CN108529645B - Preparation method of prismatic microporous small-grain mordenite molecular sieve - Google Patents
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Abstract
The preparation method of the prismatic microporous small-grain mordenite molecular sieve comprises the following steps of: the preparation method comprises the steps of preparing an aluminum source clear liquid, uniformly mixing an aluminum source, sodium hydroxide and deionized water, adding an organic amine template agent in a certain proportion, and uniformly stirring to obtain an alkaline aluminum source clear liquid; secondly, preparing a crystal precursor, dropwise adding a silicon source into the aluminum source clear liquid, and carrying out crystallization reaction in a high-pressure kettle to obtain the crystal precursor; thirdly, centrifuging, washing, drying and roasting the crystal precursor at a high speed to obtain the prismatic microporous small-crystal-grain mordenite molecular sieve; the invention uses N, N, N-trimethyl-1-adamantyl ammonium hydroxide template agent as a single structure directing agent to synthesize the zeolite molecular sieve with a prismatic structure and a mordenite structure by a one-step method; has good adsorption, separation and catalysis performances, low synthesis cost and little pollution to the environment, and is suitable for industrial large-scale production and application.
Description
Technical Field
The invention relates to the technical field of zeolite molecular sieve synthesis, in particular to a preparation method for directly preparing a prismatic microporous small-crystal-grain mordenite molecular sieve by using N, N, N-trimethyl-1-adamantyl ammonium hydroxide as a template agent through a hydrothermal synthesis method.
Technical Field
Mordenite was first synthesized in 1948. The channel system of mordenite is composed of 12-membered ring (0.65nm x 0.70nm) and 8-membered ring (0.26nm x 0.57nm) channels along the c-axis direction and 8-membered ring (0.34nm x 0.48nm) channels along the b-axis direction. Mordenite is one of the few molecular sieves widely used in industrialization at present because of its good adsorption, separation and catalytic properties. Among them, the hydrogen mordenite shows excellent catalytic performance in toluene disproportionation, alkylation, carbonylation and toluene selective disproportionation reactions.
At present, the mordenite synthesis technology mainly comprises a template-free method and an organic template-oriented method. Chinese patent CN1837046A discloses that mordenite which is not dealuminated is used as a seed crystal, and a method of fractional crystallization is used to prepare a nano-sized mordenite molecular sieve, but the synthesis steps are relatively complicated. Chinese patent CN10500llA discloses the preparation of mordenite with high silica-alumina ratio by using cheap water glass as silicon source and non-dealuminated mordenite as seed crystal, the highest silica-alumina ratio can reach 25, but the synthesized particle size is less than 1.0 pm. Chinese patent CN1093513C discloses a "synthesis strategy for synthesizing high-silicon mordenite without organic template", in which the molar ratio of silicon to aluminum is 60, but the synthesis strategy uses F ions as mineralizer, which causes severe corrosion of equipment and environmental pollution, and the crystallization time is long.
The use of organic templating agents as structure directing agents is a basic strategy for the synthesis of different crystal forms of mordenite, with organic amines or their halogenated derivative salts being the most commonly used structure directing agents. Chinese patent CN106542538A discloses that N-bis (N-methylpyrrolidine) alkylene bromide is used as a template to synthesize a lamellar mordenite molecular sieve with high crystallinity and small crystal grain thickness, however, the two crystallization periods required by the method are about 10 days in total, and the reaction period is too long, which is not suitable for industrial application. Chinese patent CN103482645A discloses that a novel cationic surfactant is used as a template agent to directly synthesize a nano mordenite molecular sieve with hierarchical pores through hydrothermal synthesis, but the nano mordenite molecular sieve is roasted for 3-6 hours at 550-900 ℃, the required roasting temperature is high, the time is long, and the synthesis condition is not economical. Chinese patent ZL201210125572.3 discloses the preparation of layered nano mordenite molecular sieve using hexadecyl trimethyl p-methyl benzene sulfonic acid ammonium salt as template agent, however, from its XRD result, it can be found that the mordenite synthesized by this method has a low crystallinity.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of a prismatic microporous small-grain mordenite molecular sieve, which uses N, N, N-trimethyl-1-adamantyl ammonium hydroxide as a template agent to directly prepare the mordenite molecular sieve with the prismatic microporous small grains by a hydrothermal synthesis method.
In order to achieve the purpose, the invention adopts the following technical scheme.
