CN110342532B - Preparation method of bifunctional MFI zeolite nano-layer sheet - Google Patents
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Abstract
The invention discloses a preparation method of a bifunctional MFI zeolite nano-layer sheet, which comprises the following steps: (1) placing the MFI layered zeolite into a 15wt% ammonium nitrate aqueous solution, carrying out ion exchange for 2-4 times, drying at 110 ℃, and roasting at 550 ℃ for 4 hours in an air atmosphere to obtain hydrogen type MFI layered zeolite; (2) grafting alkaline functionalized silane into hydrogen type MFI zeolite or modifying the MFI zeolite by using silane, and then obtaining the novel organic-inorganic composite material of the MFI zeolite with both acidic and alkaline functions through the action of the grafted silane and an alkaline group. The MFI zeolite prepared by the method has adjustable and controllable distribution of acid strength, acid amount and acid active sites, and has a layered structure with larger specific surface area and rich silicon hydroxyl groups (grafting sites) on the surface.
Description
Technical Field
The invention belongs to the field of material chemistry and catalyst preparation, and particularly relates to a preparation method of a bifunctional MFI zeolite nano-layer sheet catalyst.
Background
Aromatic compounds play an important role in the fields of medicine, pesticide, petrochemical industry and the like. Deacetalization-Knoevenagel reaction is an effective way to synthesize aromatic compounds. The reaction needs the synergistic catalysis of acid-base double-activity centers, and the key for realizing the effective operation is to select a bifunctional catalytic material with different properly dispersed active sites and matched functions.
Researchers have performed a great deal of work on the preparation of acid-base bifunctional catalysts. Such as grafting organic bases and various organic amines that provide acidic functional sulfonic acids, phosphoric acids, carboxylic acids, and the like, and basic functions, onto a silicon-based catalyst (j. call., 2007, 247, 379; j. call., 2012, 291, 63; chem. mater., 2012, 24, 2433; call. sci. technol., 2015, 5, 690). Although these methods can be used to prepare catalysts with acid-base function, the following disadvantages are faced in the preparation and catalytic reaction of the catalysts: 1) the acid strength and the alkali strength of the prepared catalyst are not easy to regulate and control. An appropriate catalyst for the acid-base strength is crucial for the activity and selectivity of the deacetalization-Knoevenagel reaction. However, the method is limited by the self acid strength or alkali strength of the selected grafting acid or alkali, and the corresponding catalytic material is difficult to prepare according to the requirements of different reactions on the acid strength and the alkali strength; 2) and the distance between the acidic active site and the basic active site is difficult to regulate. In the case of deacetalization-Knoevenagel catalysts, the catalytic performance is not only related to the amount and strength of the acidic and basic active sites, but also to the spacing between the two. However, in the preparation of the existing bifunctional catalyst, the combination of the acidic active site and the basic active site with the inherent inorganic active site of the carrier is random, so that the distance between the acidic active site and the basic active site is difficult to regulate and control, and the method is especially prominent when the silicon-based carrier is used for preparing the multifunctional acid-base catalyst.
Compared with numerous carrier materials, the MFI zeolite molecular sieve has an acidic function, the acid strength and the acid type of the MFI zeolite molecular sieve can be effectively modulated by changing the composition and the structure of the MFI zeolite molecular sieve, the requirement of deacylation-Knoevenagel reaction on the acidic function is met, the defect that the acid strength is not easy to modulate in the preparation process of the conventional acid-base bifunctional catalyst is effectively overcome, and due to the inherent acid property of the zeolite, the bifunctional can be realized only by grafting alkaline silane on the surface of the zeolite molecular sieve, so that the preparation procedure of the catalyst is simplified. Therefore, theoretically, the MFI zeolite has potential advantages as an acid-base bifunctional catalyst carrier.
