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CN116947068B - A method for rapidly synthesizing single-layer MWW molecular sieves by adding organic amine cosolvents - Google Patents

A method for rapidly synthesizing single-layer MWW molecular sieves by adding organic amine cosolvents

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CN116947068B
CN116947068B CN202310952355.XA CN202310952355A CN116947068B CN 116947068 B CN116947068 B CN 116947068B CN 202310952355 A CN202310952355 A CN 202310952355A CN 116947068 B CN116947068 B CN 116947068B
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organic amine
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CN116947068A (en
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郝青青
安宁
任芳
梁奔
刘梦楠
陈汇勇
孙鸣
徐龙
马晓迅
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NORTHWEST UNIVERSITY
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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
    • C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
    • C01B39/48—Other types characterised by their X-ray diffraction pattern and their defined composition using at least one organic template directing agent
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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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    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like

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  • Silicates, Zeolites, And Molecular Sieves (AREA)

Abstract

The invention discloses a method for quickly synthesizing a single-layer MWW molecular sieve by adding an organic amine cosolvent, which takes silicon dioxide sol as a silicon source, sodium metaaluminate as an aluminum source, hexamethyleneimine and dimethyl octadecyl [3- (trimethoxy silicon-based) propyl ] ammonium chloride as a structure directing agent, and organic amines such as ethylenediamine, diethylamine and the like as the cosolvent, and synthesizes the single-layer MWW molecular sieve by a one-step hydrothermal method. The synthesis method is simple and feasible, the yield of the synthesized product is high, and the nucleation rate is effectively accelerated by adding the organic amine cosolvent such as ethylenediamine, diethylamine and the like, so that the crystallization time is greatly shortened, and the single-layer MWW molecular sieve with good crystallinity is obtained, thereby providing possibility for being applied to industrial production.

