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CN110627084B - Preparation method of organic functional group functionalized MCM molecular sieve - Google Patents

Preparation method of organic functional group functionalized MCM molecular sieve Download PDF

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CN110627084B
CN110627084B CN201810662317.XA CN201810662317A CN110627084B CN 110627084 B CN110627084 B CN 110627084B CN 201810662317 A CN201810662317 A CN 201810662317A CN 110627084 B CN110627084 B CN 110627084B
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molecular sieve
functional group
organic functional
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mcm
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CN110627084A (en
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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
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China Petroleum and Chemical Corp
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    • 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
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    • 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 relates to a preparation method of an organic functional group functionalized MCM molecular sieve, which comprises the following steps: s1, providing MCM molecular sieve raw powder; preferably, mixing an organic template agent, water, a silicon source and an alkali source to form gel, carrying out hydrothermal crystallization on the gel-formed mixture, then carrying out solid-liquid separation, and washing and drying the separated solid phase to provide the MCM molecular sieve raw powder; s2, mixing the MCM molecular sieve raw powder with a passivating agent for passivation, then adding an organic functional group modifier for modification reaction, then carrying out solid-liquid separation on the product, and washing and drying the separated solid sample; and S3, mixing the dried product obtained in the step S2 with an extracting agent for extraction, then removing a liquid phase, and drying a solid phase to obtain the organic functional group functionalized MCM molecular sieve. The method does not damage the structure and the crystallinity of the molecular sieve pore canal, but can evenly graft organic functional groups on the interior of the molecular sieve pore canal.

Description

Preparation method of organic functional group functionalized MCM molecular sieve
Technical Field
The invention provides a preparation method of a modified MCM molecular sieve, and particularly relates to a preparation method of an organic functional group functionalized MCM molecular sieve.
Background
Since the 20 th century 90 s, the mesoporous molecular sieve MCM-41 was synthesized, and has become the most studied mesoporous silica-based material due to its special property and structure. Its remarkable characteristics are represented as: regular hexagonal pore structure, narrow pore size distribution, extremely high specific surface area, thicker pore wall, adjustable pore size, and higher chemical stability and hydrothermal stability. The organic functionalization of mesoporous materials has been receiving much attention from researchers in materials, physics, chemistry, etc. for the past decade. The material has the characteristics that the mesoporous material and the organic group carried by the mesoporous material are cooperated and complemented: the organic group provides the surface characteristics or the reaction activity which is expected to be obtained by the material, and the inorganic mesoporous silicon framework provides the material with stable structure, chemical inertness, controllable pore channel structure, high specific surface area and uniform pore diameter distribution. MCM-41 surface contained free silicon hydroxyl-SiOH and = Si (OH) 2 Can react with silane coupling agent to introduce functional groups such as olefin group, ether group, cyano group and the like into mesoporous channels, and the active groups can further react to introduce different functional groups, thereby developing a new functional material.
In the prior art, generally, a thiol 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 a silicon hydroxyl group on the surface of the pore channel of a mesoporous material to generate a corresponding covalent bond, so as to fix the functional group on the pore wall 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 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 and mutually generate cross-linking, the system is placed in a high-pressure reaction kettle for crystallization after a certain time of reaction, 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
Aiming at the defects in the prior art, the invention provides a preparation method of an organic functional group functionalized MCM molecular sieve, which adopts a passivating agent to passivate silicon hydroxyl on the surface of the MCM molecular sieve, then uses an organic functional group modifier to ensure that the organic functional group enters molecular sieve pore channels to coordinate with the silicon hydroxyl in the pore channels, and successfully grafts the organic functional group into the molecular sieve pore channels under the condition of not damaging the structure and the crystallinity of the molecular sieve pore channels.
To this end, the first aspect of the present invention provides a method for preparing an organic functional group functionalized MCM molecular sieve, comprising the steps of:
s1, providing MCM molecular sieve raw powder; preferably, mixing an organic template agent, water, a silicon source and an alkali source to form gel, performing hydrothermal crystallization on the gel-formed mixture, performing solid-liquid separation, and washing and drying a separated solid phase to provide the MCM molecular sieve raw powder;
s2, mixing the MCM molecular sieve raw powder with a passivating agent for passivation, then adding an organic functional group modifier for modification reaction, then carrying out solid-liquid separation on the product, and washing and drying the separated solid sample;
and S3, mixing the dried product obtained in the step S2 with an extracting agent for extraction, then removing a liquid phase, and drying a solid phase to obtain the organic functional group functionalized MCM molecular sieve.
