CN112320813A - Preparation method and application of amino-functionalized SBA molecular sieve - Google Patents

Preparation method and application of amino-functionalized SBA molecular sieve Download PDF

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CN112320813A
CN112320813A CN201910717057.6A CN201910717057A CN112320813A CN 112320813 A CN112320813 A CN 112320813A CN 201910717057 A CN201910717057 A CN 201910717057A CN 112320813 A CN112320813 A CN 112320813A
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molecular sieve
amino
sba
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pore
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CN112320813B (en
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吴凯
任行涛
裴庆君
贾志光
杨光
刘艳惠
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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Abstract

The invention provides a preparation method and application of an amino functionalized SBA molecular sieve. The preparation method of the amino-functionalized SBA molecular sieve comprises the following steps: 1) mixing an organic template agent, water, a pore-expanding agent, an amino modifier, an organic solvent, a silicon source and acid to obtain a colloidal mixture; 2) carrying out hydrothermal crystallization on the colloidal mixture to obtain a product after the hydrothermal crystallization; 3) and filtering, washing and drying the product after hydrothermal crystallization to obtain amino functionalized SBA molecular sieve raw powder. The amino-functionalized SBA molecular sieve provided by the invention not only has the thermal stability of the SBA molecular sieve, but also has the surface characteristics brought by an organic component molecular sieve.

Description

Preparation method and application of amino-functionalized SBA molecular sieve
Technical Field
The invention provides a preparation method and application of an amino functionalized SBA molecular sieve.
Background
Since Mobil company succeeded in synthesizing regular MCM-41 for the first time in 1992, mesoporous materials have shown many potential application values in the aspects of adsorbents, catalysts and catalyst carriers. In 1998, Zhao Dongyuan successfully synthesized novel mesoporous materials SBA-15 and SBA-16 which have larger specific surface area, regular pore size distribution, thicker pore wall and better thermal stability than M41S molecular sieve for the first time, and the materials show larger application value in the aspect of catalysts. Compared with the conventional M41S series molecular sieve, the three-dimensional pore channels can make reactants enter the interior of the molecular sieve more easily for reaction, and the blockage of the pore channels of the molecular sieve is not caused. However, the pure silicon SBA molecular sieve does not have any acidic, basic and redox centers, and only one functional group, namely silicon hydroxyl (Si-OH), exists on the surface, so that the application of the pure silicon SBA molecular sieve in certain fields is limited to a great extent. People utilize abundant silicon hydroxyl on the surface of the SBA molecular sieve to react with a silane coupling agent with organic functional groups to prepare the functional mesoporous silicon oxide material containing various functional groups, so that the functional mesoporous silicon oxide material has good application prospects in the fields of catalysis, optics, biomedicine and the like.
The organic functional modification of the inner and outer surfaces of the mesoporous material can improve the original structural property and add new functional characteristics. The material obtained by carrying out organic functional modification on the mesoporous material SBA molecular sieve has the characteristics of both SBA and a modifying group, and the two characteristics also have a certain synergistic effect, and the synergistic characteristic is generally superior to that of a single mesoporous material SBA molecular sieve or functional group. In the organic functionalized mesoporous material, the inorganic component ensures the basic structure and stability of the material, and the organic group component endows the inner and outer surfaces of the material with unique functions. In the prior art, an amino functional group is modified on the surface of a molecular sieve or inside a pore channel by a post-grafting method or a copolycondensation method, wherein the post-grafting method is to generate a condensation reaction between an organic functional group and silicon hydroxyl on the surface of the pore channel of a mesoporous material to generate a corresponding covalent bond, so that the functional group is fixed on the wall of the pore channel of the mesoporous material. The modification method does not destroy the pore channel structure of the original mesoporous material and can access more organic functional groups, but the distribution of the functional groups on the surface of the modified mesoporous material prepared by the method is not uniform, most of the functional groups are gathered in the areas of the outer surface and the inner surface of the pore channel close to the orifice, and the content of the functional groups distributed in the pore channel is less. The copolycondensation method is characterized in that a functional organic modifier is directly added into a sol consisting of a template agent and a silicon source for reaction, namely, the modifier is directly added into a system containing the silicon source and the template agent, so that the silicon source and the template agent can be simultaneously hydrolyzed with orthosilicate ester and mutually generate cross-linking, after a certain time of reaction, the system is placed in a high-pressure reaction kettle for crystallization, and a modified mesoporous material containing functional groups is formed through a self-assembly process. However, functionalized materials prepared by copolycondensation generally have the disadvantage of poor order, and the order decreases with increasing incorporation of organic groups.
Disclosure of Invention
In a first aspect, the invention provides a method for preparing amino-functionalized SBA molecular sieve raw powder, which comprises the following steps:
1) mixing an organic template agent, water, a pore-expanding agent, an amino modifier, an organic solvent, a silicon source and acid to obtain a colloidal mixture;
2) carrying out hydrothermal crystallization on the colloidal mixture to obtain a product after the hydrothermal crystallization;
3) and filtering, washing and drying the product after hydrothermal crystallization to obtain amino functionalized SBA molecular sieve raw powder.
According to some embodiments of the invention, the silicon source is SiO2Measured as H, acid+Measured as solvent H2Calculated by O, the organic template agent is calculated by R, and the molar ratio of the used amount of each raw material is SiO2：aH2O：bR：cH+Wherein, the value of a is 80-200, the value of b is 0.005-0.030, and the value of c is 0.10-0.25.
Preferably, the value of a is 100-160.
Preferably, b has a value of 0.010-0.025.
Preferably, c has a value of 0.15 to 0.20.
According to some embodiments of the invention, the SBA molecular sieve of the invention is, inter alia, SBA-15 or SBA-16.
According to some embodiments of the invention, the organic templating agent is selected from one or more of amphiphilic nonionic triblock surfactants and polycyclic heterocyclic amines.
According to some preferred embodiments of the present invention, the organic templating agent is one or more of F127(EO106PO70EO106), F108(EO132PO50EO132), P123(EO20PO70EO20), P104(EO27PO61EO27), and Hexamethylenetetramine (HMTA).
According to some preferred embodiments of the present invention, when the SBA molecular sieve is SBA-15, the organic templating agent is selected from P123 and/or P104.
According to some preferred embodiments of the present invention, when the SBA molecular sieve is SBA-16, the organic templating agent is selected from one or more of F127, F108 and HMTA.
According to some embodiments of the invention, the pore-expanding agent is selected from a compound of formula I, C1-C4Alkyl substituted benzene and C5-C12One or more of the alkanes may be present,
Figure BDA0002155790780000031
in the formula I, R1And R2Same, selected from C1-C4Alkyl radical, R3Is selected from C8-C16An alkyl group.
According to some preferred embodiments of the invention, in formula I, R1And R2Selected from methyl, ethyl, n-propyl and isopropyl.
According to some preferred embodiments of the inventionIn the formula I, R3Is selected from C10-C14An alkyl group.