Although MFI zeolites have the potential advantage of being a support for acid-base bifunctional catalysts, it is difficult to effectively graft organosilanes containing basic functional groups thereon, limited by their small pore size and outer surface. In addition, when deacylation-Knoevenagel reaction is used for preparing aromatic compounds, large-size reaction substrates are often involved, and the small pore size of the zeolite can limit the diffusion of the large-size reaction substrates. In recent years, the r. Ryoo group has proposed a new method for synthesizing zeolite nano-platelets using a bis-quaternary ammonium cationic surfactant as a template. For example, MFI zeolite nanolaminates having a thickness of only 2nm in the b-axis direction were successfully synthesized using this method (Nature, 2009, 461, 246). Compared with the conventional zeolite, the zeolite nano-layer sheet has the characteristics of accessibility of acid active sites, high macromolecular diffusion performance and the like, and can provide larger specific surface area and silicon hydroxyl (grafting sites) with rich surface. Although abundant silicon hydroxyl groups among MFI nano-layer sheets are subjected to condensation polymerization in the process of roasting to remove the template agent, further researches on K, Na and the like show that the assembly and arrangement mode of the MFI zeolite nano-layer sheets can be changed by adjusting crystallization conditions and synthesis system composition, and products of the disordered arranged zeolite nano-layer sheets after roasting to remove the template agent can still maintain mesoporous characteristics (chem. Mater., 2011, 23, 1273).
Therefore, the acid-base bifunctional catalyst is prepared by utilizing the characteristics that the distribution of the MFI zeolite nano-layer sheet in acid strength, acid amount and acid active sites is adjustable and controllable, the MFI zeolite nano-layer sheet has a larger specific surface area and silicon hydroxyl groups (grafting sites) with rich surfaces and the like, and the quantity strength and the positions of the grafted basic active sites are regulated, so that the MFI zeolite nano-layer sheet has an important application value in deacetalization-Knoevenagel reaction.
Disclosure of Invention
The invention aims to provide a preparation method of a bifunctional MFI zeolite nano-layer sheet, which is based on the main defects that the acid strength and the alkali strength of a catalyst are difficult to regulate and control, the spacing between an acid active site and an alkaline active site is difficult to regulate and control and the like in the process of catalyzing deacylation-Knoevenagel reaction by using MFI zeolite as a main material, so that the technical scheme of the method for preparing the multifunctional material of the acid-base bifunctional MFI zeolite nano-layer sheet by directly reacting alkaline functionalized silane with surface hydroxyl on the MFI nano-layer sheet is disclosed.
The invention is realized by adopting the following technical scheme:
a preparation method of a bifunctional MFI zeolite nano-layer sheet comprises the following steps:
(1) placing the MFI layered zeolite into a 15wt% ammonium nitrate aqueous solution, carrying out ion exchange for 2-4 times, drying at 110 ℃, and roasting at 550 ℃ for 4 hours in an air atmosphere to obtain hydrogen type MFI layered zeolite;
(2) grafting alkaline functionalized silane into hydrogen type MFI zeolite or modifying the MFI zeolite by using silane, and then obtaining the novel organic-inorganic composite material of the MFI zeolite with both acidic and alkaline functions through the action of the grafted silane and an alkaline group.
Wherein the silane is a linear alkylamine, an alkyldiamine, an alkyltriamine, a meta-or para-substituted aromatic amine.
Wherein, the step (2) is specifically as follows:
i, drying hydrogen type MFI layered zeolite at 120 ℃ for 3 hours in vacuum, placing the dried hydrogen type MFI layered zeolite in a dehydrated toluene solution, adding alkaline functionalized silane, refluxing for 24 hours at 90 ℃, cooling and filtering, performing Soxhlet extraction on the obtained solid in a mixed solution of dichloromethane and diethyl ether for 24 hours, and then drying for 12 hours at 80 ℃, wherein the obtained solid is a novel organic-inorganic composite material of MFI zeolite with both acidic and alkaline functions.
In step I, the basic functionalized silane is aminopropyltrimethoxysilane.
