SSZ-13 zeolite molecular sieve as well as production method and application thereof
By adding ethylenediamine and seed crystals to the synthesis of SSZ-13 zeolite molecular sieve, and combining hydrothermal crystallization and calcination processes, the preparation problem of nano-sized SSZ-13 zeolite molecular sieve was solved, and the industrial production of nano-sized SSZ-13 zeolite molecular sieve with adjustable particle size and low cost was realized.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- SOUTH CHINA UNIV OF TECH
- Filing Date
- 2025-12-30
- Publication Date
- 2026-04-21
AI Technical Summary
Existing technologies are difficult to efficiently prepare nanoscale SSZ-13 zeolite molecular sieves, and the high cost leads to uneven particle size distribution and excessively high production costs, making it difficult to meet industrial needs.
By adding ethylenediamine and seed crystals to the synthesis system and controlling the amount of template agent, nanoscale SSZ-13 zeolite molecular sieves were prepared using hydrothermal crystallization and calcination processes. The particle size is adjustable and the cost is low.
The efficient preparation of nanoscale SSZ-13 zeolite molecular sieves with uniform particle size distribution has been achieved, reducing production costs and making it suitable for large-scale industrial applications.
Smart Images
Figure CN121894680A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of zeolite molecular sieve technology, specifically relating to an SSZ-13 zeolite molecular sieve, its production method, and its application. Background Technology
[0002] Zeolite molecular sieves are a class of crystalline materials with regular microporous structures. Due to their unique pore structure, high specific surface area, and tunable acidity, they are widely used in catalysis, adsorption, membrane separation, and ion exchange. Among them, SSZ-13 is a small-porous zeolite with a CHA topology. Its unique eight-membered ring channel and three-dimensional cross-channel system give it excellent performance in reactions such as methanol-to-olefins (MTO) and selective catalytic reduction (SCR). In particular, it shows great promise as an NH3-SCR catalyst (such as copper-based SSZ-13) in diesel vehicle exhaust denitrification.
[0003] Controlling the particle size of SSZ-13 zeolite molecular sieves has important applications in catalysis and membrane separation. However, conventional synthesis systems typically only yield micron-sized SSZ-13 zeolite molecular sieves. A common method for preparing nanoscale SSZ-13 zeolite molecular sieves involves high-speed ball milling of micron-sized SSZ-13 zeolite molecular sieves followed by centrifugation to obtain nanoscale particles. However, this method results in materials with a wide particle size distribution and low yield, is time-consuming and inefficient, and easily introduces other impurities. Furthermore, some studies have reported the synthesis of nanoscale SSZ-13 zeolite molecular sieves through inter-zeolite conversion using FAU molecular sieves; however, using FAU molecular sieves as a raw material significantly increases production costs, making it uneconomical and unsuitable for industrial production.
[0004] In summary, proposing a new preparation method to achieve particle size control of SSZ-13 zeolite molecular sieve is of great significance for its practical industrial application. Summary of the Invention
[0005] To solve the above-mentioned technical problems, the purpose of this invention is to provide an SSZ-13 zeolite molecular sieve, its production method and application, which has the advantages of simple and efficient operation and low cost, and the particle size of the obtained SSZ-13 molecular sieve is adjustable.
[0006] To achieve the above-mentioned objectives, the technical solution adopted by the present invention is as follows:
[0007] In a first aspect, the present invention provides a method for producing SSZ-13 zeolite molecular sieve, as follows:
[0008] S1. Mix the silicon source, aluminum source, alkali source, template agent, ethylenediamine and deionized water evenly to obtain the precursor solution;
[0009] S2. Add seed crystals to the forward driving solution and stir until homogeneous;
[0010] S3. The precursor solution containing seed crystals is subjected to hydrothermal crystallization. After crystallization, the product is washed and dried, and then calcined to obtain nanoscale SSZ-13 zeolite molecular sieve.
[0011] Preferably, in step S1, the silicon source, aluminum source, and alkali source are represented in oxide form, and calculated by molar amount as SiO2:Al2O3:T:EDA:M x O y :H2O=1:(0.001~0.15):(0.001~0.5):(0.01~0.6):(0.05~0.4):(10~80), where T represents the template agent, EDA represents ethylenediamine, and M represents the metal element in the alkali source. x O y This indicates the metal oxide corresponding to the metal element in the alkali source.
