CN109437233B - Method for synthesizing nano GaZSM-5 silicon gallate molecular sieve by dry glue conversion method - Google Patents
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Abstract
The invention discloses a method for synthesizing a nano GaZSM-5 silicogallate molecular sieve by a dry glue conversion method, and aims to solve the problems of long crystallization time, environmental pollution caused by waste liquid discharge and large molecular sieve particle size in the conventional hydrothermal synthesis method of the ZSM-5 molecular sieve. The synthesis method comprises the following steps: firstly, weighing raw materials; secondly, adding tetrapropyl ammonium hydroxide aqueous solution and deionized water into the gallium sesquioxide, and heating and reacting to prepare reaction solution; thirdly, dropwise adding ethyl orthosilicate into the reaction solution to prepare mixed gel; fourthly, stirring and mixing the gel at the rotating speed of 300-500 r/min; and fifthly, adding the dry glue into a closed reaction kettle, carrying out solid phase crystallization reaction at 160-185 ℃, and drying to obtain the nano GaZSM-5 silicate gallate molecular sieve. The dry gel conversion method adopted by the invention has short crystallization time and no waste water discharge, and Ga atoms successfully enter a molecular sieve framework, and the size of a single crystal grain is about 20-30 nm.
Description
Technical Field
The invention belongs to the field of preparation of zeolite molecular sieve catalysts, and particularly relates to a preparation method of a nano GaZSM-5 silicogallate molecular sieve.
Background
As an important shape-selective catalyst, the ZSM-5 molecular sieve has a proper pore structure and size, adjustable acidity and good hydrothermal stability, and is widely applied to shape-selective alkylation, toluene disproportionation, methanol-to-olefin (MTG) and other acid catalytic reactions. The nanometer ZSM-5 molecular sieve shows higher catalytic activity and stability due to larger external surface area and more accessible acid sites. However, the acid strength of the nano ZSM-5 aluminosilicate molecular sieve is high, and carbon deposition is easy to occur in the acid catalysis reaction to cause catalyst inactivation. In order to weaken the acid strength of the ZSM-5 molecular sieve, a second metal active component is typically introduced to prepare the bifunctional catalyst. Ga atoms are introduced into a molecular sieve framework to prepare the nano GaZSM-5 silicate gallate molecular sieve by an in-situ synthesis technology, so that the strength of a B acid center of the molecular sieve can be effectively reduced, the density and the acid strength of an L acid center are increased, the dehydrogenation reaction is promoted, active Ga species are not easy to run off, the acid site density of the nano GaZSM-5 molecular sieve can be finely regulated and controlled by changing the silicon-gallium ratio, and the reaction activity of catalyzing MTG and the gasoline yield are remarkably improved.
Disclosure of Invention
The invention aims to solve the problems that a large amount of wastewater containing alkalis and nitrogenous organic matters is generated in the process of synthesizing a GaZSM-5 molecular sieve by the traditional hydrothermal method, the particle size of the synthesized molecular sieve is large, and the mass transfer capacity is poor when the synthesized molecular sieve is used as a catalyst, so that a novel green synthesis method for preparing the nano GaZSM-5 silicon gallate molecular sieve by a dry gel solid-phase conversion method is provided.