According to some preferred embodiments of the present invention, the pore-expanding agent is selected from one or more of N, N-dimethyldodecylamine, 1,3, 5-trimethylbenzene and decane.
According to some embodiments of the invention, the molar ratio of the pore-expanding agent to the organic templating agent is from 15.5:1 to 10: 1.
According to some embodiments of the invention, the amino modifier is selected from organosilanes bearing an amino structure.
According to some preferred embodiments of the present invention, the amino modifier is selected from the group consisting of organosilanes of formula II,
Figure BDA0002155790780000032
in the formula II, R1、R2And R3Same, selected from C1-C4Alkyl radical, R4C selected from amino with amino or phenyl substitution3-C6An alkyl group.
According to some preferred embodiments of the invention, in formula II, R1、R2And R3And is selected from methyl, ethyl, n-propyl and isopropyl.
According to some preferred embodiments of the invention, in formula II, R4Selected from propyl with amino or phenyl substituted amino.
According to some preferred embodiments of the present invention, the amino modifier is selected from one or more of 3-aminopropyltrimethoxysilane, 3- (phenylamino) propyltrimethoxysilane and 3-aminopropyltriethoxysilane.
According to some embodiments of the invention, the silicon source is one or more of white carbon black, ethyl orthosilicate and silica sol.
According to some embodiments of the invention, the silicon source is tetraethyl orthosilicate.
According to some embodiments of the invention, the organic solvent is an alcohol compound. The organic solvent serves to sufficiently dissolve the amino modifier and the silicon source material constituting the molecular sieve together.
According to some preferred embodiments of the invention, the organic solvent is of the formula R5Alcohols of-OH, in which R5Is selected from C1-C6An alkyl group.
According to some preferred embodiments of the invention, the organic solvent is ethanol.
According to some embodiments of the invention, the molar ratio of the amino modifier to the silicon source is from 0.8:1 to 0.3: 1.
According to some embodiments of the invention, the mass ratio of the organic solvent to the amino modifier is from 1:2 to 2: 1.
According to some preferred embodiments of the present invention, the mass ratio of the organic solvent to the amino modifier is 1: 1.
According to some embodiments of the invention, the acid is one of hydrochloric acid, sulfuric acid or nitric acid.
According to some preferred embodiments of the invention, the acid is hydrochloric acid.
According to some embodiments of the invention, in step 1), the temperature of the mixing reaction is between 20 and 70 ℃.
According to some preferred embodiments of the present invention, in step 1), the temperature of the mixing reaction is 30 to 70 ℃.
According to some embodiments of the present invention, in the step 2), the temperature of the hydrothermal crystallization is 80 to 130 ℃, and the time of the hydrothermal crystallization is 24 to 90 hours.
According to some preferred embodiments of the present invention, in the step 2), the temperature of the hydrothermal crystallization is 90 to 120 ℃, and the time of the hydrothermal crystallization is 40 to 70 hours.
According to some embodiments of the invention, the temperature of the drying in step 3) is 100-140 ℃.
According to some preferred embodiments of the present invention, the temperature of the drying in step 3) is 110-.
In a second aspect, the present invention provides a method for preparing an amino-functionalized SBA molecular sieve, comprising the steps of:
mixing the amino-functionalized SBA molecular sieve raw powder obtained by the preparation method according to the first aspect with an extracting agent, and then filtering, washing and drying to obtain the amino-functionalized SBA molecular sieve.
According to some embodiments of the invention, the extractant is an ether compound.
According to some preferred embodiments of the invention, the extractant is of the formula R6-O-R7Ether compound of (2), wherein R6And R7Are the same or different and are each independently selected from C1-C6An alkyl group.
According to some preferred embodiments of the invention, R is in the formula6-O-R7In, R6And R7Each independently selected from C1-C3An alkyl group.
According to some preferred embodiments of the invention, the extractant is dimethyl ether or diethyl ether.
According to some embodiments of the invention, the mass ratio of the extractant to the molecular sieve raw powder is 4:1 to 2:1, and the extraction time is 2 to 4 hours. And removing the organic template agent in the pore channels of the molecular sieve by extraction.
According to some embodiments of the invention, the SBA molecular sieve of the invention is, inter alia, SBA-15 or SBA-16.
In a third aspect, the invention provides amino-functionalized SBA molecular sieve raw powder, the Fourier infrared spectrogram of which has a spectrum of 1564-1574cm-1Absorption peak in the range.
According to some preferred embodiments of the present invention, the Fourier infrared spectrum of the molecular sieve raw powder has a spectrum of 1567-1571cm-1Absorption peak in the range.
According to some preferred embodiments of the present invention, the molecular sieve raw powder has a Fourier infrared spectrum at 1569cm-1The absorption peak at (c).
According to some embodiments of the invention, the molecular sieve raw powder further has a Fourier infrared spectrumIs selected from 460 and 470cm-1And 1075-1085cm-1Absorption peak in the range.
According to some preferred embodiments of the present invention, the molecular sieve raw powder further has a Fourier infrared spectrum at 467cm selected from 463--1And 1078 and 1082cm-1Absorption peak in the range.
According to some preferred embodiments of the present invention, the molecular sieve raw powder further has a Fourier infrared spectrum at a wavelength selected from 465cm-1And 1080cm-1The absorption peak at (c).
According to some preferred embodiments of the present invention, the molecular sieve raw powder has a fourier infrared spectrum substantially similar to that of fig. 2 or fig. 4.
According to some embodiments of the present invention, the molecular sieve raw powder has a specific surface area of 700-1200m2/g。
According to some preferred embodiments of the present invention, the molecular sieve raw powder has a specific surface area of 800-1000m2/g。
According to some embodiments of the invention, the mesoporous pore size of the molecular sieve raw powder is 4.5-10nm.
According to some preferred embodiments of the present invention, the mesoporous pore size of the molecular sieve raw powder is 7 to 9 nm.
According to some embodiments of the invention, the molecular sieve raw powder comprises a reaction product of an organic templating agent, water, a pore-expanding agent, an amino modifier, an organic solvent, a silicon source, and an acid.
According to some embodiments of the invention, the organic templating agent is selected from one or more of amphiphilic nonionic triblock surfactants and polycyclic heterocyclic amines.
According to some preferred embodiments of the present invention, the organic templating agent is one or more of F127(EO106PO70EO106), F108(EO132PO50EO132), P123(EO20PO70EO20), P104(EO27PO61EO27), and Hexamethylenetetramine (HMTA).
According to some preferred embodiments of the present invention, when the SBA molecular sieve is SBA-15, the organic templating agent is selected from P123 and/or P104.
According to some preferred embodiments of the present invention, when the SBA molecular sieve is SBA-16, the organic templating agent is selected from one or more of F127, F108 and HMTA.
According to some embodiments of the invention, the pore-expanding agent is selected from a compound of formula I, C1-C4Alkyl substituted benzene and C5-C12One or more of the alkanes may be present,
Figure BDA0002155790780000061
in the formula I, R1And R2Same, selected from C1-C4Alkyl radical, R3Is selected from C8-C16An alkyl group.
