CN110624524A - Preparation method and application of amino-functionalized MCM molecular sieve - Google Patents

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

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CN110624524A
CN110624524A CN201810663150.9A CN201810663150A CN110624524A CN 110624524 A CN110624524 A CN 110624524A CN 201810663150 A CN201810663150 A CN 201810663150A CN 110624524 A CN110624524 A CN 110624524A
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molecular sieve
mcm
amino
temperature
changed
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吴凯
任行涛
贾志光
赵岚
刘艳惠
杨光
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
China Petrochemical Corp
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China Petrochemical Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/16—Alumino-silicates
    • B01J20/18—Synthetic zeolitic molecular sieves
    • B01J20/186—Chemical treatments in view of modifying the properties of the sieve, e.g. increasing the stability or the activity, also decreasing the activity
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/04—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound

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Abstract

The invention discloses a preparation method of an amino-functionalized MCM mesoporous molecular sieve, which comprises the following steps: s1, mixing an organic template agent, water, a silicon source and an alkali source to form glue, and carrying out hydrothermal crystallization on the glue-formed mixture to obtain a crystallization liquid mother liquor; s2, mixing the mother liquor of the crystallization liquid with weakly acidic substances, and then carrying out solid-liquid separation, washing and drying on a product to obtain MCM molecular sieve raw powder; and S3, mixing the MCM molecular sieve raw powder with a passivating agent, passivating, adding an amino modifier, reacting, and carrying out solid-liquid separation, washing and drying on a product to obtain the amino functionalized MCM mesoporous molecular sieve.

Description

Preparation method and application of amino-functionalized MCM molecular sieve
Technical Field
The invention provides a preparation method of a modified molecular sieve, and particularly relates to a preparation method and application of an amino-functionalized MCM molecular sieve.
Background
Due to the large specific surface area, the large pore volume and the uniform pore size, people show great interest in molecular sieves of MCM mesoporous series molecular sieves. The MCM mesoporous material not only widens the application range of the molecular sieve, but also makes up the defects of the microporous material. However, the performance of the porous material due to the ordered pore structure and the high specific surface area cannot meet the requirements of specific conditions. For example, in catalytic applications, biomolecular reactions and chromatographic applications, the activity of the inner and outer surfaces of mesoporous materials is still not high enough, and the inner and outer surfaces of MCM mesoporous materials lack active groups, and cannot effectively adsorb certain specific pollutants, and the chemical reactivity of the inner and outer surfaces of pore channels needs to be improved. Therefore, more and more researchers begin to modify the inner and outer surfaces of mesoporous material MCM (such as MCM-41 mesoporous molecular sieve).
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 MCM has two characteristics of the MCM and a modifying group, and the two characteristics also have a certain synergistic effect, and the synergistic characteristic is generally superior to that of the single mesoporous material MCM or the 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 to directly add a functional organic modifier into a sol consisting of a template agent and a silicon source for reaction, and in the prepared organic functional mesoporous material, organic groups can participate in the construction of pore walls and can uniformly fix the functional groups on the surfaces of pore channels of the mesoporous material. 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
Aiming at the defects in the prior art, the invention provides a preparation method of an amino-functionalized MCM (such as an MCM-41 molecular sieve) molecular sieve, which comprises the steps of passivating silicon hydroxyl on the surface of the MCM molecular sieve by adopting a passivating agent, enabling amino groups to enter molecular sieve pore channels and coordinate with the silicon hydroxyl in the pore channels by using an amino modifier, and successfully grafting the amino groups into the molecular sieve pore channels under the condition of not damaging the structure and the crystallinity of the molecular sieve pore channels; meanwhile, the weakly acidic substance is adopted to remove the organic template, so that the organic template is prevented from influencing the structure and catalytic performance of the molecular sieve, and the influence of the traditional organic template removing mode (such as roasting) on the existence of amino groups is avoided.
According to a first aspect of the present invention, there is provided a method for preparing an amino-functionalized MCM mesoporous molecular sieve, comprising the steps of:
s1, mixing an organic template agent, water, a silicon source and an alkali source to form a colloid, and carrying out hydrothermal crystallization on the colloid mixture after the colloid is formed to obtain a crystallization liquid mother liquor;
s2, mixing the mother liquor of the crystallization liquid with weakly acidic substances, and then carrying out solid-liquid separation, washing and drying on a product to obtain MCM molecular sieve raw powder;
and S3, mixing the MCM molecular sieve raw powder with a passivating agent, passivating, adding an amino modifier, reacting, and carrying out solid-liquid separation, washing and drying on a product to obtain the amino functionalized MCM mesoporous molecular sieve.
According to a preferred embodiment of the method, in the step S1, the molar ratio of each component in the colloidal mixture is in a range commonly used in the art for preparing MCM mesoporous molecular sieves, such as MCM-41 mesoporous molecular sieves. In a preferred embodiment, the molar ratio of the components is expressed as SiO2(representing a silicon source): a H2O：b R：c OH-(representing an alkali source), wherein R is an organic template, and the value of a is 80-160, preferably 100-140; the value of b is 0.1-0.7, preferably 0.2-0.5; the value of c is 2 to 7, preferably 4 to 5.
According to a preferred embodiment of the method, in step S1, the gelling temperature is a gelling temperature conventional in the art, such as a gelling temperature of 0 to 60 ℃, preferably 40 to 60 ℃.