[0012] More preferably, when the ratio of (T+EDA) / SiO2 in the current driving fluid is greater than 0.4 and the ratio of EDA / T is greater than 0.3, nanoscale SSZ-13 zeolite molecular sieves with a particle size of <900nm are prepared.
[0013] Preferably, the silicon source includes silica gel and / or silica.
[0014] The aluminum source includes one or more of sodium aluminate, boehmite, aluminum hydroxide, and aluminum isopropoxide;
[0015] Alkali sources include sodium hydroxide and / or potassium hydroxide.
[0016] Preferably, in step S2, the seed crystals include CHA-type zeolite seed crystals.
[0017] Preferably, in step S2, the amount of seed crystal added is 0.01 to 5 wt% of the silicon source mass.
[0018] Preferably, in step S3, the temperature of hydrothermal crystallization is 140–180°C.
[0019] Preferably, in steps S1 and S2, the stirring temperature is 20–100°C.
[0020] In step S3, the calcination temperature is 500–600°C.
[0021] In a second aspect, the present invention provides an SSZ-13 zeolite molecular sieve, which is prepared by the above-described production method.
[0022] In a third aspect, the present invention proposes an application of SSZ-13 zeolite molecular sieve, wherein the SSZ-13 zeolite molecular sieve produced by the above-described production method is used in the fields of catalysis, adsorption, membrane separation and ion exchange.
[0023] Beneficial effects:
[0024] This invention, by adding ethylenediamine to the synthesis system, not only achieves effective control over the particle size of SSZ-13 zeolite molecular sieves but also reduces the amount of template agent required during the synthesis of SSZ-13 zeolite molecular sieves, effectively lowering the production cost. The production method of this invention is simple, efficient, and low-cost, and has significant application value in the low-cost, large-scale synthesis of SSZ-13 zeolite molecular sieves. Attached Figure Description
[0025] Figure 1 The XRD patterns of the SSZ-13 zeolite molecular sieves prepared in Examples 1-4 are shown.
[0026] Figure 2 The image shown is a SEM image of the SSZ-13 zeolite molecular sieve prepared in Example 1.
[0027] Figure 3 The image shown is a SEM image of the SSZ-13 zeolite molecular sieve prepared in Example 2.
[0028] Figure 4 The image shown is a SEM image of the SSZ-13 zeolite molecular sieve prepared in Example 3.
[0029] Figure 5 The image shown is a SEM image of the SSZ-13 zeolite molecular sieve prepared in Example 4.
[0030] Figure 6 The image shown is a SEM image of the SSZ-13 zeolite molecular sieve prepared in Comparative Example 1. Detailed Implementation
[0031] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the specific implementation methods of the present invention will be described below with reference to the accompanying drawings. Obviously, the drawings described below are merely some embodiments of the present invention. For those skilled in the art, other drawings and other implementation methods can be obtained based on these drawings without any creative effort.
[0032] This invention proposes a method for producing SSZ-13 zeolite molecular sieve, as follows:
[0033] S1. Mix the silicon source, aluminum source, alkali source, template agent, ethylenediamine and deionized water evenly to obtain the precursor solution;
[0034] S2. Add seed crystals to the forward driving solution and stir until homogeneous;
[0035] S3. The precursor solution containing seed crystals is subjected to hydrothermal crystallization. After crystallization, the product is washed and dried, and then calcined to obtain nanoscale SSZ-13 zeolite molecular sieve.
[0036] This invention incorporates ethylenediamine into the synthesis system, which synergistically promotes the nucleation of SSZ-13 molecular sieves with organic template agents, thereby achieving efficient control over the particle size of SSZ-13 and enabling the formation of nanoscale particles during the synthesis process. Ethylenediamine can be removed during the final calcination process. Compared to conventional template agents, ethylenediamine is inexpensive; its addition reduces the amount of template agent required, thus lowering production costs and subsequent wastewater treatment costs. The production method of this invention is simple, efficient, and low-cost, facilitating the low-cost, large-scale industrial production of nanoscale SSZ-13 zeolite molecular sieves.