According to some preferred embodiments of the invention, in formula I, R1And R2Selected from methyl, ethyl, n-propyl and isopropyl.
According to some preferred embodiments of the invention, in formula I, R3Is selected from C10-C14An alkyl group.
According to some preferred embodiments of the present invention, the pore-expanding agent is selected from one or more of N, N-dimethyldodecylamine, 1,3, 5-trimethylbenzene and decane.
According to some embodiments of the invention, the molar ratio of the pore-expanding agent to the organic templating agent is from 15.5:1 to 10: 1.
According to some embodiments of the invention, the amino modifier is selected from organosilanes bearing an amino structure.
According to some preferred embodiments of the present invention, the amino modifier is selected from the group consisting of organosilanes of formula II,
Figure BDA0002155790780000071
in the formula II, R1、R2And R3Same, selected from C1-C4Alkyl radical, R4Selected from ammonia substituted with amino or phenylC of radical3-C6An alkyl group.
According to some preferred embodiments of the invention, in formula II, R1、R2And R3And is selected from methyl, ethyl, n-propyl and isopropyl.
According to some preferred embodiments of the invention, in formula II, R4Selected from propyl with amino or phenyl substituted amino.
According to some preferred embodiments of the present invention, the amino modifier is selected from one or more of 3-aminopropyltrimethoxysilane, 3- (phenylamino) propyltrimethoxysilane and 3-aminopropyltriethoxysilane.
According to some embodiments of the invention, the silicon source is one or more of white carbon black, ethyl orthosilicate and silica sol.
According to some embodiments of the invention, the silicon source is tetraethyl orthosilicate.
According to some embodiments of the invention, the organic solvent is an alcohol compound. The organic solvent serves to sufficiently dissolve the amino modifier and the silicon source material constituting the molecular sieve together.
According to some preferred embodiments of the invention, the organic solvent is of the formula R5Alcohols of-OH, in which R5Is selected from C1-C6An alkyl group.
According to some preferred embodiments of the invention, the organic solvent is ethanol.
According to some embodiments of the invention, the molar ratio of the amino modifier to the silicon source is from 0.8:1 to 0.3: 1.
According to some embodiments of the invention, the mass ratio of the organic solvent to the amino modifier is from 1:2 to 2: 1.
According to some preferred embodiments of the present invention, the mass ratio of the organic solvent to the amino modifier is 1: 1.
According to some embodiments of the invention, the acid is one of hydrochloric acid, sulfuric acid or nitric acid.
According to some preferred embodiments of the invention, the acid is hydrochloric acid.
According to some embodiments of the invention, the silicon source is SiO2Measured as H, acid+Measured as solvent H2Calculated by O, the organic template agent is calculated by R, and the molar ratio of the used amount of each raw material is SiO2：aH2O：bR：cH+Wherein, the value of a is 80-200, the value of b is 0.005-0.030, and the value of c is 0.10-0.25.
Preferably, the value of a is 100-160.
Preferably, b has a value of 0.010-0.025.
Preferably, c has a value of 0.15 to 0.20.
According to some embodiments of the invention, the SBA molecular sieve of the invention is, inter alia, SBA-15 or SBA-16.
In a fourth aspect, the invention provides an amino-functionalized SBA molecular sieve, the Fourier infrared spectrum of which has a spectrum of 1564-1574cm-1Absorption peak in the range.
According to some preferred embodiments of the present invention, the molecular sieve has a Fourier infrared spectrum at 1567-1571cm-1Absorption peak in the range.
According to some preferred embodiments of the present invention, the molecular sieve has a Fourier infrared spectrum at 1569cm-1The absorption peak at (c).
According to some embodiments of the invention, the molecular sieve further has a Fourier infrared spectrum at a value selected from the group consisting of 460 and 470cm-1And 1075-1085cm-1Absorption peak in the range.
According to some preferred embodiments of the present invention, the molecular sieve further has a Fourier infrared spectrum at 467cm selected from 463--1And 1078 and 1082cm-1Absorption peak in the range.
According to some preferred embodiments of the present invention, the molecular sieve further has a Fourier infrared spectrum at a wavelength selected from 465cm-1And 1080cm-1The absorption peak at (c).
According to some preferred embodiments of the present invention, the molecular sieve has a fourier infrared spectrum substantially similar to that of fig. 2 or fig. 4.
According to some embodiments of the invention, the molecular sieve has a specific surface area of 700-1200m2/g。
According to some preferred embodiments of the present invention, the molecular sieve has a specific surface area of 800-2/g。
According to some embodiments of the invention, the molecular sieve has a mesoporous pore size of 4.5 to 10nm.
According to some preferred embodiments of the present invention, the molecular sieve has a mesoporous pore size of 7 to 9 nm.
According to some embodiments of the invention, the molecular sieve raw powder comprises a reaction product of an organic templating agent, water, a pore-expanding agent, an amino modifier, an organic solvent, a silicon source, and an acid.
According to some embodiments of the invention, the organic templating agent is selected from one or more of amphiphilic nonionic triblock surfactants and polycyclic heterocyclic amines.
According to some preferred embodiments of the present invention, the organic templating agent is one or more of F127(EO106PO70EO106), F108(EO132PO50EO132), P123(EO20PO70EO20), P104(EO27PO61EO27), and Hexamethylenetetramine (HMTA).
According to some preferred embodiments of the present invention, when the SBA molecular sieve is SBA-15, the organic templating agent is selected from P123 and/or P104.
According to some preferred embodiments of the present invention, when the SBA molecular sieve is SBA-16, the organic templating agent is selected from one or more of F127, F108 and HMTA.
According to some embodiments of the invention, the pore-expanding agent is selected from a compound of formula I, C1-C4Alkyl substituted benzene and C5-C12One or more of the alkanes may be present,
Figure BDA0002155790780000091
in the formula I, R1And R2Same, selected from C1-C4Alkyl radical, R3Is selected from C8-C16An alkyl group.
According to some preferred embodiments of the invention, in formula I, R1And R2Selected from methyl, ethyl, n-propyl and isopropyl.
According to some preferred embodiments of the invention, in formula I, R3Is selected from C10-C14An alkyl group.
According to some preferred embodiments of the present invention, the pore-expanding agent is selected from one or more of N, N-dimethyldodecylamine, 1,3, 5-trimethylbenzene and decane.
According to some embodiments of the invention, the molar ratio of the pore-expanding agent to the organic templating agent is from 15.5:1 to 10: 1.
According to some embodiments of the invention, the amino modifier is selected from organosilanes bearing an amino structure.
According to some preferred embodiments of the present invention, the amino modifier is selected from the group consisting of organosilanes of formula II,
Figure BDA0002155790780000101
in the formula II, R1、R2And R3Same, selected from C1-C4Alkyl radical, R4C selected from amino with amino or phenyl substitution3-C6An alkyl group.