According to a preferred embodiment of the method, in the step S1, the conditions of the hydrothermal crystallization are as conventional in the art. For example, the temperature of the hydrothermal crystallization is 110 to 140 ℃, preferably 120 to 130 ℃; the hydrothermal crystallization time is 72-108 h, preferably 84-100 h.
According to a preferred embodiment of the method, in the step S1, the organic template, the silicon source, the alkali source, and the like are commonly used in the art. In a preferred embodiment, the organic templating agent comprises at least one of cationic surfactants having 12-20 carbon atoms, preferably at least one of cationic surfactants having 12-16 carbon atoms, and more preferably at least one of cetyltrimethylammonium bromide, cetyltrimethylammonium chloride, and cetyltriethylammonium bromide. In a preferred embodiment, the silicon source comprises at least one of white carbon black, ethyl orthosilicate, sodium silicate, and silica sol. In a preferred embodiment, the alkali source comprises at least one of sodium hydroxide, tetramethylammonium hydroxide, and ammonia.
According to a preferred embodiment of the method, in the step S2, the weakly acidic material is used for neutralizing the organic template to remove the organic template. The weakly acidic substance means that the pH value of the aqueous solution is 4.0-7.0, preferably 4.0-6.0. The weak acidic substance is solid or liquid organic weak acid; preferably, the weak acid includes at least one of metasilicic acid, sulfurous acid, formic acid, and acetic acid. The dosage of the weakly acidic material is 5-10 wt%, preferably 6-8 wt% of the total feeding weight of the colloid mixture (the total mass of the organic template agent, the water, the silicon source and the alkali source).
According to a preferred embodiment of the method, in step S2, the content of the organic templating agent in the mixed solution is < 800ppm, preferably < 500ppm, more preferably < 200 ppm. By adding the weakly acidic substance, the organic template is removed as much as possible, so that the organic template is prevented from occupying pore channels of the molecular sieve and causing activity reduction. The lower the content of the organic template in the above-mentioned content range, the less the influence on the activity.
According to a preferred embodiment of the method, in the step S2, the passivating agent can react with the silicon hydroxyl groups on the surface of the MCM molecular sieve raw powder, but does not destroy the inherent structure of the molecular sieve and does not react with the subsequent amino modifier, and a compound capable of achieving the above requirements can be used as the passivating agent. According to a preferred embodiment of the method, in step S3, the passivating agent comprises the general formula RaRbRcSiRdOrganosilanes of the formula, wherein Ra、Rb、RcAnd RdSame or different, independently selected from hydrogen, halogen, C1-C20Alkyl of (C)1-C20Alkoxy group of (C)3-C20Cycloalkyl of, C6-C20Aryl and C1-C20And R is any one of a haloalkyl group ofa、Rb、RcAnd RdNot simultaneously hydrogen and/or halogen; preferably RdIs halogen, Ra、RbAnd RcNot simultaneously hydrogen and/or halogen; the passivating agent further preferably comprises at least one of diphenyldichlorosilane, trimethylchlorosilane, and dimethyldichlorosilane. The passivator can react with silicon hydroxyl on the surface (including orifices) of MCM molecular sieve raw powder, and is beneficial for an amino modifier to enter a pore channel in the MCM molecular sieve to react with the silicon hydroxyl, so that the amino functionalized MCM mesoporous molecular sieve with amino in the pore channel in the MCM molecule is prepared.
According to a preferred embodiment of the method, in the step S3, the ratio of the molar weight of the passivating agent to the mass of the MCM molecular sieve raw powder is (0.001 to 0.04) mol:5g, preferably (0.001 to 0.03) mol:5g, and more preferably (0.002 to 0.02) mol:5 g. The passivating agent with the proportion is more beneficial to the subsequent reaction of the amino modifier entering the inner pore channel of the MCM molecular sieve, so as to prepare the amino functionalized MCM mesoporous molecular sieve with amino in the inner pore channel of the MCM molecule.
According to a preferred embodiment of the method, in the step S3, the passivation temperature is 30-90 ℃, preferably 50-70 ℃; the passivation time is 2-10 hours, preferably 4-7 hours.
According to a preferred embodiment of the method, in the step S3, the amino modifier is a modifier commonly used in the art for amino modification, such as an organosilane with an amino structure, preferably comprising at least one of 3-aminopropyltrimethoxysilane, 3- (phenylamino) propyltrimethoxysilane and 3-aminopropyltriethoxysilane. The ratio of the molar weight of the amino modifier to the mass of the MCM molecular sieve raw powder is (0.01-0.1) mol:5 g.
According to a preferred embodiment of the method, in the step S3, the temperature of the reaction is 60 to 120 ℃, preferably 80 to 100 ℃; the reaction time is 4-8 h, preferably 5-7 h.
According to a preferred embodiment of the method, in the step S3, an organic solvent is added while adding the amino modifier for mixing. The organic solvent is added to better mix the modifier and the passivated molecular sieve together. The organic solvent may be a commonly used solvent, such as one containing at least one of alcohol compounds, such as ethanol. The amount of organic solvent is sufficient to mix the modifier and passivated molecular sieve. In a preferred embodiment, the amount of the organic solvent is equal to the amount of the modifier in a mass ratio.
According to a preferred embodiment of the method, the temperature of the drying is 100 to 140 ℃, preferably 110 to 130 ℃ in the steps S2 and S3. By drying, the moisture on the surface of the molecular sieve can be removed.
