阅读说明：本技术 一种多功能杂化沸石分子筛的制备方法及其催化应用 (Preparation method and catalytic application of multifunctional hybrid zeolite molecular sieve ) 是由 周丹 张欣兰 鲁新环 夏清华 于 2021-09-02 设计创作，主要内容包括：本发明公开了一种多功能杂化沸石分子筛的制备方法及其催化应用,制备方法包括以下步骤：步骤一、将有机硅源分散于氢氧化钠水溶液中,再加入非贵金属源,常温下搅拌至全部溶解,再依次加入铝源和无机硅源,搅拌得到反应物凝胶,烘干得到干凝胶,再将其研磨成粉末,转移至聚四氟乙烯内衬的不锈钢反应釜中密封,静态晶化后得到杂化沸石分子筛；步骤二、将制得的杂化沸石分子筛和亚乙基多胺类有机胺加入到有机溶剂中进行超声处理,经旋蒸和烘干处理得到多功能杂化沸石分子筛。本发明制备的多功能杂化沸石分子筛集合了过渡金属、有机功能基团和氮活性物种于一身,在催化CO-(2)和环氧化物环加成反应制备环碳酸酯中具有催化活性高、循环稳定性好等优点。(The invention discloses a preparation method of a multifunctional hybrid zeolite molecular sieve and catalytic application thereof, wherein the preparation method comprises the following steps: dispersing an organic silicon source into a sodium hydroxide aqueous solution, adding a non-noble metal source, stirring at normal temperature until the non-noble metal source is completely dissolved, sequentially adding an aluminum source and an inorganic silicon source, stirring to obtain a reactant gel, drying to obtain a dry gel, grinding the dry gel into powder, transferring the dry gel into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and sealingObtaining the hybrid zeolite molecular sieve after static crystallization; and step two, adding the prepared hybrid zeolite molecular sieve and ethylene polyamine organic amine into an organic solvent for ultrasonic treatment, and performing rotary evaporation and drying treatment to obtain the multifunctional hybrid zeolite molecular sieve. The multifunctional hybrid zeolite molecular sieve prepared by the invention integrates transition metal, organic functional groups and nitrogen active species into a whole and is used for catalyzing CO 2 The catalyst has the advantages of high catalytic activity, good cycling stability and the like in the cyclic carbonate preparation by the cycloaddition reaction of the catalyst and epoxide.)

1. A preparation method of a multifunctional hybrid zeolite molecular sieve is characterized by comprising the following steps:

dispersing an organic silicon source in an aqueous solution of sodium hydroxide under the ultrasonic condition with the power of 200-400W at normal temperature, adding a non-noble metal source, stirring at normal temperature until the organic silicon source is completely dissolved to obtain a solution I, adding an aluminum source into the solution I, then adding an inorganic silicon source, stirring for 2-4 hours to obtain a reactant gel, placing the reactant gel in a constant-temperature oven for treatment to obtain a dry gel, grinding the dry gel into powder, transferring the powder into a stainless steel reaction kettle with a polytetrafluoroethylene lining for sealing, then placing the stainless steel reaction kettle in the constant-temperature oven with the temperature of 120-200 ℃ for static crystallization for 0.5-7 days, taking the reaction kettle out, performing quenching with cold water, performing suction filtration, washing and drying on a mixture in the kettle to obtain a hybrid zeolite molecular sieve;

and step two, adding the prepared hybrid zeolite molecular sieve and ethylene polyamine organic amine into an organic solvent, carrying out ultrasonic treatment on the mixture, and carrying out rotary evaporation and drying treatment by using a rotary evaporator to obtain the multifunctional hybrid zeolite molecular sieve.

2. The method for preparing the multifunctional hybrid zeolite molecular sieve of claim 1, wherein in the second step, the organic solvent is one or more selected from absolute ethyl alcohol, isopropyl alcohol, N-dimethylformamide, methanol, acetone, acetonitrile and ethyl acetate, and the ethylenepolyamine organic amine is one or more selected from diethylenetriamine, triethylenediamine, tetraethylenepentamine, ethyleneimine and triethylenetetramine.

3. The method for preparing the multifunctional hybrid zeolite molecular sieve of claim 1, wherein in the second step, the mass of the hybrid zeolite molecular sieve is 2-4% of the mass of the organic solvent, and the mass of the ethylene polyamine organic amine is 0.2-2% of the mass of the organic solvent.

4. The preparation method of the multifunctional hybrid zeolite molecular sieve of claim 1, wherein in the second step, the ultrasonic treatment is performed at 30-100 ℃, 100-600W of power and 50-400 r/min of stirring speed for 3-8 h.

5. The preparation method of the multifunctional hybrid zeolite molecular sieve of claim 4, wherein in the second step, the ultrasonic treatment is performed at 60-80 ℃ and 400-500W for 4-6 h at a stirring speed of 250-400 r/min.

6. The method for preparing the multifunctional hybrid zeolite molecular sieve of claim 1, wherein in the first step, the molar ratio of each substance in the xerogel is aluminum source: an organic silicon source: inorganic silicon source: a sodium source: non-noble metal sources: water 1 (0.4-6.0), (15.2-20.8), (4-10.5), (0.05-0.15), (42-98);

wherein: the aluminum source is Al₂O₃The inorganic silicon source and the organic silicon source are both SiO₂In terms of Na as the sodium source₂And O, the non-noble metal source is calculated as non-noble metal M.

7. The method for preparing the multifunctional hybrid zeolite molecular sieve of claim 1, wherein in the first step, the organic silicon source is one or more of methyltriethoxysilane, dimethyldiethoxysilane, hexadecyltriethoxysilane, N- (β -aminoethyl- γ -aminopropyl) methyldimethoxysilane, vinyltriethoxysilane, 3-mercaptopropyltriethoxysilane, and 3-aminopropyltriethoxysilane;

the aluminum source is one or more of sodium metaaluminate or aluminum isopropoxide;

the inorganic silicon source is one or more of silica sol, water glass, tetraethyl orthosilicate, gas-phase silica and silicon tetrachloride.

8. The method for preparing the multifunctional hybrid zeolite molecular sieve of claim 1, wherein in step one, the non-noble metal source is one or more of nickel acetate tetrahydrate, nickel sulfate, nickel chloride hexahydrate, ferric nitrate nonahydrate, ferric chloride anhydrous, ferrous sulfate, manganese nitrate tetrahydrate, manganese sulfate, manganese acetate tetrahydrate, chromium acetate, chromium nitrate, cobalt sulfate heptahydrate, cobalt acetate tetrahydrate, cobalt hexaammine trichloride, copper nitrate trihydrate, and copper chloride dihydrate.