According to some preferred embodiments of the invention, in formula II, R1、R2And R3And is selected from methyl, ethyl, n-propyl and isopropyl.
According to some preferred embodiments of the invention, in formula II, R4Selected from propyl with amino or phenyl substituted amino.
According to some preferred embodiments of the present invention, the amino modifier is selected from one or more of 3-aminopropyltrimethoxysilane, 3- (phenylamino) propyltrimethoxysilane and 3-aminopropyltriethoxysilane.
According to some embodiments of the invention, the silicon source is one or more of white carbon black, ethyl orthosilicate and silica sol.
According to some embodiments of the invention, the silicon source is tetraethyl orthosilicate.
According to some embodiments of the invention, the organic solvent is an alcohol compound. The organic solvent serves to sufficiently dissolve the amino modifier and the silicon source material constituting the molecular sieve together.
According to some preferred embodiments of the invention, the organic solvent is of the formula R5Alcohols of-OH, in which R5Is selected from C1-C6An alkyl group.
According to some preferred embodiments of the invention, the organic solvent is ethanol.
According to some embodiments of the invention, the molar ratio of the amino modifier to the silicon source is from 0.8:1 to 0.3: 1.
According to some embodiments of the invention, the mass ratio of the organic solvent to the amino modifier is from 1:2 to 2: 1.
According to some preferred embodiments of the present invention, the mass ratio of the organic solvent to the amino modifier is 1: 1.
According to some embodiments of the invention, the acid is one of hydrochloric acid, sulfuric acid or nitric acid.
According to some preferred embodiments of the invention, the acid is hydrochloric acid.
According to some embodiments of the invention, the silicon source is SiO2Measured as H, acid+Measured as solvent H2Calculated by O, the organic template agent is calculated by R, and the molar ratio of the used amount of each raw material is SiO2：aH2O：bR：cH+Wherein, the value of a is 80-200, the value of b is 0.005-0.030, and the value of c is 0.10-0.25.
Preferably, the value of a is 100-160.
Preferably, b has a value of 0.010-0.025.
Preferably, c has a value of 0.15 to 0.20.
According to some embodiments of the invention, the SBA molecular sieve of the invention is, inter alia, SBA-15 or SBA-16.
In a fifth aspect, the present invention provides the use of an amino-functionalized SBA molecular sieve in gas adsorption.
According to some embodiments of the invention, the applying comprises contacting the molecular sieve obtained by the preparation method according to the second aspect of the invention or the molecular sieve according to the fourth aspect with a gas.
According to some preferred embodiments of the invention, the gas is an acid gas.
According to some preferred embodiments of the invention, the gas is CO2。
According to some embodiments of the invention, the SBA molecular sieve of the invention is, inter alia, SBA-15 or SBA-16.
The method is characterized in that in the prepared amino functionalized SBA molecular sieve, a pore expanding agent expands a pore passage of the molecular sieve in the in-situ synthesis process, meanwhile, amino groups enter the pore passage of the molecular sieve in a directional manner and are combined with silicon hydroxyl on the pore wall, the original order degree and regularity of the molecular sieve are not damaged, and the amino groups are uniformly dispersed in the pore passage of the molecular sieve.
When the SBA molecular sieve is subjected to organic functional modification by adopting a conventional grafting treatment method, silicon hydroxyl groups existing on the outer surface of a material and close to the orifice of a mesoporous channel are easier to generate silanization modification reaction relative to silicon hydroxyl groups on the inner surface of the mesoporous channel of the material due to steric hindrance, so that organic groups are difficult to enter the channel of the molecular sieve. The SBA molecular sieve is modified by adopting a conventional copolycondensation method, although amino groups can be introduced into the molecular sieve pore channels in one step, because the pore channels of the SBA molecular sieve are small, a large number of amino modifier macromolecules also enter the pore channels of the molecular sieve simultaneously in the reaction process, and a large number of organic matters can continuously enlarge the pore channel structure of the SBA, so that the order degree of the molecular sieve is sharply reduced, and the service life of the molecular sieve is influenced. According to the method provided by the invention, firstly, the pore diameter structure of the SBA molecular sieve is enlarged by adopting a pore-enlarging agent mode in the in-situ synthesis process of the molecular sieve, the pore size of the obtained SBA molecular sieve is larger than that of the conventional SBA molecular sieve, at this time, when organic functional modification is carried out in the in-situ synthesis process, the pore structure of the molecular sieve cannot be damaged by amino groups, and the obtained amino functional SBA molecular sieve not only has the thermal stability of the SBA molecular sieve, but also has the surface characteristics brought by the organic component molecular sieve.
Drawings
FIG. 1 is a small angle XRD pattern of amino functionalized SBA-16 molecular sieve obtained according to example 3 of the present invention.
FIG. 2 is a diagram of an amino-functionalized SBA-16 molecular sieve FT-IR obtained according to example 3 of the present invention.
FIG. 3 is a small angle XRD pattern of amino functionalized SBA-15 molecular sieve obtained according to example 5 of the present invention.
FIG. 4 is a diagram of amino functionalized SBA-15 molecular sieve FT-IR obtained according to example 5 of the present invention.
Detailed Description
The present invention will be more fully understood by those skilled in the art by describing the present invention in detail with reference to the following examples, which should not be construed as limiting the scope of the present invention in any way.
In the examples of the present invention, XRD was carried out by means of an X-ray diffractometer of Philips X-Pert series, FT-IR was carried out by means of a Fourier transform infrared spectrometer of Thermo Nicolet Nexus 470 type by Thermo company to determine the presence of amino groups in the molecular sieve, and BET was carried out by means of a full-automatic specific surface analyzer of ASAP2020 type by Micromeritics company. The silicon source of the invention is SiO2Measured as H, acid+Measured as solvent H2And O is counted, and the organic template is counted as R.
Example 1
Adding 3.5g F127 g and 76g deionized water into the reactor in turn at 60 ℃, stirring uniformly, adding 53mL of 0.1mol/L hydrochloric acid solution, then adding 0.8g N, N-dimethyldodecylamine (DMDA), stirring for 1 hour at 60 ℃, adding a mixed solution of 6.6g of 3-aminopropyltrimethoxysilane and 6.6g of ethanol, slowly and dropwise adding 11g of Tetraethoxysilane (TEOS), and obtaining the productThe molar ratio of the reaction mixture is SiO2：80H2O：0.005R：0.1H+And transferring the mixture to a crystallization kettle, heating to 90 ℃, and crystallizing for 40 hours at constant temperature. And after crystallization is completed, cooling to room temperature, separating, washing and drying the reacted mixture at 100 ℃ to obtain the amino-functionalized SBA-16 molecular sieve. 5.0g of amino-functionalized SBA-16 molecular sieve and 20g of methyl ether are uniformly mixed and stirred for 2 hours, the obtained product is filtered, washed, dried at the temperature of 100 ℃ and analyzed by BET, and the specific surface area of the obtained product is 830m2The mesoporous aperture is 7.6 nm.