According to a preferred embodiment of the method, the MCM molecular sieve raw powder is MCM-41 molecular sieve raw powder, and the obtained MCM-41 mesoporous molecular sieve is amino-functionalized. In a specific embodiment, the preparation method specifically comprises the following steps: uniformly mixing an organic template agent, water, a silicon source and alkali into glue at the temperature of between room temperature and 70 ℃, wherein the molar ratio of each component in the obtained glue mixture is expressed as SiO2：a H2O：b R：c OH-Wherein R is an organic template, a is 80-160 (preferably 100-140), b is 0.1-0.7 (preferably 0.2-0.5), c is 2-7 (preferably 4-5), the reaction mixture is subjected to hydrothermal crystallization for a period of time at a certain crystallization temperature, the crystallized product is mixed with a weak acid, then the product is filtered, washed and dried to obtain the pure silicon MCM-41 molecular sieve, the pure silicon MCM-41 molecular sieve and a passivating agent are stirred for a period of time at a certain temperature, then an amino modifier and ethanol are added into the obtained product, and after the reaction for a period of time at a certain temperature, the product is filtered, washed and dried to finally obtain the amino functionalized MCM-41 molecular sieve.
According to the invention, because the existence of the amino group can not adopt the traditional roasting mode to remove the organic template agent, but can influence the structure and the catalytic performance of the molecular sieve without removing the organic template agent, the organic template agent is neutralized by adopting weak acidic substances (such as weak acid) to remove the template agent; passivating silicon hydroxyl on the surface and the orifice of the molecular sieve by adopting a passivating agent, then enabling amino groups to enter a molecular sieve pore passage and coordinate with the silicon hydroxyl in the pore passage by using an amino modifier, and successfully grafting the amino groups into the molecular sieve pore passage under the condition of not damaging the structure and the crystallinity of the molecular sieve pore passage.
According to a second aspect of the present invention there is provided an amino functionalized MCM mesoporous molecular sieve prepared according to the process of the first aspect of the present invention.
According to a third aspect of the present invention, there is also provided a use of the amino functionalized MCM mesoporous molecular sieve in gas adsorption, comprising the amino functionalized MCM mesoporous molecular sieve prepared by the method of the first aspect or the amino functionalized MCM mesoporous molecular sieve of the second aspect, and then used for gas adsorptive separation. For example, for the adsorption of acid gases, e.g. for the adsorptive separation of CO2。
When the surface organic functional modification is carried out on the MCM (such as MCM-41) molecular sieve by adopting a conventional grafting treatment method, the silanization modification reaction is easier to occur on the silicon hydroxyl groups existing on the outer surface of the material and close to the orifice of a mesoporous channel relative to the silicon hydroxyl groups on the inner surface of the mesoporous channel of the material due to steric hindrance. If the specific amino organic component is grafted on the surface of the molecular sieve pore channel by the grafting treatment method, the silicon hydroxyl on the outer surface of the molecular sieve is passivated before the amino organic group is grafted on the inner surface of the molecular sieve pore channel. In the method provided by the invention, firstly, passivating treatment is carried out on surface hydroxyl and orifice hydroxyl of the synthesized MCM (such as MCM-41) molecular sieve by adopting a passivating agent, then amino groups are grafted onto the inner surface of a molecular sieve pore channel in one step, and the obtained amino functionalized MCM (such as MCM-41) molecular sieve not only has the thermal stability of the MCM (such as MCM-41) molecular sieve, but also has the surface characteristics brought by organic components of the molecular sieve. Compared with the conventional copolycondensation method, although the copolycondensation method can introduce amino groups into the molecular sieve pore channels in one step, a large amount of amino modifier macromolecules enter the interior of the molecular sieve pore channels simultaneously in the reaction process, and the order degree of the molecular sieve is sharply reduced due to a large amount of organic matters, so that the service life of the molecular sieve is influenced.
According to the invention, the organic template is neutralized by a weak acidic substance (such as weak acid) to remove the organic template; passivating the molecular sieve by adopting a passivating agent, covering the surface and silicon hydroxyl groups at the orifice by using the passivating agent, modifying by using an amino modifier, enabling amino groups to directionally enter a molecular sieve pore passage and combine with the silicon hydroxyl groups in the pore passage, successfully grafting the amino groups into the molecular sieve pore passage under the condition of not damaging the structure and the crystallinity of the molecular sieve pore passage, and uniformly dispersing the amino groups in the pore passage of the molecular sieve; thereby improving the performance of the modified molecular sieve.
Drawings
FIG. 1 is a small angle XRD pattern of an amino functionalized MCM-41 molecular sieve according to an embodiment of the invention;
FIG. 2 is a graph of an amino functionalized MCM-41 molecular sieve FT-IR according to an embodiment of the 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 present invention, the content of the organic template was analyzed by gas chromatography, model Agilent6890, from Agilent corporation. XRD adopts X-Pert series X-ray diffractometer manufactured by Philips company to measure the structure of the molecular sieve, FT-IR adopts Thermo Nicolet Nexus 470 type Fourier transform infrared spectrometer manufactured by Thermo company to measure the existence state of amino groups in the molecular sieve, and BET adopts ASAP2020 type full-automatic specific surface analyzer manufactured by Micromeritics company to measure. The silicon source of the invention is SiO2Calculated as OH, base-Measured as solvent H2And O is counted, and the organic template is counted as R.