9. A multifunctional hybrid zeolite molecular sieve prepared by the method of any one of claims 1-8.

10. Use of the multifunctional hybrid zeolite molecular sieve of claim 9 for catalyzing the cycloaddition of carbon dioxide and an epoxide to form a cyclic carbonate, the catalytic process comprising the steps of:

adding a multifunctional hybrid zeolite molecular sieve into a stainless steel intermittent pressure reaction kettle, adding an epoxide or a mixture of the epoxide and a solvent, sealing the reaction kettle, replacing air in the reaction kettle with carbon dioxide gas for three times, filling the carbon dioxide gas to ensure that the pressure in the reaction kettle reaches 0.5-3.0 MPa, starting stirring, heating the reaction kettle to ensure that the reaction temperature reaches 60-150 ℃, and reacting at constant temperature for 2-8 hours to obtain cyclic carbonate.

Technical Field

The invention belongs to the field of preparation of catalytic materials, and particularly discloses a preparation method and catalytic application of a multifunctional hybrid zeolite molecular sieve catalyst.

Background

In 1970-2004, the emission of smoke in the open environment increased, with the annual global emission of carbon dioxide rising dramatically, which led to global climate changes, embodied as global warming. Therefore, how to control global warming by reducing carbon dioxide emissions is an urgent problem to be solved. The method for synthesizing chemicals (such as green solvents, polymers, functional reinforcing agents and the like) by taking carbon dioxide as a C source is one of effective ways for reducing carbon dioxide emission, and has extremely important research values.

Cyclic carbonates are an important chemical raw material and are useful as solvents, electrolytes, polymer synthesis monomers, fine chemicals, industrial lubricants, etc. Thus, by catalyzing CO₂The synthesis of cyclic carbonates by cycloaddition with epoxy compounds is of particular interest. Among them, development of a green, economical and efficient catalyst has become a core problem. The catalysts developed at present can be divided into two broad categories, homogeneous catalysts and heterogeneous catalysts. Among them, the ionic liquid is one of the most popular catalysts because it has both anions and cations coexisting and satisfies the dual-function catalytic system composed of lewis acid sites and nucleophilic groups (lewis bases). For example, patents CN101811067B and CN103706330B report a series of preparation methods for synthesizing cyclic carbonates using ionic liquid as a catalyst. However, the ionic liquid is expensive, the preparation process is complicated, the use conditions are very harsh, and the catalyst cannot be recycled. In addition, toHeterogeneous catalysts represented by mesoporous molecular sieve supported coupled organosilane are also reported, but the preparation process is complex, the framework is easy to collapse, and the cyclic utilization rate is generally low. Therefore, the preparation of new and efficient heterogeneous catalysts under the conditions of high efficiency and green economy is urgently needed.

The zeolite molecular sieve is one of the most important inorganic porous materials as an aluminosilicate inorganic crystal material, is widely applied to the fields of adsorption separation and catalysis, and plays an important strategic position in national economy. Meanwhile, the framework composition and the surface of the zeolite molecular sieve have adjustable denaturation and modifiability, for example, the framework can be doped with organic groups, metal heteroatoms or non-metal heteroatoms, the surface can be grafted with organic functional groups and the like, so that the application of the traditional zeolite molecular sieve is greatly expanded, and new activity is continuously generated.

Therefore, a green, economical and efficient preparation method of the multifunctional hybrid zeolite molecular sieve heterogeneous catalyst is needed, and the method has the advantages of simple preparation process, easiness in operation, low cost, greenness, environmental friendliness and the like.

Disclosure of Invention

The invention aims to solve the defects of the background technology and provide a preparation method of a green, economical and efficient multifunctional hybrid zeolite molecular sieve heterogeneous catalyst. According to the method, non-noble metal salt, an organic silicon source, an inorganic silicon source, an aluminum source, a sodium source and deionized water are used as raw materials, a hybrid zeolite molecular sieve is synthesized in one step through a dry glue conversion method, and then the hybrid zeolite molecular sieve is modified and modified by using ethylene polyamine organic amine under an ultrasonic condition to prepare the multifunctional hybrid zeolite molecular sieve catalyst.

The technical scheme of the invention is as follows: a preparation method of a multifunctional hybrid zeolite molecular sieve is characterized by comprising the following steps:

dispersing an organic silicon source in an aqueous solution of sodium hydroxide under the ultrasonic condition with the power of 200-400W at normal temperature, adding a non-noble metal source, stirring at normal temperature until the organic silicon source is completely dissolved to obtain a solution I, adding an aluminum source into the solution I, then adding an inorganic silicon source, stirring for 2-4 hours to obtain a reactant gel, placing the reactant gel in a constant-temperature oven for treatment to obtain a dry gel, grinding the dry gel into powder, transferring the powder into a stainless steel reaction kettle with a polytetrafluoroethylene lining for sealing, then placing the stainless steel reaction kettle in the constant-temperature oven with the temperature of 120-200 ℃ for static crystallization for 0.5-7 days, taking the reaction kettle out, performing quenching with cold water, performing suction filtration, washing and drying on a mixture in the kettle to obtain a hybrid zeolite molecular sieve;

and step two, adding the prepared hybrid zeolite molecular sieve and ethylene polyamine organic amine into an organic solvent, carrying out ultrasonic treatment on the mixture, and carrying out rotary evaporation and drying treatment by using a rotary evaporator to obtain the multifunctional hybrid zeolite molecular sieve.

Preferably, in the second step, the organic solvent is one or more of absolute ethyl alcohol, isopropyl alcohol, N-dimethylformamide, methanol, acetone, acetonitrile and ethyl acetate, and the ethylenepolyamine organic amine is one or more of diethylenetriamine, triethylenediamine, tetraethylenepentamine, ethyleneimine and triethylenetetramine.

Preferably, in the second step, the mass of the hybrid zeolite molecular sieve is 2-4% of that of the organic solvent, and the mass of the ethylene polyamine organic amine is 0.2-2% of that of the organic solvent.

Preferably, in the second step, the ultrasonic treatment is carried out for 3-8 hours under the conditions of the temperature of 30-100 ℃, the power of 100-600W and the stirring speed of 50-400 r/min. In the invention, the multifunctional hybrid zeolite molecular sieve obtained by the ultrasonic process is used as a catalyst in CO₂The conversion rate of the propylene oxide in the reaction with the propylene oxide can reach 69.03-90.89%.

Further, in the second step, ultrasonic treatment is carried out for 4-6 hours under the conditions that the temperature is 60-80 ℃, the power is 400-500W, and the stirring speed is 250-400 r/min. In the invention, the multifunctional hybrid zeolite molecular sieve obtained by the ultrasonic process is used as a catalyst in CO₂The conversion rate of the propylene oxide in the reaction with the propylene oxide can reach 81.62-90.89%.