II, drying hydrogen type MFI layered zeolite at 120 ℃ for 3 hours in vacuum, placing the dried hydrogen type MFI layered zeolite in a dehydrated toluene solution, adding organic silane, refluxing for 24 hours at 90 ℃, cooling and filtering, performing Soxhlet extraction on the obtained solid in a mixed solution of dichloromethane and ether for 24 hours, and then drying for 12 hours at 80 ℃ to obtain silanized MFI;
placing silanized MFI, zinc chloride, acetic acid, cyclohexane and formaldehyde solution into a three-neck flask, stirring for 24 hours at room temperature under the atmosphere of hydrogen chloride gas, then filtering the product, washing with ethanol and deionized water, and drying for 4 hours in vacuum at 120 ℃ to obtain a chloromethylated MFI product;
mixing chloromethylated MFI with piperazine in a dehydrated toluene solution, stirring for 12 hours, and then performing Soxhlet extraction on the obtained solid in a mixed solution of dichloromethane and diethyl ether for 24 hours to obtain the product, namely the novel MFI zeolite organic-inorganic composite material with both acidic and alkaline functions.
In step II, the organosilane is phenyltrimethoxy.
The preparation method of the MFI layered zeolite comprises the following steps: firstly, dissolving sodium hydroxide, an organic template agent and ethanol into an aqueous solution, then slowly dropwise adding a solution consisting of an aluminum source and sulfuric acid into the solution at 65 ℃ under a continuous stirring state, and maintaining for 2 hours; cooling, and adding a silicon source into the mixed solution in a stirring state; then stirring for 2 hours at 65 ℃; and (3) putting the mixed solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining, putting the stainless steel reaction kettle into a rotary oven at 140 ℃ and 50rmp for crystallization for 3-9 days, washing, and drying at 110 ℃ to obtain the MFI layered zeolite.
The aluminum source, the silicon source, the sodium hydroxide, the organic template, the sulfuric acid, the ethanol and the water are in a molar ratio of (0-4) 100:30:10:18 (200-800) 4000.
The silicon source is tetraethoxysilane, water glass, silica sol or white carbon black.
The aluminum source is sodium metaaluminate, aluminum isopropoxide or aluminum sulfate.
The organic template agent is a dimer (C) of tetrabutyl quaternary ammonium hydroxide and tetrapropyl quaternary ammonium hydroxide3H7)3N+(CH2)nN+(C3H7)3。
The MFI nano-layer sheet prepared by the invention has adjustable and controllable distribution of acid strength, acid amount and acid active sites, and has a layered structure with larger specific surface area and rich silicon hydroxyl groups (grafting sites) on the surface.
The preparation method of the bifunctional MFI zeolite nano-layer sheet has the advantages that: by adopting the method, various basic groups with different properties can be immobilized on the MFI zeolite material, the prepared composite material has acidic and basic active sites and has acidic and basic catalytic functions, and the acid-base active sites are highly matched in number, strength and position and can catalyze complex series reaction.
Drawings
FIG. 1 shows FT-IR spectra of hydrogen type MFI zeolite nano-layer sheet samples.
Figure 2 shows the FT-IR spectra of aminopropyltrimethoxysilanized MFI zeolite nano-platelets samples.
Detailed Description
The following provides a detailed description of specific embodiments of the present invention.
Firstly, preparing organic template agent
1. Dimer of organic templating agent tetrapropyl quaternary ammonium base (C)3H7)3N+(CH2)nN+(C3H7)3The synthesis of (2) was as shown below.
Scheme 1
Mixing 0.1mol of iodopropane and 0.8-1.2 mol of diaminoalkane in 100mL of butanone solution, adding 0.1mol of potassium carbonate, stirring at 65 ℃ for 12h, cooling to room temperature, carrying out suction filtration, washing with diethyl ether, and carrying out vacuum drying at 60 ℃ to obtain a solid, namely the quaternary ammonium base.
2. Synthesis of organic templating agent tetrabutyl quaternary ammonium base dimer was synthesized according to Scheme 1 diagram.
Mixing 0.1mol of iodobutane and 0.8-1.2 mol of diaminoalkane in 100mL of butanone solution, adding 0.1mol of potassium carbonate, stirring at 65 ℃ for 12h, cooling to room temperature, carrying out suction filtration, washing with diethyl ether, and carrying out vacuum drying at 60 ℃ to obtain a solid, namely the quaternary ammonium base.