According to some preferred embodiments of the method, in step S1, the molar ratio of the components in the mixture after colloid formation is in the range commonly used in the art for preparing MCM mesoporous molecular sieves. In some embodiments of the invention, inIn the step S1, the molar ratio of each component in the mixture is SiO 2 ：a H 2 O：b R：c OH - (representing a base), wherein R is an organic template, and the value of a is 80-160, preferably 100-140; the value of b is 0.1 to 0.7, preferably 0.2 to 0.5; the value of c is from 2 to 7, preferably from 4 to 5.
In some preferred embodiments of the present invention, in step S1, the gelling temperature is a gelling temperature conventional in the art, and the gelling temperature is 30 to 70 ℃, preferably 40 to 60 ℃.
According to the present invention, in the step S1, the organic template, the silicon source, the alkali source, and the like are reagents commonly used in the art. In some preferred embodiments of the present invention, the organic templating agent comprises at least one of cationic surfactants having from 12 to 20 carbon atoms, preferably at least one of cationic surfactants having from 12 to 16 carbon atoms, and more preferably at least one of cetyltrimethylammonium bromide, cetyltrimethylammonium chloride, and cetyltriethylammonium bromide. The silicon source comprises one or more of white carbon black, ethyl orthosilicate, sodium silicate or silica sol, such as ethyl orthosilicate. The alkali source comprises one or more of sodium hydroxide, tetramethylammonium hydroxide and ammonia water, such as sodium hydroxide.
According to the present invention, in the step S1, the conditions of the hydrothermal crystallization are as conventional in the art. In some embodiments of the present invention, in the step S1, the temperature of the hydrothermal crystallization is 110 to 140 ℃, preferably 120 to 130 ℃; the time of the hydrothermal crystallization is 72 to 108 hours, preferably 84 to 100 hours.
In some embodiments of the present invention, the MCM molecular sieve raw powder is MCM-41 molecular sieve raw powder, and the resulting MCM-41 mesoporous molecular sieve is functionalized with organic functional groups.
According to the invention, in the step S2, the passivating agent can react with silicon hydroxyl on the surface of the MCM molecular sieve raw powder, but does not destroy the inherent structure of the molecular sieve and react with a subsequent organic functional group modifier, and the compound capable of meeting the requirements is preparedCan be used as passivator. In some embodiments of the invention, the passivating agent comprises the general formula R a R b R c SiR d An organosilane of formula wherein R a 、R b 、R c And R d Same or different, independently selected from hydrogen, halogen, C 1 -C 20 Alkyl of (C) 1 -C 20 Alkoxy group of (C) 3 -C 20 Cycloalkyl of, C 6 -C 20 Aryl and C 1 -C 20 And R is any one of a halogenated alkyl group of (1), and a 、R b 、R c and R d Not simultaneously hydrogen and/or halogen; preferably, said R is d Is halogen, R a 、R b And R c Not both hydrogen and/or halogen. The halogen is chlorine, bromine, etc. In some preferred embodiments of the invention, the passivating agent comprises at least one of diphenyldichlorosilane, trimethylchlorosilane, and dimethyldichlorosilane. The passivating agent can react with silicon hydroxyl on the surface (including an orifice) of MCM molecular sieve raw powder, and the organic functional group modifier enters a pore channel in the MCM molecular sieve and reacts with the silicon hydroxyl to prepare the organic functional group functionalized MCM molecular sieve with organic functional groups in the pore channel in the MCM molecules.
In some preferred embodiments of the invention, 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 (0.002 to 0.03) mol:5g, and more preferably (0.002 to 0.02) mol:5g. The passivating agent with the proportion is more beneficial to the subsequent organic functional group modifier to enter a pore channel in the MCM molecular sieve for reaction, so that the organic functional group functionalized MCM molecular sieve with the organic functional group in the pore channel in the MCM molecule is prepared.