Preferably, in the first step, the molar ratio of each substance in the xerogel is aluminum source: an organic silicon source: inorganic silicon source: a sodium source: non-noble metal sources: water 1 (0.4-6.0), (15.2-20.8), (4-10.5), (0.05-0.15), (42-98);

wherein: the aluminum source is Al₂O₃The inorganic silicon source and the organic silicon source are both SiO₂In terms of Na as the sodium source₂And O, the non-noble metal source is calculated as non-noble metal M.

Preferably, in the first step, the organic silicon source is one or more of methyltriethoxysilane, dimethyldiethoxysilane, hexadecyltriethoxysilane, N- (. beta. -aminoethyl-. gamma. -aminopropyl) methyldimethoxysilane, vinyltriethoxysilane, 3-mercaptopropyltriethoxysilane, and 3-aminopropyltriethoxysilane;

the aluminum source is one or more of sodium metaaluminate or aluminum isopropoxide;

the inorganic silicon source is one or more of silica sol, water glass, tetraethyl orthosilicate, gas-phase silica and silicon tetrachloride.

Preferably, in the first step, the non-noble metal source is one or more of nickel acetate tetrahydrate, nickel sulfate, nickel chloride hexahydrate, ferric nitrate nonahydrate, anhydrous ferric chloride, ferrous sulfate, manganese nitrate tetrahydrate, manganese sulfate, manganese acetate tetrahydrate, chromium acetate, chromium nitrate, cobalt sulfate heptahydrate, cobalt acetate tetrahydrate, cobalt hexaammine trichloride, copper nitrate trihydrate and copper chloride dihydrate.

Preferably, in the step one, the concentration of the aqueous solution of sodium hydroxide is 0.5-1.5 mol/L.

The invention also provides a multifunctional hybrid zeolite molecular sieve which is prepared by the preparation method of any one of the multifunctional hybrid zeolite molecular sieves.

The invention also provides application of the multifunctional hybrid zeolite molecular sieve, wherein the multifunctional hybrid zeolite molecular sieve is used for catalyzing cycloaddition of carbon dioxide and epoxide to synthesize cyclic carbonate, and the catalysis process comprises the following steps:

adding a multifunctional hybrid zeolite molecular sieve into a stainless steel intermittent pressure reaction kettle, adding an epoxide or a mixture of the epoxide and a solvent, sealing the reaction kettle, replacing air in the reaction kettle with carbon dioxide gas for three times, filling the carbon dioxide gas to ensure that the pressure in the reaction kettle reaches 0.5-3.0 MPa, starting stirring, heating the reaction kettle to ensure that the reaction temperature reaches 60-150 ℃, and reacting at constant temperature for 2-8 hours to obtain cyclic carbonate. In the invention, the epoxide is 1, 2-epoxypropane or epichlorohydrin, the solvent is N, N-dimethylformamide, and 30-60mg of the multifunctional hybrid zeolite molecular sieve catalyst is used for every 10mmol of epoxide.

The type and the adding amount of the ethylene polyamine organic amine in the organic amine modification process are critical to the power, the temperature, the stirring speed and the time of ultrasonic treatment:

the ethylene polyamine organic amine selects primary amines with lone pair electrons, and the ethylene polyamine organic amine containing the lone pair electrons can provide nucleophilic group (Lewis basic) active sites, so that the catalytic performance of the catalyst is greatly improved, and the catalytic performance of the catalyst modified by the organic amine without the lone pair electrons is obviously reduced; the catalytic performance of the hybrid zeolite molecular sieve catalyst is influenced by the addition of the ethylene polyamine organic amine, and the excessive ethylene polyamine organic amine can cause the complete package of the surface of the hybrid zeolite molecular sieve, so that the effect of transition metal and organic functional groups in catalysis is influenced, and the catalytic performance of the catalyst is reduced.

The ultrasonic treatment conditions determine the effect of the organic amine on the modification of the hybrid zeolite molecular sieve. Proper ultrasonic power, ultrasonic temperature, stirring speed and ultrasonic time can ensure that organic amine is well and uniformly dispersed in an organic reagent, ensure that the organic amine is not agglomerated on the surface of the hybrid zeolite molecular sieve, and realize chemical bonding between the organic amine and the hybrid zeolite molecular sieve through the energy conversion of ultrasonic. Therefore, the multifunctional hybrid zeolite molecular sieve catalyst with good uniformity can be prepared by regulating and controlling ultrasonic power, ultrasonic temperature, stirring speed and ultrasonic time.

Compared with the prior art, the invention has the beneficial effects that:

1. the hybrid zeolite molecular sieve synthesized by the one-step dry glue method is characterized in that firstly, transition metal and organic functional groups are simultaneously introduced into the zeolite molecular sieve, and then the surface of the hybrid zeolite molecular sieve is further modified by organic amine functions through ultrasonic treatment, so that the multifunctional hybrid zeolite molecular sieve catalyst is synthesized. Compared with other zeolite molecular sieves, the multifunctional hybrid zeolite molecular sieve integrates transition metal, organic functional groups and nitrogen active species, has acid and alkali dual catalytic active sites and a surface beneficial to reaction, and has the advantages of stable chemical composition, stable framework structure, high catalytic activity, high recovery rate and the like.

2. The energy conversion by ultrasound effectively promotes the bonding between the organic amine and the hybrid zeolite molecular sieve. Therefore, the regulation and control of the ultrasonic power, the ultrasonic temperature, the stirring speed and the ultrasonic time are the key points for preparing the excellent multifunctional hybrid zeolite molecular sieve catalyst.

3. The catalyst has the advantages of simple preparation process, low cost, easy operation, convenient recycling and environmental protection. The catalyst is used for catalyzing CO₂Has excellent catalytic performance in the reaction of cycloaddition with epoxy compound to synthesize cyclic carbonate.

Drawings

FIG. 1 is an XRD pattern of the multifunctional hybrid zeolite molecular sieve catalyst prepared in example 1.

Detailed Description

The present invention is further illustrated in detail in the following specific examples (in the following examples, both the organic silicon source and the inorganic silicon source are SiO₂The non-noble metal salt is calculated as M, and the sodium source is Na₂Calculated by O, the aluminum source is Al₂O₃Meter).

Example 1

The synthesis method of the multifunctional hybrid zeolite molecular sieve provided by the embodiment comprises the following steps:

1) weighing 1.5g of 3-mercaptopropyltriethoxysilane in a 100mL polytetrafluoroethylene beaker, adding 50mL of deionized water and 1.48g of NaOH to prepare a NaOH aqueous solution, and dispersing under the ultrasonic condition at room temperature until the solid is completely dissolved, wherein the ultrasonic power is 400W. Then 0.049g of cobalt acetate tetrahydrate (C) was added to the solution₄H₆CoO₄·4H₂O), fully stirring for 3 hours to obtain a solution I; solution I0.65 g NaAlO was added with stirring₂4.627g of fumed silica were then added slowly and stirring was continued for 3h to form a reaction gel. The formed reaction gel is dried in an oven at 80 ℃ to obtain dry gel, the water content of the dry gel is controlled to be 4g, and the molar ratio of the aluminum source, the organic silicon source, the inorganic silicon source, the sodium source, the non-noble metal source and the water in the dry gel is 1:1.6:19.4:5.68:0.05: 56.