Example 1
Sequentially adding 9.6g of Cetyl Trimethyl Ammonium Bromide (CTAB) and 85.5g of deionized water into a reactor at the temperature of 30 ℃, uniformly stirring, slowly dropwise adding 11g of Tetraethoxysilane (TEOS), and finally adding 10.6g of NaOH to adjust the pH value of the solution to 11-13 to obtain a mixture (namely a colloidal mixture) containing SiO in a molar ratio2：90H2O：0.5R：5OH-And transferring the mixture to a crystallization kettle, heating to 110 ℃, and crystallizing for 72 hours at constant temperature. Finish the crystallizationAnd after the reaction, cooling to room temperature, adding 7.1g of metasilicic acid into the crystallized mother liquor, stirring and mixing for 1h, reducing the CTAB content to 700ppm, and then separating, washing and drying the reacted mixture at 110 ℃ to obtain the MCM-41 mesoporous molecular sieve raw powder. 5g of the obtained MCM-41 molecular sieve raw powder is taken to be stirred with 0.0193mol (2.1g) of trimethylchlorosilane for 3 hours at the temperature of 40 ℃, then the product is uniformly mixed with 0.0587mol (15g) of 3- (phenylamino) propyl trimethoxy silane and 15g of ethanol, the mixture is stirred for 4 hours at the temperature of 70 ℃, the obtained product is filtered, washed and dried at the temperature of 110 ℃, the product of the MCM-41 mesoporous molecular sieve with functionalized amino is obtained, and the specific surface area of the obtained product is 819m by BET analysis2/g。
Applying the obtained molecular sieve to CO2Adsorption experiment, 10% CO2And 90% N2Introducing the mixed gas into the molecular sieve at 35 deg.C, and measuring adsorbed CO2The results are shown in Table 1.
Example 2
The difference from example 1 is that the charging temperature is changed to 40 ℃, the template agent is changed to cetyltrimethylammonium chloride (CTAC), the dosage is 4.1g, the amount of water is changed to 46.1g, the silicon source is changed to sodium silicate, the dosage is 9.1g, the amount of NaOH is changed to 7.7g, the crystallization temperature is changed to 120 ℃, the crystallization time is changed to 80h, the weak acid is changed to sulfurous acid, the dosage is 5.3g, the content of CTAC is reduced to 500ppm, the drying temperature is changed to 120 ℃, the passivating agent is changed to dimethyldichlorosilane, the dosage is changed to 0.0044mol (0.58g), the passivation temperature is changed to 30 ℃, the passivation time is changed to 2h, the amino modifier is changed to 3-aminopropyltriethoxysilane, the dosage is changed to 0.0391mol (10g), the modification temperature is changed to 60 ℃, the modification time is changed to 5h, the amount of ethanol is changed to 10g, the rest components and the synthesis conditions are not changed, and the molar ratio of the obtained reaction mixture is SiO.2：80H2O：0.4R：6OH-Obtaining the product of MCM-41 mesoporous molecular sieve with functionalized amino, and obtaining the product with specific surface area of 768m through BET analysis2/g。
The obtained mesoporous molecular sieve is used for CO2Adsorption experiment, 10% CO2And 90% N2The mixed gas is at 35 deg.CIntroducing into the molecular sieve, and measuring adsorbed CO2The results are shown in Table 1.
Example 3
The difference from example 1 is that the charging temperature is changed to 50 ℃, the template agent is changed to cetyltrimethylammonium chloride (CTAC), the dosage is 3g, the amount of water is changed to 56.1g, the amount of TEOS is changed to 6.5g, the alkali source is changed to ammonia water, the dosage is 4.4g, the crystallization temperature is changed to 130 ℃, the crystallization time is changed to 90h, the weak acid is changed to formic acid, the dosage is 5.6g, the CTAC content is reduced to 150ppm, the drying temperature is changed to 130 ℃, the passivating agent is changed to diphenyldichlorosilane, the dosage is 0.0049mol (1.25g), the passivation temperature is changed to 60 ℃, the passivation time is changed to 6h, the amino modifier is changed to 3-aminopropyltrimethoxysilane, the dosage is 0.0557mol (10g), the modification temperature is changed to 90 ℃, the modification time is changed to 6h, the ethanol dosage is changed to 10g, the rest components and the synthesis conditions are not changed, and the molar ratio of the obtained reaction mixture is SiO2：100H2O：0.3R：4OH-Obtaining the product of MCM-41 mesoporous molecular sieve with functionalized amino, and obtaining the product with the specific surface area of 867m through BET analysis2/g。
The amino-functionalized MCM-41 mesoporous molecular sieve is characterized, and the small-angle XRD pattern and the FT-IR pattern are respectively shown in figure 1 and figure 2.
As can be seen from FIG. 1, the amino-functionalized MCM-41 molecular sieve obtained by the method provided by the invention has a characteristic diffraction peak of MCM-41, which indicates that the MCM-41 molecular sieve is successfully synthesized, and the existence of amino groups does not influence the order degree of the MCM-41 molecular sieve.
As can be seen from FIG. 2, 463cm-1、807cm-1And 1088cm-1The peak is the symmetric vibration peak and the asymmetric vibration peak of Si-O-Si of MCM-41, 1634cm-1Is positioned at the vibration peak of water absorbed by the MCM-41 molecular sieve and 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.