Applying the obtained molecular sieve to CO2Adsorption experiment, firstly, a certain amount of product is dried in a vacuum drying oven at 100 ℃ for 1H to remove adsorbed H2O, when the temperature is reduced to room temperature and balanced, the weight is m0. Then 10% CO was introduced2And 90% N2Introducing the mixed gas into an amino-functionalized MCM-41 molecular sieve at 35 ℃, weighing m after the adsorption reaches balance1Finally regenerating in a vacuum drying oven at 100 deg.C for 30min to adsorb CO2All released and weighed as m2。m2The effect of (a) is to0And comparing, wherein the two are the same under normal conditions, and if the difference between the two is too large, carrying out the experiment again. Regeneration followed by repetition of CO2The adsorption and desorption experiments are carried out for 5 times, and the average value is taken. CO 22The adsorption amount of (c) is calculated by the formula:
CCO2＝(m1-m0)/44m0. Determination of adsorbed CO2The results are shown in Table 1.
Example 2
The difference from example 1 is that the feeding temperature is changed to 40 ℃, the organic template agent is changed to F108, the dosage is 10.9g, the dosage of water is changed to 135g, the pore-expanding agent is changed to 1,3, 5-trimethylbenzene, the dosage is 0.9g, the amino modifier is changed to 3- (phenylamino) propyl trimethoxy silane, the dosage is 11.5g, the dosage of ethanol is changed to 11.5g, the silicon source is changed to silica white (the content of silica is 90 wt%), the dosage is 5g, the acid is changed to sulfuric acid, the dosage is 112mL, the crystallization temperature is changed to 100 ℃, the crystallization time is changed to 11.5g, the dosage is changed to 112mL, the crystallization temperature50h, the drying temperature is changed to 110 ℃, the extractant is changed to ether, the dosage is changed to 15g, the extraction time is changed to 3h, the rest components and the synthesis conditions are not changed, and the molar ratio of the obtained reaction mixture is SiO2：100H2O：0.01R：0.15H+The obtained sample was subjected to BET analysis to obtain a product having a specific surface area of 884m2The mesoporous aperture is 7.9 nm.
Applying the obtained molecular sieve to CO2Adsorption experiment, 10% CO2And 90% N2Introducing the mixed gas into an amino-functionalized SBA-16 molecular sieve at 35 ℃, and determining the adsorbed CO2The results are shown in Table 1.
Example 3
The difference from example 1 is that the feeding temperature is changed to 50 ℃, the organic template agent is changed to HMTA, the dosage is 0.15g, the dosage of water is changed to 82.5g, the pore-expanding agent is changed to decane, the dosage is 1.8g, the amino modifier is changed to 3-aminopropyltriethoxysilane, the dosage is 4.6g, the dosage of ethanol is changed to 4.6g, the silicon source is changed to silica sol (SW-25, the content of silica is 25 wt%), the dosage is 10g, the acid source is changed to nitric acid, the dosage is 83mL, the crystallization temperature is changed to 110 ℃, the crystallization time is changed to 60h, the drying temperature is changed to 120 ℃, the extractant is changed to diethyl ether, the dosage is changed to 10g, the extraction time is changed to 4h, the rest components and the synthesis conditions are not changed, and the molar ratio of the obtained reaction mixture is SiO2：110H2O：0.025R：0.2H+The sample obtained was subjected to BET analysis to obtain a product having a specific surface area of 944m2The mesoporous aperture is 8.3 nm.
The molecular sieve after the amino modification is characterized, and the small-angle XRD pattern and the FT-IR pattern are respectively shown in figure 1 and figure 2.
Applying the obtained molecular sieve to CO2Adsorption experiment, 10% CO2And 90% N2Introducing the mixed gas into an amino-functionalized SBA-16 molecular sieve at 35 ℃, and determining the adsorbed CO2The results are shown in Table 1.
Example 4
At the temperature of 30 ℃, 9.3g P104 and 85.5g deionized water are added into a reactor in turn, stirred evenly, then 132mL of 0.1mol/L hydrochloric acid solution is added,5.0g of 5.0g N, N-dimethyldodecylamine (DMDA) was then added, stirring was continued and a mixed solution of 6.6g of 3-aminopropyltrimethoxysilane and 6.6g of ethanol was added, 11g of Tetraethylorthosilicate (TEOS) was slowly added dropwise, the molar ratio of the reaction mixture obtained being SiO2：90H2O：0.03R：0.25H+And transferring the mixture to a crystallization kettle, heating to 130 ℃, and crystallizing for 90 hours at constant temperature. And after crystallization is completed, cooling to room temperature, separating, washing and drying the reacted mixture at 130 ℃ to obtain the amino-functionalized SBA-15 molecular sieve. 5.0g of amino-functionalized SBA-15 molecular sieve and 20g of methyl ether are uniformly mixed and stirred for 2 hours, the obtained product is filtered, washed, dried at the temperature of 100 ℃ and analyzed by BET, and the specific surface area of the obtained product is 914m2The mesoporous aperture is 8.1 nm.
Applying the obtained molecular sieve to CO2Adsorption experiment, 10% CO2And 90% N2Introducing the mixed gas into an amino-functionalized SBA-15 molecular sieve at 35 ℃, and determining the adsorbed CO2The results are shown in Table 1.
Example 5
The difference from example 4 is that the charging temperature was changed to 70 ℃, the organic template agent was changed to P123, the amount used was 4.4g, the amount of water was changed to 175.5g, the pore-expanding agent was changed to 1,3, 5-trimethylbenzene, the amount used was 1.1g, the amino modifier was changed to 3- (phenylamino) propyltrimethoxysilane, the amount used was 9.6g, the amount of ethanol was changed to 9.6g, the silicon source was changed to silica (silica content 90 wt%), the amount used was 5g, the acid source was changed to nitric acid, the amount used was 112.5mL, the crystallization temperature was changed to 120 ℃, the crystallization time was changed to 70h, the drying temperature was changed to 120 ℃, the extractant was changed to diethyl ether, the amount used was 15g, the extraction time was changed to 3h, the rest components and the synthesis conditions were not changed, and the molar ratio of the obtained reaction mixture was SiO 123, the amount used was 42：130H2O：0.01R：0.15H+The obtained sample was subjected to BET analysis to obtain a product having a specific surface area of 917m2The mesoporous aperture is 8.1 nm.
The molecular sieve after the amino modification is characterized, and the small-angle XRD pattern and the FT-IR pattern are respectively shown in figure 3 and figure 4.
Applying the obtained molecular sieve to CO2Adsorption experiment, 10% CO2And 90% N2Introducing the mixed gas into an amino-functionalized SBA-15 molecular sieve at 35 ℃, and determining the adsorbed CO2The results are shown in Table 1.
