A ssz-112 zeolitic molecular sieve, method of making and use thereof
By using a novel organic template agent to synthesize highly crystalline SSZ-112 zeolite molecular sieve, the problem of poor crystallinity was solved, and excellent performance in carbon dioxide adsorption separation and denitrification catalysis was achieved, thus expanding its application range.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- JILIN UNIVERSITY
- Filing Date
- 2024-06-18
- Publication Date
- 2026-06-05
AI Technical Summary
The crystallinity of the existing SSZ-112 zeolite molecular sieve is extremely poor, which limits its application in DeNOx denitrification reaction and gas adsorption separation. In addition, the traditional liquid amine solution adsorption and separation of carbon dioxide has problems of high energy consumption and instability.
Highly crystalline SSZ-112 zeolite molecular sieves were synthesized by hydrothermal crystallization and calcination using Et6-diquat-n dibromide and 1-propyl-1-methylpyrrole bromide as organic template agents. These sieves are used for the selective adsorption and separation of carbon dioxide and are applied in the field of denitrification catalysis.
The system achieves high regeneration performance and denitrification catalytic performance of SSZ-112 zeolite molecular sieve in selective adsorption and separation of carbon dioxide, solves the crystallinity problem, and expands its application field.
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Figure CN118702122B_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of molecular sieve technology, and in particular to an SSZ-112 zeolite molecular sieve, its preparation method, and its application. Background Technology
[0002] SSZ-112 zeolite is a small-pore, eight-membered ring silica-alumina zeolite molecular sieve with an AFT topology. In 2021, Xie, D. synthesized the AFT topology silica-alumina zeolite molecular sieve SSZ-112 for the first time using two dual organic template agents: bis(hexamethylamine) / 1-butyl-1-methylpiperidine and bis(hexamethylamine) / 1-propyl-1-methylpyrrole. However, the SSZ-112 zeolite molecular sieve synthesized using these two dual organic template agents faces problems such as extremely poor crystallinity and the presence of a large amount of amorphous material in the synthesized product, which in turn leads to difficulties in the DeNOx assay of SSZ-112 zeolite molecular sieve. x The common applications of small-pore zeolite molecular sieves, such as denitration reactions, methylamine-catalyzed synthesis, and gas adsorption separation, have not been explored. This also indicates that the two dual organic templater systems used by Xie, D., namely bis(hexamethylamine) / 1-butyl-1-methylpiperidine and bis(hexamethylamine) / 1-propyl-1-methylpyrrole, do not provide good guidance for the synthesis of SSZ-112 zeolite molecular sieves.
[0003] In 2016, Nature (Nature, 532, 435-437, 2016) listed adsorption and separation technology for low-concentration greenhouse gases in emissions as one of the seven gas adsorption and separation technologies that could change the world. Carbon dioxide, as a typical greenhouse gas, is receiving increasing attention. Some predict that atmospheric carbon dioxide levels will rise from the current 400 ppm to 900 ppm by the end of this century. Currently, industrial applications mainly use liquid amine solutions to adsorb and separate carbon dioxide from flue gas. However, regenerating liquid amine solutions requires a large amount of energy, and its alkalinity can cause corrosion to equipment, significantly increasing industrial costs. Furthermore, liquid amine solutions are unstable and subject to oxidative degradation. Zeolite molecular sieves, due to their excellent hydrothermal stability and easy regeneration, are widely used for the adsorption and separation of small-molecule carbon dioxide gases. In addition, AFT (Alternating Thermal Phosphate), as a small-pore zeolite molecular sieve, also has great potential in the field of denitrification catalysis. Summary of the Invention
[0004] The purpose of this invention is to provide an SSZ-112 zeolite molecular sieve, its preparation method, and its applications. The SSZ-112 zeolite molecular sieve prepared by this invention has high crystallinity, can be used for selective adsorption and separation of carbon dioxide, is easily regenerated, and exhibits excellent structural stability. Furthermore, SSZ-112 also demonstrates excellent catalytic performance in the field of denitrification catalysis.