Applying the obtained molecular sieve to CO2Adsorption experiment, 10% CO2And 90% N2Introducing the mixed gas into the reactor at 35 deg.CMeasuring CO adsorption in amino-functionalized MCM-41 mesoporous molecular sieve2The results are shown in Table 1.
Example 4
The difference from example 1 is that the charging temperature was changed to 60 ℃, the template agent was changed to hexadecyltriethylammonium bromide, the amount used was 6.7g, the amount of water was changed to 195g, the silicon source was changed to silica sol (JN-25, silica content was 25 wt%), the amount used was 20g, the alkali source was changed to tetramethylammonium hydroxide, the amount used was 15.2g, the crystallization temperature was changed to 140 ℃, the crystallization time was changed to 100h, the weak acid was changed to acetic acid, the amount used was 18.8g, the content of hexadecyltriethylammonium bromide was reduced to 200ppm, the drying temperature was changed to 140 ℃, the passivating agent was changed to diphenyldichlorosilane, the amount used was changed to 0.0021mol (0.55g), the passivation temperature was changed to 70 ℃, the passivation time was changed to 7h, the amino modifier was changed to 3-aminopropyltrimethoxysilane, the amount used was 0.0278mol (5g), the modification temperature was changed to 80 ℃, the modification time was changed to 7h, the amount of ethanol was changed to 5g, the rest components and the synthesis conditions are unchanged, and the molar ratio of the obtained reaction mixture is SiO2：130H2O：0.2R：2OH-Obtaining the product of MCM-41 mesoporous molecular sieve with functionalized amino, and the specific surface area of the obtained product is 515m by BET analysis2/g。
Applying the obtained molecular sieve to CO2Adsorption experiment, 10% CO2And 90% N2Introducing the mixed gas into the amino-functionalized MCM-41 mesoporous molecular sieve at the temperature of 35 ℃, and measuring the adsorption of CO2The results are shown in Table 1.
Example 5
The difference from the example 1 is that the feeding temperature is changed to 70 ℃, the CTAB amount is changed to 16.4g, the water amount is changed to 189g, the silicon source is changed to white carbon black (the content of silicon dioxide is 90 wt%), the using amount is 5g, the alkali source is changed to ammonia water, the using amount is 18.4g, the crystallization temperature is changed to 120 ℃, the crystallization time is changed to 108h, the weak acid is changed to formic acid, the using amount is 16g, the CTAB content is reduced to 600ppm, the drying temperature is changed to 100 ℃, the passivating agent is changed to dimethyldichlorosilane, the using amount is changed to 0.0096mol (1.25g), the passivation temperature is changed to 50 ℃, the passivation time is changed to 9h, the amino modifier is changed to 3-aminopropyltriethoxysilane, the using amount is changed to 0.0225mol (5g), the modification temperature is changed to 100 ℃, the modification time is changed to 8h, the ethanol dosage is changed to 5g, the other components and the synthesis conditions are not changed, and the molar ratio of the obtained reaction mixture is SiO2：140H2O：0.6R：7OH-Obtaining the product of MCM-41 mesoporous molecular sieve with functionalized amino, wherein the specific surface area of the obtained product is 741m2/g。
Applying the obtained molecular sieve to CO2Adsorption experiment, 10% CO2And 90% N2Introducing the mixed gas into the molecular sieve at 35 deg.C, and measuring adsorbed CO2The results are shown in Table 1.
Comparative example 1
Adding 9.6g of hexadecyl trimethyl ammonium bromide (CTAB) and 85.5g of deionized water into a reactor in sequence at 30 ℃, uniformly stirring, slowly dropwise adding 11g of Tetraethoxysilane (TEOS), then adding 0.0587mol (15g) of 3- (phenylamino) propyl trimethoxy silane and 15g of ethanol, and finally adding 10.6g of NaOH to adjust the pH value of the solution to be 11-13, wherein the molar ratio of the obtained mixture is SiO2：90H2O：0.5R：5OH-And transferring the mixture to a crystallization kettle, heating to 110 ℃, and crystallizing for 72 hours at constant temperature. After crystallization is completed, cooling the temperature to room temperature, adding 7.1g of metasilicic acid into crystallized mother liquor, stirring and mixing for 1h, reducing the CTAB content to 800ppm, separating and washing the reacted mixture, and drying at 110 ℃ to obtain the amino functionalized MCM-41 molecular sieve. The product was subjected to BET analysis to obtain a product having a specific surface area of 545m2/g。
Applying the obtained molecular sieve to CO2Adsorption experiment, 10% CO2And 90% N2Introducing the mixed gas into the molecular sieve at 35 deg.C, and measuring adsorbed CO2The results are shown in Table 1.