Example 6
The difference from example 4 is that the feeding temperature was changed to 50 ℃, the organic template agent was changed to P123, the amount used was 4.8g, the amount of water was changed to 112.5g, the pore-expanding agent was changed to decane, the amount used was 1.2g, the amino modifier was changed to 3-aminopropyltriethoxysilane, the amount used was 2.8g, the amount of ethanol was changed to 2.8g, the silicon source was changed to silica sol (SW-25, silica content 25 wt%), the amount used was 10g, the acid source was changed to nitric acid, the amount used was 41.7mL, the crystallization temperature was changed to 110 ℃, the crystallization time was changed to 80h, the drying temperature was changed to 110 ℃, the extractant was changed to diethyl ether, the amount used was 10g, the extraction time was changed to 4h, the remaining components and the synthesis conditions were not changed, and the molar ratio of the obtained reaction mixture was SiO2：150H2O：0.02R：0.1H+The obtained sample was subjected to BET analysis to obtain a product having a specific surface area of 892m2The mesoporous aperture is 8.0 nm.
Applying the obtained molecular sieve to CO2Adsorption experiment, 10% CO2And 90% N2Introducing the mixed gas into an amino-functionalized SBA-15 molecular sieve at 35 ℃, and determining the adsorbed CO2The results are shown in Table 1.
Example 7
The only difference from example 1 is that the amino modifier was 3- (phenylamino) propyltrimethoxysilane in an amount of 9.4g, and the sample obtained was analyzed by BET to give a product having a specific surface area of 829m2The mesoporous aperture is 7.6 nm.
Example 8
The only difference from example 1 was that the amino modifier was used in an amount of 7.5g, ethanol was used in an amount of 7.5g, and the sample obtained was analyzed by BET to give a product having a specific surface area of 821m2The mesoporous aperture is 7.5 nm.
Example 9
The only difference from example 1 is that the amount of the amino modifier used was 4.7g,the amount of ethanol used was 4.7g, and the obtained sample was subjected to BET analysis to obtain a product having a specific surface area of 845m2The mesoporous aperture is 7.7 nm.
Example 10
The difference from example 1 is only that the pore-expanding agent is 1,3, 5-trimethylbenzene and the amount is 0.47g, and the sample obtained was analyzed by BET to obtain a product having a specific surface area of 857m2The mesoporous aperture is 7.7 nm.
Example 11
The difference from example 1 was only that the amount of the pore-expanding agent used was 0.83g, and the specific surface area of the obtained product was 823m by BET analysis of the obtained sample2The mesoporous aperture is 7.5 nm.
Example 12
Except that the amount of the pore-expanding agent used was 0.53g as compared with example 1, and the obtained sample was subjected to BET analysis to obtain a product having a specific surface area of 851m2The mesoporous aperture is 7.6 nm.
Example 13
Except that 3.5g F127, 76g of deionized water, 53mL of a 0.1mol/L hydrochloric acid solution, 0.8g N, N-dimethyldodecylamine (DMDA), a mixed solution of 6.6g of 3-aminopropyltrimethoxysilane and 6.6g of ethanol, and 11g of ethyl orthosilicate (TEOS) were simultaneously charged into a reactor, and the obtained sample was analyzed by BET to obtain a product having a specific surface area of 826m2The mesoporous aperture is 7.5 nm.
Example 14
Except that after stirring at 60 ℃ for 2 hours after adding the pore-expanding agent, the sample obtained was subjected to BET analysis to obtain a product having a specific surface area of 832m2The mesoporous aperture is 7.5 nm.
Example 15
Except that the specific surface area of the product obtained by BET analysis after stirring at 60 ℃ for 30min after adding the pore-expanding agent was 823m2The mesoporous aperture is 7.3 nm.
Example 16
The difference from example 1 is only that after the pore-expanding agent was added, stirring was carried out at 80 ℃After stirring for 1 hour, the sample obtained was subjected to BET analysis to obtain a product having a specific surface area of 827m2The mesoporous aperture is 7.3 nm.
Example 17
Except that the specific surface area of the product obtained by BET analysis was 824m after stirring at 80 ℃ for 1 hour after adding the pore-expanding agent in example 12The mesoporous aperture is 7.3 nm.
Comparative example 1
Sequentially adding 3.5g F127 g and 76g of deionized water into a reactor at 60 ℃, stirring uniformly, adding 53mL of 0.1mol/L hydrochloric acid solution, then adding a mixed solution of 6.6g of 3-aminopropyltrimethoxysilane and 6.6g of ethanol, continuing stirring, slowly and dropwise adding 11g of Tetraethoxysilane (TEOS) to obtain a reaction mixture with the molar ratio of SiO2：80H2O：0.005R：0.1H+And transferring the mixture to a crystallization kettle, heating to 90 ℃, and crystallizing for 40 hours at constant temperature. And after crystallization is completed, cooling to room temperature, separating, washing and drying the reacted mixture at 100 ℃ to obtain the amino-functionalized SBA-16 molecular sieve. Then uniformly mixing the amino-functionalized SBA-16 molecular sieve with 20g of methyl ether, stirring for 2 hours, separating, washing, drying at 100 ℃, and performing BET analysis on the product to obtain the product with the specific surface area of 620m2The mesoporous aperture is 4.0 nm.
Applying the obtained molecular sieve to CO2Adsorption experiment, 10% CO2And 90% N2Introducing the mixed gas into an amino-functionalized SBA-16 molecular sieve at 35 ℃, and determining the adsorbed CO2The results are shown in Table 1.
Comparative example 2
Sequentially adding 3.5g F127 g and 76g of deionized water into a reactor at 60 ℃, uniformly stirring, adding 53mL of 0.1mol/L hydrochloric acid solution, continuously stirring, slowly dropwise adding 11g of Tetraethoxysilane (TEOS) to obtain a reaction mixture with the molar ratio of SiO2：80H2O：0.005R：0.1H+And transferring the mixture to a crystallization kettle, heating to 90 ℃, and crystallizing for 40 hours at constant temperature. After the crystallization is completed, the temperature is reduced to the room temperature,separating, washing and drying the reacted mixture at 100 ℃ to obtain the SBA-16 molecular sieve raw powder. 5g of the obtained SBA-16 molecular sieve raw powder is uniformly mixed with 6.6g of 3- (phenylamino) propyl trimethoxy silane and 6.6g of ethanol, the mixture is stirred for 4 hours at the temperature of 60 ℃, then the product is uniformly mixed with 20g of methyl ether and stirred for 2 hours, the obtained product is filtered, washed, dried at the temperature of 100 ℃ and analyzed by BET, and the specific surface area of the obtained product is 622m2The mesoporous aperture is 3.9 nm.
Applying the obtained molecular sieve to CO2Adsorption experiment, 10% CO2And 90% N2Introducing the mixed gas into an amino-functionalized SBA-16 molecular sieve at 35 ℃, and determining the adsorbed CO2The results are shown in Table 1.
