Preparation method and application of ping-pong-like SAPO-15 zeolite molecular sieve
Through a new preparation method, the ping-pong chrysanthemum SAPO-15 zeolite molecular sieve was successfully synthesized, which solved the problem of low application caused by its single morphology, significantly improved its catalytic activity and selectivity, especially in the hydrogenation of carbon dioxide to methanol reaction.
Patent Information
- Application Number
- CN202510194568.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-02-21
- Publication Date
- 2025-05-30
AI Technical Summary
The SAPO-15 zeolite molecular sieve has few studies and a single morphology, which leads to its low application. The morphology has an impact on structural integrity, active specific surface area and the distribution of active species, which in turn affects adsorption and catalytic efficiency.
A method of preparing a SAPO-15 zeolite molecular sieve like pingpong chrysanthemum-like SAPO-15 zeolite molecular sieve is obtained by adding aluminum source, phosphorus source, silicon source, organic amine structure guide agent and inorganic structure guide agent to water in sequence, and performing a crystallization reaction of 48-60 hours at 190-220°C.
This method successfully synthesized SAPO-15 zeolite molecular sieve with special morphology, which significantly improved its catalytic activity and selectivity, and showed high efficiency in the hydrogenation of carbon dioxide to methanol.
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Figure CN120057950A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of zeolite molecular sieves, and particularly relates to a preparation method and application of a ping-pong chrysanthemum-like SAPO-15 zeolite molecular sieve. Background Art
[0002] Silicoaluminophosphate zeolite molecular sieves (SAPOs) are a kind of silicoaluminophosphate with a new crystal structure obtained by introducing Si atoms into the aluminophosphate framework. Its framework consists of PO 4 , AlO 4 , SiO 4 tetrahedrons as primary structural units, which are interconnected by oxygen bridge bonds to form ring structures such as six-membered rings and twelve-membered rings. These unique framework compositions and structural characteristics endow silicoaluminophosphate zeolite molecular sieves with rich pore structures, high specific surface areas, strong ion exchange properties and surface acidity, so they have been widely studied and applied in catalysis, adsorption and separation, etc.
[0003] Common silicoaluminophosphate zeolite molecular sieves include SAPO-11, SAPO-18, SAPO-31, SAPO-41, SAPO-56, etc. Others such as SAPO-15, SAPO-20, etc. are rarely reported. Among them, as a typical silicoaluminophosphate zeolite molecular sieve, the framework of SAPO-15 is also composed of silicon-oxygen tetrahedrons, aluminum-oxygen tetrahedrons and phosphorus-oxygen tetrahedrons connected by oxygen bridges, and has a multi-dimensional pore structure composed of four-membered rings and six-membered rings. All along, there has been little research on SAPO-15, and the synthesized zeolite samples are all in the shape of flakes or cubic shapes stacked by flakes. The morphology is relatively single, and this flaky morphology is extremely vulnerable to damage, which affects the integrity of the zeolite particles and is not conducive to its subsequent application and promotion. It should be noted that for zeolite molecular sieves, the morphology can not only affect their structural integrity, active specific surface area and the distribution of active species, thus changing their adsorption and catalytic efficiency, but also an appropriate morphology can promote the optimization of the diffusion paths of reactants and products in the zeolite pores, thereby improving the selectivity and efficiency of specific reactions. Therefore, we propose to synthesize a SAPO-15 zeolite molecular sieve with a special ping-pong chrysanthemum-like morphology. This unique morphology is beneficial to expose more surface active sites, thereby enhancing its catalytic and adsorption efficiency, and showing high catalytic activity and selectivity for the hydrogenation of carbon dioxide to methanol. Summary of the Invention
[0004] In view of the problems of less research, single morphology, and low application value of SAPO-15 zeolite molecular sieve, the present invention provides a preparation method of a ping-pong chrysanthemum-like SAPO-15 zeolite molecular sieve. The SAPO-15 zeolite molecular sieve synthesized by the method of the present invention has a flower-like microstructure similar to that of a ping-pong chrysanthemum, and when used as a carrier to load transition metals to form a catalyst for the reaction of hydrogenating carbon dioxide to methanol, it exhibits high catalytic activity and selectivity.
