CN113830789A - KL molecular sieve dynamically synthesized by using seed crystal as structure directing agent and preparation method thereof - Google Patents

KL molecular sieve dynamically synthesized by using seed crystal as structure directing agent and preparation method thereof Download PDF

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CN113830789A
CN113830789A CN202111034558.8A CN202111034558A CN113830789A CN 113830789 A CN113830789 A CN 113830789A CN 202111034558 A CN202111034558 A CN 202111034558A CN 113830789 A CN113830789 A CN 113830789A
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陈会民
王苹
李珂
王海丽
丁湘浓
王熙
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Guangdong Laboratory Of Chemistry And Fine Chemicals
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Abstract

The invention discloses a KL molecular sieve dynamically synthesized by using a seed crystal as a structure directing agent and a preparation method thereof, wherein potassium hydroxide, an aluminum source, a silicon source and water are mixed according to the following ratio of (1-3.5): 1: (5-9): (150-300), then dripping a KL molecular sieve seed crystal solution, stirring and aging, then performing dynamic hydrothermal crystallization, separating, washing and drying to obtain the KL molecular sieve. Compared with other seed crystal guiding methods of the KL molecular sieve, the method provided by the invention has the following advantages: 1. can be synthesized under dynamic conditions, and is easy to carry out industrial amplification; 2. the synthesis yield is high and reaches more than 80 percent, and the method has obvious cost advantage.

Description

KL molecular sieve dynamically synthesized by using seed crystal as structure directing agent and preparation method thereof
Technical Field
The invention relates to the technical field of molecular sieves, in particular to a KL molecular sieve dynamically synthesized by taking a seed crystal as a structure directing agent and a preparation method thereof.
Background
At the end of the 70's of the 20 th century, Bernard researches found that the KL molecular sieve supported Pt catalyst shows very high aromatization catalytic activity and selectivity on C6-C10 normal paraffins. Therefore, in the field of light naphtha aromatization, a non-acidic carrier-supported single-function noble metal catalyst system represented by a Pt/KL catalyst is attracting much attention.
KL molecular sieves, commonly used as basic carriers, belong to the hexagonal system (P6/mmm,
Figure BDA0003246479120000011
Figure BDA0003246479120000012
) The crystal is formed by alternately stacking hexagonal column cages (D6R) and cancrinite cages (CAN cages) in the C-axis direction, and has a one-dimensional twelve-membered ring pore channel structure with a wave-shaped contour and a pore channel diameter
Figure BDA0003246479120000013
The synthesis of the KL molecular sieve usually adopts a hydrothermal synthesis method, but the synthesis area is narrow, and mixed crystals are easy to appear in an alkaline system through direct hydrothermal synthesis by changing the feeding silicon-aluminum ratio and the system alkalinity. Therefore, in recent years, many synthesis methods such as a seed crystal method, a structure directing agent method, and the like are also commonly used for synthesizing the KL molecular sieve.
The Chinese patent application with the publication number of CN107473238A discloses a method for statically synthesizing a KL molecular sieve by taking an HY molecular sieve as a seed crystal, wherein the KL molecular sieve synthesized by the method is cylindrical, has large crystal grains and is easy to separate. However, the static synthesis method is not suitable for large-scale batch production of the KL molecular sieve due to limited heat transfer problem under the condition of vertical liter and even cubic industrial amplification.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a KL molecular sieve dynamically synthesized by using a seed crystal as a structure directing agent and a preparation method thereof so as to overcome the defect that a static synthesis method is not easy to industrially amplify. The KL molecular sieve prepared by the method has high relative crystallinity, and the yield of the molecular sieve can reach more than 80%.
In order to achieve the purpose of the invention, the invention adopts the technical scheme that: a KL molecular sieve dynamic synthesis method taking seed crystal as a structure directing agent comprises the following steps:
(1) fully mixing potassium hydroxide, an aluminum source and water, heating to obtain a clear solution, slowly adding a silicon source, and stirring to obtain a synthetic sol, wherein the feeding molar ratio of the potassium hydroxide to the aluminum source to the silicon source to the water is (1-3.5): 1: (5-9): (150-300);
(2) adding KL molecular sieve seed crystal solution into the synthetic sol, and stirring and aging to form KL molecular sieve synthetic solution;
(3) and (3) carrying out hydrothermal crystallization on the synthetic liquid, and then sequentially separating, washing and drying crystallized products to obtain the KL molecular sieve.