2) And grinding the dry gel into powder, and transferring the powder into a stainless steel reaction kettle with a polytetrafluoroethylene lining. And sealing the stainless steel reaction kettle, and then placing the stainless steel reaction kettle in a constant-temperature oven at 170 ℃ for crystallization for 3 d. Taking out, rapidly chilling with cold water, then performing suction filtration, washing to be neutral, and drying in an oven at 80 ℃ to obtain the hybrid zeolite molecular sieve.

3) And then carrying out organic amine functionalization treatment, specifically comprising the following steps: adding 0.214g of organic amine tetraethylenepentamine, 0.5g of the hybrid zeolite molecular sieve and 25g of absolute ethyl alcohol (the mass of the hybrid zeolite molecular sieve is 2 percent of the mass of the absolute ethyl alcohol, and the mass of the tetraethylenepentamine is 0.85 percent of the mass of the absolute ethyl alcohol) into a round-bottom flask, and placing the round-bottom flask into an ultrasonic instrument, wherein the ultrasonic treatment temperature is 60 ℃, the ultrasonic treatment power is 500W, the stirring rate is 400r/min, and the ultrasonic treatment time is 4 h; then carrying out rotary evaporation at the temperature of 85 ℃ for 3 h; and finally, drying in a constant-temperature oven at the temperature of 80 ℃ for 12 hours to finally prepare the multifunctional hybrid zeolite molecular sieve. The XRD pattern is shown in figure 1.

Example 2

The synthesis method of the multifunctional hybrid zeolite molecular sieve provided by the embodiment comprises the following steps:

1) 0.378g of 3-mercaptopropyltriethoxysilane was weighed into a 100mL polytetrafluoroethylene beaker, and 50mL of deionized water and 1.48g of NaOH were added to prepare an aqueous NaOH solution, which was dispersed under ultrasonic conditions at room temperature until the solid was completely dissolved, and the ultrasonic power was 400W. Then 0.049g of cobalt acetate tetrahydrate (C) was added to the solution₄H₆CoO₄·4H₂O), fully stirring for 3 hours to obtain a solution I; solution I0.65 g NaAlO was added with stirring₂4.898g of fumed silica were then added slowly and stirring was continued for 3h to form a reaction gel. The formed reaction gel is placed in an oven at 80 DEG CThe dried gel is dried to obtain dried gel, and the water content of the dried gel is controlled to be 4g, wherein the molar ratio of the aluminum source, the organic silicon source, the inorganic silicon source, the sodium source, the non-noble metal source and the water in the dried gel is 1:0.4:20.6:5.68:0.05: 56.

2) And grinding the dry gel into powder, and transferring the powder into a stainless steel reaction kettle with a polytetrafluoroethylene lining. The stainless steel reaction kettle is sealed and then is placed in a constant temperature oven at 120 ℃ for crystallization for 72 hours. Taking out, rapidly chilling with cold water, filtering, washing to neutrality, and drying in an oven at 80 deg.C to obtain the hybrid zeolite molecular sieve.

3) And then carrying out organic amine functionalization treatment, specifically comprising the following steps: adding 0.214g of organic amine tetraethylenepentamine, 0.5g of the hybrid zeolite molecular sieve and 25g of absolute ethyl alcohol (the mass of the hybrid zeolite molecular sieve is 2% of the mass of the absolute ethyl alcohol, and the mass of the tetraethylenepentamine is 0.85% of the mass of the absolute ethyl alcohol) into a round-bottom flask, and placing the round-bottom flask into an ultrasonic instrument, wherein the ultrasonic treatment temperature is 50 ℃, the ultrasonic treatment power is 100W, the stirring rate is 200r/min, and the ultrasonic treatment time is 3 h; then carrying out rotary evaporation at the temperature of 85 ℃ for 3 h; and finally, drying in a constant-temperature oven at the temperature of 80 ℃ for 12 hours to finally prepare the multifunctional hybrid zeolite molecular sieve.

Example 3

The synthesis method of the multifunctional hybrid zeolite molecular sieve provided by the embodiment comprises the following steps:

1) 1.891g of 3-mercaptopropyltriethoxysilane was weighed into a 100mL polytetrafluoroethylene beaker, 50mL of deionized water and 1.48g of NaOH were added to prepare an aqueous NaOH solution, and the aqueous NaOH solution was dispersed under ultrasonic conditions at room temperature until the solid was completely dissolved, wherein the ultrasonic power was 400W. Then 0.049g of cobalt acetate tetrahydrate (C) was added to the solution₄H₆CoO₄·4H₂O), fully stirring for 3 hours to obtain a solution I; adding 0.65g NaAlO into the solution I under the condition of stirring₂4.566g of fumed silica were then added slowly and stirring was continued for 3h to form a reaction gel. The formed reaction gel is dried in an oven at 80 ℃ to obtain dry gel, the water content of the dry gel is controlled to be 4g, and the molar ratio of an aluminum source, an organic silicon source, an inorganic silicon source, a sodium source, a non-noble metal source and water in the dry gel is controlledThe ratio is 1:2:19.2:5.68:0.05: 56.

2) And grinding the dry gel into powder, and transferring the powder into a stainless steel reaction kettle with a polytetrafluoroethylene lining. The stainless steel reaction kettle is sealed and then is placed in a constant temperature oven at 150 ℃ for crystallization for 72 hours. Taking out, rapidly chilling with cold water, filtering, washing to neutrality, and drying in an oven at 80 deg.C to obtain the hybrid zeolite molecular sieve.

3) And then carrying out organic amine functionalization treatment, specifically comprising the following steps: adding 0.214g of organic amine tetraethylenepentamine, 0.5g of the hybrid zeolite molecular sieve and 25g of absolute ethyl alcohol (the mass of the hybrid zeolite molecular sieve is 2% of the mass of the absolute ethyl alcohol, and the mass of the tetraethylenepentamine is 0.85% of the mass of the absolute ethyl alcohol) into a round-bottom flask, and placing the round-bottom flask into an ultrasonic instrument, wherein the ultrasonic treatment temperature is 50 ℃, the ultrasonic treatment power is 250W, the stirring rate is 200r/min, and the ultrasonic treatment time is 3 h; then carrying out rotary evaporation at the temperature of 85 ℃ for 3 h; and finally, drying in a constant-temperature oven at the temperature of 80 ℃ for 12 hours to finally prepare the multifunctional hybrid zeolite molecular sieve.