[0005] To achieve the above-mentioned objectives, the present invention provides the following technical solution:
[0006] This invention provides a method for preparing SSZ-112 zeolite molecular sieve, comprising the following steps:
[0007] Water, alkali source, first template agent, second template agent, silicon source and aluminum source are mixed to obtain an initial reaction gel; the silicon source and aluminum source are calculated as SiO2 and Al2O3 respectively, and the molar ratio of the first template agent, second template agent, silicon source, aluminum source, alkali source and water is (1~15):(6~30):(10~80):1:(10~50):(1000~5000);
[0008] The first template agent is Et6-diquat-n dibromide, where n is an integer from 2 to 10, and has the structure shown in Equation 1;
[0009] The second template agent is bromopropyl-1-methylpyrrole, having the structure shown in Formula 2;
[0010]
[0011] The initial reactive gel was subjected to hydrothermal crystallization to obtain the SSZ-112 zeolite molecular sieve precursor.
[0012] The SSZ-112 zeolite molecular sieve precursor was calcined to obtain the SSZ-112 zeolite molecular sieve.
[0013] Preferably, the silicon source includes one or more of LTA zeolite, FAU zeolite, MFI zeolite, tetraethyl orthosilicate, HS-40, sodium silicate, and silica.
[0014] Preferably, the aluminum source includes one or more of aluminum hydroxide, aluminum oxide, aluminum chloride, aluminum sulfate, sodium aluminate, boehmite, FAU zeolite, LTA zeolite, and MFI zeolite.
[0015] Preferably, the alkali source includes one or more of sodium hydroxide, potassium hydroxide, cesium hydroxide, and lithium hydroxide.
[0016] Preferably, the hydrothermal crystallization temperature is 110–220°C, and the time is 1–10 days.
[0017] Preferably, the hydrothermal crystallization is static hydrothermal crystallization or dynamic hydrothermal crystallization, and the rotation speed of the dynamic hydrothermal crystallization is 5 to 100 rpm.
[0018] Preferably, the calcination temperature is 400–600°C, and the holding time is 5–10 hours.
[0019] The present invention provides SSZ-112 zeolite molecular sieve prepared by the preparation method described above.
[0020] This invention provides the application of the SSZ-112 zeolite molecular sieve described above in the selective adsorption and separation of carbon dioxide in a mixed gas.
[0021] This invention provides the application of the SSZ-112 zeolite molecular sieve described above as a catalyst in the field of denitrification.
[0022] This invention provides a method for preparing SSZ-112 zeolite molecular sieve, comprising the following steps: mixing water, an alkali source, a first template agent, a second template agent, a silicon source, and an aluminum source to obtain an initial reaction gel; wherein the silicon source and aluminum source are respectively calculated as SiO2 and Al2O3, and the molar ratio of the first template agent, the second template agent, the silicon source, the aluminum source, the alkali source, and water is (1-15):(6-30):(10-80):1:(10-50):(1000-5000); the first template agent is Et6-diquat-n dibromide, where n is an integer from 2 to 10, and has the structure shown in Formula 1; the second template agent is bromo-1-propyl-1-methylpyrrole, and has the structure shown in Formula 2; hydrothermally crystallizing the initial reaction gel to obtain an SSZ-112 zeolite molecular sieve precursor; calcining the SSZ-112 zeolite molecular sieve precursor to obtain the SSZ-112 zeolite molecular sieve.
[0023] This invention uses Et6-diquat-n dibromide (n = 2-10) and bromo-1-propyl-1-methylpyrrole as organic template agents. The SSZ-112 zeolite molecular sieve (AFT topology) synthesized by this new dual organic template agent system has high crystallinity and no amorphous structure.
[0024] The SSZ-112 zeolite molecular sieve prepared by this invention exhibits excellent selective adsorption and separation performance of carbon dioxide, showing broad prospects in the field of flue gas carbon dioxide capture. Simultaneously, SSZ-112 also demonstrates excellent catalytic performance in the field of denitrification catalysis. Attached Figure Description
[0025] Figure 1 The XRD patterns are of sample S1 prepared in Example 1 and sample S2 prepared in Comparative Example 1.