In some embodiments of the present invention, in step S2, the passivation temperature is 10 to 90 ℃, such as 20 to 90 ℃, such as 40 to 90 ℃, and further such as 50 to 70 ℃. The passivation time is 0.5 to 20 hours, such as 1 to 10 hours, further such as 3 to 10 hours, preferably 4 to 7 hours.
According to the invention, in the step S2, the organic functional group modifier is a modifier commonly used in the field of organic functional group modification, such as organosilane with organic functional group structure. In some preferred embodiments of the present invention, the organofunctional group comprises an alkene group (C = C), an alkyne group (C ≡ C), an ether group, a carboxyl group, an ester group, and a cyano group. In some further preferred embodiments of the present invention, the organofunctional modifier comprises allyltrimethylsilane, ethynyltrimethylsilane, hexamethyldisiloxane, methylsilicic acid, dimethyltrimethylsilylphosphonate, or trimethylcyanosilane.
In some embodiments of the invention, the ratio of the molar amount of the organic functional group modifier to the mass of the MCM molecular sieve is (0.02 to 0.16) mol:5g, preferably (0.05 to 0.11) mol:5g.
In other embodiments of the present invention, in the step S2, the temperature of the modification reaction is 60 to 120 ℃, preferably 80 to 100 ℃; the time of the modification reaction is 4 to 8 hours, preferably 5 to 7 hours.
In some preferred embodiments of the present invention, in the step S2, an organic solvent is added while the organic functional group modifier is added. The organic solvent is added to better mix the organofunctional 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 such that the organofunctional modifier and the passivated molecular sieve are mixed. In a preferred example, the amount of the organic solvent to the amount of the organic functional group modifier is in an equal mass ratio, i.e., a mass ratio of 1.
According to the present invention, in the step S3, the extraction conditions are those commonly used in the art. For example, the extractant is an ether, the mass ratio of the extractant to the MCM molecular sieve raw powder is preferably 4. And removing the organic template agent in the pore channels of the molecular sieve by extraction.
In some embodiments of the invention, the temperature of drying in said S1-S3 is between 100 and 140 ℃, preferably between 110 and 130 ℃. By drying, the molecular sieve can be dehydrated and a part of the organic template, such as surface moisture and/or organic template, can be removed.
In some embodiments of the present invention, the method for preparing the organic functional group functionalized MCM molecular sieve comprises the steps of: uniformly mixing an organic template agent, water, a silicon source and an alkali source into glue at the temperature of 30-70 ℃, wherein the molar ratio of the obtained reaction mixture is SiO 2 ：a H 2 O：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 hydrothermally crystallized at 110-140 ℃ for 72-108 h, and the product is filtered, washed and dried to finally obtain the pure silicon MCM molecular sieve (i.e. MCM molecular sieve raw powder). Stirring a pure silicon MCM molecular sieve and a passivating agent at a certain temperature for a period of time, then adding an organic functional group modifier and an organic solvent, reacting at a certain temperature for a period of time, filtering, washing and drying a product, mixing the dried product with an extracting agent for a period of time, filtering and washing to finally obtain the organic functional group functionalized MCM molecular sieve.
According to the method provided by the invention, firstly, passivating treatment is carried out on surface hydroxyl and pore hydroxyl of the synthesized MCM molecular sieve by adopting a passivating agent, then modification is carried out by using an organic functional group modifier, organic functional groups directionally enter pore channels of the molecular sieve to be combined with pore wall silicon hydroxyl, so that the organic functional groups are grafted to the inner surfaces of the pore channels of the molecular sieve in one step, and the organic functional groups can be uniformly dispersed in the pore channels of the molecular sieve. The obtained organic functional group functionalized MCM molecular sieve not only has the thermal stability of the MCM molecular sieve, but also has the surface characteristics brought by the molecular sieve of organic components.
In a second aspect of the invention there is provided an organofunctional functionalized MCM molecular sieve prepared according to the method of the first aspect of the invention.