Description

Method for rapidly synthesizing monolayer MWW molecular sieve by adding organic amine cosolvent
Technical Field
The invention belongs to the technical field of molecular sieves and porous materials, and particularly relates to a method for rapidly synthesizing a single-layer MWW molecular sieve by adding an organic amine cosolvent.
Background
MCM-22 is a layered molecular sieve with MWW topological structure, and is widely applied to reactions such as catalytic cracking and alkylation due to its unique pore structure. The structure of MCM-22 was studied extensively by Leonow icz et al in 1994, and the MWW cage {4 35663[43 ] } was proposed as its primary building block. The MWW cages are connected by oxygen bridges in the horizontal direction to form a monolithic layer of MCM-22, the thickness of which is about 2.5nm, and the monolithic layers are connected by intra-layer ten-membered ring channels in the vertical direction. MCM-22P is a precursor of MCM-22, and has a two-dimensional lamellar structure, and is formed by sequentially stacking MWW single-sheet layers in the vertical direction, wherein acting force between the single-sheet layers is hydrogen bond formed between Si-OH. The hydrogen bond can be post-treated because of weak acting force. For example, a monolayer molecular sieve may be prepared by ultrasonic exfoliation after swelling of MCM-22P.
ITQ-2 is a zeolite molecular sieve material having a single-layer structure, which is obtained by initially swelling MCM-22P with a cationic surfactant (CTAB) under alkaline conditions (TPAOH) and then ultrasonic stripping. Compared with MCM-22, the ITQ-2 has the advantages of large external specific surface area, short diffusion path and accessible acid position, thereby being more beneficial to the reaction participated by macromolecules. However, the traditional preparation method is complicated, and comprises three steps of MCM-22P synthesis, swelling and stripping, and the severe swelling process (pH=13.0-13.8 and T=80 ℃) can lead to partial amorphization of the molecular sieve, so that single-layer MWW molecular sieve is formed into a research hot spot through one-step hydrothermal synthesis.
Luo et al (chem. Sci.2015,6, 6320-6324) successfully synthesized a single-layer MWW nanosheet molecular sieve, designated MIT-1, in one step using a novel bifunctional structure directing agent (designated Ada-i-16) synthesized by self-design in 2015. Margarit et al (Angew.chem.int.ed.2015, 54, 13724-13728) also achieved one-step synthesis of MWW two-dimensional layered molecular sieve DS-ITQ-2 by co-action of self-designed structure directing agent C 16DC1 with HMI. However, the above-mentioned research has the disadvantages that the template agent with a special structure is not easy to obtain and has high cost, and is not suitable for industrial production. Chinese patent CN 110615446A reports the controlled synthesis of single-to-oligolayer MWW nanosheet zeolites using commonly used commercial long chain amphoteric organosilanes (TPOAC) as auxiliary structure directing agents. The method has the defects that the single-layer MWW zeolite is obtained after 14 days under the condition of lower alkalinity, and the long crystallization time is unfavorable for being applied to industrialization.
Disclosure of Invention
The invention aims to provide a method for synthesizing a single-layer MWW molecular sieve in a short time by adding an organic amine cosolvent into gel of the double-template oriented single-layer MWW molecular sieve.
In order to achieve the above object, the technical scheme adopted by the present invention comprises the following steps:
Step 1, weighing raw materials of sodium hydroxide, sodium metaaluminate, silica sol, hexamethyleneimine, dimethyl octadecyl [3- (trimethoxysilyl) propyl ] ammonium chloride, deionized water and an organic amine cosolvent according to a molar ratio of SiO2/Al2O3＝30、NaOH/SiO2＝0.10～0.15、HMI/SiO2＝0.25～0.35、TPOAC/SiO2＝0.025～0.035、 of the organic amine cosolvent/SiO 2＝0.1～0.8、H2O/SiO2 = 45-52, wherein HMI is hexamethyleneimine, TPOAC is dimethyl octadecyl [3- (trimethoxysilyl) propyl ] ammonium chloride, and the organic amine cosolvent is any one or more of ethylenediamine, diethylamine, triethylamine and mercaptoethylamine;