Example 4

The synthesis method of the multifunctional hybrid zeolite molecular sieve provided by the embodiment comprises the following steps:

1) 3.779g of 3-mercaptopropyltriethoxysilane was weighed into a 100mL polytetrafluoroethylene beaker, 50mL of deionized water and 1.48g of NaOH aqueous solution were added, and the mixture was dispersed under ultrasonic conditions at room temperature until the solid was completely dissolved, with the ultrasonic power of 400W. Then 0.049g of cobalt acetate tetrahydrate (C) was added to the solution₄H₆CoO₄·4H₂O), fully stirring for 3 hours to obtain a solution I; solution I0.65 g NaAlO was added with stirring₂Then 4.090g of fumed silica was added slowly and stirring was continued for 3h to form a reaction gel. The formed reaction gel is dried in an oven at 80 ℃ to obtain dry gel, the water content of the dry gel is controlled to be 4g, and the molar ratio of the aluminum source, the organic silicon source, the inorganic silicon source, the sodium source, the non-noble metal source and the water in the dry gel is 1:4:17.2:5.68:0.05: 56.

2) And grinding the dry gel into powder, and transferring the powder into a stainless steel reaction kettle with a polytetrafluoroethylene lining. The stainless steel reaction kettle is sealed and then is placed in a constant temperature oven at 200 ℃ for crystallization for 48 hours. Taking out, rapidly chilling with cold water, filtering, washing to neutrality, and drying in an oven at 80 deg.C to obtain the hybrid zeolite molecular sieve.

3) And then carrying out organic amine functionalization treatment, specifically comprising the following steps: adding 0.214g of organic amine tetraethylenepentamine, 0.5g of the hybrid zeolite molecular sieve and 25g of absolute ethyl alcohol (the mass of the hybrid zeolite molecular sieve is 2% of the mass of the absolute ethyl alcohol, and the mass of the tetraethylenepentamine is 0.85% of the mass of the absolute ethyl alcohol) into a round-bottom flask, and placing the round-bottom flask into an ultrasonic instrument, wherein the ultrasonic treatment temperature is 50 ℃, the ultrasonic treatment power is 300W, the stirring rate is 200r/min, and the ultrasonic treatment time is 3 h; then carrying out rotary evaporation at the temperature of 85 ℃ for 3 h; and finally, drying in a constant-temperature oven at the temperature of 80 ℃ for 12 hours to finally prepare the multifunctional hybrid zeolite molecular sieve.

Example 5

The synthesis method of the multifunctional hybrid zeolite molecular sieve provided by the embodiment comprises the following steps:

1) 5.669g of 3-mercaptopropyltriethoxysilane was weighed into a 100mL polytetrafluoroethylene beaker, and 50mL of deionized water and 1.48g of NaOH were added to prepare an aqueous NaOH solution, which was dispersed under ultrasonic conditions at room temperature until the solid was completely dissolved, and the ultrasonic power was 400W. Then 0.049g of cobalt acetate tetrahydrate (C) was added to the solution₄H₆CoO₄·4H₂O), fully stirring for 3 hours to obtain a solution I; solution I0.65 g NaAlO was added with stirring₂3.615g of fumed silica were then added slowly and stirring was continued for 3h to form a reaction gel. The formed reaction gel is dried in an oven at 80 ℃ to obtain dry gel, the water content of the dry gel is controlled to be 4g, and the molar ratio of the aluminum source, the organic silicon source, the inorganic silicon source, the sodium source, the non-noble metal source and the water in the dry gel is 1:6:15.2:5.68:0.05: 56.

2) And grinding the dry gel into powder, and transferring the powder into a stainless steel reaction kettle with a polytetrafluoroethylene lining. The stainless steel reaction kettle is sealed and then is placed in a constant temperature oven at 170 ℃ for crystallization for 72 hours. Taking out, rapidly chilling with cold water, filtering, washing to neutrality, and drying in an oven at 80 deg.C to obtain the hybrid zeolite molecular sieve.

3) And then carrying out organic amine functionalization treatment, specifically comprising the following steps: adding 0.214g of organic amine tetraethylenepentamine, 0.5g of the hybrid zeolite molecular sieve and 25g of absolute ethyl alcohol (the mass of the hybrid zeolite molecular sieve is 2% of the mass of the absolute ethyl alcohol, and the mass of the tetraethylenepentamine is 0.85% of the mass of the absolute ethyl alcohol) into a round-bottom flask, and placing the round-bottom flask into an ultrasonic instrument, wherein the ultrasonic treatment temperature is 50 ℃, the ultrasonic treatment power is 300W, the stirring rate is 100r/min, and the ultrasonic treatment time is 3 h; then carrying out rotary evaporation at the temperature of 85 ℃ for 3 h; and finally, drying in a constant-temperature oven at the temperature of 80 ℃ for 12 hours to finally prepare the multifunctional hybrid zeolite molecular sieve.

Example 6

The synthesis method of the multifunctional hybrid zeolite molecular sieve provided by the embodiment comprises the following steps:

1) weighing 1.5g of 3-mercaptopropyltriethoxysilane in a 100mL polytetrafluoroethylene beaker, adding 50mL of deionized water and 1.48g of NaOH to prepare a NaOH aqueous solution, and dispersing under the ultrasonic condition at room temperature until the solid is completely dissolved, wherein the ultrasonic power is 400W. Then 0.148g of cobalt acetate tetrahydrate (C) was added to the solution₄H₆CoO₄·4H₂O), fully stirring for 3 hours to obtain a solution I; solution I0.65 g NaAlO was added with stirring₂4.627g of fumed silica were then added slowly and stirring was continued for 3h to form a reaction gel. The formed reaction gel is dried in an oven at 80 ℃ to obtain dry gel, the water content of the dry gel is controlled to be 4g, and the molar ratio of the aluminum source, the organic silicon source, the inorganic silicon source, the sodium source, the non-noble metal source and the water in the dry gel is 1:1.6:19.4:5.68:0.15: 56.

2) And grinding the dry gel into powder, and transferring the powder into a stainless steel reaction kettle with a polytetrafluoroethylene lining. The stainless steel reaction kettle is sealed and then is placed in a constant temperature oven at 170 ℃ for crystallization for 72 hours. Taking out, rapidly chilling with cold water, filtering, washing to neutrality, and drying in an oven at 80 deg.C to obtain the hybrid zeolite molecular sieve.