When the surface organic functional modification is carried out on the MCM 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 the mesoporous channel relative to the silicon hydroxyl groups on the inner surface of the mesoporous channel of the material due to steric hindrance. If it is desired to graft a specific organofunctional organic component onto the surface of a molecular sieve pore channel by a grafting process, the silicon hydroxyl groups (including the pore openings) on the outer surface of the molecular sieve are passivated before the organofunctional organic component is grafted onto 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 molecular sieve by adopting a passivating agent, and then organic functional groups are grafted onto the inner surface of a molecular sieve pore channel in one step, so that the obtained organic functional group functionalized MCM molecular sieve not only has the thermal stability of the MCM molecular sieve, but also has the surface characteristics brought by the organic functional groups as the molecular sieve. Compared with the conventional copolycondensation method, although the copolycondensation method can introduce organic functional groups into the molecular sieve pore channels in one step, a large amount of organic functional group modifier macromolecules enter the molecular sieve pore channels simultaneously in the reaction process, and the large amount of organic matters can cause the order degree of the molecular sieve to be sharply reduced, thereby influencing the service life of the molecular sieve.
According to the method provided by the invention, the passivating agent is used for passivating silicon hydroxyl on the surface (including an orifice) of the molecular sieve, and then the organic functional group modifier is used for enabling the organic functional group to enter a molecular sieve pore channel and coordinate with the silicon hydroxyl in the pore channel, so that the structure and the crystallinity of the molecular sieve pore channel cannot be damaged, but the organic functional group can be grafted in the molecular sieve pore channel, and the performance of the modified molecular sieve is improved. The organic functional group functionalized MCM molecular sieve obtained by the method has good adsorption performance and high specific surface area.
Drawings
FIG. 1 shows an olefin-based functionalized MCM-41 molecular sieve FT-IR map according to example 1 of this disclosure;
FIG. 2 shows FT-IR diagram of ether-based functionalized MCM-41 molecular sieve of example 3 according to the invention;
FIG. 3 shows a cyano-functionalized MCM-41 molecular sieve FT-IR map according to example 5 of the invention.
Detailed Description
The present invention will be more fully understood by those skilled in the art by describing in detail the present invention with reference to the following examples, which are not intended to limit the scope of the present invention in any way. In the examples, FT-IR was measured by using a Fourier transform infrared spectrometer model 470 from Thermo Nicolet Nexus, inc. to determine the presence of organic functional groups in a molecular sieve, and BET was measured by using a full-automatic specific surface analyzer model 2020 ASAP, inc. from Micromeritics, inc. The silicon source of the invention is SiO 2 Calculated as OH as base - Calculated as H, solvent 2 And O is counted, and the organic template is counted as R.
Example 1
Sequentially adding 2.1g of hexadecyl trimethyl ammonium bromide (CTAB) and 83g of deionized water into a reactor at the temperature of 30 ℃, uniformly stirring, slowly dropwise adding 12g of Tetraethoxysilane (TEOS), and finally adding 4.6g of NaOH to adjust the pH of the solution to be 10-11 to obtain a reaction mixture, wherein the molar ratio of the obtained reaction mixture is SiO 2 ：80H 2 O：0.1R：2OH - And transferring the mixture to a crystallization kettle, heating to 110 ℃, and crystallizing for 72 hours at constant temperature. After crystallization is completed, cooling to room temperature, separating, washing and drying the reacted mixture at 100 ℃ to obtain MCM-41 molecular sieve raw powder. 5g of the obtained MCM-41 molecular sieve raw powder is taken to be stirred with 0.0193mol (2.1 g) of trimethylchlorosilane for 3 hours at the temperature of 40 ℃, then the product is uniformly mixed with 0.1315mol (15 g) of allyltrimethylsilane and 15g of ethanol and is stirred for 4 hours at the temperature of 60 ℃, then the product is uniformly mixed with 20g of methyl ether and is 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 726m 2 /g。
The olefin-based functionalized MCM-41 molecular sieve is characterized, and the FT-IR diagram is shown in figure 1.