A preparation method of a prismatic microporous small-grain mordenite molecular sieve is characterized by comprising the following steps:
(1) preparing clear liquid of aluminum source
Uniformly mixing an aluminum source, sodium hydroxide and deionized water, and magnetically stirring at room temperature to obtain a clear solution; then adding a certain proportion of organic amine template agent and stirring uniformly to obtain an alkaline aluminum source clear solution;
(2) preparation of Crystal precursors
Slowly dripping a certain proportion of silicon source into the aluminum source clarified liquid obtained in the step (1) by using a constant pressure funnel at room temperature, continuously stirring and mixing for 1.5 hours, adjusting the pH value of the reaction mixture to 12, covering and sealing the autoclave, and placing the autoclave in a rotating convection oven for crystallization reaction for 4 days at the temperature of 150-180 ℃; after the crystallization reaction is finished, naturally cooling the mixture to 20 ℃, and taking out the mixture from the high-pressure kettle to obtain a crystal precursor;
(3) centrifugal washing, drying and roasting
Separating a solid product from the crystal precursor obtained in the step (2) on a high-speed centrifuge, washing the solid product with deionized water until the pH value is 7, and drying at the temperature of 110 ℃ for 12 hours; finally, roasting the mixture for 3 hours at 550 ℃ in a muffle furnace to obtain a target product, namely the prismatic microporous small-grain mordenite molecular sieve.
Further, the aluminum source in the step (1) is one of aluminum nitrate, sodium metaaluminate, aluminum sulfate or aluminum isopropoxide.
Further, the organic amine template agent in the step (1) is N, N, N-trimethyl-1-adamantyl ammonium hydroxide.
Further, the silicon source in the step (2) is one of white carbon black, silica sol solution, column chromatography silica gel or water glass.
Furthermore, the molar ratio of the silicon source to the aluminum source to the sodium hydroxide to the organic amine template to the deionized water is 1: 0.01-0.1: 0.18-0.33: 0.1-0.3: 20-80.
The preparation method of the prismatic microporous small-grain mordenite molecular sieve has the following positive effects:
synthesizing a zeolite molecular sieve with a prismatic structure and a mordenite structure by using an N, N, N-trimethyl-1-adamantyl ammonium hydroxide template as a single structure directing agent through a one-step method; has good adsorption, separation and catalysis performances, low synthesis cost and little pollution to the environment, and is suitable for industrial large-scale production and application.
Drawings
FIG. 1 is a flow chart of the preparation method of the prismatic microporous small-grain mordenite molecular sieve.
Figure 2 is an X-ray powder diffraction (XRD) pattern of the prismatic microporous small-grained mordenite molecular sieve prepared in accordance with the present invention.
FIG. 3 is the Scanning Electron Microscope (SEM) image of the prismatic microporous small-grain mordenite molecular sieve prepared by the present invention.
Fig. 4 is a scanning electron microscope (TEM) image of the prismatic microporous small grain mordenite molecular sieve prepared in the present invention.
FIG. 5 shows the conversion rate of dimethyl ether in the prepared microporous prismatic mordenite molecular sieve with small crystal grains.
Figure 6 is a graph showing the selectivity of the prismatic microporous small-grained mordenite molecular sieve methyl acetate prepared by the present invention.
Detailed Description
The following provides a specific implementation of the preparation method of the prismatic microporous small-grain mordenite molecular sieve of the present invention, which is combined with the attached drawings to provide 7 examples. However, it should be noted that the present invention is not limited to the following embodiments.
Example 1
See fig. 1. A preparation method of a prismatic microporous small-grain mordenite molecular sieve comprises the following steps:
(1) preparing clear liquid of aluminum source
Uniformly mixing 1.7g of sodium metaaluminate, 1.5g of sodium hydroxide and 50g of deionized water, and magnetically stirring at room temperature to obtain a clear solution; then 6.7g of N, N, N-trimethyl-1-adamantyl ammonium hydroxide template agent is added and stirred evenly; obtaining the alkaline aluminum source clear solution.
(2) Preparation of Crystal precursors
And (2) slowly dripping 30.4g of silica sol solution into the aluminum source clear solution obtained in the step (1) at room temperature by using a constant-pressure funnel, continuously stirring and mixing for 1.5 hours, adjusting the pH value of the reaction mixture to 12, covering and sealing the autoclave, placing the autoclave in a rotary convection oven for crystallization reaction at the temperature of 170 ℃ for 4 days, and after the crystallization reaction is finished, naturally cooling the mixture to 20 ℃, and taking out the mixture from the autoclave to obtain a crystal precursor.