3) And then carrying out organic amine functionalization treatment, specifically comprising the following steps: adding 0.214g of organic amine tetraethylenepentamine, 0.5g of the hybrid zeolite molecular sieve and 25g of absolute ethyl alcohol (the mass of the hybrid zeolite molecular sieve is 2% of the mass of the absolute ethyl alcohol, and the mass of the tetraethylenepentamine is 0.85% of the mass of the absolute ethyl alcohol) into a round-bottom flask, and placing the round-bottom flask into an ultrasonic instrument, wherein the ultrasonic treatment temperature is 70 ℃, the ultrasonic treatment power is 450W, the stirring rate is 250r/min, and the ultrasonic treatment time is 5 h; then carrying out rotary evaporation at the temperature of 85 ℃ for 3 h; and finally, drying in a constant-temperature oven at the temperature of 80 ℃ for 12h to finally prepare the multifunctional hybrid zeolite molecular sieve catalyst.

Example 7

The synthesis method of the multifunctional hybrid zeolite molecular sieve provided by the embodiment comprises the following steps:

1) weighing 1.5g of 3-mercaptopropyltriethoxysilane in a 100mL polytetrafluoroethylene beaker, adding 50mL of deionized water and 1.48g of NaOH to prepare a NaOH aqueous solution, and dispersing under the ultrasonic condition at room temperature until the solid is completely dissolved, wherein the ultrasonic power is 400W. Then 0.049g of cobalt acetate tetrahydrate (C) was added to the solution₄H₆CoO₄·4H₂O), fully stirring for 3 hours to obtain a solution I; solution I0.65 g NaAlO was added with stirring₂4.627g of fumed silica were then added slowly and stirring was continued for 3h to form a reaction gel. The formed reaction gel is dried in an oven at 80 ℃ to obtain dry gel, the water content of the dry gel is controlled to be 7g, and the molar ratio of the aluminum source, the organic silicon source, the inorganic silicon source, the sodium source, the non-noble metal source and the water in the dry gel is 1:1.6:19.4:5.68:0.05: 98.

2) And grinding the dry gel into powder, and transferring the powder into a stainless steel reaction kettle with a polytetrafluoroethylene lining. The stainless steel reaction kettle is sealed and then is placed in a constant temperature oven at 170 ℃ for crystallization for 72 hours. Taking out, rapidly chilling with cold water, filtering, washing to neutrality, and drying in an oven at 80 deg.C to obtain the hybrid zeolite molecular sieve.

3) And then carrying out organic amine functionalization treatment, specifically comprising the following steps: adding 0.214g of organic amine tetraethylenepentamine, 0.5g of the hybrid zeolite molecular sieve and 25g of absolute ethyl alcohol (the mass of the hybrid zeolite molecular sieve is 2% of the mass of the absolute ethyl alcohol, and the mass of the tetraethylenepentamine is 0.85% of the mass of the absolute ethyl alcohol) into a round-bottom flask, and placing the round-bottom flask in an ultrasonic instrument, wherein the ultrasonic treatment temperature is 50 ℃, the ultrasonic treatment power is 350W, the stirring rate is 150r/min, and the ultrasonic treatment time is 3 h; then carrying out rotary evaporation at the temperature of 85 ℃ for 3 h; and finally, drying in a constant-temperature oven at the temperature of 80 ℃ for 12 hours to finally prepare the multifunctional hybrid zeolite molecular sieve.

Example 8

The synthesis method of the multifunctional hybrid zeolite molecular sieve provided by the embodiment comprises the following steps:

1) weighing 1.5g of 3-mercaptopropyltriethoxysilane in a 100mL polytetrafluoroethylene beaker, adding 50mL of deionized water and 1.745g of NaOH to prepare NaOH aqueous solution, and dispersing under the ultrasonic condition at room temperature until the solid is completely dissolved, wherein the ultrasonic power is 400W. Then 0.049g of cobalt acetate tetrahydrate (C) was added to the solution₄H₆CoO₄·4H₂O), fully stirring for 3 hours to obtain a solution I; solution I0.65 g NaAlO was added with stirring₂4.627g of fumed silica were then added slowly and stirring was continued for 3h to form a reaction gel. The formed reaction gel is dried in an oven at 80 ℃ to obtain dry gel, the water content of the dry gel is controlled to be 4g, and the molar ratio of the aluminum source, the organic silicon source, the inorganic silicon source, the sodium source, the non-noble metal source and the water in the dry gel is 1:1.6:19.4:6.5:0.05: 56.

2) And grinding the dry gel into powder, and transferring the powder into a stainless steel reaction kettle with a polytetrafluoroethylene lining. The stainless steel reaction kettle is sealed and then is placed in a constant temperature oven at 170 ℃ for crystallization for 72 hours. Taking out, rapidly chilling with cold water, filtering, washing to neutrality, and drying in an oven at 80 deg.C to obtain the hybrid zeolite molecular sieve.

3) And then carrying out organic amine functionalization treatment, specifically comprising the following steps: adding 0.055g of organic amine tetraethylenepentamine, 0.5g of the hybrid zeolite molecular sieve and 25g of absolute ethyl alcohol (the mass of the hybrid zeolite molecular sieve is 2% of the mass of the absolute ethyl alcohol, and the mass of the tetraethylenepentamine is 0.22% of the mass of the absolute ethyl alcohol) into a round-bottom flask, and placing the round-bottom flask in an ultrasonic instrument, wherein the ultrasonic treatment temperature is 50 ℃, the ultrasonic treatment power is 300W, the stirring rate is 150r/min, and the ultrasonic treatment time is 3 h; then carrying out rotary evaporation at the temperature of 85 ℃ for 3 h; and finally, drying in a constant-temperature oven at the temperature of 80 ℃ for 12 hours to finally prepare the multifunctional hybrid zeolite molecular sieve.

Example 9

The synthesis method of the multifunctional hybrid zeolite molecular sieve provided by the embodiment comprises the following steps:

1) weighing 1.5g of 3-mercaptopropyltriethoxysilane in a 100mL polytetrafluoroethylene beaker, adding 50mL of deionized water and 1.745g of NaOH to prepare NaOH aqueous solution, and dispersing under the ultrasonic condition at room temperature until the solid is completely dissolved, wherein the ultrasonic power is 400W. Then 0.049g of cobalt acetate tetrahydrate (C) was added to the solution₄H₆CoO₄·4H₂O), fully stirring for 3 hours to obtain a solution I; solution I0.65 g NaAlO was added with stirring₂4.627g of fumed silica were then added slowly and stirring was continued for 3h to form a reaction gel. Drying the formed reaction gel in an oven at 80 ℃ to obtain dry gel, and controlling the water content of the dry gel to be 4g, wherein the molar ratio of an aluminum source to an organic silicon source to an inorganic silicon source to a sodium source to a non-noble metal source to water in the dry gel is 1:1.6:19.4:6.5:0.05: 56;

2) and grinding the dry gel into powder, and transferring the powder into a stainless steel reaction kettle with a polytetrafluoroethylene lining. The stainless steel reaction kettle is sealed and then is placed in a constant temperature oven at 170 ℃ for crystallization for 72 hours. Taking out, rapidly chilling with cold water, filtering, washing to neutrality, and drying in an oven at 80 deg.C to obtain the hybrid zeolite molecular sieve.