[0026] Figure 2 SEM images of sample S1 (a) prepared in Example 1 and sample S2 (b) prepared in Comparative Example 1;
[0027] Figure 3 The CO2 and N2 adsorption isotherms of the S1 sample prepared in Example 1 at 298 K;
[0028] Figure 4CO2 and N2 adsorption isotherms of the S2 sample prepared for Comparative Example 1 at 298 K;
[0029] Figure 5 Catalytic performance curves of sample S1 prepared in Example 1 and sample S2 prepared in Comparative Example 1 in the field of denitrification. Detailed Implementation
[0030] This invention provides a method for preparing SSZ-112 zeolite molecular sieve, comprising the following steps:
[0031] Water, alkali source, first template agent, second template agent, silicon source and aluminum source are mixed to obtain an initial reaction gel; the silicon source and aluminum source are calculated as SiO2 and Al2O3 respectively, and the molar ratio of the first template agent, second template agent, silicon source, aluminum source, alkali source and water is (1~15):(6~30):(10~80):1:(10~50):(1000~5000);
[0032] The first template agent is Et6-diquat-n dibromide, where n is an integer from 2 to 10, and has the structure shown in Equation 1;
[0033] The second template agent is bromopropyl-1-methylpyrrole, having the structure shown in Formula 2;
[0034]
[0035] The initial reactive gel was subjected to hydrothermal crystallization to obtain the SSZ-112 zeolite molecular sieve precursor.
[0036] The SSZ-112 zeolite molecular sieve precursor was calcined to obtain the SSZ-112 zeolite molecular sieve.
[0037] Unless otherwise specified, all raw materials used in this invention are commercially available products well known in the art.
[0038] The present invention mixes water, an alkali source, a first template agent, a second template agent, a silicon source, and an aluminum source to obtain an initial reaction gel.
[0039] In this invention, the alkali source preferably includes one or more of sodium hydroxide, potassium hydroxide, cesium hydroxide, and lithium hydroxide, more preferably sodium hydroxide or potassium hydroxide; the silicon source preferably includes one or more of LTA zeolite, FAU zeolite, MFI zeolite, tetraethyl orthosilicate, HS-40, sodium silicate, and silica; the aluminum source preferably includes one or more of aluminum hydroxide, alumina, aluminum chloride, aluminum sulfate, sodium aluminate, boehmite, FAU zeolite, LTA zeolite, and MFI zeolite.
[0040] In this invention, the first template agent is Et6-diquat-n dibromide, where n is an integer from 2 to 10; in a specific embodiment of this invention, n is 3.
[0041] In this invention, the first and second template agents can be prepared using commercially available products or methods well-known in the art. Preferably, the first and second template agents are prepared in-house.
[0042] In this invention, the preferred method for preparing the first template agent includes the following steps: triethylamine is mixed with 1,n-dibromo-n-alkyl (n = 2 to 10, corresponding to the Chinese names ethyl, propane, butane, pentane, hexane, heptane, octane, nonane, decane, such as 1,3-dibromo-n-propane) and methanol at a molar ratio of 2:1:3, stirred at room temperature for 24 hours, and after the reaction is completed, the solid product is washed with diethyl ether and dried in an oven at 50°C for 12 hours to obtain the first template agent Et6-diquat-n dibromide (structure shown in Formula 1, n = 2 to 10, corresponding to the Chinese names ethyl, propane, butane, pentane, hexane, heptane, octane, nonane, decane).
[0043]
[0044] In this invention, the preparation method of the second template agent preferably includes the following steps:
[0045] 1-Methylpyrrole, bromopropane and methanol were mixed in a molar ratio of 1:1:2 and stirred at room temperature for 24 hours. After the reaction was completed, the solid product was washed with tetrahydrofuran and dried in an oven at 50°C for 12 hours to obtain the second template agent, bromo-1-propyl-1-methylpyrrole (structure shown in Formula 2).