The method for synthesizing the nano GaZSM-5 silicogallate molecular sieve by the dry glue conversion method is realized by the following steps:
weighing 1 part of gallium trioxide, 84.8-141.3 parts of tetrapropyl ammonium hydroxide aqueous solution, 110.0-182.4 parts of deionized water and 136.1-226.7 parts of ethyl orthosilicate as raw materials in parts by weight;
wherein the mass fraction of tetrapropylammonium hydroxide in the tetrapropylammonium hydroxide aqueous solution is 50-55%;
secondly, adding tetrapropyl ammonium hydroxide aqueous solution and deionized water into the gallium trioxide weighed in the first step, placing the mixture into a stainless steel closed reaction kettle with a polytetrafluoroethylene inner liner, treating the mixture at the temperature of 155-165 ℃ for 2.5-3.5 hours, and cooling the mixture to 25 ℃ to prepare reaction solution;
thirdly, dropwise adding the ethyl orthosilicate weighed in the first step into the reaction solution prepared in the second step under the stirring condition of the rotating speed of 260-350 r/min, and uniformly mixing to prepare mixed gel;
fourthly, stirring and mixing the gel for 8-18 hours at the rotating speed of 300-500 r/min to prepare dry glue, wherein the silicon-gallium ratio (atomic ratio) is 60-100: 1;
and fifthly, adding the dry glue obtained in the fourth step into a stainless steel closed reaction kettle with a polytetrafluoroethylene inner liner, performing solid phase crystallization for 2-10 hours at 160-185 ℃, cooling to 25 ℃, then sequentially performing centrifugal filtration, washing and drying to obtain the nano GaZSM-5 silicate molecular sieve.
Compared with the traditional hydrothermal synthesis method, the method for synthesizing the zeolite molecular sieve by adopting the dry gel conversion method and the solid-phase crystallization is to prepare the dry gel from the mixed gel and then directly crystallize the dry gel in the crystallization kettle, and has the advantages of simple operation, no generation of organic matter and alkaline wastewater, avoidance of the separation operation process of a crystallization product and a mother solution, short crystallization time, high single-kettle yield, environmental friendliness and the like. Meanwhile, compared with the molecular sieve synthesized by the traditional hydrothermal method, the nano GaZSM-5 silicogallate molecular sieve prepared by the dry glue conversion method has higher crystallinity, smaller crystal grain size, larger external surface area and milder acidity, and more Ga in the silicogallate molecular sieve prepared by the in-situ synthesis method enters a molecular sieve framework to form
Acid center, which avoids the formation of structural defect sites and more non-framework Ga species caused by a hydrothermal synthesis method.
The method for synthesizing the nano GaZSM-5 silicon gallate molecular sieve by the dry glue conversion method has the following beneficial effects:
1. the invention provides a novel method for synthesizing a nano GaZSM-5 silicate molecular sieve by adopting a dry glue conversion method. Compared with the traditional hydrothermal synthesis method, no waste liquid containing alkaline and nitrogen-containing organic matters is discharged in the process of synthesizing the molecular sieve, no environmental pollution is caused, and the method is a new green synthesis method of the molecular sieve. The GaZSM-5 molecular sieve synthesized by the method provided by the invention has the advantages of uniform grain size, spherical aggregate shape, single grain size of about 20-30nm, high relative crystallinity and large specific surface area.
2. The Ga atoms in the nano GaZSM-5 silicate molecular sieve synthesized by the method successfully enter the framework of the molecular sieve, and the acid site distribution and the acid strength of the nano GaZSM-5 silicate zeolite molecular sieve are finely regulated and controlled by controlling the ratio of silicon to gallium of the initial gel, so that the synthesized nano GaZSM-5 silicate molecular sieve has milder acidity, effectively inhibits carbon deposition inactivation and obviously improves the stability of the molecular sieve in catalyzing MTG reaction.
Drawings
FIG. 1 is an XRD spectrum of GaZSM-5(60) sample of example one;
FIG. 2 is an SEM image of a sample of GaZSM-5(60) in example one;
FIG. 3 is a Ga solid nuclear magnetic spectrum of a sample GaZSM-5(60) in example one;
FIG. 4 is an XRD pattern of GaZSM-5(80) sample of example two;
FIG. 5 is an SEM image of a sample of GaZSM-5(80) of example two;
FIG. 6 is a Ga solid nuclear magnetic spectrum of a sample GaZSM-5(80) in example two;
FIG. 7 is an XRD spectrum of GaZSM-5(100) sample of EXAMPLE III;
FIG. 8 is an SEM image of a sample of GaZSM-5(100) of example III;
FIG. 9 is a Ga solid nuclear magnetic spectrum of a sample GaZSM-5(100) in example three.