[0005] To achieve the above object, the present invention is realized through the following technical solutions:
[0006] A preparation method of a ping-pong chrysanthemum-like SAPO-15 zeolite molecular sieve, comprising the following steps:
[0007] (1) Add an aluminum source, a phosphorus source, a silicon source, an organic amine structure-directing agent, and an inorganic structure-directing agent to water in sequence. After adding each raw material, stir evenly and then add other raw materials;
[0008] (2) Continue to stir for several hours after all raw materials are added;
[0009] (3) Carry out a crystallization reaction on the mixture at 190-220 °C for 48-60 hours;
[0010] (4) After the crystallization reaction ends, filter and wash to obtain a ping-pong chrysanthemum-like SAPO-15 zeolite molecular sieve;
[0011] Wherein, the inorganic structure-directing agent is an inorganic compound of ammonium salt or ammonia water, and R represents the organic amine structure-directing agent;
[0012] The aluminum source is measured by Al 2 O 3 The phosphorus source is measured by P 2 O 5 The silicon source is measured by SiO 2 The inorganic structure-directing agent is measured by NH 4 + The molar ratio of the feed amounts of each raw material is Al 2 O 3 :H 2 O:P 2 O 5 :SiO 2 :NH 4 + :R = 1.0:41.3:0.87:(0.73-0.79):(0.75-1.3):1.48.
[0013] Preferably, the above aluminum source is pseudo-boehmite.
[0014] Preferably, the above phosphorus source is an 85% wt phosphoric acid aqueous solution.
[0015] Preferably, the above-mentioned silicon source is tetraethyl orthosilicate.
[0016] Preferably, the above-mentioned inorganic structure-directing agent is ammonium chloride.
[0017] Preferably, the above-mentioned organic amine structure-directing agent is morpholine.
[0018] Preferably, the pH of the above-mentioned control system is 2.5 - 12.5; preferably pH = 5.5.
[0019] Preferably, the temperature of the above-mentioned crystallization reaction is 180 - 220 °C; the time of the crystallization reaction is 24 - 72 h.
[0020] Furthermore, the temperature of the crystallization reaction is 190 - 200 °C; the time of the crystallization reaction is 48 - 60 h.
[0021] Furthermore, the time of the continued stirring is 24 h; after the crystallization reaction, the operations of washing the product with water and drying are also included.
[0022] The present invention also provides an application of the ping-pong chrysanthemum-like SAPO-15 zeolite molecular sieve in the reaction of hydrogenating carbon oxides to prepare alcohol compounds, and the ping-pong chrysanthemum-like SAPO-15 zeolite molecular sieve is loaded with a transition metal or a transition metal oxide to be used as a catalyst.
[0023] Preferably, the above-mentioned transition metal is one or more of Zr, Ni, Co, Zn, Cu, and Fe.
[0024] Preferably, the above-mentioned transition metal is a Cu-containing metal or a Cu-containing metal oxide.
[0025] In addition, the present invention also provides a ping-pong chrysanthemum-like SAPO-15 zeolite molecular sieve obtained by the above preparation method.
[0026] In addition, the present invention also provides a catalyst comprising the above-mentioned ping-pong chrysanthemum-like SAPO-15 zeolite molecular sieve and a transition metal or a transition metal oxide.
[0027] Preferably, the above-mentioned transition metal is one or more of Zr, Ni, Co, Zn, Cu, and Fe.
[0028] Preferably, the above-mentioned transition metal is a Cu-containing metal or a Cu-containing metal oxide.