[0046]
[0047] In this invention, the silicon source and aluminum source are SiO2 and Al2O3, respectively. The molar ratio of the first template agent, the second template agent, the silicon source, the aluminum source, the alkali source and water is (1-15):(6-30):(10-80):1:(10-50):(1000-5000), preferably (1-15):(8-25):(15-70):1:(15-40):(1000-4500), and more preferably (3-15):(10-20):(15-60):1:(15-40):(1500-4000).
[0048] In this invention, the mixing of water, alkali source, first template agent, second template agent, silicon source and aluminum source preferably includes: adding water, alkali source, first template agent and second template agent into a beaker and stirring for 10 min to form a transparent solution; then adding silicon source into the beaker and stirring until the silicon source is completely dissolved; then adding aluminum source into the beaker and letting it stand and stir for 12 h to obtain the initial reaction gel.
[0049] After obtaining the initial reactive gel, the present invention performs hydrothermal crystallization on the initial reactive gel to obtain the SSZ-112 zeolite molecular sieve precursor.
[0050] In this invention, the hydrothermal crystallization temperature is preferably 110–220°C, more preferably 140–210°C, and even more preferably 150–180°C. The hydrothermal crystallization time is preferably 1–10 days, more preferably 1–13 days, and even more preferably 3–10 days. In this invention, the hydrothermal crystallization is preferably carried out in a high-pressure reactor. The hydrothermal crystallization is preferably static or dynamic, and the rotation speed of the dynamic hydrothermal crystallization is preferably 5–100 rpm, more preferably 10–80 rpm, and even more preferably 20–70 rpm.
[0051] After hydrothermal crystallization, the present invention preferably performs solid-liquid separation on the resulting system, and washes and dries the resulting solid material to obtain the SSZ-112 zeolite molecular sieve precursor. The present invention does not have a particular limitation on the method of solid-liquid separation; any solid-liquid separation method well known in the art can be used, such as vacuum filtration or centrifugation. In the present invention, the washing is preferably water washing, and the water washing is preferably performed multiple times until the washing liquid is neutral. The present invention does not have a particular limitation on the drying method; any drying method well known to those skilled in the art can be used. In the embodiments of the present invention, the drying method is preferably oven drying, the drying temperature is preferably 50–140°C, more preferably 70–120°C, and even more preferably 80°C; the drying time is preferably 12 hours.
[0052] After obtaining the SSZ-112 zeolite molecular sieve precursor, the present invention calcines the SSZ-112 zeolite molecular sieve precursor to obtain the SSZ-112 zeolite molecular sieve.
[0053] In this invention, the calcination temperature is preferably 400–600°C, more preferably 400–550°C; the holding time is preferably 5–10 h, more preferably 6–8 h; and the calcination is preferably carried out in an air atmosphere. This invention removes organic template agents through calcination.
[0054] The present invention provides SSZ-112 zeolite molecular sieve prepared by the preparation method described above.
[0055] This invention uses Et6-diquat-n dibromide (n = 2-10) and bromo-1-propyl-1-methylpyrrole as organic template agents. The SSZ-112 zeolite molecular sieve (AFT topology) synthesized by this new dual organic template agent system has high crystallinity and no amorphous structure.
[0056] This invention provides the application of the SSZ-112 zeolite molecular sieve described above in the selective adsorption and separation of carbon dioxide in a mixed gas, specifically, the SSZ-112 zeolite molecular sieve serves as a selective adsorbent for carbon dioxide. In this invention, the mixed gas preferably comprises carbon dioxide and nitrogen. This invention does not impose any special requirements on the ratio of carbon dioxide to nitrogen in the mixed gas; any ratio is acceptable. In the embodiments of this invention, the SSZ-112 zeolite molecular sieve serves as a selective adsorbent for carbon dioxide in a mixture of carbon dioxide and nitrogen (CO2-N2).