Step 2, sequentially dissolving sodium hydroxide and sodium metaaluminate into deionized water, gradually dropwise adding silicon dioxide sol in a stirring state, stirring for 20-30 minutes at room temperature, then adding hexamethyleneimine, dimethyl octadecyl [3- (trimethoxy silicon) propyl ] ammonium chloride and organic amine cosolvent, and continuously stirring for 1-2 hours at room temperature;
Transferring the mixed solution obtained in the step 2 into a polytetrafluoroethylene-lined hydrothermal reaction kettle, stirring and crystallizing for 3-6 days at 150 ℃ under a closed condition, taking out the hydrothermal reaction kettle after the reaction is finished, putting the hydrothermal reaction kettle into cold water for quenching, centrifuging the reaction solution, washing the reaction solution to be neutral, and finally drying the reaction solution at 80-120 ℃;
And 4, grinding the solid product obtained after the drying in the step 3 into powder, and then placing the powder in a muffle furnace for roasting for 6 hours at 500-550 ℃ to obtain the single-layer MWW molecular sieve.
In the above step 1, the starting materials are preferably weighed according to a molar ratio SiO2/Al2O3＝30、NaOH/SiO2＝0.15、HMI/SiO2＝0.3、TPOAC/SiO2＝0.035、 of organic amine cosolvent/SiO 2＝0.5、H2O/SiO2 =51.4.
In the step 3, the crystallization is preferably carried out under a sealed condition at 150 ℃ and 50-60 rpm for 4-5 days.
The beneficial effects of the invention are as follows:
according to the invention, silica sol is used as a silicon source, sodium metaaluminate is used as an aluminum source, hexamethyleneimine and dimethyl octadecyl [3- (trimethoxy silicon based) propyl ] ammonium chloride are used as structure directing agents, organic amine such as ethylenediamine and diethylamine is used as a cosolvent, and a one-step hydrothermal method is adopted to synthesize the single-layer MWW molecular sieve. The preparation method is simple and easy to implement, the yield of the synthesized product is high, and the nucleation rate is effectively accelerated by adding the organic amine cosolvent such as ethylenediamine, diethylamine and the like, so that the crystallization time is greatly shortened, and the single-layer MWW molecular sieve with good crystallinity is obtained, thereby providing possibility for being applied to industrial production.
Drawings
FIG. 1 is an XRD pattern of MCM-22, the MWW molecular sieves prepared in comparative example 1 and example 1.
FIG. 2 is an N 2 -adsorption and desorption isotherm plot of an MCM-22 molecular sieve and a monolayer MWW molecular sieve prepared in example 1.
Fig. 3 is a TEM image of a single-layer MWW molecular sieve prepared in example 1.
Fig. 4 is an XRD pattern of the single-layer MWW molecular sieve prepared in examples 2 to 5.
Detailed Description
The invention will be described in further detail with reference to the drawings and practical examples, but the scope of the invention is not limited to these examples.
Example 1
1. 0.123G sodium hydroxide, 0.127g sodium metaaluminate, 2.325g silica sol, 0.469g HMI, 0.64g TPOAC, 0.465g EDA, 12.54g deionized water were weighed according to a molar ratio SiO2/Al2O3＝30、NaOH/SiO2＝0.15、HMI/SiO2＝0.3、TPOAC/SiO2＝0.035、EDA/SiO2＝0.5、H2O/SiO2＝51.4,.
2. 0.123G of sodium hydroxide and 0.127g of sodium metaaluminate are sequentially dissolved in 12.54g of deionized water, 2.325g of silica sol is dropwise added under stirring after complete dissolution, stirring is carried out for 30 minutes at room temperature, then 0.469g of HMI, 0.64g of TPOAC and 0.465g of EDA are sequentially added, and stirring is continued for 2 hours at room temperature.