In the preparation method, the aluminum source is aluminum hydroxide, pseudo-boehmite, aluminum nitrate, aluminum sulfate, aluminum isopropoxide or potassium aluminate, and preferably aluminum hydroxide; the silicon source is silica sol, ethyl orthosilicate or water glass, and the silica sol is preferred.
In the preparation method, the heating temperature in the step (1) can be 70-150 ℃, and the time can be 0.5-24 hours.
In the above preparation method, the preparation method of the KL molecular sieve seed solution in step (2) includes the following steps: mixing barium salt, potassium hydroxide, an aluminum source, a silicon source and water in a molar ratio (0.005-0.1): (1-5): 1: (5-15): (150-350), stirring and aging for a certain time to form sol, and carrying out static hydrothermal crystallization on the obtained sol at 160-180 ℃ for 12-48 hours to obtain a KL molecular sieve seed crystal solution.
In the preparation method, the KL molecular sieve seed crystal solution in the step (2) and SiO in the synthetic sol2The mass ratio of (A) to (B) is 1-10%; the stirring and aging temperature is 10-80 ℃, and the time is 8-24 h.
In the preparation method, the hydrothermal crystallization in the step (3) is dynamic hydrothermal crystallization, the temperature is 160-180 ℃, and the time is 12-48 hours; the separation is suction filtration or centrifugal separation; the washing is carried out until the pH value of the washing liquid is 7-9; the drying temperature is 100-200 ℃, and the drying time is 12-24 hours. Preferably, the crystallization temperature is 175 ℃ and the crystallization time is 24 hours.
The invention also provides the KL molecular sieve which is prepared by the dynamic synthesis method and takes the seed crystal as the structure directing agent.
Compared with the prior art, the invention has the following advantages and effects:
(1) the KL molecular sieve prepared by the method has better purity and crystallinity;
(2) the invention adopts dynamic hydrothermal crystallization, thus being easy for industrial amplification;
(3) the KL molecular sieve prepared by the method has the advantages of high single-kettle yield, low synthesis cost and cost advantage.
Drawings
FIG. 1 is an XRD spectrum of KL molecular sieve seed crystal prepared in example 1 of the present invention.
Figure 2 is an SEM photograph of KL molecular sieve seeds prepared in example 1 of the present invention.
Figure 3 is an XRD spectrum of KL molecular sieve seed crystal prepared in example 2 of the present invention.
Figure 4 is an SEM photograph of KL molecular sieve seeds prepared in example 2 of the present invention.
Figure 5 is an XRD spectrum of KL molecular sieve prepared in example 3 of the present invention.
FIG. 6 is an SEM photograph of KL molecular sieve prepared in example 3 of the present invention.
Figure 7 is an XRD spectrum of KL molecular sieve prepared in example 4 of the present invention.
Figure 8 is an SEM photograph of KL molecular sieve prepared in example 4 of the present invention.
Figure 9 is an XRD spectrum of KL molecular sieve prepared in example 5 of the present invention.
Figure 10 is an SEM photograph of KL molecular sieve prepared in example 5 of the present invention.
Figure 11 is an XRD spectrum of KL molecular sieve prepared in example 6 of the present invention.
Figure 12 is an SEM photograph of KL molecular sieve prepared in example 6 of the present invention.
Figure 13 is an XRD spectrum of KL molecular sieve prepared in example 7 of the present invention.
Figure 14 is an SEM photograph of KL molecular sieve prepared in example 7 of the present invention.
Figure 15 is an XRD spectrum of KL molecular sieve prepared in example 8 of the present invention.
Figure 16 is an SEM photograph of KL molecular sieve prepared in example 8 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but the present invention is not limited to these specific embodiments. Unless otherwise specified, the experimental devices, materials, reagents and the like used in the following examples are commercially available.