Detailed Description
The first embodiment is as follows: the method for synthesizing the nano GaZSM-5 silicogallate molecular sieve by the dry glue conversion method is implemented according to the following steps:
weighing 1 part of gallium trioxide, 84.8-141.3 parts of tetrapropyl ammonium hydroxide aqueous solution, 110.0-182.4 parts of deionized water and 136.1-226.7 parts of ethyl orthosilicate as raw materials in parts by weight;
wherein the mass fraction of tetrapropylammonium hydroxide in the tetrapropylammonium hydroxide aqueous solution is 50-55%;
secondly, adding tetrapropyl ammonium hydroxide aqueous solution and deionized water into the gallium trioxide weighed in the first step, placing the mixture into a stainless steel closed reaction kettle with a polytetrafluoroethylene inner liner, treating the mixture at the temperature of 155-165 ℃ for 2.5-3.5 hours, and cooling the mixture to 25 ℃ to prepare reaction solution;
thirdly, dropwise adding the ethyl orthosilicate weighed in the first step into the reaction solution prepared in the second step under the stirring condition of the rotating speed of 260-350 r/min, and uniformly mixing to prepare mixed gel;
fourthly, stirring and mixing the gel for 8-18 hours at the rotating speed of 300-500 r/min to prepare dry glue, wherein the silicon-gallium ratio (atomic ratio) is 60-100: 1;
and fifthly, adding the dry glue obtained in the fourth step into a stainless steel closed reaction kettle with a polytetrafluoroethylene inner liner, performing solid phase crystallization for 2-10 hours at 160-185 ℃, cooling to 25 ℃, then sequentially performing centrifugal filtration and washing, and drying to obtain the nano GaZSM-5 silicate molecular sieve.
The embodiment provides a method for synthesizing a nano GaZSM-5 silicon gallate molecular sieve by a dry gel solid-phase conversion method without steam assistance. The crystallization of the dry glue in the step five is solid phase crystallization, water is not required to be added into a crystallization kettle, and more Ga in the silicon gallate molecular sieve prepared by adopting the in-situ synthesis method enters a molecular sieve framework to form
An acid center.
The second embodiment is as follows: the difference between the embodiment and the first embodiment is that the mass fraction of the tetrapropylammonium hydroxide in the tetrapropylammonium hydroxide aqueous solution in the first step is 54-55%.
The third concrete implementation mode: the present embodiment is different from the second embodiment in that the mass fraction of tetrapropylammonium hydroxide in the tetrapropylammonium hydroxide aqueous solution in the first step is 54.78%.
The fourth concrete implementation mode: this embodiment differs from one of the first to third embodiments in that step two is treated at 160 ℃ for 3 hours.
The fifth concrete implementation mode: the difference between the present embodiment and one of the first to fourth embodiments is that the gel is stirred and mixed for 10 to 14 hours at a rotation speed of 300 to 500r/min in the fourth step.
The sixth specific implementation mode: the present embodiment is different from the first to the fifth embodiments in that the crystallization temperature in the fifth step is 170 to 180 ℃.
The seventh embodiment: the sixth embodiment is different from the sixth embodiment in that the crystallization time in the fifth step is 4 to 8 hours.
The specific implementation mode is eight: the difference between the present embodiment and one of the first to seventh embodiments is that the drying in the fifth step is performed at 80 to 100 ℃ for 6 to 10 hours.