[0029] Beneficial technical effects:
[0030] The present invention provides a method for preparing a ping-pong chrysanthemum-like SAPO-15 zeolite molecular sieve. The template agent used in the present invention for synthesizing SAPO-15 zeolite is morpholine. By using tetraethyl orthosilicate as the silicon source and changing the reaction time and temperature, a ping-pong chrysanthemum-like SAPO-15 zeolite molecular sieve can be obtained, providing a new method for the morphology research of SAPO-15 molecular sieve. Moreover, after the obtained ping-pong chrysanthemum-like SAPO-15 zeolite molecular sieve is used as a catalyst support to load transition metals in the reaction of hydrogenating carbon dioxide to methanol, it can effectively catalyze the conversion of carbon dioxide to methanol. Description of the Drawings
[0031] Figure 1 XRD patterns of SAPO-15 zeolite molecular sieves synthesized with silicon sources; Example 1 is tetraethyl orthosilicate, Example 2 is water glass, and Example 3 is fumed silica.
[0032] Figure 2 XRD patterns of SAPO-15 zeolite molecular sieves synthesized at different pH values; Example 4 is pH = 2.5, Example 5 is pH = 5.5, Example 6 is pH = 7.5, Example 7 is pH = 10.5, and Example 8 is pH = 12.5.
[0033] Figure 3 XRD patterns of SAPO-15 zeolite molecular sieves synthesized at different crystallization reaction temperatures; Example 9 is 180 °C, Example 10 is 190 °C (Example 10), Example 11 is 200 °C, Example 12 is 210 °C, and Example 13 is 220 °C.
[0034] Figure 4 XRD patterns of SAPO-15 zeolite molecular sieves synthesized at different crystallization reaction times; Example 14 is 24 h, Example 15 is 36 h, Example 16 is 48 h, Example 17 is 60 h, and Example 18 is 72 h.
[0035] Figure 5 SEM scanning electron microscope of the ping-pong chrysanthemum-like SAPO-15 zeolite molecular sieve prepared in Example 11 Figure 1 .
[0036] Figure 6 SEM scanning electron microscope of the ping-pong chrysanthemum-like SAPO-15 zeolite molecular sieve prepared in Example 11 Figure 2 .
[0037] Figure 7 SEM scanning electron microscope of the ping-pong chrysanthemum-like SAPO-15 zeolite molecular sieve prepared in Example 11 Figure 3 .
[0038] Figure 8SEM scanning electron microscopy of the ping-pong chrysanthemum-like SAPO-15 zeolite molecular sieve prepared in Example 11 Figure 4 。
[0039] Figure 9 It is the catalytic activity diagram of each catalyst for carbon dioxide conversion in Application Example 1. Detailed implementation manners
[0040] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the embodiments and drawings of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all of the embodiments. The following description of at least one exemplary embodiment is actually only illustrative and in no way limits the present invention and its application or use. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts belong to the scope of protection of the present invention.
[0041] Unless otherwise specifically stated, the numerical values set forth in these embodiments do not limit the scope of the present invention. Technologies and methods known to those of ordinary skill in the relevant art may not be discussed in detail, but where appropriate, the said technologies and methods should be regarded as part of the specification. In all examples shown and discussed herein, any specific value should be construed as merely exemplary and not as a limitation. Thus, other examples of the exemplary embodiments may have different values.
[0042] Solution A used in the following examples: Dissolve 4.6 g of pseudo-boehmite in 14 mL of H 2 O to obtain.
[0043] In the expression of "molar ratio of each material Al 2 O 3 :H 2 O:P 2 O 5 :SiO 2 :NH 4 + :R" in the following examples: Al 2 O 3 refers to the aluminum source, and the number of moles of the aluminum source is the number of moles of aluminum element in pseudo-boehmite; SiO 2 refers to the silicon source, and the number of moles of the silicon source is the number of moles of silicon element in tetraethyl orthosilicate or water glass or fumed silica; P 2 O 5 refers to the phosphorus source, and the number of moles of the phosphorus source is the number of moles of phosphorus element in phosphoric acid; NH 4 + refers to the inorganic structure directing agent, and R is the organic amine structure directing agent.
[0044] Example 1
[0045] Solution B: Obtained by dissolving 6.4729 g of tetraethyl orthosilicate in 7.5 mL of H 2 O.