Comparative example 2
Sequentially adding 9.6g of Cetyl Trimethyl Ammonium Bromide (CTAB) and 85.5g of deionized water into a reactor at the temperature of 30 ℃, uniformly stirring, slowly dropwise adding 11g of Tetraethoxysilane (TEOS), and finally adding 10.6g of NaOH to adjust the pH value of the solution to 11-13 to obtain a mixture, wherein the molar ratio of the obtained mixture is SiO2：90H2O：0.5R：5OH-And transferring the mixture to a crystallization kettle, heating to 110 ℃, and crystallizing for 72 hours at constant temperature. After crystallization is completed, cooling the temperature to room temperature, adding 7.1g of metasilicic acid into crystallized mother liquor, stirring and mixing for 1h, reducing the CTAB content to 700ppm, and then separating, washing and drying the reacted mixture at 110 ℃ to obtain the MCM-41 molecular sieve raw powder. Uniformly mixing 5g of the obtained MCM-41 molecular sieve raw powder with 0.0587mol (15g) of 3- (phenylamino) propyl trimethoxy silane and 15g of ethanol, stirring for 4 hours at 70 ℃, filtering and washing the obtained product, and drying at 110 ℃ to obtain the product, namely the amino-functionalized molecular sieve; and the specific surface area of the obtained product was 811m by BET analysis2/g。
Applying the obtained molecular sieve to CO2Adsorption experiment, 10% CO2And 90% N2Introducing the mixed gas into the molecular sieve at 35 deg.C, and measuring adsorbed CO2The results are shown in Table 1.
Comparative example 3
Sequentially adding 15.4g of Cetyl Trimethyl Ammonium Bromide (CTAB) and 66.5g of deionized water into a reactor at the temperature of 30 ℃, uniformly stirring, slowly dropwise adding 11g of Tetraethoxysilane (TEOS), and finally adding 16.9g of NaOH to adjust the pH value of the solution to be 11-13 to obtain a mixture, wherein the molar ratio of the obtained mixture is SiO2：70H2O：0.8R：8OH-And transferring the mixture to a crystallization kettle, heating to 110 ℃, and crystallizing for 72 hours at constant temperature. After crystallization is completed, cooling the temperature to room temperature, adding 7.1g of metasilicic acid into the crystallized mother liquor, stirring and mixing for 1h, reducing the CTAB content to 1100ppm, separating and washing the reacted mixture, and drying at 110 ℃. Stirring 5g of the obtained product with 0.0193mol (2.1g) of trimethylchlorosilane for 3h at 40 ℃, then uniformly mixing the product with 0.0587mol (15g) of 3- (phenylamino) propyl trimethoxy silane and 15g of ethanol, stirring for 4h at 70 ℃, filtering, washing and drying at 110 ℃ to obtain the product, and analyzing by BET (BET analysis) the specific surface area of the obtained product is 20m2/g。
Applying the obtained molecular sieve to CO2AdsorptionExperiment, 10% CO2And 90% N2Introducing the mixed gas into the molecular sieve at 35 deg.C, and measuring adsorbed CO2The results are shown in Table 1.
Comparative example 4
Sequentially adding 9.6g of Cetyl Trimethyl Ammonium Bromide (CTAB) and 85.5g of deionized water into a reactor at the temperature of 30 ℃, uniformly stirring, slowly dropwise adding 11g of Tetraethoxysilane (TEOS), and finally adding 10.6g of NaOH to adjust the pH value of the solution to 11-13 to obtain a mixture, wherein the molar ratio of the obtained mixture is SiO2：90H2O: 0.5R: 5OH-, transferring the mixture to a crystallization kettle, heating to 110 ℃, and crystallizing for 72 hours at constant temperature. After crystallization is completed, cooling the temperature to room temperature, adding 7.1g of metasilicic acid into crystallized mother liquor, stirring and mixing for 1h, reducing the CTAB content to 700ppm, separating and washing the reacted mixture, and drying at 110 ℃ to obtain the MCM-41 molecular sieve raw powder. 5g of the obtained MCM-41 molecular sieve raw powder and 0.046mol (5g) of trimethylchlorosilane are stirred for 3 hours at the temperature of 40 ℃, then the product is uniformly mixed with 0.0587mol (15g) of 3- (phenylamino) propyl trimethoxy silane and 15g of ethanol, the mixture is stirred for 4 hours at the temperature of 70 ℃, the obtained product is filtered, washed and dried at the temperature of 110 ℃ to obtain the product of the amino functionalized molecular sieve, and the specific surface area of the obtained product is 670m after BET analysis2/g。
Applying the obtained molecular sieve to CO2Adsorption experiment, 10% CO2And 90% N2Introducing the mixed gas into the molecular sieve at 35 deg.C, and measuring adsorbed CO2The results are shown in Table 1.
Comparative example 5
Sequentially adding 9.6g of Cetyl Trimethyl Ammonium Bromide (CTAB) and 85.5g of deionized water into a reactor at the temperature of 30 ℃, uniformly stirring, slowly dropwise adding 11g of Tetraethoxysilane (TEOS), and finally adding 10.6g of NaOH to adjust the pH value of the solution to 11-13 to obtain a mixture, wherein the molar ratio of the obtained mixture is SiO2：90H2O: 0.5R: 5OH-, transferring the mixture to a crystallization kettle, heating to 110 ℃, and crystallizing for 72 hours at constant temperature. After crystallization is completed, the temperature is reduced to room temperature, 23.3g of metasilicic acid is added into the mother liquor after crystallizationStirring and mixing for 1h, reducing the CTAB content to 100ppm, separating and washing the reacted mixture, and drying at 110 ℃ to obtain the MCM-41 molecular sieve raw powder. 5g of the obtained MCM-41 molecular sieve raw powder and 0.046mol (5g) of trimethylchlorosilane are stirred for 3 hours at the temperature of 40 ℃, then the product is uniformly mixed with 0.0587mol (15g) of 3- (phenylamino) propyl trimethoxy silane and 15g of ethanol, the mixture is stirred for 4 hours at the temperature of 70 ℃, the obtained product is filtered, washed and dried at the temperature of 110 ℃ to obtain the product of the amino functionalized molecular sieve, and the BET analysis shows that the specific surface area of the obtained product is 322m2/g。
Applying the obtained molecular sieve to CO2Adsorption experiment, 10% CO2And 90% N2Introducing the mixed gas into the molecular sieve at 35 deg.C, and measuring adsorbed CO2The results are shown in Table 1.