Example 2
The difference from the example 1 is that the feeding temperature is changed to 40 ℃, the template agent is changed to cetyltrimethylammonium chloride (CTAC), the dosage is 9.5g, the water dosage is changed to 121.6g, the silicon source is changed to sodium silicate, the dosage is 12g, the NaOH dosage is changed to 11.8g, the crystallization temperature is changed to 140 ℃, and the crystallization time is changed to 11108 hours, the drying temperature is changed to 140 ℃, the passivating agent is changed to dimethyldichlorosilane, the using amount is changed to 0.0043mol (0.56 g), the passivating temperature is changed to 90 ℃, the passivating time is changed to 10 hours, the organic functional group modifying agent is changed to ethynyltrimethylsilane, the using amount is changed to 0.0510mol (5 g), the modifying temperature is changed to 120 ℃, the modifying time is changed to 8 hours, the using amount of ethanol is changed to 5g, the extracting agent is changed to ether, the using amount is changed to 10g, the extracting time is changed to 4 hours, the rest components and the synthesis conditions are not changed, and the molar ratio of the obtained reaction mixture is SiO 2 ：160H 2 O：0.7R：7OH - The sample obtained was subjected to BET analysis to obtain a product having a specific surface area of 714m 2 /g。
Example 3
The difference from the example 1 is that the feeding temperature is changed to 50 ℃, the template agent is changed to cetyltrimethylammonium chloride (CTAC), the dosage is 7.4g, the amount of water is changed to 165.9g, the amount of TEOS is changed to 16g, the alkali source is changed to ammonia water, the dosage is 10.7g, the crystallization temperature is changed to 130 ℃, the crystallization time is changed to 90h, the drying temperature is changed to 120 ℃, the passivating agent is changed to diphenyldichlorosilane, the dosage is changed to 0.0049mol (1.25 g), the passivation temperature is changed to 60 ℃, the passivation time is changed to 5h, the organic functional group modifier is changed to hexamethyldisiloxane, the dosage is changed to 0.0617mol (10 g), the modification temperature is changed to 90 ℃, the modification time is changed to 6h, the dosage of ethanol is changed to 10g, the extractant is changed to diethyl 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 SiO 2 ：120H 2 O：0.3R：4OH - The sample obtained was subjected to BET analysis to obtain a product having a specific surface area of 776m 2 /g。
The ether group functionalized MCM-41 molecular sieve is characterized, and the FT-IR diagram is shown in figure 2.
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 was 6.7g, the amount of water was 150g, the silicon source was changed to silica sol (JN-25, silica content 25 wt%), the amount was 20g, the alkali source was changed to tetramethylammonium hydroxide, the amount was 45.6g, the crystallization temperature was changed to 120 ℃, and the crystallization time was changed to 120 ℃Changing the time to 84h, the drying temperature to 110 ℃, the passivating agent to diphenyldichlorosilane, the dosage to 0.0118mol (3 g), the passivating temperature to 50 ℃, the passivating time to 4h, the organic functional group modifier to methyl silicic acid, the dosage to 0.0531mol (5 g), the modifying temperature to 80 ℃, the modifying time to 5h, the ethanol dosage to 5g, the extractant to diethyl ether, the dosage to 10g, the extraction time to 4h, the rest components and the synthesis conditions are not changed, the molar ratio of the obtained reaction mixture is SiO 2 ：100H 2 O：0.2R：6OH - The sample obtained was subjected to BET analysis to obtain a product having a specific surface area of 771m 2 /g。
Example 5
The difference from example 1 is that the charging temperature is changed to 70 ℃, the CTAB amount is changed to 13.7g, 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 alkali source is changed to 5g, the alkali source is changed to ammonia water, the amount is 13.1g, the crystallization temperature is changed to 120 ℃, the crystallization time is changed to 100h, the drying temperature is changed to 130 ℃, the passivating agent is changed to dimethyldichlorosilane, the amount is changed to 0.0309mol (4 g), the passivation temperature is changed to 70 ℃, the passivation time is changed to 7h, the mercapto modifier amount is changed to 0.0509mol (10 g), the modification temperature is changed to 100 ℃, the modification time is changed to 7h, the ethanol amount is changed to 10g, the extractant is changed to diethyl ether, the extraction time is changed to 3h, the rest components and the synthesis conditions are not changed, the molar ratio of the obtained reaction mixture is SiO 2 ：140H 2 O：0.5R：5OH - The sample obtained was subjected to BET analysis to obtain a product having a specific surface area of 725m 2 /g。
The cyano-functionalized MCM-41 molecular sieve is characterized, and an FT-IR diagram is shown in a figure 3.