(3) Centrifugal washing, drying and roasting
Separating a solid product from the crystal precursor obtained in the step (2) on a high-speed centrifuge, washing the solid product to be neutral (the pH value is 7) by using deionized water, and drying the solid product for 12 hours at the temperature of 110 ℃; finally, roasting the mixture for 3 hours at 550 ℃ in a muffle furnace to obtain a target product, namely the prismatic microporous small-grain mordenite molecular sieve.
A Scanning Electron Microscope (SEM) image of the prismatic microporous small crystallite mordenite molecular sieve obtained in example 1 is shown in fig. 3; a scanning electron microscope (TEM) image is shown in FIG. 4.
Example 2
A preparation method of a prismatic microporous small-grain mordenite molecular sieve comprises the following steps:
(1) preparing clear liquid of aluminum source
Uniformly mixing 0.87g of sodium metaaluminate, 2.01g of sodium hydroxide and 50g of deionized water, and magnetically stirring at room temperature to obtain a clear solution; then 6.7g of N, N, N-trimethyl-1-adamantyl ammonium hydroxide template agent is added and stirred evenly; obtaining the alkaline aluminum source clear solution.
(2) Preparation of Crystal precursors
And (2) slowly dripping 30.4g of silica sol solution into the aluminum source clear solution obtained in the step (1) at room temperature by using a constant-pressure funnel, continuously stirring and mixing for 1.5 hours, adjusting the pH value of the reaction mixture to 13, covering and sealing the autoclave, placing the autoclave in a rotary convection oven for crystallization reaction at the temperature of 170 ℃ for 4 days, and after the crystallization reaction is finished, naturally cooling the mixture to 20 ℃, and taking out the mixture from the autoclave to obtain a crystal precursor.
(3) Centrifugal washing, drying and roasting
The same example 1 is followed to obtain the prismatic microporous small-grain mordenite molecular sieve.
Example 3
A preparation method of a prismatic microporous small-grain mordenite molecular sieve comprises the following steps:
(1) preparing clear liquid of aluminum source
Uniformly mixing 1.7g of aluminum nitrate, 1.5g of sodium hydroxide and 50g of deionized water, and magnetically stirring at room temperature to obtain a clear solution; then 6.7g of N, N, N-trimethyl-1-adamantyl ammonium hydroxide template agent is added and stirred evenly; obtaining the alkaline aluminum source clear solution.
(2) Preparation of Crystal precursors
Slowly dripping 30.4g of white carbon black into the aluminum source clear liquid obtained in the step (1) at room temperature by using a constant-pressure funnel, continuously stirring and mixing for 1.5 hours, adjusting the pH value of the reaction mixture to 12, covering and sealing the autoclave, placing the autoclave in a rotary convection oven for crystallization reaction at the temperature of 170 ℃ for 4 days, and after the crystallization reaction is finished, naturally cooling the mixture to 20 ℃, and taking out the mixture from the autoclave to obtain a crystal precursor.
(3) Centrifugal washing, drying and roasting
The same example 1 is followed to obtain the prismatic microporous small-grain mordenite molecular sieve.
Example 4
A preparation method of a prismatic microporous small-grain mordenite molecular sieve comprises the following steps:
(1) preparing clear liquid of aluminum source
Uniformly mixing 4.31g of aluminum sulfate, 1.5g of sodium hydroxide and 50g of deionized water, and magnetically stirring at room temperature to obtain a clear solution; then 6.7g of N, N, N-trimethyl-1-adamantyl ammonium hydroxide template agent is added and stirred evenly; obtaining the alkaline aluminum source clear solution.
(2) Preparation of Crystal precursors
And (2) slowly dripping 30.4g of column chromatography silica gel into the aluminum source clarified liquid obtained in the step (1) at room temperature by using a constant-pressure funnel, continuously stirring and mixing for 1.5 hours, adjusting the pH value of the reaction mixture to 12, covering and sealing the autoclave, placing the autoclave in a rotary convection oven for crystallization reaction at the temperature of 170 ℃ for 4 days, and after the crystallization reaction is finished, naturally cooling the mixture to 20 ℃, and taking out the mixture from the autoclave to obtain a crystal precursor.