3. Transferring the mixed solution obtained in the step 2 into a polytetrafluoroethylene-lined hydrothermal reaction kettle, putting the hydrothermal reaction kettle into a homogeneous phase reactor, reacting for 114 hours at the rotating speed of 60 revolutions per minute and 150 ℃, taking out the hydrothermal reaction kettle after the reaction is finished, putting the hydrothermal reaction kettle into cold water for quenching, carrying out centrifugal water washing on the reaction solution to be neutral, and finally drying a sample at 120 ℃ for 12 hours.
4. Grinding the solid product dried in the step 3 into powder, and placing the powder in a muffle furnace for roasting at 550 ℃ for 6 hours to obtain the single-layer MWW molecular sieve with the yield of 95.5%.
Comparative example 1
In example 1, ethylenediamine was not added, and the other steps were the same as in example 1.
As can be seen from fig. 1, MCM-22 presents a clear (002) diffraction peak, and the (101) and (102) diffraction peaks between 2θ=8° to 10 ° are clearly split, indicating a highly ordered arrangement of the MWW layers. The XRD pattern of the sample of comparative example 1 clearly shows that the intensity of diffraction peak is low, and the sample contains a large amount of amorphous substances, which means that the crystallization time is too short to form a single-layer MWW molecular sieve with good crystallinity when ethylenediamine is not added. The XRD pattern of the sample obtained in example 1 has no (002) diffraction peak, and the (101) and (102) diffraction peaks are combined into one broad peak, which indicates that the organosilane is uniformly bonded to the MWW sheet, so that the MWW sheet is arranged randomly along the c-axis, and a single-layer MWW molecular sieve with good crystallinity is obtained in a short time. As can be seen from fig. 2, in the high-pressure zone, compared with MCM-22, the two isotherms of the single-layer MWW molecular sieve obtained in example 1 do not coincide to form a hysteresis loop, which is an adsorption isotherm of a typical mesoporous material, indicating the presence of mesopores in the crystallized product. As can be seen from fig. 3, the MWW molecular sieve prepared in example 1 is a monolayer nanosheet.
Example 2
1. 0.123G sodium hydroxide, 0.127g sodium metaaluminate, 2.325g silica sol, 0.469g HMI, 0.64g TPOAC, 0.744g EDA, 12.54g deionized water were weighed according to a molar ratio SiO2/Al2O3＝30、NaOH/SiO2＝0.15、HMI/SiO2＝0.3、TPOAC/SiO2＝0.035、EDA/SiO2＝0.8、H2O/SiO2＝51.4,.
2. After 0.123g of sodium hydroxide and 0.127g of sodium metaaluminate are sequentially dissolved in 12.54g of deionized water and completely dissolved, 2.325g of silica sol is dropwise added under stirring, stirring is carried out for 30 minutes at room temperature, then 0.469g of HMI, 0.64g of TPOAC and 0.744g of EDA are sequentially added, and stirring is continued for 2 hours at room temperature.
3. Transferring the mixed solution obtained in the step 2 into a polytetrafluoroethylene-lined hydrothermal reaction kettle, putting the hydrothermal reaction kettle into a homogeneous phase reactor, reacting for 114 hours at the rotating speed of 60 revolutions per minute and at the temperature of 150 ℃, taking out the hydrothermal reaction kettle after the reaction is finished, putting the hydrothermal reaction kettle into cold water for quenching, carrying out centrifugal water washing on the reaction solution to be neutral, and finally drying the sample at the temperature of 120 ℃ for 12 hours.
4. The solid product dried in step 3 was ground into a powder and calcined in a muffle furnace at 550 ℃ for 6 hours to obtain a single-layer MWW molecular sieve (see fig. 4) with a yield of 95.8%.
Example 3
1. 0.123G sodium hydroxide, 0.127g sodium metaaluminate, 2.325g silica sol, 0.469g HMI, 0.64g TPOAC, 0.238. 0.238gMEA and 12.54g deionized water are weighed according to a molar ratio of SiO2/Al2O3＝30、NaOH/SiO2＝0.15、HMI/SiO2＝0.3、TPOAC/SiO2＝0.035、MEA/SiO2＝0.2、H2O/SiO2＝51.4,.