Example 6
The difference from the example 1 is that the feeding temperature is changed to 70 ℃, the CTAB amount is changed to 10.6g, the water amount is changed to 90g, the silicon source is changed to silica sol (JN-25, the silicon dioxide content is 25 wt%), the dosage is 10g, the sodium hydroxide dosage is changed to 10g, the crystallization temperature is changed to 130 ℃, the crystallization time is changed to 95h, the drying temperature is changed to 110 ℃, the passivating agent is changed to diphenyldichlorosilane, and the dosage is changed to 0.0049mol (1.25 g)) The passivation temperature is changed to 50 ℃, the passivation time is changed to 5h, the organic functional group modifier is changed to dimethyl trimethylsilyl phosphonate, the using amount is 0.0549mol (10 g), the modification temperature is changed to 80 ℃, the modification time is changed to 7h, the using amount of ethanol is changed to 10g, the extractant is changed to ether, the using amount is changed to 15g, the extraction time is changed to 4h, the rest components and the synthesis condition are not changed, the molar ratio of the obtained reaction mixture is SiO 2 ：120H 2 O：0.7R：6OH - The BET analysis of the obtained sample gave a product with a specific surface area of 763m 2 /g。
Example 7
The difference from example 3 is that the passivation temperature was changed to 30 ℃. The obtained sample was subjected to BET analysis to obtain a product having a specific surface area of 701m 2 /g。
Example 8
The difference from example 3 is that the passivation time was changed to 2h. The sample obtained was subjected to BET analysis to obtain a product having a specific surface area of 710m 2 /g。
Comparative example 1
Sequentially adding 2.1g of hexadecyl trimethyl ammonium bromide (CTAB) and 83g of deionized water into a reactor at the temperature of 30 ℃, uniformly stirring, slowly dropwise adding 12g of Tetraethoxysilane (TEOS), adding 0.1315mol (15 g) of allyl trimethylsilane and 15g of ethanol, and finally adding 4.6g of NaOH to adjust the pH value of the solution to be 10-11 to obtain a reaction mixture with the molar ratio of SiO 2 ：80H 2 O：0.1R：2OH - And 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, and the mixture after reaction is separated, washed and dried at 100 ℃ to obtain the alkenyl functionalized MCM-41 molecular sieve. Then evenly mixing the olefin-based functionalized MCM-41 molecular sieve with 20g of methyl ether, stirring for 2h, separating and washing the product, drying at 100 ℃, performing BET analysis on the product, and performing BET analysis on the product to obtain the product with the specific surface area of 500m 2 /g。
Comparative example 2
2.1g of cetyltrimethylammonium bromide (CTAB) and 83g were removed at 30 deg.CSequentially adding ionized water into a reactor, uniformly stirring, slowly and dropwise adding 12g of Tetraethoxysilane (TEOS), finally adding 4.6g of NaOH to adjust the pH value of the solution to 10-11, and obtaining a reaction mixture with the molar ratio of SiO 2 ：80H 2 O：0.1R：2OH - And transferring the mixture to a crystallization kettle, heating to 110 ℃, and crystallizing for 72 hours at constant temperature. After crystallization is completed, cooling to room temperature, separating, washing and drying the reacted mixture at 100 ℃ to obtain MCM-41 molecular sieve raw powder. 5g of the obtained MCM-41 molecular sieve raw powder is taken to be uniformly mixed with 0.1315mol (15 g) of allyltrimethylsilane and 15g 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 657m 2 /g。
Comparative example 3
Sequentially adding 15.4g of hexadecyl 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 reaction mixture, wherein the molar ratio of the obtained reaction mixture is SiO 2 ：70H 2 O：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, the temperature is reduced to room temperature, and the mixture after reaction is separated, washed and dried at 100 ℃.5g of the obtained product is taken and stirred with 0.0193mol (2.1 g) of trimethylchlorosilane for 3 hours at the temperature of 40 ℃, then the product is uniformly mixed with 0.1315mol (15 g) of allyltrimethylsilane and 15g of ethanol and 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 31m 2 /g。
Comparative example 4