Example 1
Weighing 13.66g KOH dissolved in an appropriate amount of water, then weighing 4.50g Al (OH)3Adding into a three-neck flask, heating to 120 ℃, stirring and refluxing for 1h, and adding Al (OH)3Completely dissolving, and clarifying the solution; after the solution was cooled to room temperature, it was transferred to a beaker and 0.3864g of Ba (NO) was added3)2And the remaining water were stirred well, and then 68.11g of silica Sol (SiO) was weighed2Content of 30 wt.%) was slowly added to the above solution, and stirred and aged at room temperature for 20 hours to obtain KL molecular sieve seed crystal synthetic sol, the molar ratio of each material in the sol was 0.05Ba2+：3.5K2O：11.5SiO2：1.0Al2O3：292.65H2And O. And transferring the sol to a polytetrafluoroethylene lining crystallization kettle, performing static hydrothermal crystallization at 175 ℃ for 24 hours, and cooling to room temperature to obtain a KL molecular sieve seed crystal solution.
Taking part of KL molecular sieve seed crystal solution, centrifuging, washing with deionized water to neutrality, drying at 120 ℃ for 24 hours to obtain KL molecular sieve seed crystal raw powder, and carrying out X-ray diffraction characterization on part of samples, wherein the result is shown in figure 1, and the obtained product is a KL molecular sieve; FIG. 2 is an SEM image of a sample, and the result shows that the crystal grain size of the prepared KL molecular sieve seed crystal is 150-250 nm.
Example 2
Weighing 12.25g KOH dissolved in an appropriate amount of water, then weighing 7.06g Al (OH)3Adding into a three-neck flask, heating to 100 ℃, stirring and refluxing for 2h, and adding Al (OH)3Completely dissolving, and clarifying the solution; after the solution was cooled to room temperature, it was transferred to a beaker and 0.1212g of Ba (NO) was added3)2And the remaining water were stirred well, and then 55.75g of silica Sol (SiO) was weighed2Content of 40 wt.%) was slowly added to the above solution, and stirred and aged at room temperature for 20 hours to obtain KL molecular sieve seed crystal synthetic sol, the molar ratio of each material in the sol was 0.01Ba2+：2.0K2O：8.0SiO2：1.0Al2O3：200H2And O. And transferring the sol to a polytetrafluoroethylene lining crystallization kettle, performing static hydrothermal crystallization at 165 ℃ for 36 hours, and cooling to room temperature to obtain a KL molecular sieve seed crystal solution.
Taking part of KL molecular sieve seed crystal solution, centrifuging, washing with deionized water to neutrality, drying at 180 ℃ for 12 hours to obtain KL molecular sieve seed crystal raw powder, and carrying out X-ray diffraction characterization on part of samples, wherein the result is shown in figure 3, and the obtained product is a KL molecular sieve; FIG. 4 is an SEM image of a sample, and the result shows that the crystal grain size of the prepared KL molecular sieve seed crystal is 200-300 nm.
Example 3
Weighing 15.30g KOH dissolved in an appropriate amount of water, then weighing 7.06g Al (OH)3Adding into a three-neck flask, heating to 120 ℃, stirring and refluxing for 1h, and adding Al (OH)3Completely dissolving, and clarifying the solution; after the solution was cooled to room temperature, the solution was transferred to a beaker, the remaining water was added and stirred well, and then 50.87g of silica Sol (SiO) was weighed2 Content 40 wt.%) was slowly added to the above solution, 4g of KL molecular sieve seed solution obtained in example 1 was added dropwise after stirring for 1 hour, and aging was performed at room temperature for 20 hours to obtain a KL molecular sieve synthesis solution, in which the molar ratio of each material was 2.5K2O：7.3SiO2：1.0Al2O3：190.0H2SiO in O, KL molecular sieve crystal seed solution2With SiO in the molecular sieve synthetic solution2The mass ratio of (2%). And transferring the synthetic sol to a 200mL polytetrafluoroethylene lining, filling the polytetrafluoroethylene lining into a stainless steel crystallization kettle, performing dynamic hydrothermal crystallization in a homogeneous reactor at 175 ℃ at the rotating speed of 15r/min for 24 hours, performing suction filtration and deionized water washing on the obtained product to neutrality, and drying at 120 ℃ for 24 hours to obtain KL molecular sieve raw powder, wherein the yield can reach more than 80%.