3) And then carrying out organic amine functionalization treatment, specifically comprising the following steps: adding 0.25g of organic amine tetraethylenepentamine, 0.5g of the hybrid zeolite molecular sieve and 25g of absolute ethyl alcohol (the mass of the hybrid zeolite molecular sieve is 2% of the mass of the absolute ethyl alcohol, and the mass of the tetraethylenepentamine is 1% of the mass of the absolute ethyl alcohol) into a round-bottom flask, and placing the round-bottom flask in an ultrasonic instrument, wherein the ultrasonic treatment temperature is 50 ℃, the ultrasonic treatment power is 350W, the stirring rate is 150r/min, and the ultrasonic treatment time is 3 h; then carrying out rotary evaporation at the temperature of 85 ℃ for 3 h; and finally, drying in a constant-temperature oven at the temperature of 80 ℃ for 12 hours to finally prepare the multifunctional hybrid zeolite molecular sieve.

Example 10

The synthesis method of the multifunctional hybrid zeolite molecular sieve provided by the embodiment comprises the following steps:

1) weighing 1.5g of 3-mercaptopropyltriethoxysilane in a 100mL polytetrafluoroethylene beaker, adding 50mL of deionized water and 1.48g of NaOH to prepare a NaOH aqueous solution, and dispersing under the ultrasonic condition at room temperature until the solid is completely dissolved, wherein the ultrasonic power is 400W. Then 0.049g of cobalt acetate tetrahydrate (C) was added to the solution₄H₆CoO₄·4H₂O), fully stirring for 3 hours to obtain a solution I; solution I0.65 g NaAlO was added with stirring₂4.627g of fumed silica were then added slowly and stirring was continued for 3h to form a reaction gel. The formed reaction gel is dried in an oven at 80 ℃ to obtain dry gel, the water content of the dry gel is controlled to be 4g, and the molar ratio of the aluminum source, the organic silicon source, the inorganic silicon source, the sodium source, the non-noble metal source and the water in the dry gel is 1:1.6:19.4:5.68:0.05: 56.

2) And grinding the dry gel into powder, and transferring the powder into a stainless steel reaction kettle with a polytetrafluoroethylene lining. The stainless steel reaction kettle is sealed and then is placed in a constant temperature oven at 170 ℃ for crystallization for 72 hours. Taking out, rapidly chilling with cold water, filtering, washing to neutrality, and drying in an oven at 80 deg.C to obtain the hybrid zeolite molecular sieve.

3) And then carrying out organic amine functionalization treatment, specifically comprising the following steps: adding 0.5g of organic amine tetraethylenepentamine, 0.5g of the hybrid zeolite molecular sieve and 25g of absolute ethyl alcohol (the mass of the hybrid zeolite molecular sieve is 2% of the mass of the absolute ethyl alcohol, and the mass of the tetraethylenepentamine is 2% of the mass of the absolute ethyl alcohol) into a round-bottom flask, and placing the round-bottom flask in an ultrasonic instrument, wherein the ultrasonic treatment temperature is 50 ℃, the ultrasonic treatment power is 600W, the stirring rate is 150r/min, and the ultrasonic treatment time is 3 h; then carrying out rotary evaporation at the temperature of 85 ℃ for 3 h; and finally, drying in a constant-temperature oven at the temperature of 80 ℃ for 12 hours to finally prepare the multifunctional hybrid zeolite molecular sieve.

Example 11

The synthesis method of the multifunctional hybrid zeolite molecular sieve provided by the embodiment comprises the following steps:

1) weighing 1.5g of 3-mercaptopropyltriethoxysilane in a 100mL polytetrafluoroethylene beaker, adding 50mL of deionized water and 1.48g of NaOH to prepare a NaOH aqueous solution, and dispersing under the ultrasonic condition at room temperature until the solid is completely dissolved, wherein the ultrasonic power is 200W. Then 0.049g of cobalt acetate tetrahydrate (C) was added to the solution₄H₆CoO₄·4H₂O), fully stirring for 3 hours to obtain a solution I; solution I0.65 g NaAlO was added with stirring₂4.627g of fumed silica were then added slowly and stirring was continued for 3h to form a reaction gel. The formed reaction gel is dried in an oven at 80 ℃ to obtain dry gel, the water content of the dry gel is controlled to be 4g, and the molar ratio of the aluminum source, the organic silicon source, the inorganic silicon source, the sodium source, the non-noble metal source and the water in the dry gel is 1:1.6:19.4:5.68:0.05: 56.

2) And grinding the dry gel into powder, and transferring the powder into a stainless steel reaction kettle with a polytetrafluoroethylene lining. The stainless steel reaction kettle is sealed and then is placed in a constant temperature oven at 170 ℃ for crystallization for 72 hours. Taking out, rapidly chilling with cold water, filtering, washing to neutrality, and drying in an oven at 80 deg.C to obtain the hybrid zeolite molecular sieve.

3) And then carrying out organic amine functionalization treatment, specifically comprising the following steps: adding 0.214g of organic amine tetraethylenepentamine, 0.5g of the hybrid zeolite molecular sieve and 25g of absolute ethyl alcohol (the mass of the hybrid zeolite molecular sieve is 2 percent of the mass of the absolute ethyl alcohol, and the mass of the tetraethylenepentamine is 0.85 percent of the mass of the absolute ethyl alcohol) into a round-bottom flask, and placing the round-bottom flask into an ultrasonic instrument, wherein the ultrasonic treatment temperature is 70 ℃, the ultrasonic treatment power is 400W, the stirring rate is 300r/min, and the ultrasonic treatment time is 4 h; then carrying out rotary evaporation at the temperature of 85 ℃ for 3 h; and finally, drying in a constant-temperature oven at the temperature of 80 ℃ for 12 hours to finally prepare the multifunctional hybrid zeolite molecular sieve.

Example 12

The synthesis method of the multifunctional hybrid zeolite molecular sieve provided by the embodiment comprises the following steps:

1) 1.5g of 3-mercaptopropyltriethoxysilane was weighed into 100mL of polyAnd adding 50mL of deionized water and 1.48g of NaOH to prepare an NaOH aqueous solution in a tetrafluoroethylene beaker, and dispersing under the ultrasonic condition at room temperature until the solid is completely dissolved, wherein the ultrasonic power is 300W. Then 0.049g of cobalt acetate tetrahydrate (C) was added to the solution₄H₆CoO₄·4H₂O), fully stirring for 3 hours to obtain a solution I; solution I0.65 g NaAlO was added with stirring₂4.627g of fumed silica were then added slowly and stirring was continued for 3h to form a reaction gel. The formed reaction gel is dried in an oven at 80 ℃ to obtain dry gel, the water content of the dry gel is controlled to be 4g, and the molar ratio of the aluminum source, the organic silicon source, the inorganic silicon source, the sodium source, the non-noble metal source and the water in the dry gel is 1:1.6:19.4:5.68:0.05: 56.