The first embodiment is as follows: the method for synthesizing the nano GaZSM-5 silicogallate molecular sieve by the dry glue conversion method is realized by the following steps:
weighing 0.108g of gallium trioxide, 9.127g of tetrapropyl ammonium hydroxide aqueous solution, 11.833g of deionized water and 14.647g of ethyl orthosilicate as raw materials, wherein the mass fraction of tetrapropyl ammonium hydroxide in the tetrapropyl ammonium hydroxide aqueous solution is 54.78%;
secondly, 9.127g of tetrapropyl ammonium hydroxide aqueous solution and 11.833g of deionized water are added into 0.108g of the gallium trioxide weighed in the step one, the mixture is placed in a stainless steel closed reaction kettle with a polytetrafluoroethylene inner liner, the mixture is treated for 3 hours at 160 ℃, and then the mixture is cooled to 25 ℃ to prepare reaction solution;
thirdly, under the stirring condition of the rotating speed of 260r/min, 14.647g of tetraethoxysilane weighed in the first step is dropwise added into the reaction solution prepared in the second step, and mixed uniformly to prepare mixed gel;
fourthly, stirring the mixed gel obtained in the third step for 12 hours at the rotating speed of 450r/min to prepare dry gel;
and fifthly, placing the dry glue prepared in the fourth step into a stainless steel closed reaction kettle with a polytetrafluoroethylene inner liner, performing solid phase crystallization for 10 hours at 180 ℃, cooling to 25 ℃, then sequentially performing centrifugal filtration and washing, and drying at 90 ℃ for 6 hours to obtain the nano GaZSM-5 silicate gallate molecular sieve with the silicon-gallium ratio of 60, which is marked as GaZSM-5 (60).
The XRD spectrum, SEM photograph and Ga solid nuclear magnetic spectrum of the nano GaZSM-5 galliumate molecular sieve obtained in this example are shown in fig. 1, fig. 2 and fig. 3, respectively; the specific surface area and pore volume data for this sample are shown in table 1.
The XRD spectrum of the nano GaZSM-5(60) molecular sieve sample synthesized in this example is shown in fig. 1, and as can be seen from fig. 1, the molecular sieve sample GaZSM-5(60) prepared in this example has characteristic diffraction peaks of MFI topology at 2 θ of 23.09 °, 23.95 ° and 24.38 °, and no diffraction peaks of other heterocrystals appear, indicating that a pure-phase GaZSM-5 molecular sieve is synthesized.
The SEM photograph of the synthesized nano GaZSM-5(60) molecular sieve sample is shown in fig. 2, and it can be seen from fig. 2 that the nano GaZSM-5(60) molecular sieve prepared in this example exists in the form of aggregates formed by stacking nanocrystals having a single crystal size of about 20 to 30 nm.
The Ga solid nuclear magnetic spectrum of the nano GaZSM-5(60) molecular sieve prepared in this example is shown in fig. 3, and it can be seen from fig. 3 that a resonance signal peak attributed to a four-coordinate Ga species appears near 160ppm, indicating that Ga enters the framework of the molecular sieve.
Example two: the method for synthesizing the nano GaZSM-5 silicogallate molecular sieve by the dry glue conversion method is realized by the following steps:
firstly, 0.081g of gallium trioxide, 9.127g of tetrapropyl ammonium hydroxide aqueous solution, 11.826g of deionized water and 14.647g of tetraethoxysilane are weighed as raw materials, wherein the mass fraction of tetrapropyl ammonium hydroxide in the tetrapropyl ammonium hydroxide aqueous solution is 54.78%;
secondly, 9.127g of tetrapropyl ammonium hydroxide aqueous solution and 11.826g of deionized water are added into 0.081g of gallium trioxide weighed in the step one, the mixture is placed in a stainless steel closed reaction kettle with a polytetrafluoroethylene inner liner, the mixture is treated for 2.5 hours at the temperature of 160 ℃, and then the mixture is cooled to 25 ℃ to prepare reaction solution;
thirdly, under the stirring condition of the rotating speed of 260r/min, 14.647g of tetraethoxysilane weighed in the first step is dropwise added into the reaction solution prepared in the second step, and mixed uniformly to prepare mixed gel;
fourthly, stirring the mixed gel obtained in the third step for 12 hours at the rotating speed of 400r/min to prepare dry gel;
and fifthly, placing the dry glue prepared in the fourth step into a stainless steel closed reaction kettle with a polytetrafluoroethylene inner liner, performing solid phase crystallization for 6 hours at 175 ℃, cooling to 25 ℃, then sequentially performing centrifugal filtration and washing, and drying at 90 ℃ for 6 hours to obtain the nano GaZSM-5 silicate gallate molecular sieve with the silicon-gallium ratio of 80, which is marked as GaZSM-5 (80).