[0046] Add 4.6 mL of phosphoric acid to Solution A, stir evenly, then add Solution B drop by drop, stir well, add 5.8 mL of morpholine, stir for 1 h, then add 2.6 g of ammonium chloride and 12 mL of H 2 O, stir for another 24 h to obtain a mixture. Then put the obtained mixture into a high-pressure reactor and place it in an oven at 190 °C for hydrothermal crystallization reaction for 48 h. After the crystallization is completed, cool the synthesis kettle to room temperature. Filter and wash the obtained product, place it in an oven at 90 °C and dry it overnight to obtain the product SAPO-15 molecular sieve. The molar ratio of each material fed in the system is Al 2 O 3 :H 2 O:P 2 O 5 :SiO 2 :NH 4 + :R = 1.0:41.3:0.87:0.76:0.75:1.48.
[0047] The crystallinity of the prepared SAPO-15 zeolite molecular sieve is shown in Table 1.
[0048] Example 2
[0049] Solution B: Obtained by dissolving 9.8 g of water glass in 7.5 mL of H 2 O.
[0050] Add 4.6 mL of phosphoric acid to Solution A, stir evenly, then add Solution B drop by drop, stir well, add 5.8 mL of morpholine, stir for 1 h, then add 2.6 g of ammonium chloride and 12 mL of H 2 O, stir for another 24 h to obtain a mixture. Then put the obtained mixture into a high-pressure reactor and place it in an oven at 190 °C for hydrothermal crystallization reaction for 48 h. After the crystallization is completed, cool the synthesis kettle to room temperature. Filter and wash the obtained product, place it in an oven at 90 °C and dry it overnight to obtain the product SAPO-15 molecular sieve. The molar ratio of each material fed in the system is Al 2 O 3 :H 2 O:P 2 O 5 :SiO 2 :NH 4 + :R = 1.0:41.3:0.87:0.76:0.75:1.48.
[0051] The crystallinity of the obtained SAPO-15 zeolite molecular sieve is shown in Table 1.
[0052] Example 3
[0053] Solution B: Obtained by dissolving 2.1 g of fumed silica in 7.5 mL of H 2 O.
[0054] Add 4.6 mL of phosphoric acid to Solution A, stir evenly, then add Solution B drop by drop, stir well, add 5.8 mL of morpholine, stir for 1 h, then add 2.6 g of ammonium chloride and 12 mL of H 2 O, and stir for another 24 h to obtain a mixture. Then put the obtained mixture into a high-pressure reaction kettle and place it in an oven at 190 °C for hydrothermal crystallization reaction for 48 h. After the crystallization is completed, cool the synthesis kettle to room temperature. The obtained product is filtered and washed by suction, and placed in an oven at 90 °C to dry overnight to obtain the product SAPO-15 molecular sieve. The molar ratio of each material in the system is Al 2 O 3 :H 2 O:P 2 O 5 :SiO 2 :NH 4 + :R = 1.0:41.3:0.87:0.76:0.75:1.48.
[0055] The crystallinity of the obtained SAPO-15 zeolite molecular sieve is shown in Table 1.
[0056] Experimental Example 4
[0057] Solution B: Obtained by dissolving 6.4729 g of tetraethyl orthosilicate in 7.5 mL of H 2 O.
[0058] Add 4.6 mL of phosphoric acid to Solution A, stir evenly, then add Solution B drop by drop, stir well, add 5.8 mL of morpholine, stir for 1 h, then add 2.6 g of ammonium chloride and 12 mL of H 2 O, and stir for another 24 h to obtain a mixture. Add hydrochloric acid to control the pH = 2.5. Then put the obtained mixture into a high-pressure reaction kettle and place it in an oven at 190 °C for hydrothermal crystallization reaction for 48 h. After the crystallization is completed, cool the synthesis kettle to room temperature. The obtained product is filtered and washed by suction, and placed in an oven at 90 °C to dry overnight to obtain the product SAPO-15 molecular sieve. The molar ratio of each material in the system is Al 2 O 3 :H 2 O:P 2 O 5 :SiO 2 :NH 4 +:R = 1.0:41.3:0.87:0.76:0.75:1.48。
[0059] The crystallinity of the obtained SAPO-15 zeolite molecular sieve is shown in Table 1.