[0037] In step S1, in the precursor solution, the silicon source, aluminum source, and alkali source are represented in oxide form, and calculated by molar amount as SiO2:Al2O3:T:EDA:M x O y :H2O=1:(0.001~0.15):(0.001~0.5):(0.01~0.6):(0.05~0.4):(10~80), where T represents the template agent, EDA represents ethylenediamine, and M represents the metal element in the alkali source. x O y This indicates the metal oxide corresponding to the metal element in the alkali source.
[0038] The preparation method of the present invention can produce micron-sized or nano-sized materials. Preferably, when the ratio of (T+EDA) / SiO2 in the current driving fluid is greater than 0.4 and the ratio of EDA / T is greater than 0.3, high-quality nano-sized SSZ-13 zeolite molecular sieves (i.e., nano-sized SSZ-13 zeolite molecular sieves with smaller particle size) can be obtained by molar calculation.
[0039] In step S1, silicon source, aluminum source and alkali source are commonly used substances in the art for preparing zeolite membranes. Any substance in the art that can be used to produce zeolite membranes and does not react directly with ethylenediamine meets the requirements of this invention.
[0040] Preferably, the silicon source includes one or more of silica sol, silica gel, and silica fume.
[0041] Preferably, the aluminum source includes one or more of sodium aluminate, boehmite, aluminum hydroxide, and aluminum isopropoxide.
[0042] Preferably, the alkali source includes sodium hydroxide and / or potassium hydroxide.
[0043] Preferably, the template agent is a conventional organic template agent, such as N,N,N-trimethyl-1-adamantyl ammonium hydroxide (TMAdaOH), choline chloride, etc. This invention is not limited to these methods.
[0044] When the alkali source is sodium hydroxide and / or potassium hydroxide, M represents potassium and / or sodium. Calculated by molar amount, SiO2:Al2O3:T:EDA:M2O:H2O=1:(0.001~0.15):(0.001~0.5):(0.01~0.6):(0.05~0.4):(10~80).
[0045] Preferably, in steps S1 and S2, the stirring temperature is 20–100°C. More preferably, the stirring temperature is room temperature, i.e., 25°C.
[0046] In step S2, the seed crystal is preferably a seed crystal with a structure similar to that of SSZ-13 zeolite molecular sieve, and preferably, the seed crystal is a CHA type zeolite seed crystal.
[0047] More preferably, the amount of seed crystal added is 0.01 to 5 wt% of the silicon source mass.
[0048] Preferably, in step S3, the hydrothermal crystallization temperature is 140–180°C. More preferably, the crystallization time is 3–96 hours.
[0049] This invention can prepare micron-sized and nano-sized SSZ-13 zeolite molecular sieves with uniform particle size distribution. The particle size can be controlled by adjusting the content and ratio of template agent and ethylenediamine.
[0050] The SSZ-13 zeolite molecular sieve prepared by this invention has great application prospects in catalysis, membrane separation and other fields.
[0051] In step S3, the calcination temperature is 500–600°C. During the calcination process, the template agent and ethylenediamine in the SSZ-13 channels are removed.
[0052] Example 1
[0053] S1. Dissolve aluminum hydroxide (aluminum source), sodium hydroxide (alkali source), TMAdaOH (organic template agent), and ethylenediamine in deionized water. Then, add silica sol dropwise under stirring at room temperature and continue stirring until homogeneous. In the precursor solution, the silicon source, aluminum source, and alkali source are represented in oxide form. The molar composition of the precursor solution is SiO2:Al2O3:T:EDA:Na2O:H2O=1:0.025:0.1:0.3:0.1:44.
[0054] S2. Add CHA-type seed crystals to the precursor solution and stir at room temperature for 12 hours. The amount of seed crystals added is 0.1 wt% of the silicon source mass.
[0055] S3. The precursor solution containing seed crystals is transferred into a stainless steel reactor with a polytetrafluoroethylene liner, sealed, and then hydrothermally crystallized at 160℃ for 96 hours. After the reaction is completed, the obtained powder is repeatedly washed with deionized water until neutral and then dried. Then it is calcined at 550℃ for 10 hours to obtain SSZ-13 zeolite molecular sieve.