(3) Centrifugal washing, drying and roasting
The same example 1 is followed to obtain the prismatic microporous small-grain mordenite molecular sieve.
Example 5
A preparation method of a prismatic microporous small-grain mordenite molecular sieve comprises the following steps:
(1) preparing clear liquid of aluminum source
Uniformly mixing 4.36g of aluminum isopropoxide, 1.5g of sodium hydroxide and 50g of deionized water, and magnetically stirring at room temperature to obtain a clear solution; then 6.7g of N, N, N-trimethyl-1-adamantyl ammonium hydroxide template agent is added and stirred evenly; obtaining the alkaline aluminum source clear solution.
(2) Preparation of Crystal precursors
And (2) slowly dripping 30.4g of water glass into the aluminum source clear liquid obtained in the step (1) at room temperature by using a constant-pressure funnel, continuously stirring and mixing for 1.5 hours, adjusting the pH value of the reaction mixture to 12, covering and sealing the autoclave, placing the autoclave in a rotary convection oven for crystallization reaction at the temperature of 170 ℃ for 4 days, and after the crystallization reaction is finished, naturally cooling the mixture to 20 ℃, and taking out the mixture from the autoclave to obtain a crystal precursor.
(3) Centrifugal washing, drying and roasting
The same example 1 is followed to obtain the prismatic microporous small-grain mordenite molecular sieve.
Example 6
A preparation method of a prismatic microporous small-grain mordenite molecular sieve comprises the following steps:
(1) preparing clear liquid of aluminum source
Uniformly mixing 3.55g of aluminum sulfate, 1.5g of sodium hydroxide and 50g of deionized water, and magnetically stirring at room temperature to obtain a clear solution; then 6.7g of N, N, N-trimethyl-1-adamantyl ammonium hydroxide template agent is added and stirred evenly; obtaining the alkaline aluminum source clear solution.
(2) Preparation of Crystal precursors
And (2) slowly dripping 30.4g of water glass into the aluminum source clear liquid obtained in the step (1) at room temperature by using a constant-pressure funnel, continuously stirring and mixing for 1.5 hours, adjusting the pH value of the reaction mixture to 12, covering and sealing the autoclave, placing the autoclave in a rotary convection oven for crystallization reaction at the temperature of 170 ℃ for 4 days, and after the crystallization reaction is finished, naturally cooling the mixture to 20 ℃, and taking out the mixture from the autoclave to obtain a crystal precursor.
(3) Centrifugal washing, drying and roasting
The same example 1 is followed to obtain the prismatic microporous small-grain mordenite molecular sieve.
Example 7
A preparation method of a prismatic microporous small-grain mordenite molecular sieve comprises the following steps:
(1) preparing clear liquid of aluminum source
Uniformly mixing 1.7g of aluminum isopropoxide, 1.5g of sodium hydroxide and 50g of deionized water, and magnetically stirring at room temperature to obtain a clear solution; then 6.7g of N, N, N-trimethyl-1-adamantyl ammonium hydroxide template agent is added and stirred evenly; obtaining the alkaline aluminum source clear solution.
(2) Preparation of Crystal precursors
And (2) slowly dripping 30.4g of silica sol solution into the aluminum source clear solution obtained in the step (1) by using a constant-pressure funnel at room temperature, continuously stirring and mixing for 1.5 hours, adjusting the pH value of the reaction mixture to 11.5), then covering and sealing the autoclave, placing the autoclave in a rotary convection oven for crystallization reaction at the temperature of 170 ℃ for 3 days, and after the crystallization reaction is finished, naturally cooling the mixture to 20 ℃, and taking out the mixture from the autoclave to obtain a crystal precursor.
(3) Centrifugal washing, drying and roasting
The same example 1 is followed to obtain the prismatic microporous small-grain mordenite molecular sieve.