Sequentially adding 2.1g of hexadecyl trimethyl ammonium bromide (CTAB) and 83g of deionized water into a reactor at the temperature of 30 ℃, uniformly stirring, then slowly dropwise adding 12g of Tetraethoxysilane (TEOS),finally, 4.6g of NaOH is added to adjust the pH value of the solution to 10-11, and the molar ratio of the obtained reaction mixture is SiO 2 ：80H 2 O：0.1R：2OH - And transferring the mixture to a crystallization kettle, heating to 110 ℃, and crystallizing for 72 hours at constant temperature. After crystallization is completed, cooling to room temperature, separating, washing and drying the reacted mixture at 100 ℃ to obtain MCM-41 molecular sieve raw powder. 5g of the obtained MCM-41 molecular sieve raw powder is taken to be stirred with 0.046mol (5 g) of trimethylchlorosilane for 3 hours at the temperature of 40 ℃, then the product is uniformly mixed with 0.1315mol (15 g) of allyltrimethylsilane and 15g of ethanol and is stirred for 4 hours at the temperature of 60 ℃, then the product is uniformly mixed with 20g of methyl ether and is 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 608m 2 /g。
As can be seen from comparative examples 1-4 and example 1, the olefin-based modifier is directly added in the synthesis process by adopting a copolycondensation method in the comparative example 1, the preparation method is simple, olefin-based 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 therefore the specific surface area of the molecular sieve is reduced; in contrast, in comparative example 2, the conventional grafting method is adopted, most of the olefin-based modifier introduced by the method is on the specific surface of the molecular sieve or at the opening of the molecular sieve pore, and the olefin-based group is difficult to enter the molecular sieve pore. And the comparison example 3 exceeds the synthesis proportion of the molecular sieve, so the MCM-41 molecular sieve with the hexagonal mesopores is not synthesized. In comparative example 4, due to the existence of excessive passivating agent, the excessive passivating agent can enter the pore channels of the molecular sieve to occupy the silicon hydroxyl groups in the pore channels, so that the order degree of the molecular sieve is reduced.
As can be seen from FIGS. 1 to 3, 463cm -1 、807cm -1 And 1088cm -1 The symmetric vibration peak and the asymmetric vibration peak of Si-O-Si of MCM-41 are positioned at 1618cm -1 606cm of vibration peak in pore canal of propenyl and silicon hydroxyl -1 The vibration peak in the pore canal of the ether group and the silicon hydroxyl group is 2220cm -1 Is represented by cyanogenAnd (3) vibration peaks in the channels of the silicon hydroxyl groups indicate that organic groups exist in the channels of the molecular sieve but do not exist on the surface and the openings 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 the 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, 8230, 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 in relation to an exemplary embodiment, and it is understood that the words which have been used herein are words of description and illustration, rather than words of limitation. Modifications may be made to the invention as defined within the scope of the claims and modifications may be made 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 (34)

1. A preparation method of an organic functional group functionalized MCM molecular sieve comprises the following steps:
s1, providing MCM molecular sieve raw powder; specifically, mixing an organic template agent, water, a silicon source and an alkali source into gel, carrying out hydrothermal crystallization on the gel-formed mixture, then carrying out solid-liquid separation, and washing and drying the separated solid phase to provide the MCM molecular sieve raw powder;
s2, mixing the MCM molecular sieve raw powder with a passivator for passivation, adding an organic functional group modifier for modification reaction, performing solid-liquid separation on a product, and washing and drying a separated solid sample; the passivating agent comprises organosilane shown in a general formula RaRbRcSiRd, wherein Ra, rb, rc and Rd are the same or different and are independently selected from any one of hydrogen, halogen, C1-C20 alkyl, C1-C20 alkoxy, C3-C20 cycloalkyl, C6-C20 aryl and C1-C20 halogenated alkyl, and Ra, rb, rc and Rd are not hydrogen and/or halogen at the same time;
and S3, mixing the dried product obtained in the step S2 with an extracting agent for extraction, then removing a liquid phase, and drying a solid phase to obtain the organic functional group functionalized MCM molecular sieve.
2. The method of claim 1, wherein in step S2, rd is halogen, and Ra, rb and Rc are not simultaneously hydrogen and/or halogen.
3. The method of claim 1 or 2, wherein in step S2, the passivating agent 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.
4. A method as claimed in claim 3, wherein the ratio of the molar quantity of passivating agent to the mass of MCM molecular sieve raw powder is (0.002-0.03) mol:5g.
5. The method as claimed in claim 4, wherein the ratio of the molar weight of the passivating agent to the mass of the MCM molecular sieve raw powder is (0.002-0.02) mol:5g.