[0056] Figure 1 The XRD pattern of the product of this embodiment is shown, confirming that the synthesized product is SSZ-13 zeolite molecular sieve.
[0057] Figure 2 The image shown is an SEM image of the product of this embodiment. The product has a cubic morphology with no agglomeration between particles and an average grain size of about 1.5 μm.
[0058] Example 2
[0059] The difference between this embodiment and Embodiment 1 is that in step S1, the molar composition of the precursor liquid is SiO2:Al2O3:T:EDA:Na2O:H2O = 1:0.025:0.2:0.2:0.1:44; the remaining steps are the same as in Embodiment 1.
[0060] Figure 1 The XRD pattern of the product of this embodiment is shown, confirming that the synthesized product is SSZ-13 zeolite molecular sieve.
[0061] Figure 3 The image shown is an SEM image of the product of this embodiment. The product has a cubic morphology, with no agglomeration between particles and an average grain size of about 1.2 μm.
[0062] Example 3
[0063] The difference between this embodiment and Embodiment 1 is that in step S1, the molar composition of the precursor liquid is SiO2:Al2O3:T:EDA:Na2O:H2O = 1:0.025:0.3:0.1:0.1:44; the remaining steps are the same as in Embodiment 1.
[0064] Figure 1 The XRD pattern of the product of this embodiment is shown, confirming that the synthesized product is SSZ-13 zeolite molecular sieve.
[0065] Figure 4 The image shown is an SEM image of the product of this embodiment. The product has a cubic morphology with no agglomeration between particles and an average grain size of about 900 nm.
[0066] Example 4
[0067] The difference between this embodiment and Embodiment 1 is that in step S1, the molar composition of the precursor liquid is SiO2:Al2O3:T:EDA:Na2O:H2O = 1:0.025:0.3:0.3:0.1:44; the remaining steps are the same as in Embodiment 1.
[0068] Figure 1 The XRD pattern of the product of this embodiment is shown, confirming that the synthesized product is SSZ-13 zeolite molecular sieve.
[0069] Figure 5 The image shown is an SEM image of the product of this embodiment. The product has a cubic morphology, with no agglomeration between particles, uniform grain size, and an average grain size of about 400 nm.
[0070] Example 5
[0071] The difference between this embodiment and Embodiment 1 is that in step S1, the molar composition of the precursor liquid is SiO2:Al2O3:T:EDA:Na2O:H2O = 1:0.025:0.01:0.5:0.1:28; the remaining steps are the same as in Embodiment 1.
[0072] The results showed that the average size of the product was approximately 300 nm.
[0073] Example 6
[0074] The difference between this embodiment and Embodiment 1 is that in step S1, the molar composition of the precursor liquid is SiO2:Al2O3:T:EDA:Na2O:H2O = 1:0.025:0.03:0.1:0.1:28; the remaining steps are the same as in Embodiment 1.
[0075] The results showed that the average size of the product was approximately 1 μm.
[0076] Example 7
[0077] The difference between this embodiment and Embodiment 1 is that in step S1, the molar composition of the precursor liquid is SiO2:Al2O3:T:EDA:Na2O:H2O = 1:0.005:0.03:0.5:0.1:28; the remaining steps are the same as in Embodiment 1.
[0078] The results showed that the average size of the product was approximately 250 nm.
[0079] Example 8
[0080] The difference between this embodiment and Embodiment 1 is that in step S1, the molar composition of the precursor liquid is SiO2:Al2O3:T:EDA:K2O:H2O = 1:0.025:0.03:0.1:0.12:28; the remaining steps are the same as in Embodiment 1.
[0081] The results showed that the average size of the product was approximately 1.2 μm.
[0082] Comparative Example 1
[0083] The difference between this comparative example and Example 1 is that ethylenediamine was not added to the precursor solution in step S1, while the remaining steps are the same as in Example 1.
[0084] Figure 6 The image shown is an SEM image of the product of this comparative example. The average grain size is about 1 μm, indicating that there is obvious agglomeration between the product particles, resulting in uneven particle size distribution.