Comparative example 3
Sequentially adding 0.7g F127 and 66.5g of deionized water into a reactor at the temperature of 60 ℃, stirring uniformly, adding 158.4mL of 0.1mol/L hydrochloric acid solution, then adding a mixed solution of 6.6g of 3-aminopropyl trimethoxy silane and 6.6g of ethanol, continuing stirring, slowly and dropwise adding 11g of Tetraethoxysilane (TEOS) to obtain a reaction mixture with the molar ratio of SiO2：70H2O：0.001R：0.3H+And transferring the mixture to a crystallization kettle, heating to 90 ℃, and crystallizing for 40 hours at constant temperature. After crystallization is completed, the temperature is reduced to room temperature, and the mixture after reaction is separated, washed and dried at 100 ℃ to obtain the product. 5.0g of the product obtained is taken and mixed uniformly with 20g of methyl ether and stirred for 2 hours, the product obtained is filtered, washed and dried at 100 ℃ and analyzed by BET, the specific surface area of the product obtained is 18m2/g。
Applying the obtained molecular sieve to CO2Adsorption experiment, 10% CO2And 90% N2Introducing mixed gas into the obtained product at 35 deg.C, and measuring adsorbed CO2The results are shown in Table 1.
Comparative example 4
0.3g P104 and 66.5g of deionized water are added into the reactor in turn at 30 ℃, stirred evenly, then 158.4mL of 0.1mol/L hydrochloric acid solution is added, and 6.6g of 3-aminopropyl tris (isopropyl) amine is addedThe mixture of methoxysilane and 6.6g of ethanol was stirred continuously and 11g of Tetraethylorthosilicate (TEOS) was added slowly dropwise to obtain a reaction mixture with a molar ratio of SiO2：70H2O：0.001R：0.3H+And transferring the mixture to a crystallization kettle, heating to 130 ℃, and crystallizing for 90 hours at constant temperature. After crystallization is completed, the temperature is reduced to room temperature, and the mixture after reaction is separated, washed and dried at 130 ℃ to obtain the product. 5.0g of the product obtained is taken and mixed uniformly with 20g of methyl ether and stirred for 2 hours, the product obtained is filtered, washed and dried at 100 ℃ and analyzed by BET, the specific surface area of the product obtained is 34m2/g。
Applying the obtained molecular sieve to CO2Adsorption experiment, 10% CO2And 90% N2Introducing mixed gas into the obtained product at 35 deg.C, and measuring adsorbed CO2The results are shown in Table 1.
Comparative example 5
Sequentially adding 3.5g F127 and 76g of deionized water into a reactor at 60 ℃, uniformly stirring, adding 53mL of 0.1mol/L hydrochloric acid solution, then adding 1.8g N, N-dimethyldodecylamine (DMDA), continuously stirring, adding a mixed solution of 6.6g of 3-aminopropyltrimethoxysilane and 6.6g of ethanol, continuously stirring, slowly dropwise adding 11g of Tetraethoxysilane (TEOS), and obtaining a reaction mixture with the molar ratio of SiO2：80H2O：0.005R：0.1H+And transferring the mixture to a crystallization kettle, heating to 90 ℃, and crystallizing for 40 hours at constant temperature. After crystallization is completed, cooling to room temperature, separating, washing and drying the reacted mixture at 100 ℃ to obtain the SBA-16 molecular sieve. Mixing 5.0g of the obtained SBA-16 molecular sieve and 20g of methyl ether uniformly, stirring for 2h, filtering, washing, drying at 100 ℃, and performing BET analysis to obtain a product with a specific surface area of 411m2The mesoporous aperture is 3.8 nm.
Applying the obtained molecular sieve to CO2Adsorption experiment, 10% CO2And 90% N2Introducing the mixed gas into an amino-functionalized SBA-16 molecular sieve at 35 ℃, and determining the adsorbed CO2The results are shown in Table 1.
TABLE 1 adsorption of CO by amino-functionalized SBA molecular sieves2Performance meter
CO2Adsorption Capacity (mmol/g) Specific surface area (m)2/g) Pore size (nm)
Example 1 1.49 830 7.6
Example 2 1.54 884 7.9
Example 3 1.60 944 8.3
Example 4 1.57 914 8.1
Example 5 1.57 917 8.0
Example 6 1.56 892 7.6
Example 7 1.49 829 7.5
Example 8 1.47 821 7.7
Example 9 1.50 845 7.7
Example 10 1.52 857 7.5
Example 11 1.47 823 7.6
Example 12 1.51 851 7.5
Example 13 1.48 826 7.5
Example 14 1.49 832 7.3
Example 15 1.47 823 7.3
Example 16 1.48 827 7.3
Example 17 1.46 824 4.0
Comparative example 1 0.51 620 3.9
Comparative example 2 0.54 622 3.8
Comparative example 3 0 18 -
Comparative example 4 0 34 -
Comparative example 5 0.36 411 3.8
Compared with the embodiment 1, the amino modifier is directly added in the synthesis process by adopting a copolycondensation method in the comparative example 1, the preparation method is simple, amino groups are introduced into the pore channels of the molecular sieve in one step, but a large amount of organic groups also enter the pore channels of the molecular sieve, the pore diameter of the molecular sieve is increased in the synthesis process, the order degree of the molecular sieve is reduced due to the larger pore diameter of the molecular sieve, and the specific surface area of the molecular sieve is reduced; comparative example 2 adopts a conventional grafting method, most of the amino modifier introduced by the method is on the specific surface of the molecular sieve or at the opening of the molecular sieve pore, and amino groups are difficult to enter the molecular sieve pore; comparative example 3 and comparative example 4 exceed the synthesis ratio of the molecular sieve, so that the SBA-16 molecular sieve and the SBA-15 molecular sieve are not synthesized; in comparative example 5, due to the existence of excessive pore-expanding agent, the pore channels of the molecular sieve are increased in disorder by the excessive pore-expanding agent, so that the order degree of the molecular sieve is reduced.
As can be seen from FIGS. 1 and 3, the amino-functionalized SBA molecular sieve obtained by the method provided by the invention has characteristic diffraction peaks of SBA-16 and SBA-15 molecular sieves, which indicates that the SBA series molecular sieves are successfully synthesized, and the existence of amino groups does not influence the order degree of the SBA molecular sieves.
As can be seen from FIGS. 2 and 4, 465cm-1And 1080cm-1Si-O-Si in which the radical is SBASymmetric vibration peak and asymmetric vibration peak of 1569cm-1Of formula NH2And the vibration peak in the pore canal with the silicon hydroxyl shows that the amino exists in the interior of the pore canal of the molecular sieve but not on the surface and the pore mouth of the molecular sieve.
As can be seen from Table 1, the amino-functionalized SBA molecular sieves prepared according to the present process are directed to CO2The preparation method of the molecular sieve has obvious adsorption effect, and although the preparation method of the comparative example 1 is simple, the adsorption amount is low because the order degree of the molecular sieve is destroyed by a large number of organic groups; in comparative example 2, although the specific surface area was high, the adsorption amount was limited because a large number of amino groups were concentrated on the surface and pore openings of the molecular sieve; comparative examples 3 and 4 had an adsorption amount of 0 since the porous structure of the SBA molecular sieve was not formed; in comparative example 5, the whole order degree of the molecular sieve is greatly reduced due to excessive pore-expanding agent, thereby influencing CO2The amount of adsorption.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.