[0057] Before adsorbing carbon dioxide, the present invention preferably activates the SSZ-112 zeolite molecular sieve; the activation preferably includes: activating the SSZ-112 zeolite molecular sieve under vacuum and at 200-450°C. The present invention does not have a particular limitation on the vacuum degree, and a vacuum degree well known in the art can be used; the activation time is preferably 8-12 hours.
[0058] This invention provides the application of the SSZ-112 zeolite molecular sieve described above as a catalyst in the field of denitrification. Preferably, the SSZ-112 zeolite molecular sieve is pressed into tablets and crushed under a pressure of 1–4 MPa, then sieved to obtain granular SSZ-112 zeolite molecular sieve catalyst with a particle size of 40–60 mesh. In this invention, the denitrification temperature is preferably 300–550 °C. In an embodiment of this invention, the denitrification reaction conditions are: 500 ppm NO, 500 ppm NH3, 5 vol% O2, 5 vol% water vapor, with N2 as the equilibrium gas, a total flow rate of 500 mL / min, and a gas space velocity (GHSV) of 200,000 h⁻¹. -1 The composition of inlet and outlet gases was monitored using an FTIR spectrometer (MKS, MultiGas 2030HS).
[0059] The following detailed description of the SSZ-112 zeolite molecular sieve, its preparation method, and its application provided by the present invention, with reference to specific embodiments, should not be construed as limiting the scope of protection of the present invention.
[0060] Example 1
[0061] The novel dual-organic templater system was used to prepare SSZ-112 zeolite molecular sieves, as follows:
[0062] Triethylamine was mixed with 1,3-dibromo-n-propane and methanol in a molar ratio of 2:1:3 and stirred at room temperature for 24 hours. After the reaction was completed, the solid product was washed with diethyl ether and dried in an oven at 50°C for 12 hours to obtain the organic template agent Et6-diquat-3dibromide.
[0063] 1-Methylpyrrole was mixed with bromopropane and methanol in a molar ratio of 1:1:2 and stirred at room temperature for 24 hours. After the reaction was completed, the solid product was washed with tetrahydrofuran and dried in an oven at 50°C for 12 hours to obtain the organic template agent bromopropyl-1-methylpyrrole.
[0064] Using an electronic balance, 10.00 g of water, 0.312 g of potassium hydroxide, 1.682 g of organic template agent Et6-diquat-3-dibromide, and 0.866 g of organic template agent 1-propyl-1-methylpyrrole were weighed and added sequentially to a beaker. The mixture was stirred for 10 min to form a transparent solution. Then, 0.334 g of silica was added to the beaker and stirred until completely dissolved. Next, 0.118 g of aluminum nitrate was added to the beaker, and the mixture was allowed to stand and stir for 12 h to obtain the initial reaction gel (Et6-diquat-3-dibromide: 1-propyl-1-methylpyrrole: SiO2: Al2O3: KOH: H2O = 15:15:20:1:20:2000). This invention involves hydrothermal crystallization of the initial reaction gel to obtain the SSZ-112 zeolite molecular sieve precursor. After hydrothermal treatment, the product was washed with deionized water until the washing solution was neutral. The washed product was then placed in an oven to dry. Finally, it was calcined in a muffle furnace at 550°C for 6 hours. The final product was designated as sample S1.
[0065] The XRD pattern of sample S1 obtained in Example 1 is shown below. Figure 1 As shown. (The sentence is incomplete and requires more context.) Figure 1 XRD characterization showed that the new dual organic template system successfully synthesized highly crystalline SSZ-112 zeolite molecular sieve.
[0066] The SEM image of sample S1 obtained in Example 1 is shown below. Figure 2 As shown in (a). Figure 2 (a) shows that the particle size of sample S1 is around 220 nm and there is no amorphous particle.
[0067] Comparative Example 1
[0068] SSZ-112 zeolite molecular sieve was synthesized using the dihexamethylene hydroxide / 1-propyl-1-methylpiperidine hydroxide dual organic templater system proposed by Xie, D., and the same initial gel ratio as in the experimental example.