The prismatic microporous small-grain mordenite molecular sieves prepared in examples 1-7 were tested, and the results were:
the prismatic mordenite molecular sieve prepared in the embodiment 1-7 is used for the carbonylation reaction of dimethyl ether, and the carbonylation reaction of the dimethyl ether is carried out in a fixed bed stainless steel reactor with the inner diameter of 8 mm. 0.5g (examples 1 to 7) of the catalyst (40 to 60 mesh) was loaded into a reactor, and the reactor pressure was maintained at 1.0 MPa; the catalyst was first exposed to feed gas at 500 ℃ under N2Pretreatment in atmosphere (99.99%, Tianjin Xisen gas Co., Ltd.); the reactant mixture was then cooled down to 473K (DME: CO: N)2He (1: 25: 1.5: 22.5, mol/mol) was introduced into the reactor, and the flow rate was controlled at 23 mL/min. The effluent of the reactor was analyzed using an in-line coupled gas chromatograph (Agilent 7890A GC) equipped with FID and TCD. The reaction results are shown in FIGS. 5 and 6.
The H-MOR characteristic structure of the prismatic mordenite molecular sieve prepared in the examples 1-7 is shown as (see figure 2), and the wide-angle X-ray results show that: the diffraction peaks appearing at 19, 23, 26, the 2-fold diffraction angles belong to the characteristic peaks of the H-MOR prism-like structure, respectively.
The phase structure and the crystallinity of the crystal can be analyzed by utilizing an X-ray diffraction technology, the appearance and the grain size of the crystal can be observed by using an SEM (scanning electron microscope), and the crystal lattice of the crystal can be observed by using a TEM (transmission electron microscope). Judging the mordenite molecular sieve by diffraction peak energy in an X-ray powder diffraction (XRD) pattern, and judging the crystallinity intensity by judging the diffraction peak intensity; the Scanning Electron Microscope (SEM) image shows that the structure is a prismatic structure, and the size of the structure is between hundreds of nanometers; the channel structure of mordenite can be clearly seen through a scanning electron microscope (TEM) image.
Through observation, the following results are found: the structures of the prismatic microporous small-grain mordenite molecular sieves of examples 2 to 7 are the same as those of the prismatic microporous small-grain mordenite molecular sieve of example 1, belong to prismatic structures, and belong to mordenite molecular sieves through X-ray diffraction analysis.
Claims (4)
1. The application of the prismatic microporous small-grain mordenite molecular sieve as a catalyst for carbonylation reaction of dimethyl ether comprises the following steps:
(1) preparing clear liquid of aluminum source
Uniformly mixing an aluminum source, sodium hydroxide and deionized water, and magnetically stirring at room temperature to obtain a clear solution; then adding a certain proportion of organic amine template agent and stirring uniformly to obtain an alkaline aluminum source clear solution; the organic amine template agent in the step (1) is N, N, N-trimethyl-1-adamantyl ammonium hydroxide;
(2) preparation of Crystal precursors
Slowly dripping a certain proportion of silicon source into the aluminum source clarified liquid obtained in the step (1) by using a constant pressure funnel at room temperature, continuously stirring and mixing for 1.5 hours, adjusting the pH value of the reaction mixture to 12, covering and sealing the autoclave, and placing the autoclave in a rotating convection oven for crystallization reaction for 4 days at the temperature of 150-180 ℃; after the crystallization reaction is finished, naturally cooling the mixture to 20 ℃, and taking out the mixture from the high-pressure kettle to obtain a crystal precursor;
(3) centrifugal washing, drying and roasting
Separating a solid product from the crystal precursor obtained in the step (2) on a high-speed centrifuge, washing the solid product with deionized water until the pH value is 7, and drying at the temperature of 110 ℃ for 12 hours; finally, roasting the mixture for 3 hours at 550 ℃ in a muffle furnace to obtain a target product, namely the prismatic microporous small-grain mordenite molecular sieve.
2. The use of a prismatic, microporous, small crystallite mordenite molecular sieve as claimed in claim 1, wherein the aluminium source in step (1) is one of aluminium nitrate, sodium metaaluminate, aluminium sulphate or aluminium isopropoxide.
3. The use of the microporous prismatic, small crystallite mordenite molecular sieve of claim 1, wherein the silicon source of step (2) is one of silica white, a silica sol solution, column chromatography silica gel or water glass.
4. The application of the prismatic microporous small-grain mordenite molecular sieve as claimed in claim 2 or 3, wherein the molar ratio of the silicon source to the aluminum source, the sodium hydroxide, the organic amine template and the deionized water is 1: 0.01-0.1: 0.18-0.33: 0.1-0.3: 20-80.
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| CN101613274B (en) * | 2008-06-25 | 2012-12-05 | 中国科学院大连化学物理研究所 | Method for preparing methyl acetate by carbonylating dimethyl ether |
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