Taking part of the sample for X-ray diffraction characterization, wherein the result is shown in figure 5, and the obtained product is the KL molecular sieve; FIG. 6 is an SEM image of a sample, and the result shows that the crystal grain size of the prepared KL molecular sieve is about 600 nm.
Example 4
Weighing 15.30g KOH dissolved in an appropriate amount of water, then weighing 7.06g Al (OH)3Adding into a three-neck flask, heating to 100 ℃, stirring and refluxing for 2h, and adding Al (OH)3Completely dissolving, and clarifying the solution; after the solution was cooled to room temperature, the solution was transferred to a beaker, the remaining water was added and stirred well, and then 50.87g of silica Sol (SiO) was weighed2 Content 40 wt.%) was slowly added to the above solution, 10g of KL molecular sieve seed solution obtained in example 1 was added dropwise after stirring for 1 hour, and aging was performed at 60 ℃ for 12 hours to obtain a KL molecular sieve synthetic solution, in which the molar ratio of each material was 2.5K2O：7.3SiO2：1.0Al2O3：190.0H2SiO in O, KL molecular sieve crystal seed solution2With SiO in the molecular sieve synthetic solution2The mass ratio of (B) is 5%. And transferring the synthetic sol to a 200mL polytetrafluoroethylene lining, filling the polytetrafluoroethylene lining into a stainless steel crystallization kettle, performing dynamic hydrothermal crystallization for 16h in a homogeneous reactor at the rotating speed of 15r/min and the temperature of 180 ℃, performing suction filtration and deionized water washing on the obtained product to neutrality, and drying for 16h at the temperature of 150 ℃ to obtain KL molecular sieve raw powder, wherein the yield can reach more than 80%.
Taking a part of samples for X-ray diffraction characterization, wherein the result is shown in figure 7, and the obtained product is the KL molecular sieve; FIG. 8 is an SEM image of a sample, and the result shows that the prepared KL molecular sieve has cylindrical crystal grains and the length of 600-900 nm.
Example 5
Weighing 15.30g KOH dissolved in an appropriate amount of water, then weighing 7.06g Al (OH)3Adding into a three-neck flask, heating to 80 ℃, stirring and refluxing for 12h, and adding Al (OH)3Completely dissolving, and clarifying the solution; after the solution was cooled to room temperature, the solution was transferred to a beaker, the remaining water was added and stirred well, and then 50.87g of silica Sol (SiO) was weighed2 Content 40 wt.%) was slowly added dropwise to the above solution, and after stirring for 1 hour, 16g of KL molecular sieve seed solution obtained in example 1, 6g were added dropwiseStirring and aging for 12h at 0 ℃ to obtain KL molecular sieve synthetic fluid, wherein the molar ratio of materials in the synthetic fluid is 2.5K2O：7.3SiO2：1.0Al2O3：190.0H2SiO in O, KL molecular sieve crystal seed solution2With SiO in the molecular sieve synthetic solution2The mass ratio of (2) is 8%. And transferring the synthetic sol to a 200mL polytetrafluoroethylene lining, filling the polytetrafluoroethylene lining into a stainless steel crystallization kettle, performing dynamic hydrothermal crystallization for 36 hours in a homogeneous reactor at 165 ℃ at the rotating speed of 15r/min, centrifuging the obtained product, washing the product to be neutral by deionized water, and drying the product for 12 hours at 180 ℃ to obtain KL molecular sieve raw powder, wherein the yield can reach more than 80%.
Taking a part of samples for X-ray diffraction characterization, wherein the result is shown in figure 9, and the obtained product is the KL molecular sieve; FIG. 10 is an SEM image of a sample, and the result shows that the crystal grain size of the prepared KL molecular sieve is about 400-600 nm.