Secondly, preparing MFI layered zeolite
Firstly, dissolving sodium hydroxide, an organic template agent and ethanol into an aqueous solution, and then slowly dropwise adding a solution consisting of an aluminum source and sulfuric acid into the solution at 65 ℃ under a continuous stirring state for 2 hours. And after cooling, adding a silicon source into the mixed solution under the stirring state. Then stirred at 65 ℃ for 2 h. And (3) putting the mixed solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining, putting the stainless steel reaction kettle into a rotary oven at 140 ℃ and 50rmp for crystallization for 3-9 days, washing, and drying at 110 ℃ to obtain the MFI layered zeolite.
Wherein, the mol ratio of the aluminum source (sodium metaaluminate, aluminum isopropoxide or aluminum sulfate), the silicon source (tetraethoxysilane, water glass, silica sol or white carbon black), the sodium hydroxide, the organic template agent, the sulfuric acid, the ethanol and the water is (0,0.25,0.5,1,2,4):100:30:10:18, (200,400, 800): 4000.
Thirdly, preparing hydrogen type MFI layered zeolite
And (2) placing the MFI layered zeolite into a 15wt% ammonium nitrate aqueous solution, performing ion exchange for 2-4 times, drying at 110 ℃, and roasting at 550 ℃ for 4 hours in an air atmosphere to obtain the hydrogen type MFI layered zeolite.
970cm as shown in FIG. 1-1The nearby characteristic peak is assigned to the absorption peak of Si-OH, 3460cm-1The nearby characteristic peak belongs to an-OH stretching vibration absorption peak, which shows that the MFI zeolite nano-layer sheet has zeolite characteristics and grafting modification capability.
Fourthly, preparing the double-function MFI zeolite nano-layer slice
1. Basic active sites were introduced into MFI nanolayers in a grafting manner as shown in Scheme 2 under different solvent, temperature and time conditions, and the organosilanes used included linear alkylamines, alkyldiamines, alkyltriamines, meta-and para-substituted aromatic amines.
Scheme 2
The method comprises the following specific steps: 2.0g of hydrogen type MFI layered zeolite is dried in vacuum at 120 ℃ for 3h, placed in 50mL of dehydrated toluene solution, added with 3.0g of aminopropyltrimethoxysilane, refluxed at 90 ℃ for 24h, cooled and filtered, the obtained solid is subjected to Soxhlet extraction in a mixed solution of dichloromethane and diethyl ether for 24h, and then dried at 80 ℃ for 12h, and the obtained solid is the novel organic-inorganic composite material of MFI zeolite with both acidic and alkaline functions.
As shown in FIG. 2, 3300cm-1And 1640cm-1The characteristic peaks near the peaks are attributed to-NH2The characteristic peak of stretching vibration shows that aminopropyl trimethoxy silane is successfully grafted on the MFI zeolite nano-lamina.
2. Basic active sites were introduced into MFI nanolayers in a grafting manner as shown in Scheme3 under various solvent, temperature and time conditions, and the organosilanes used included linear alkylamines, alkyldiamines, alkyltriamines, meta-and para-substituted aromatic amines.
Scheme 3
The method comprises the following specific steps: (1) 2.0g of hydrogen type MFI layered zeolite is dried in vacuum at 120 ℃ for 3h, placed in 50mL of dehydrated toluene solution, added with 3.0g of phenyltrimethoxysilane, refluxed at 90 ℃ for 24h, cooled and filtered, and the obtained solid is subjected to Soxhlet extraction in a mixed solution of dichloromethane and diethyl ether for 24h and then dried at 80 ℃ for 12h to obtain silanized MFI.
(2) 2.0g of silanized MFI, 4g of zinc chloride, 3mL of acetic acid, 20mL of cyclohexane and 10mL of formaldehyde solution (37%) were placed in a three-neck flask, stirred at room temperature for 24h under the atmosphere of hydrogen chloride gas, and then the product was filtered, washed with ethanol and deionized water, and vacuum-dried at 120 ℃ for 4h, whereby the obtained product was chloromethylated MFI.
(3) Mixing chloromethylated MFI with piperazine in a dehydrated toluene solution, stirring for 12 hours, and then performing Soxhlet extraction on the obtained solid in a mixed solution of dichloromethane and diethyl ether for 24 hours to obtain the product, namely the novel organic-inorganic composite material of MFI zeolite with both acidic and alkaline functions.