2. 0.123G of sodium hydroxide and 0.127g of sodium metaaluminate are sequentially dissolved in 12.54g of deionized water, 2.325g of silica sol is dropwise added under stirring after complete dissolution, stirring is carried out for 30 minutes at room temperature, then 0.469g of HMI, 0.64g of TPOAC and 0.238g of gMEA are sequentially added, and stirring is continued for 2 hours at room temperature.
3. Transferring the mixed solution obtained in the step 2 into a polytetrafluoroethylene-lined hydrothermal reaction kettle, putting the hydrothermal reaction kettle into a homogeneous phase reactor, reacting for 5 days at the rotating speed of 60 rpm and the temperature of 150 ℃, taking out the hydrothermal reaction kettle after the reaction is finished, putting the hydrothermal reaction kettle into cold water for quenching, carrying out centrifugal water washing on the reaction solution to be neutral, and finally drying the sample at the temperature of 120 ℃ for 12 hours.
4. The solid product dried in step 3 was ground into a powder and calcined in a muffle furnace at 550 ℃ for 6 hours to obtain a single-layer MWW molecular sieve (see fig. 4) with a yield of 95.1%.
Example 4
1. 0.123G sodium hydroxide, 0.127g sodium metaaluminate, 2.325g silica sol, 0.469g HMI, 0.64g TPOAC, 0.78gTEA, 12.54g deionized water were weighed according to a molar ratio SiO2/Al2O3＝30、NaOH/SiO2＝0.15、HMI/SiO2＝0.3、TPOAC/SiO2＝0.035、TEA/SiO2＝0.5、H2O/SiO2＝51.4,.
2. 0.123G of sodium hydroxide and 0.127g of sodium metaaluminate are sequentially dissolved in 12.54g of deionized water, 2.325g of silica sol is dropwise added under stirring after complete dissolution, stirring is carried out for 30 minutes at room temperature, then 0.469g of HMI, 0.64g of TPOAC and 0.78g of TEA are sequentially added, and stirring is continued for 2 hours at room temperature.
3. Transferring the mixed solution obtained in the step 2 into a polytetrafluoroethylene-lined hydrothermal reaction kettle, putting the hydrothermal reaction kettle into a homogeneous phase reactor, reacting for 114 hours at the rotating speed of 60 revolutions per minute and 150 ℃, taking out the hydrothermal reaction kettle after the reaction is finished, putting the hydrothermal reaction kettle into cold water for quenching, carrying out centrifugal water washing on the reaction solution to be neutral, and finally drying a sample at 120 ℃ for 12 hours.
4. The solid product dried in step 3 was ground into a powder and calcined in a muffle furnace at 550 ℃ for 6 hours to obtain a single-layer MWW molecular sieve (see fig. 4) with a yield of 95.4%.
Example 5
1. 0.123G of sodium hydroxide, 0.127g of sodium metaaluminate, 2.325g of silica sol, 0.469g of HMI, 0.54g of TPOAC, 0.566g of DEA and 10.8g of deionized water are weighed according to a molar ratio of SiO2/Al2O3＝30、NaOH/SiO2＝0.15、HMI/SiO2＝0.3、TPOAC/SiO2＝0.03、DEA/SiO2＝0.5、H2O/SiO2＝45,.
2. 0.123G of sodium hydroxide and 0.127g of sodium metaaluminate are sequentially dissolved in 10.8g of deionized water, 2.325g of silica sol is dropwise added under stirring after complete dissolution, stirring is carried out for 30 minutes at room temperature, then 0.469g of HMI, 0.54g of TPOAC and 0.566g of DEA are sequentially added, and stirring is continued for 2 hours at room temperature.
3. Transferring the mixed solution obtained in the step 2 into a polytetrafluoroethylene-lined hydrothermal reaction kettle, putting the hydrothermal reaction kettle into a homogeneous phase reactor, reacting for 6 days at the rotating speed of 60 rpm and 150 ℃, taking out the hydrothermal reaction kettle after the reaction is finished, putting the hydrothermal reaction kettle into cold water for quenching, carrying out centrifugal water washing on the reaction solution to be neutral, and finally drying the sample at 120 ℃ for 12 hours.
4. The solid product dried in step 3 was ground into a powder and calcined in a muffle furnace at 550 ℃ for 6 hours to obtain a single-layer MWW molecular sieve (see fig. 4) with a yield of 94.6%.