2) And grinding the dry gel into powder, and transferring the powder into a stainless steel reaction kettle with a polytetrafluoroethylene lining. The stainless steel reaction kettle is sealed and then is placed in a constant temperature oven at 170 ℃ for crystallization for 72 hours. Taking out, rapidly chilling with cold water, filtering, washing to neutrality, and drying in an oven at 80 deg.C to obtain the hybrid zeolite molecular sieve.

3) And then carrying out organic amine functionalization treatment, specifically comprising the following steps: adding 0.214g of organic amine tetraethylenepentamine, 0.5g of the hybrid zeolite molecular sieve and 25g of absolute ethyl alcohol (the mass of the hybrid zeolite molecular sieve is 2 percent of the mass of the absolute ethyl alcohol, and the mass of the tetraethylenepentamine is 0.85 percent of the mass of the absolute ethyl alcohol) into a round-bottom flask, and placing the round-bottom flask into an ultrasonic instrument, wherein the ultrasonic treatment temperature is 80 ℃, the ultrasonic treatment power is 500W, the stirring rate is 400r/min, and the ultrasonic treatment time is 6 h; then carrying out rotary evaporation at the temperature of 85 ℃ for 3 h; and finally, drying in a constant-temperature oven at the temperature of 80 ℃ for 12 hours to finally prepare the multifunctional hybrid zeolite molecular sieve.

Example 13

The synthesis method of the multifunctional hybrid zeolite molecular sieve provided by the embodiment comprises the following steps:

1) 3.167g of 3-mercaptopropyltriethoxysilane is weighed in a 100mL polytetrafluoroethylene beaker, 50mL of deionized water and 1.48g of NaOH prepared NaOH aqueous solution are added, the mixture is dispersed under the ultrasonic condition at room temperature until the solid is completely dissolved, and the ultrasonic power is highIs 400W. Then 0.049g of cobalt acetate tetrahydrate (C) was added to the solution₄H₆CoO₄·4H₂O), fully stirring for 3 hours to obtain a solution I; solution I0.65 g NaAlO was added with stirring₂4.627g of fumed silica were then added slowly and stirring was continued for 3h to form a reaction gel. The formed reaction gel is dried in an oven at 80 ℃ to obtain dry gel, the water content of the dry gel is controlled to be 4g, and the molar ratio of the aluminum source, the organic silicon source, the inorganic silicon source, the sodium source, the non-noble metal source and the water in the dry gel is 1:3.35:19.4:5.68:0.05: 56.

2) And grinding the dry gel into powder, and transferring the powder into a stainless steel reaction kettle with a polytetrafluoroethylene lining. The stainless steel reaction kettle is sealed and then is placed in a constant temperature oven at 170 ℃ for crystallization for 72 hours. Taking out, rapidly chilling with cold water, filtering, washing to neutrality, and drying in an oven at 80 deg.C to obtain the hybrid zeolite molecular sieve.

3) And then carrying out organic amine functionalization treatment, specifically comprising the following steps: adding 0.214g of organic amine tetraethylenepentamine, 0.5g of the hybrid zeolite molecular sieve and 25g of absolute ethyl alcohol (the mass of the hybrid zeolite molecular sieve is 2 percent of the mass of the absolute ethyl alcohol, and the mass of the tetraethylenepentamine is 0.85 percent of the mass of the absolute ethyl alcohol) into a round-bottom flask, and placing the round-bottom flask into an ultrasonic instrument, wherein the ultrasonic treatment temperature is 100 ℃, the ultrasonic treatment power is 350W, the stirring speed is 50r/min, and the ultrasonic treatment time is 8 h; then carrying out rotary evaporation at the temperature of 85 ℃ for 3 h; and finally, drying in a constant-temperature oven at the temperature of 80 ℃ for 12 hours to finally prepare the multifunctional hybrid zeolite molecular sieve.

Comparative example 1

Comparative example 1 and example 1 differ only in that: and 3) directly carrying out ultrasonic treatment on the hybrid zeolite molecular sieve without adding organic amine. The catalytic effect of the prepared catalyst is shown in the data in the table, and the conversion rate of the cycloaddition reaction of the epoxide and the carbon dioxide is only 34%.

Comparative example 2

Comparative example 2 differs from example 1 only in that: in the step 3), the hybrid zeolite molecular sieve with the organic amine tetraethylenepentamine accounting for 0.85 percent and 2 percent of the mass percent of the organic reagent is weighed in a round-bottom flask, the hybrid zeolite molecular sieve is not subjected to ultrasonic treatment, the catalytic effect of the prepared catalyst is shown in data in a table, and the conversion rate of the cycloaddition reaction of the epoxide and the carbon dioxide is only 60 percent.

Performance testing

From FIG. 1, it can be seen that the multifunctional hybrid zeolite molecular sieve catalyst prepared by the process of the present invention exhibits a complete MOR topology.

The multifunctional hybrid zeolite molecular sieve obtained in example 1 is used as a catalyst to participate in' CO₂Cycloaddition reaction with an epoxide ", the catalytic process comprising the steps of:

adding 50mg of multifunctional hybrid zeolite molecular sieve into a stainless steel intermittent pressure reaction kettle, adding an epoxide or a mixture of the epoxide and a solvent, wherein the epoxide is 10mmol of 1, 2-epoxypropane, the solvent-free or solvent-free is 2ml of N, N-dimethylformamide, sealing the reaction kettle, replacing air in the reaction kettle with carbon dioxide gas for three times, filling the carbon dioxide gas to ensure that the pressure in the reaction kettle reaches 2MPa, starting stirring, heating the reaction kettle to ensure that the reaction temperature reaches 120 ℃, and carrying out constant-temperature reaction for 4 hours to obtain cyclic carbonate. The results are shown in table 1 for propylene oxide conversion data. (in Table 1, the catalysts prepared in comparative example 1 and comparative example 2 were catalyzed under the same reaction conditions as in the present catalytic process).

Table 2 shows the experimental data obtained after a number of cycles of the catalyst: (1, 2-propylene oxide 10 mmol; P_CO22 MPa; 2ml of solvent-free or N, N-dimethylformamide; the reaction time is 4 h; the reaction temperature was 120 ℃).

TABLE 1 catalysis results of the multifunctional hybrid zeolitic molecular sieves obtained in examples 1-13 as catalysts

TABLE 2 results of the cyclic reaction of the multifunctional hybrid zeolite molecular sieve catalyst