The XRD spectrum, SEM photograph and Ga solid nuclear magnetic spectrum obtained in the example are respectively shown in figure 4, figure 5 and figure 6; the specific surface area and pore volume data for this sample are shown in table 1.
The XRD spectrum of the nano GaZSM-5(80) molecular sieve sample synthesized in this example is shown in fig. 4, and as can be seen from fig. 4, the molecular sieve sample GaZSM-5(80) prepared in this experiment shows characteristic diffraction peaks of MFI topology at 2 θ of 23.09 °, 23.95 ° and 24.38 °, and no diffraction peaks of other heterocrystals appear, indicating that a pure-phase GaZSM-5 molecular sieve is synthesized.
The SEM photograph of the synthesized nano GaZSM-5(80) molecular sieve sample is shown in fig. 5, and it can be seen from fig. 5 that the nano GaZSM-5(80) molecular sieve prepared in this example exists in the form of aggregates formed by stacking nanocrystals having a single crystal size of about 20 to 30 nm.
The Ga solid nuclear magnetic spectrum of the nano GaZSM-5(80) molecular sieve prepared in this example is shown in fig. 6, and as can be seen from fig. 6, a resonance signal peak attributed to a four-coordinate Ga species appears near 160ppm, indicating that Ga enters the framework of the molecular sieve.
Example three: the method for synthesizing the nano GaZSM-5 silicogallate molecular sieve by the dry glue conversion method is realized by the following steps:
weighing 0.065g of gallium trioxide, 9.127g of tetrapropyl ammonium hydroxide aqueous solution, 11.784g of deionized water and 14.647g of ethyl orthosilicate as raw materials, wherein the mass fraction of tetrapropyl ammonium hydroxide in the tetrapropyl ammonium hydroxide aqueous solution is 54.78%;
secondly, 9.127g of tetrapropyl ammonium hydroxide aqueous solution and 11.784g of deionized water are added into 0.065g of gallium trioxide weighed in the step one, the mixture is placed in a stainless steel closed reaction kettle with a polytetrafluoroethylene inner liner, the mixture is treated for 2.5 hours at the temperature of 160 ℃, and then the mixture is cooled to 25 ℃ to prepare a reaction solution;
thirdly, under the stirring condition of the rotating speed of 260r/min, 14.647g of tetraethoxysilane weighed in the first step is dropwise added into the reaction solution prepared in the second step, and mixed uniformly to prepare mixed gel;
fourthly, stirring the mixed gel obtained in the third step for 12 hours at the rotating speed of 400r/min to prepare dry gel;
and fifthly, placing the dry glue prepared in the fourth step into a stainless steel closed reaction kettle with a polytetrafluoroethylene inner liner, performing solid phase crystallization for 2 hours at 180 ℃, cooling to 25 ℃, then sequentially performing centrifugal filtration and washing, and drying at 90 ℃ for 6 hours to obtain the nano GaZSM-5 silicate gallate molecular sieve with the silicon-gallium ratio of 100, which is marked as GaZSM-5 (100).
The XRD spectrum, SEM photograph and Ga solid nuclear magnetic spectrum of the nano GaZSM-5(100) molecular sieve synthesized in this example are shown in fig. 7, fig. 8 and fig. 9, respectively; the specific surface area and pore volume data for this sample are shown in table 1.
The XRD spectrum of the nano GaZSM-5(100) molecular sieve sample synthesized in this example is shown in fig. 7, and as can be seen from fig. 7, the molecular sieve sample GaZSM-5(100) prepared in this example shows characteristic diffraction peaks of MFI topology at 2 θ of 23.09 °, 23.95 ° and 24.38 °, and no diffraction peaks of other heterocrystals appear, indicating that a pure-phase GaZSM-5 molecular sieve is synthesized.