[0069] Trimethylamine was mixed with 1,6-dibromohexane and methanol in a molar ratio of 2:1:3 and stirred at room temperature for 24 hours. After the reaction was complete, the solid product was washed with diethyl ether and dried in an oven at 50°C for 12 hours to obtain bromodihexamethylenediamine. Then, bromodihexamethylenediamine was exchanged with an ion exchange resin to form a solution of bromodihexamethylenediamine hydroxide. Finally, the concentration of the bromodihexamethylenediamine hydroxide solution was titrated with standard concentration hydrochloric acid solution to obtain 21 wt%.
[0070] 1-Methylpiperidine was mixed with propane bromide and methanol in a molar ratio of 1:1:2 and stirred at room temperature for 24 hours. After the reaction was complete, the solid product was washed with tetrahydrofuran and dried in an oven at 50°C for 12 hours to obtain 1-propyl-1-methylpiperidine bromide. Then, 1-propyl-1-methylpyrrole bromide was exchanged with an ion exchange resin to form a solution of 1-propyl-1-methylpiperidine hydroxide. Finally, the concentration of the 1-propyl-1-methylpiperidine hydroxide solution was titrated with standard concentration hydrochloric acid solution to obtain a concentration of 16 wt%.
[0071] 10.00 g of water, 1.104 g of potassium hydroxide, 16.589 g of hexamethylamine hydroxide solution, and 14.669 g of 1-propyl-1-methylpyrrole hydroxide solution were weighed using an electronic balance and added sequentially to a beaker. The mixture was stirred for 10 min to form a transparent solution. Then, 1.182 g of silica was added to the beaker and stirred until completely dissolved. Next, 0.419 g of aluminum nitrate was added to the beaker, and the mixture was allowed to stand and stir for 12 h to obtain the initial reaction gel (hexamethylamine hydroxide solution: 1-propyl-1-methylpiperidine hydroxide: SiO2: Al2O3: KOH: H2O = 15:15:20:1:20:2000). The initial reaction gel was then subjected to hydrothermal crystallization to obtain the SSZ-112 zeolite molecular sieve precursor. After hydrothermal treatment, the product was washed with deionized water until the washing solution was neutral, and then dried in an oven. Finally, the sample was placed in a muffle furnace and calcined at 550°C for 6 hours. The final product was recorded as sample S2.
[0072] The XRD pattern of sample S2 obtained in Comparative Example 1 is shown below. Figure 1 As shown. (The sentence is incomplete and requires more context.) Figure 1 XRD characterization showed that the SSZ-112 zeolite molecular sieve synthesized by this dual organic template system had very poor crystallinity.
[0073] The SEM image of sample S2 obtained in Comparative Example 1 is shown below. Figure 2 As shown in (b). Figure 2 (b) shows that the S2 sample contains a large amount of amorphous material.
[0074] Application Example 1
[0075] The S1 sample prepared in Example 1 and the S2 sample prepared in Comparative Example 1 were subjected to gas selective adsorption separation tests. The sample after calcination to remove the organic template agent was activated under vacuum at 350°C for 10 h. After the sample cooled to room temperature, a single-component gas isothermal adsorption-desorption test was performed at a test temperature of 298 K and a test pressure of 0 to 1 bar.
[0076] Figure 3 and Figure 4 The CO2 and N2 adsorption isotherms at 298 K are shown for sample S1 prepared in Example 1 and sample S2 prepared in Comparative Example 1, respectively. The CO2 / N2 adsorption and separation performance of sample S1 prepared in Example 1 and sample S2 prepared in Comparative Example 1 are listed in Table 2.
[0077] Table 2. Adsorption and separation performance of CO2 / N2 by zeolite molecular sieves
[0078]
[0079] From Table 2 and Figures 3-4 As shown, the SSZ-112 zeolite molecular sieve prepared by the present invention with a novel dual organic templater system exhibits superior CO2 / N2 gas adsorption and separation performance compared with the SSZ-112 zeolite molecular sieve prepared with a dihexamethyleneamine / 1-butyl-1-methylpyrrole dual organic templater system, and has a high selective adsorption performance for carbon dioxide.