Finally, it should be noted that the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the detailed description is made with reference to the embodiments of the present invention, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the protection scope of the claims of the present invention.
Claims (1)
1. A preparation method of a bifunctional MFI zeolite nano-layer sheet is characterized by comprising the following steps: the method comprises the following steps:
(1) placing the MFI layered zeolite into a 15wt% ammonium nitrate aqueous solution, carrying out ion exchange for 2-4 times, drying at 110 ℃, and roasting at 550 ℃ for 4 hours in an air atmosphere to obtain hydrogen type MFI layered zeolite;
the preparation method of the MFI layered zeolite comprises the following steps: firstly, dissolving sodium hydroxide, an organic template agent and ethanol into an aqueous solution, then slowly dropwise adding a solution consisting of an aluminum source and sulfuric acid into the solution at 65 ℃ under a continuous stirring state, and maintaining for 2 hours; cooling, and adding a silicon source into the mixed solution in a stirring state; then stirring for 2 hours at 65 ℃; putting the mixed solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining, putting the stainless steel reaction kettle into a rotary oven with the temperature of 140 ℃ and the rmp of 50, crystallizing for 3-9 days, then washing, and drying at the temperature of 110 ℃ to obtain MFI layered zeolite;
wherein the molar ratio of the aluminum source, the silicon source, the sodium hydroxide, the organic template agent, the sulfuric acid, the ethanol and the water is 4:100:30:10:18:200: 4000;
the silicon source is silica sol;
the aluminum source is sodium metaaluminate or aluminum isopropoxide;
the organic template agent is a dimer (C) of tetrabutyl quaternary ammonium hydroxide and tetrapropyl quaternary ammonium hydroxide3H7)3N+(CH2)nN+(C3H7)3；
Dimer of organic templating agent tetrapropyl quaternary ammonium base (C)3H7)3N+(CH2)nN+(C3H7)3The synthesis of (2): mixing 0.1mol of iodopropane and 0.8-1.2 mol of diaminoalkane in 100mL of butanone solution, adding 0.1mol of potassium carbonate, stirring at 65 ℃ for 12h, cooling to room temperature, performing suction filtration, washing with diethyl ether, and performing vacuum drying at 60 ℃ to obtain a solid, namely quaternary ammonium base;
synthesis of organic template tetrabutyl quaternary ammonium base dimer: mixing 0.1mol of iodobutane and 0.8-1.2 mol of diaminoalkane in 100mL of butanone solution, adding 0.1mol of potassium carbonate, stirring at 65 ℃ for 12h, cooling to room temperature, performing suction filtration, washing with diethyl ether, and performing vacuum drying at 60 ℃ to obtain a solid, namely quaternary ammonium base;
(2) firstly, silane is used for modifying MFI zeolite, and then the grafted silane and an alkaline group act to obtain an MFI zeolite organic-inorganic composite material with dual functions of acidity and alkalinity;
the method specifically comprises the following steps: vacuum drying hydrogen type MFI layered zeolite at 120 ℃ for 3h, placing the dried hydrogen type MFI layered zeolite in a dehydrated toluene solution, adding organosilane, refluxing at 90 ℃ for 24h, cooling and filtering, performing Soxhlet extraction on the obtained solid in a mixed solution of dichloromethane and ether for 24h, and then drying at 80 ℃ for 12h to obtain silanized MFI; wherein the organosilane is phenyl trimethoxy silane;
placing silanized MFI, zinc chloride, acetic acid, cyclohexane and formaldehyde solution into a three-neck flask, stirring for 24 hours at room temperature under the atmosphere of hydrogen chloride gas, then filtering the product, washing with ethanol and deionized water, and drying for 4 hours in vacuum at 120 ℃ to obtain a chloromethylated MFI product;
mixing chloromethylated MFI with piperazine in a dehydrated toluene solution, stirring for 12 hours, and then performing Soxhlet extraction on the obtained solid in a mixed solution of dichloromethane and diethyl ether for 24 hours to obtain the product, namely the MFI zeolite organic-inorganic composite material with both acidic and alkaline functions.
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