Comparative example 6
Sequentially adding 9.6g of Cetyl Trimethyl Ammonium Bromide (CTAB) and 85.5g of deionized water into a reactor at the temperature of 30 ℃, uniformly stirring, slowly dropwise adding 11g of Tetraethoxysilane (TEOS), and finally adding 10.6g of NaOH to adjust the pH value of the solution to 11-13 to obtain a mixture, wherein the molar ratio of the obtained mixture is SiO2：90H2O: 0.5R: 5OH-, transferring the mixture to a crystallization kettle, heating to 110 ℃, and crystallizing for 72 hours at constant temperature. After crystallization is completed, cooling the temperature to room temperature, adding 2.3g of metasilicic acid into crystallized mother liquor, stirring and mixing for 1h, reducing the CTAB content to 1200ppm, separating and washing the reacted mixture, and drying at 110 ℃ to obtain the MCM-41 molecular sieve raw powder. 5g of the obtained MCM-41 molecular sieve raw powder and 0.046mol (5g) of trimethylchlorosilane are stirred for 3 hours at the temperature of 40 ℃, then the product is uniformly mixed with 0.0587mol (15g) of 3- (phenylamino) propyl trimethoxy silane and 15g of ethanol, the mixture is stirred for 4 hours at the temperature of 70 ℃, the obtained product is filtered, washed and dried at the temperature of 110 ℃ to obtain the product functionalized molecular sieve, and the specific surface area of the obtained product is 546m after BET analysis2/g。
Applying the obtained molecular sieve to CO2Adsorption experiment, 10% CO2And 90% N2Mixed gas at 3Introducing into the molecular sieve at 5 deg.C, and measuring adsorbed CO2The results are shown in Table 1.
TABLE 1 adsorption of CO by amino-functionalized MCM-41 molecular sieves2Performance meter
As can be seen from comparative examples 1-3 and example 1, the copolycondensation method is adopted in comparative example 1 to directly add the amino modifier in the synthesis process, the preparation method is simple, amino groups are introduced into the molecular sieve pore canals in one step, but a large amount of organic groups also enter the molecular sieve pore canals, the pore diameter of the molecular sieve is increased in the synthesis process, the larger the pore diameter of the molecular sieve is, the lower the order degree of the molecular sieve is, and therefore, the specific surface area of the molecular sieve is reduced; in contrast, the comparative example 2 adopts the 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. In contrast, the comparative example 3 exceeds the synthesis ratio of the molecular sieve, so that the MCM-41 molecular sieve with the hexagonal mesopores is not synthesized.
As can be seen from Table 1, amino functionalized MCM-41 prepared according to the method is towards CO2The adsorption effect is obvious, the adsorption amount is 0 in comparative example 3 because the porous structure of the MCM-41 molecular sieve is not formed, while the adsorption amount is lower in comparative example 1 because the degree of order of the molecular sieve is destroyed by a large amount of organic groups although the preparation method is simple, and the adsorption amount is limited in comparative example 2 because a large amount of amino groups are concentrated on the surface and the pore openings of the molecular sieve although the specific surface area is high. In comparative example 4, due to the excessive passivating agent, although the silicon hydroxyl on the surface of the MCM-41 molecular sieve is occupied by the passivating agent, the excessive passivating agent can also enter the molecular sieve pore channels to occupy the silicon hydroxyl in the pore channels, so that the amino group in the amino functionalization agent can not enter the molecular sieve pore channels, thereby influencing the CO of the molecular sieve pore channels2The amount of adsorption. In comparative example 5, due to the excessive amount of a large amount of weak acid, the order degree of the molecular sieve is greatly reduced, so that the pore structure and the order degree of the molecular sieve are irregular, and the adsorption of CO on amino groups is influenced2The performance of (c). In comparative example 6, the addition of weak acid is less, so that residual template agents still exist in the molecular sieve, and the template agents occupy the pore channels of the molecular sieve, thereby influencing the adsorption performance of the molecular sieve.
Any numerical value mentioned in this specification, if there is only a two unit interval between any lowest value and any highest value, includes all values from the lowest value to the highest value incremented by one unit at a time. For example, if it is stated that the amount of a component, or a value of a process variable such as temperature, pressure, time, etc., is 50 to 90, it is meant in this specification that values of 51 to 89, 52 to 88 … …, and 69 to 71, and 70 to 71, etc., are specifically enumerated. For non-integer values, units of 0.1, 0.01, 0.001, or 0.0001 may be considered as appropriate. These are only some specifically named examples. In a similar manner, all possible combinations of numerical values between the lowest value and the highest value enumerated are to be considered to be disclosed in this application.