Example 6
Weighing 12.25g KOH dissolved in an appropriate amount of water, then weighing 7.06g Al (OH)3Adding into a three-neck flask, heating to 120 ℃, stirring and refluxing for 1h, and adding Al (OH)3Completely dissolving, and clarifying the solution; after the solution was cooled to room temperature, the solution was transferred to a beaker, the remaining water was added and stirred well, and then 50.87g of silica Sol (SiO) was weighed2 Content 40 wt.%) was slowly added to the above solution, 16g of KL molecular sieve seed solution obtained in example 1 was added dropwise after stirring for 1 hour, and aging was performed at room temperature for 20 hours to obtain a KL molecular sieve synthesis solution, in which the molar ratio of each material was 2.0K2O：7.3SiO2：1.0Al2O3：190.0H2SiO in O, KL molecular sieve crystal seed solution2With SiO in the molecular sieve synthetic solution2The mass ratio of (2) is 8%. And transferring the synthetic sol to a 200mL polytetrafluoroethylene lining, filling the polytetrafluoroethylene lining into a stainless steel crystallization kettle, performing dynamic hydrothermal crystallization in a homogeneous reactor at 175 ℃ at the rotating speed of 15r/min for 24 hours, performing suction filtration and deionized water washing on the obtained product to neutrality, and drying at 120 ℃ for 24 hours to obtain KL molecular sieve raw powder, wherein the yield can reach more than 80%.
Taking a part of samples for X-ray diffraction characterization, wherein the result is shown in figure 11, and the obtained product is the KL molecular sieve; FIG. 12 is an SEM image of a sample, and the result shows that the crystal grain size of the prepared KL molecular sieve is about 500-800 nm.
Example 7
Weighing 18.37g KOH dissolved in an appropriate amount of water, then weighing 7.06g Al (OH)3Adding into a three-neck flask, heating to 120 ℃, stirring and refluxing for 1h, and adding Al (OH)3Completely dissolving, and clarifying the solution; after the solution was cooled to room temperature, the solution was transferred to a beaker, the remaining water was added and stirred well, and then 50.87g of silica Sol (SiO) was weighed2 Content 40 wt.%) was slowly added to the above solution, 16g of KL molecular sieve seed solution obtained in example 1 was added dropwise after stirring for 1 hour, and aging was performed at room temperature for 20 hours to obtain a KL molecular sieve synthesis solution, in which the molar ratio of each material was 3.0K2O：7.3SiO2：1.0Al2O3：190.0H2SiO in O, KL molecular sieve crystal seed solution2With SiO in the molecular sieve synthetic solution2The mass ratio of (2) is 8%. And transferring the synthetic sol to a 200mL polytetrafluoroethylene lining, filling the polytetrafluoroethylene lining into a stainless steel crystallization kettle, performing dynamic hydrothermal crystallization in a homogeneous reactor at 175 ℃ at a rotating speed of 15r/min for 24 hours, centrifuging the obtained product, washing the product with deionized water to be neutral, and drying the product at 120 ℃ for 24 hours to obtain KL molecular sieve raw powder, wherein the yield can reach over 80%.
Taking a part of samples for X-ray diffraction characterization, wherein the result is shown in figure 13, and the obtained product is the KL molecular sieve; FIG. 14 is an SEM image of a sample, and the result shows that the crystal grain size of the prepared KL molecular sieve is about 300-500 nm.
Example 8
15.31g KOH were weighed out and dissolved in an appropriate amount of water, then 7.06g Al (OH) were weighed out3Adding into a three-neck flask, heating to 120 ℃, stirring and refluxing for 1h, and adding Al (OH)3Completely dissolving, and clarifying the solution; after the solution was cooled to room temperature, the solution was transferred to a beaker, the remaining water was added and stirred well, and then 45.30g of silica Sol (SiO) was weighed2 Content 40 wt.%) was slowly added to the above solution, 16g of KL molecular sieve seed solution obtained in example 2 was added dropwise after stirring for 1 hour, and aging was carried out at room temperature for 20 hours to obtain a KL molecular sieve synthesis solution, in which the molar ratio of each material was 2.5K2O：6.5SiO2：1.0Al2O3：250.0H2SiO in O, KL molecular sieve crystal seed solution2With SiO in the molecular sieve synthetic solution2The mass ratio of (2) is 8%. And transferring the synthetic sol to a 200mL polytetrafluoroethylene lining, filling the polytetrafluoroethylene lining into a stainless steel crystallization kettle, performing dynamic hydrothermal crystallization in a homogeneous reactor at 175 ℃ at the rotating speed of 15r/min for 24 hours, performing suction filtration and deionized water washing on the obtained product to neutrality, and drying at 120 ℃ for 24 hours to obtain KL molecular sieve raw powder, wherein the yield can reach over 85%.
