and instills the sulfuric acid solution of 2mol/L dropwise into said mixture with vigorous stirring, until pH is 9-10；So
Heated at constant temperature 48 hours in 100 DEG C of baking oven afterwards by the filtering of obtained solid sediment, are washed and are dried in air,
Obtain combination product；Resulting combination product is placed in heat up in air in Muffle furnace with the speed of 1.5 DEG C/min and is heated to
600 DEG C, 5 hours getting the products of constant temperature calcining.
Embodiment 2
2.48g tetradecyltrimethylammonium bromide and 0.13g 2- hydroxyl -3- naphthoic acid is taken to be dissolved in 60 ml water at room temperature
In, 0.5 h of stirring obtains solution A, separately takes 63.11 g Na2SiO3·9H2O, which is dissolved in 60 ml water, obtains B solution；By solution A and B
Solution quickly mixes, and instills the sulfuric acid solution of 2mol/L dropwise into said mixture with vigorous stirring, until pH is 9-10；So
Heated at constant temperature 48 hours in 100 DEG C of baking oven afterwards by the filtering of obtained solid sediment, are washed and are dried in air,
Obtain combination product；Resulting combination product is placed in heat up in air in Muffle furnace with the speed of 1.5 DEG C/min and is heated to
600 DEG C, 5 hours getting the products of constant temperature calcining.
Embodiment 3
2.48g tetradecyltrimethylammonium bromide and 0.35g 2- hydroxyl -3- naphthoic acid is taken to be dissolved in 60 ml water at room temperature
In, 0.5 h of stirring obtains solution A, separately takes 63.11 g Na2SiO3·9H2O, which is dissolved in 60 ml water, obtains B solution；By solution A and B
Solution quickly mixes, and instills the sulfuric acid solution of 2mol/L dropwise into said mixture with vigorous stirring, until pH is 9-10；So
Heated at constant temperature 48 hours in 100 DEG C of baking oven afterwards by the filtering of obtained solid sediment, are washed and are dried in air,
Obtain combination product；Resulting combination product is placed in heat up in air in Muffle furnace with the speed of 1.5 DEG C/min and is heated to
600 DEG C, 5 hours getting the products of constant temperature calcining.
Embodiment 4
2.48g tetradecyltrimethylammonium bromide and 0.56g 2- hydroxyl -3- naphthoic acid is taken to be dissolved in 60 ml water at room temperature
In, 0.5 h of stirring obtains solution A, separately takes 63.11 g Na2SiO3·9H2O, which is dissolved in 60 ml water, obtains B solution；By solution A and B
Solution quickly mixes, and instills the sulfuric acid solution of 2mol/L dropwise into said mixture with vigorous stirring, until pH is 9-10；So
Heated at constant temperature 48 hours in 100 DEG C of baking oven afterwards by the filtering of obtained solid sediment, are washed and are dried in air,
Obtain combination product；Resulting combination product is placed in heat up in air in Muffle furnace with the speed of 1.5 DEG C/min and is heated to
600 DEG C, 5 hours getting the products of constant temperature calcining.
Comparative example
2.48g tetradecyltrimethylammonium bromide is taken to be dissolved in 60ml water at room temperature, 0.5 h of stirring obtains solution A, separately
Take 63.11 g Na2SiO3·9H2O, which is dissolved in 60ml water, obtains B solution；Solution A and B solution are quickly mixed, with vigorous stirring
The sulfuric acid solution of 2mol/L is instilled dropwise into said mixture, until pH is 9-10；Then the heated at constant temperature in 100 DEG C of baking oven
It 48 hours, by the filtering of obtained solid sediment, washes and dries in air, obtain combination product；It will be resulting compound
Product, which is placed in Muffle furnace to heat up in air with the speed of 1.5 DEG C/min, is heated to 600 DEG C, obtains within constant temperature calcining 5 hours
Product.
Claims (1)
1. a kind of preparation method for synthesizing MCM-48 mesoporous silicon oxide, it is characterised in that be with tetradecyltrimethylammonium bromide
Surfactant, 2- hydroxyl -3- naphthoic acid are cosurfactant, sodium metasilicate is silicon source, synthesize MCM-48 mesoporous silicon oxide,
The specific steps are that: tetradecyltrimethylammonium bromide is soluble in water, it is rear that 2- hydroxyl -3- naphthoic acid is added, it stirs 15 minutes
Afterwards, solution A is obtained；Sodium metasilicate dissolves to obtain transparent and homogeneous solution B, and solution A, B are quickly mixed, and is vigorously stirred 20 points at room temperature
Zhong Hou, adjusting pH with the sulfuric acid solution of 2mol/L is between 9-10, by 100 DEG C hydro-thermal 48 hours, filtering, washing, in air
It is dry；Resulting combination product is placed in Muffle furnace to heat up in air with the speed of 1.5 DEG C/min and is heated to 600 DEG C, perseverance
Temperature 5 hours getting the products of roasting, in the synthetic method, the molar ratio between each substance are as follows: tetradecyltrimethylammonium bromination
Ammonium: 2- hydroxyl -3- naphthoic acid: sodium metasilicate: sulfuric acid: water=1:0.15~0.27:30:30:900.
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