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 (14)

1. A preparation method of an amino-functionalized MCM mesoporous molecular sieve comprises the following steps:
s1, mixing an organic template agent, water, a silicon source and an alkali source to form a colloid, and carrying out hydrothermal crystallization on the colloid mixture after the colloid is formed to obtain a crystallization liquid mother liquor;
s2, mixing the mother liquor of the crystallization liquid with weakly acidic substances, and then carrying out solid-liquid separation, washing and drying on a product to obtain MCM molecular sieve raw powder;
and S3, mixing the MCM molecular sieve raw powder with a passivating agent, passivating, adding an amino modifier, reacting, and carrying out solid-liquid separation, washing and drying on a product to obtain the amino functionalized MCM mesoporous molecular sieve.
2. The method according to claim 1, wherein in the step S1, the molar ratio of each component in the colloidal mixture is expressed as SiO2：a H2O：b R：c OH-Wherein R is an organic template, and a has a value of 80-160, preferably 100-; the value of b is 0.1-0.7, preferably 0.2-0.5; the value of c is 2-7, preferably 4-5; and/or the temperature for gelling is 0-60 ℃, preferably 40-60 ℃.
3. The method according to claim 1 or 2, wherein in the step S1, the temperature of the hydrothermal crystallization is 110-140 ℃, preferably 120-130 ℃; the hydrothermal crystallization time is 72-108 h, preferably 84-100 h.
4. The method according to any one of claims 1 to 3, wherein in the step S1, the organic template comprises at least one of cationic surfactants having 12 to 20 carbon atoms, preferably at least one of cationic surfactants having 12 to 16 carbon atoms, more preferably at least one of cetyltrimethylammonium bromide, cetyltrimethylammonium chloride and cetyltriethylammonium bromide; and/or the silicon source comprises at least one of white carbon black, ethyl orthosilicate, sodium silicate and silica sol; and/or, the alkali source comprises at least one of sodium hydroxide, tetramethylammonium hydroxide, and ammonia water.
5. The method according to any one of claims 1 to 4, wherein in the step S2, the pH value of the aqueous solution of the weakly acidic substance is 4.0 to 7.0, preferably 4.0 to 6.0, and preferably the weakly acidic substance is a solid or liquid organic weak acid; preferably, the weak acid comprises at least one of metasilicic acid, sulfurous acid, formic acid and acetic acid; and/or the weakly acidic substance is used in an amount of 5 to 10 wt%, preferably 6 to 8 wt%, based on the total weight of the charge of the colloidal mixture.
6. The method according to any one of claims 1 to 5, wherein in step S2, the content of the organic template in the mixed solution is less than 800ppm, preferably less than 500ppm, and more preferably less than 200 ppm; and/or the MCM molecular sieve raw powder is MCM-41 molecular sieve raw powder.
7. The method of any one of claims 1 to 6, wherein in step S3, the passivating agent comprises the general formula RaRbRcSiRdOrganosilanes of the formula, wherein Ra、Rb、RcAnd RdSame or different, independently selected from hydrogen, halogen, C1-C20Alkyl of (C)1-C20Alkoxy group of (C)3-C20Cycloalkyl of, C6-C20Aryl and C1-C20And R is any one of a haloalkyl group ofa、Rb、RcAnd RdNot simultaneously hydrogen and/or halogen; preferably RdIs halogen, Ra、RbAnd RcNot simultaneously hydrogen and/or halogen; the passivating agent further preferably comprises at least one of diphenyldichlorosilane, trimethylchlorosilane and dimethyldichlorosilane; and/or the ratio of the molar weight of the passivating agent to the mass of the MCM molecular sieve raw powder is (0.001-0.04) mol:5g, preferably (0.001-0.03) mol:5g, and more preferably (0.002-0.02) mol:5 g.
8. The method according to any one of claims 1 to 7, wherein in the step S3, the passivation temperature is 30 to 90 ℃, preferably 50 to 70 ℃; the passivation time is 2-10 hours, preferably 4-7 hours.
9. The method according to any one of claims 1 to 8, wherein in step S3, the amino modifier is an organosilane with an amino structure, preferably comprising at least one of 3-aminopropyltrimethoxysilane, 3- (phenylamino) propyltrimethoxysilane and 3-aminopropyltriethoxysilane; and/or the ratio of the molar weight of the amino modifier to the mass of the MCM molecular sieve raw powder is (0.01-0.1) mol:5 g.
10. The method according to any one of claims 1 to 9, wherein in the step S3, the temperature of the reaction is 60 to 120 ℃, preferably 80 to 100 ℃; the reaction time is 4-8 h, preferably 5-7 h.
11. The method according to any one of claims 1 to 10, wherein in step S3, an organic solvent is added during the mixing with the amino modifier, preferably wherein the organic solvent comprises at least one of alcohol compounds.
12. The method according to any one of claims 1 to 11, wherein the drying temperature in steps S2 and S3 is 100 to 140 ℃, preferably 110 to 130 ℃.
13. An amino functionalized MCM mesoporous molecular sieve prepared by the process of any of claims 1-12.
14. Use of an amino functionalized MCM mesoporous molecular sieve in gas adsorption comprising using the amino functionalized MCM mesoporous molecular sieve prepared by the process of any of claims 1-12 or the amino functionalized MCM mesoporous molecular sieve of claim 13 for adsorptive separation of gases, preferablyAdsorption separation of acid gases, more preferably adsorption separation of CO2。
CN201810663150.9A 2018-06-25 2018-06-25 Preparation method and application of amino-functionalized MCM molecular sieve Pending CN110624524A (en)

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