Taking a part of samples for X-ray diffraction characterization, wherein the result is shown in figure 15, and the obtained product is the KL molecular sieve; FIG. 16 is an SEM image of a sample, and the result shows that the crystal grain size of the prepared KL molecular sieve is about 650-900 nm.
The above embodiments are only some of the embodiments of the present invention, and the embodiments are not intended to limit the scope of the present invention, and all equivalent changes made by using the contents of the present invention are covered by the scope of the present invention claimed in the claims.

Claims (9)

1. A KL molecular sieve dynamic synthesis method taking seed crystal as a structure directing agent is characterized in that: the method comprises the following steps:
(1) fully mixing potassium hydroxide, an aluminum source and water, heating to obtain a clear solution, slowly adding a silicon source, and stirring to obtain a synthetic sol, wherein the feeding molar ratio of the potassium hydroxide to the aluminum source to the silicon source to the water is (1-3.5): 1: (5-9): (150-300);
(2) adding KL molecular sieve seed crystal solution into the synthetic sol, and stirring and aging to form KL molecular sieve synthetic solution;
(3) and carrying out hydrothermal crystallization on the synthetic liquid, and then sequentially separating, washing and drying crystallized products.
2. The method according to claim 1, wherein the KL molecular sieve dynamic synthesis method using the seed crystal as the structure directing agent is characterized in that: the aluminum source is aluminum hydroxide, pseudo-boehmite, aluminum nitrate, aluminum sulfate, aluminum isopropoxide or potassium aluminate; the silicon source is silica sol, ethyl orthosilicate or water glass.
3. The method according to claim 1, wherein the KL molecular sieve dynamic synthesis method using the seed crystal as the structure directing agent is characterized in that: in the step (1), the heating temperature is 70-150 ℃ and the time is 0.5-24 h.
4. The method according to claim 1, wherein the KL molecular sieve dynamic synthesis method using the seed crystal as the structure directing agent is characterized in that: in the step (2), the preparation method of the KL molecular sieve seed crystal solution comprises the following steps: mixing barium salt, potassium hydroxide, an aluminum source, a silicon source and water according to a molar ratio (0.005-0.1): (1-5): 1: (5-15): (150-350), stirring and aging to form sol, and performing static hydrothermal crystallization on the obtained sol at 160-180 ℃ for 12-48 hours.
5. The method according to claim 1, wherein the KL molecular sieve dynamic synthesis method using the seed crystal as the structure directing agent is characterized in that: in the step (2), the KL molecular sieve seed crystal solution and SiO in the synthetic sol2The mass ratio of (A) to (B) is 1 to 10 percent.
6. The method according to claim 1, wherein the KL molecular sieve dynamic synthesis method using the seed crystal as the structure directing agent is characterized in that: in the step (2), the stirring and aging temperature is 10-80 ℃, and the time is 8-24 hours.
7. The method according to claim 1, wherein the KL molecular sieve dynamic synthesis method using the seed crystal as the structure directing agent is characterized in that: in the step (3), the hydrothermal crystallization is dynamic hydrothermal crystallization, the temperature is 160-180 ℃, and the time is 12-48 hours.
8. The method according to claim 1, wherein the KL molecular sieve dynamic synthesis method using the seed crystal as the structure directing agent is characterized in that: in the step (3), the separation is suction filtration or centrifugal separation; the washing is carried out until the pH value of the washing liquid is 7-9; the drying temperature is 100-200 ℃, and the drying time is 12-24 hours.
9. A KL molecular sieve dynamically synthesized by taking a seed crystal as a structure directing agent is characterized in that: the method is prepared by the method for dynamically synthesizing the KL molecular sieve by using the seed crystal as the structure directing agent according to any one of claims 1 to 8.
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