Claims (3)

1.一种通过添加有机胺助溶剂快速合成单层MWW分子筛的方法，其特征在于该方法由下述步骤组成：1. A method for rapidly synthesizing a single-layer MWW molecular sieve by adding an organic amine cosolvent, characterized in that the method comprises the following steps: 步骤1：按照摩尔比为SiO2/Al2O3＝30、NaOH/SiO2＝0.10～0.15、HMI/SiO2＝0.25～0.35、TPOAC/SiO2＝0.025～0.035、有机胺助溶剂/SiO2＝0.1～0.8、H2O/SiO2＝45～52，其中HMI为六亚甲基亚胺、TPOAC为二甲基十八烷基[3-(三甲氧基硅基)丙基]氯化铵、有机胺助溶剂为乙二胺、二乙胺、三乙胺、巯基乙胺中任意一种或多种，称取原料氢氧化钠、偏铝酸钠、二氧化硅溶胶、六亚甲基亚胺、二甲基十八烷基[3-(三甲氧基硅基)丙基]氯化铵、去离子水、有机胺助溶剂；Step 1: weighing raw materials sodium hydroxide, sodium metaaluminate, silica sol, hexamethyleneimine, dimethyloctadecyl[ 3- (trimethoxysilyl)propyl]ammonium chloride, deionized water, and organic amine cosolvent according to the molar ratio of SiO2 / Al2O3 = 30 , NaOH/ SiO2 =0.10-0.15, HMI/ SiO2 =0.25-0.35, TPOAC / SiO2 =0.025-0.035, organic amine cosolvent/SiO2=0.1-0.8, and H2O/SiO2=45-52, wherein HMI is hexamethyleneimine, TPOAC is dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride, and the organic amine cosolvent is any one or more of ethylenediamine, diethylamine, triethylamine, and mercaptoethylamine; 步骤2：将氢氧化钠和偏铝酸钠依次溶于去离子水中，在搅拌状态下逐渐滴加二氧化硅溶胶，室温条件下搅拌20～30分钟，然后再加入六亚甲基亚胺、二甲基十八烷基[3-(三甲氧基硅基)丙基]氯化铵和有机胺助溶剂，室温持续搅拌1～2小时；Step 2: Sodium hydroxide and sodium aluminate are dissolved in deionized water in sequence, and silica sol is gradually added dropwise under stirring, and stirred at room temperature for 20 to 30 minutes. Then, hexamethyleneimine, dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride and an organic amine cosolvent are added, and stirring is continued at room temperature for 1 to 2 hours; 步骤3：将步骤2所得混合液转移至聚四氟乙烯内衬的水热反应釜中，在密闭条件下150℃搅拌晶化3～6天；反应完成后，取出水热反应釜放入冷水中骤冷，将反应液离心、水洗至中性，最后80～120℃下干燥；Step 3: The mixed solution obtained in step 2 is transferred to a polytetrafluoroethylene-lined hydrothermal reactor, and stirred and crystallized at 150°C under closed conditions for 3 to 6 days. After the reaction is completed, the hydrothermal reactor is taken out and quenched in cold water. The reaction solution is centrifuged and washed with water until neutral, and finally dried at 80 to 120°C. 步骤4：将步骤3干燥后的固体产物研磨成粉末，然后置于马弗炉中500～550℃下焙烧6小时，得到单层MWW分子筛。Step 4: Grind the solid product dried in step 3 into powder, and then calcine it in a muffle furnace at 500-550° C. for 6 hours to obtain a single-layer MWW molecular sieve. 2.根据权利要求1所述的通过添加有机胺助溶剂快速合成单层MWW分子筛的方法，其特征在于：步骤1中，按照摩尔比为SiO2/Al2O3＝30、NaOH/SiO2＝0.15、HMI/SiO2＝0.3、TPOAC/SiO2＝0.035、有机胺助溶剂/SiO2＝0.5、H2O/SiO2＝51.4称取各原料。2. The method for rapidly synthesizing a single-layer MWW molecular sieve by adding an organic amine cosolvent according to claim 1, characterized in that: in step 1, the raw materials are weighed according to the molar ratios of SiO2 / Al2O3 = 30 , NaOH/ SiO2 =0.15, HMI/ SiO2 =0.3, TPOAC/ SiO2 =0.035, organic amine cosolvent/ SiO2 =0.5, and H2O / SiO2 =51.4. 3.根据权利要求1所述的通过添加有机胺助溶剂快速合成单层MWW分子筛的方法，其特征在于：步骤3中，在密闭条件下150℃、50～60转/分钟搅拌晶化4～5天。3. The method for rapidly synthesizing a single-layer MWW molecular sieve by adding an organic amine cosolvent according to claim 1, characterized in that: in step 3, the crystallization is carried out under closed conditions at 150°C and 50-60 rpm for 4-5 days.
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CN110615446A (en) * 2019-11-12 2019-12-27 西北大学 Method for one-step synthesis of single-layer MWW molecular sieve by aid of amphiphilic organosilane

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CN110615446A (en) * 2019-11-12 2019-12-27 西北大学 Method for one-step synthesis of single-layer MWW molecular sieve by aid of amphiphilic organosilane

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