6. The method according to claim 1 or 2, wherein in the step S2, the temperature of the passivation is 20 to 90 ℃; and/or the passivation time is 0.5-20 h.
7. The method of claim 6, wherein the temperature of the passivation is 40-90 ℃.
8. The method of claim 7, wherein the temperature of the passivation is 50-70 ℃.
9. The method according to claim 6, wherein the passivation time is 3 to 10 hours.
10. The method according to claim 9, wherein the passivation time is 4 to 7 hours.
11. The method according to claim 1 or 2, characterized in that in step S2, the organic functional group modifier is an organosilane carrying an organic functional group structure; and/or the ratio of the molar weight of the organic functional group modifier to the mass of the MCM molecular sieve is (0.02-0.16) mol:5g.
12. The method of claim 11, wherein the organic functional group comprises an alkene group, an alkyne group, an ether group, a carboxyl group, an ester group, and a cyano group.
13. The method of claim 11, wherein the organofunctional modifier comprises allyltrimethylsilane, ethynyltrimethylsilane, hexamethyldisiloxane, methylsilicic acid, dimethyltrimethylsilylphosphonate, or trimethylcyanosilane.
14. The method of claim 11, wherein the ratio of the molar amount of the organic functional group modifier to the mass of the MCM molecular sieve is (0.05-0.11) mol:5g.
15. The method according to claim 1 or 2, characterized in that, in the step S2, the temperature of the modification reaction is 60 to 120 ℃; and/or the time of the modification reaction is 4-8 h.
16. The method of claim 15, wherein the temperature of the modification reaction is 80 to 100 ℃.
17. The method according to claim 15, wherein the time of the modification reaction is 5 to 7 hours.
18. The method according to claim 1 or 2, wherein in step S2, an organic solvent is added while adding the organic functional group modifier.
19. The method of claim 18, wherein the organic solvent comprises at least one of an alcohol compound.
20. Method according to claim 1 or 2, characterized in that in step S1, step S1
The molar ratio of each component in the mixture is expressed as SiO 2 ：a H 2 O: b R: c OH, wherein R is an organic template agent, and the value of a is 80-160; the value of b is 0.1 to 0.7; the value of c is 2 to 7; and/or the gelling temperature is 30-70 ℃.
21. The method of claim 20, wherein a has a value of 100 to 140; the value of b is 0.2 to 0.5; the value of c is 4 to 5.
22. The method of claim 20, wherein the temperature of said gelling is between 40 and 60 ℃.
23. The method according to claim 1 or 2, characterized in that, in the step S1, the organic templating agent comprises at least one of cationic surfactants having 12-20 carbon atoms; and/or the silicon source comprises one or more of white carbon black, ethyl orthosilicate, sodium silicate and silica sol; and/or the alkali source comprises one or more of sodium hydroxide, tetramethyl ammonium hydroxide and ammonia water.
24. The method of claim 23, wherein the organic templating agent comprises at least one of cationic surfactants having from 12 to 16 carbon atoms.
25. The method of claim 24, wherein the organic templating agent comprises at least one of cetyltrimethylammonium bromide, cetyltrimethylammonium chloride, and cetyltriethylammonium bromide.
26. The method according to claim 1 or 2, wherein in the step S1, the temperature of the hydrothermal crystallization is 110 to 140 ℃; and/or the time of the hydrothermal crystallization is 72 to 108 hours.
27. The method of claim 26, wherein the temperature of the hydrothermal crystallization is 120-130 ℃.
28. The method as claimed in claim 26, wherein the hydrothermal crystallization time is 84-100 h.
29. The method according to claim 1 or 2, wherein the temperature of the drying in steps S1-S3 is 100-140 ℃.
30. The method as claimed in claim 29, wherein the temperature of the drying in the steps S1 to S3 is 110 to 130 ℃.
31. The process according to claim 1 or 2, wherein in step S3, the extractant is an ether.
32. The method as claimed in claim 31, wherein the mass ratio of the extracting agent to the MCM molecular sieve raw powder is 4.
33. The method of claim 1 or 2, wherein the MCM molecular sieve raw powder is MCM-41 molecular sieve raw powder.
34. An organofunctional MCM molecular sieve prepared by the method of any of claims 1 to 33.
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