[0080] Application Example 2
[0081] The S1 sample prepared in Example 1 and the S2 sample prepared in Comparative Example 1 were tested for denitrification catalytic reaction. The samples were crushed and sieved under a pressure of 1–4 MPa to obtain granular SSZ-112 zeolite molecular sieve catalyst with a particle size of 40–60 mesh. The reaction conditions were: 500 ppm nitric oxide, 500 ppm ammonia, 5 vol% O2, 5 vol% water vapor, with N2 as the equilibrium gas. The total flow rate was 500 mL / min, and the gas space velocity (GHSV) was 200,000 h⁻¹. -1 The composition of inlet and outlet gases was monitored using an FTIR spectrometer (MKS, MultiGas2030HS).
[0082] Depend on Figure 5 As shown, the SSZ-112 zeolite molecular sieve prepared by the present invention with the novel dual organic template system exhibits superior denitrification catalytic performance compared with the SSZ-112 zeolite molecular sieve prepared by the dihexamethyleneamine / 1-butyl-1-methylpyrrole dual organic template system. The specific data are shown in Table 3.
[0083] Table 3. Denitrification catalytic performance of zeolite molecular sieves
[0084] sample Temperature range (conversion rate above 80%) <![CDATA[Sample S1 of Example 1]]> 280～550℃ <![CDATA[Sample S2 of Comparative Example 1]]> 350～450℃
[0085] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.
Claims
1. A method for preparing SSZ-112 zeolite molecular sieve, characterized in that, Includes the following steps: Water, alkali source, first template agent, second template agent, silicon source and aluminum source are mixed to obtain an initial reaction gel; the silicon source and aluminum source are calculated as SiO2 and Al2O3 respectively, and the molar ratio of the first template agent, second template agent, silicon source, aluminum source, alkali source and water is (1~15):(6~30):(10~80):1:(10~50):(1000~5000); The first template agent is Et6-diquat-ndibromide, where n is an integer from 2 to 10, and has the structure shown in Equation 1; The second template agent is bromopropyl-1-methylpyrrole, having the structure shown in Formula 2; The initial reactive gel was subjected to hydrothermal crystallization to obtain the SSZ-112 zeolite molecular sieve precursor. The SSZ-112 zeolite molecular sieve precursor was calcined to obtain the SSZ-112 zeolite molecular sieve.
2. The preparation method according to claim 1, characterized in that, The silicon source includes one or more of LTA zeolite, FAU zeolite, MFI zeolite, tetraethyl orthosilicate, HS-40, sodium silicate, and silica.
3. The preparation method according to claim 1, characterized in that, The aluminum source includes one or more of aluminum hydroxide, aluminum oxide, aluminum chloride, aluminum sulfate, sodium aluminate, boehmite, FAU zeolite, LTA zeolite, and MFI zeolite.
4. The preparation method according to claim 1, characterized in that, The alkaline source includes one or more of sodium hydroxide, potassium hydroxide, cesium hydroxide, and lithium hydroxide.
5. The preparation method according to claim 1, characterized in that, The hydrothermal crystallization temperature is 110–220°C, and the time is 1–10 days.
6. The preparation method according to claim 1 or 5, characterized in that, The hydrothermal crystallization is either static or dynamic, and the rotation speed of the dynamic hydrothermal crystallization is 5 to 100 rpm.
7. The preparation method according to claim 1, characterized in that, The calcination temperature is 400–600℃, and the holding time is 5–10 hours.
8. The SSZ-112 zeolite molecular sieve prepared by the preparation method according to any one of claims 1 to 7.
9. The application of the SSZ-112 zeolite molecular sieve of claim 8 in the selective adsorption and separation of carbon dioxide in a mixed gas.
10. The application of the SSZ-112 zeolite molecular sieve of claim 8 as a catalyst in the field of denitrification.