The SEM photograph of the synthesized nano GaZSM-5(100) molecular sieve sample is shown in fig. 8, and it can be seen from fig. 8 that the nano GaZSM-5(100) molecular sieve prepared in this example exists in the form of aggregates formed by stacking nanocrystals having a single crystal size of about 20 to 30 nm.
The Ga solid nuclear magnetic spectrum of the nano GaZSM-5(100) molecular sieve prepared in this example is shown in fig. 9, and it can be seen from fig. 9 that a resonance signal peak attributed to a four-coordinate Ga species appears near 160ppm, indicating that Ga enters the framework of the molecular sieve.
Table 1 specific surface area and pore volume of nano GaZSM-5(x) (x 60,80,100) molecular sieves
Claims (8)
1. A method for synthesizing a nano GaZSM-5 silicon gallate molecular sieve by a dry glue conversion method is characterized by comprising the following steps:
weighing 1 part of gallium trioxide, 84.8-141.3 parts of tetrapropyl ammonium hydroxide aqueous solution, 110.0-182.4 parts of deionized water and 136.1-226.7 parts of ethyl orthosilicate as raw materials in parts by weight;
wherein the mass fraction of tetrapropylammonium hydroxide in the tetrapropylammonium hydroxide aqueous solution is 50-55%;
secondly, adding tetrapropyl ammonium hydroxide aqueous solution and deionized water into the gallium trioxide weighed in the first step, placing the mixture into a stainless steel closed reaction kettle with a polytetrafluoroethylene inner liner, treating the mixture at the temperature of 155-165 ℃ for 2.5-3.5 hours, and cooling the mixture to 25 ℃ to prepare reaction solution;
thirdly, dropwise adding the ethyl orthosilicate weighed in the first step into the reaction solution prepared in the second step under the stirring condition of the rotating speed of 260-350 r/min, and uniformly mixing to prepare mixed gel;
fourthly, stirring and mixing the gel for 8-18 hours at the rotating speed of 300-500 r/min to prepare dry glue, wherein the atomic ratio of silicon to gallium is 60-100: 1;
and fifthly, adding the dry glue obtained in the fourth step into a stainless steel closed reaction kettle with a polytetrafluoroethylene inner liner, performing solid phase crystallization for 2-8 hours at 160-185 ℃, cooling to 25 ℃, then sequentially performing centrifugal filtration, washing and drying to obtain the nano GaZSM-5 silicate molecular sieve.
2. The method for synthesizing nano GaZSM-5 silicogallate molecular sieve according to claim 1, wherein the mass fraction of tetrapropylammonium hydroxide in the tetrapropylammonium hydroxide aqueous solution in the first step is 54-55%.
3. The method for synthesizing nano GaZSM-5 silicogallate molecular sieve according to claim 2, wherein the mass fraction of tetrapropylammonium hydroxide in the tetrapropylammonium hydroxide aqueous solution in the first step is 54.78%.
4. The method for synthesizing nano GaZSM-5 silicogallate molecular sieve by dry gel conversion method according to claim 1, wherein the second step is carried out at 160 ℃ for 3 hours.
5. The method for synthesizing the nano GaZSM-5 silicogallate molecular sieve by the dry glue conversion method according to claim 1, wherein the gel is stirred and mixed for 10-14 hours in the fourth step under the condition that the rotating speed is 300-500 r/min.
6. The method for synthesizing the nano GaZSM-5 silicogallate molecular sieve by the dry gel conversion method according to claim 1, wherein the temperature of crystallization in the fifth step is 170-180 ℃.
7. The method for synthesizing the nano GaZSM-5 silicogallate molecular sieve by the dry glue conversion method according to claim 1, wherein the crystallization time in the fifth step is 4-8 hours.
8. The method for synthesizing the nano GaZSM-5 silicogallate molecular sieve by the dry glue conversion method according to claim 1, wherein the drying in the fifth step is drying at 80-100 ℃ for 6-10 h.
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