Claims (12)

1. A preparation method of amino-functionalized SBA, in particular SBA-15 or SBA-16 molecular sieve raw powder, comprises the following steps:
1) mixing an organic template agent, water, a pore-expanding agent, an amino modifier, an organic solvent, a silicon source and acid to obtain a colloidal mixture;
2) carrying out hydrothermal crystallization on the colloidal mixture to obtain a product after the hydrothermal crystallization;
3) and filtering, washing and drying the product after hydrothermal crystallization to obtain amino functionalized SBA molecular sieve raw powder.
2. The method of claim 1, wherein the mixing temperature in step 1) is 20-70 ℃, preferably 30-70 ℃;
in the step 2), the temperature of the hydrothermal crystallization is 80-130 ℃, preferably 90-120 ℃, and the time of the hydrothermal crystallization is 24-90 hours, preferably 40-70 hours;
in the step 3), the drying temperature is 100-140 ℃, preferably 110-130 ℃.
3. A preparation method of an amino-functionalized SBA molecular sieve comprises the following steps:
mixing the amino-functionalized SBA molecular sieve raw powder obtained by the preparation method of claim 1 or 2 with an extracting agent, and then filtering, washing and drying to obtain the amino-functionalized SBA molecular sieve.
4. The process according to claim 3, wherein the extractant is an ether compound, preferably of formula R6-O-R7Ether compound of (2), wherein R6And R7Are the same or different and are each independently selected from C1-C6Alkyl, preferably C1-C3Alkyl, more preferably methyl or ethyl ether; preferably, the mass ratio of the extracting agent to the molecular sieve raw powder is 4:1-2:1, and the extraction time is 2-4 h.
5. Amino-functionalized SBA, in particular SBA-15 or SBA-16 molecular sieve raw powder, the Fourier infrared spectrogram of which has a value of 1564-1574cm-1Absorption peaks in the range, preferably with a peak at 1567-1571cm-1An absorption peak in the range of 1569cm-1The absorption peak at (c).
6. The molecular sieve raw powder or molecular sieve of claim 5, wherein the molecular sieve raw powder or molecular sieve has Fourier infrared propertiesThe spectrogram also has a spectral density of at least 460--1And 1075-1085cm-1The absorption peak in the range is preferably selected from 463-467cm-1And 1078 and 1082cm-1An absorption peak in the range, more preferably 465cm-1And 1080cm-1The absorption peak at (a); further preferably, the molecular sieve raw powder or molecular sieve has a fourier infrared spectrum substantially similar to that of fig. 2 or fig. 4.
7. The molecular sieve raw powder or molecular sieve as claimed in claim 6, wherein the specific surface area of the molecular sieve raw powder or molecular sieve is 700-1200m2Per g, preferably 800-2(ii)/g; and/or the mesoporous aperture of the molecular sieve raw powder or the molecular sieve is 4.5-10nm, preferably 7-9 nm.
8. The molecular sieve raw powder or molecular sieve of any one of claims 5-7, wherein the molecular sieve raw powder or molecular sieve comprises a reaction product of an organic templating agent, water, a pore-expanding agent, an amino modifier, an organic solvent, a silicon source, and an acid.
9. The process according to any one of claims 1 to 4 or the molecular sieve raw powder or molecular sieve according to any one of claims 5 to 8, wherein the silicon source is SiO2Measured as H, acid+Measured as solvent H2Calculated by O, the organic template agent is calculated by R, and the molar ratio of the used amount of each raw material is SiO2：aH2O：bR：cH+Wherein, the value of a is 80-200, preferably 100-160; b has a value of 0.005 to 0.030, preferably 0.010 to 0.025; the value of c is from 0.10 to 0.25, preferably from 0.15 to 0.20.
10. The process according to any one of claims 1 to 4 or the molecular sieve powder or molecular sieve according to any one of claims 5 to 9, wherein the organic templating agent is selected from one or more of amphiphilic nonionic triblock surfactants and polycyclic heterocyclic amine compounds, such as one or more of F127(EO106PO70EO106), F108(EO132PO50EO132), P123(EO20PO70EO20), P104(EO27PO61EO27) and Hexamethylenetetramine (HMTA); preferably, when the SBA molecular sieve is SBA-15, the organic template is selected from P123 and/or P104, and further preferably, when the SBA molecular sieve is SBA-16, the organic template is selected from one or more of F127, F108 and HMTA;
and/or the pore-expanding agent is selected from a compound shown as a formula I and C1-C4Alkyl substituted benzene and C5-C12One or more alkanes, such as one or more of N, N-dimethyldodecylamine, 1,3, 5-trimethylbenzene and decane;
Figure FDA0002155790770000021
in the formula I, R1And R2Same, selected from C1-C4Alkyl, preferably selected from methyl, ethyl, n-propyl and isopropyl; r3Is selected from C8-C16Alkyl, preferably selected from C10-C14An alkyl group;
preferably, the molar ratio of the pore-expanding agent to the organic template agent is 15.5:1-10: 1.
11. The method for preparing according to any one of claims 1 to 4 or the molecular sieve raw powder or the molecular sieve according to any one of claims 5 to 10, wherein the amino modifier is an organosilane with an amino structure, preferably selected from the group consisting of organosilanes represented by formula II, more preferably selected from one or more of 3-aminopropyltrimethoxysilane, 3- (phenylamino) propyltrimethoxysilane and 3-aminopropyltriethoxysilane;
Figure FDA0002155790770000031
in the formula II, R1、R2And R3Same, selected from C1-C4Alkyl, preferably selected from methyl, ethyl, n-propyl and isopropyl;R4c selected from amino with amino or phenyl substitution3-C6Alkyl, preferably selected from propyl with amino or phenyl substituted amino; and/or
The silicon source is one or more of white carbon black, ethyl orthosilicate and silica sol, and ethyl orthosilicate is preferred; and/or the presence of a gas in the gas,
the organic solvent is an alcohol compound, preferably has a general formula of R5Alcohols of-OH, in which R5Is selected from C1-C6Alkyl, more preferably ethanol;
preferably, the molar ratio of the amino modifier to the silicon source is 0.8:1-0.3:1, and/or the mass ratio of the organic solvent to the amino modifier is 1:2-2:1, preferably 1: 1; and/or the presence of a gas in the gas,
the acid is one of hydrochloric acid, sulfuric acid or nitric acid, preferably hydrochloric acid.
12. Use of an amino functionalized SBA molecular sieve in gas adsorption, preferably comprising contacting the molecular sieve obtained by the preparation method of claim 3 or 4 or the molecular sieve of any one of claims 5 to 11 with a gas, preferably an acid gas, further preferably CO2。
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