[0085] Comparative Example 2
[0086] The difference between this comparative example and Example 4 is that ethylenediamine was not added to the precursor solution in step S1, while the remaining steps are the same as in Example 4.
[0087] The results showed that the average size of the product was about 1.5 μm, which was significantly different from the particle size of the product in Example 4.
[0088] Comparative Example 3
[0089] The difference between this comparative example and Example 5 is that ethylenediamine was not added to the precursor solution in step S1, while the remaining steps are the same as in Example 5.
[0090] The results showed that the synthesized product was an amorphous substance.
[0091] Comparative Example 4
[0092] The difference between this comparative example and Example 5 is that in step S1, triethylamine is added to the precursor solution instead of ethylenediamine; the remaining steps are the same as in Example 5.
[0093] The results showed that the synthesized product was an amorphous substance.
[0094] Comparative Example 5
[0095] The difference between this comparative example and Example 5 is that no seed crystals were added to the precursor solution in step S2, while the remaining steps are the same as in Example 5.
[0096] The results showed that the synthesized product was an amorphous substance.
[0097] According to the embodiments and comparative data of this application, the addition of ethylenediamine can prepare micron-sized and nano-sized SSZ-13 zeolite molecular sieves, and the product particles do not agglomerate and are very uniform in size. By changing the ratio of ethylenediamine and template agent, the particle size of the synthesized SSZ-13 zeolite molecular sieve can be effectively controlled. Even with extremely low template agent dosage, the addition of ethylenediamine can still synthesize small-particle-size SSZ-13 zeolite molecular sieves, which can effectively reduce production costs.
[0098] The embodiments provided by the present invention have been described in detail above. Specific examples have been used to illustrate the principles and implementation methods of the present invention, and the descriptions of the embodiments above are only for the purpose of helping to understand the core ideas of the present invention. It should be noted that those skilled in the art can make several improvements and modifications to the present invention without departing from the principles of the present invention, and these improvements and modifications also fall within the protection scope of the claims of the present invention.
Claims
1. A method for producing SSZ-13 zeolite molecular sieve, characterized in that, as follows: S1. Mix the silicon source, aluminum source, alkali source, template agent, ethylenediamine and deionized water evenly to obtain the precursor solution; S2. Add seed crystals to the forward driving solution and stir until homogeneous; S3. The precursor solution containing seed crystals is subjected to hydrothermal crystallization. After crystallization, the product is washed and dried, and then calcined to obtain nanoscale SSZ-13 zeolite molecular sieve.
2. The production method according to claim 1, characterized in that, In step S1, the silicon source, aluminum source, and alkali source are represented in oxide form and calculated by molar amount. SiO2:Al2O3:T:EDA:M x O y :H2O=1:(0.001~0.15):(0.001~0.5):(0.01~0.6):(0.05~0.4):(10~80), where T represents the template agent, EDA represents ethylenediamine, and M represents the metal element in the alkali source. x O y This indicates the metal oxide corresponding to the metal element in the alkali source.
3. The production method according to claim 2, characterized in that, Based on the amount of substance, when (T+EDA) / SiO2 > 0.4 and EDA / T > 0.3 in the current driving fluid, nanoscale SSZ-13 zeolite molecular sieves with a particle size < 900 nm can be prepared.
4. The production method according to claim 1, characterized in that, In step S2, the seed crystals include CHA-type zeolite seed crystals.
5. The production method according to claim 1, characterized in that, In step S2, the amount of seed crystal added is 0.01 to 5 wt% of the total mass of the precursor liquid silicon source.
6. The production method according to claim 1, characterized in that, In step S3, the temperature for hydrothermal crystallization is 140–180°C.
7. The production method according to claim 1, characterized in that, In steps S1 and S2, the stirring temperature is 20–100°C.
8. The production method according to claim 1, characterized in that, In step S3, the calcination temperature is 500–600°C.
9. An SSZ-13 zeolite molecular sieve, characterized in that, It is produced by the production method described in any one of claims 1-8.
10. An application of SSZ-13 zeolite molecular sieve, characterized in that, The SSZ-13 zeolite molecular sieve produced by the production method according to any one of claims 1-8 is used in the fields of catalysis, adsorption, membrane separation and ion exchange.