[0060] Experimental Example 5
[0061] Solution B: Obtained by dissolving 6.4729 g of tetraethyl orthosilicate in 7.5 mL of H 2 O.
[0062] Add 4.6 mL of phosphoric acid to Solution A, stir evenly, then add Solution B drop by drop, stir well, add 5.8 mL of morpholine, stir for 1 h, then add 2.6 g of ammonium chloride and 12 mL of H 2 O, stir for another 24 h to obtain a mixture. Then put the obtained mixture into a high-pressure reaction kettle and place it in an oven at 190 °C for hydrothermal crystallization reaction for 48 h. After the crystallization is completed, cool the synthesis kettle to room temperature. The obtained product is filtered and washed by suction, and placed in an oven at 90 °C to dry overnight to obtain the product SAPO-15 molecular sieve. The molar ratio of each material in the system is Al 2 O 3 :H 2 O:P 2 O 5 :SiO 2 :NH 4 + :R = 1.0:41.3:0.87:0.76:0.75:1.48。
[0063] The crystallinity of the obtained SAPO-15 zeolite molecular sieve is shown in Table 1.
[0064] Experimental Example 6
[0065] Solution B: Obtained by dissolving 6.4729 g of tetraethyl orthosilicate in 7.5 mL of H 2 O.
[0066] Add 4.6 mL of phosphoric acid to Solution A, stir evenly, then add Solution B drop by drop, stir well, add 5.8 mL of morpholine, stir for 1 h, then add 2.6 g of ammonium chloride and 12 mL of H 2 O, stir for another 24 h to obtain a mixture. Add NaOH to control the pH = 7.5. Then put the obtained mixture into a high-pressure reaction kettle and place it in an oven at 190 °C for hydrothermal crystallization reaction for 48 h. After the crystallization is completed, cool the synthesis kettle to room temperature. The obtained product is filtered and washed by suction, and placed in an oven at 90 °C to dry overnight to obtain the product SAPO-15 molecular sieve. The molar ratio of each material in the system is Al 2 O 3 :H 2 O:P2 O 5 :SiO 2 :NH 4 + :R = 1.0:41.3:0.87:0.76:0.75:1.48.
[0067] The crystallinity of the obtained SAPO-15 zeolite molecular sieve is shown in Table 1.
[0068] Experimental Example 7
[0069] Solution B: Obtained by dissolving 6.4729 g of tetraethyl orthosilicate in 7.5 mL of H 2 O.
[0070] Add 4.6 mL of phosphoric acid to Solution A, stir evenly, then add Solution B drop by drop, stir well, add 5.8 mL of morpholine, stir for 1 h, then add 2.6 g of ammonium chloride and 12 mL of H 2 O, stir for another 24 h to obtain a mixture. Add NaOH to control the pH = 10.5. Then put the obtained mixture into a high-pressure reaction kettle and place it in an oven at 190 °C for hydrothermal crystallization reaction for 48 h. After the crystallization is completed, cool the synthesis kettle to room temperature. The obtained product is filtered and washed, and placed in an oven at 90 °C to dry overnight to obtain the product SAPO-15 molecular sieve. The molar ratio of each material in the system is Al 2 O 3 :H 2 O:P 2 O 5 :SiO 2 :NH 4 + :R = 1.0:41.3:0.87:0.76:0.75:1.48.
[0071] The crystallinity of the obtained SAPO-15 zeolite molecular sieve is shown in Table 1.
[0072] Experimental Example 8
[0073] Solution B: Obtained by dissolving 6.4729 g of tetraethyl orthosilicate in 7.5 mL of H 2 O.
[0074] Add 4.6 mL of phosphoric acid to Solution A, stir evenly, then add Solution B drop by drop, stir well, add 5.8 mL of morpholine, stir for 1 h, then add 2.6 g of ammonium chloride and 12 mL of H 2O, stir for another 24 h to obtain a mixture. Add NaOH and control the pH = 12.5. Then put the obtained mixture into a high-pressure reactor and place it in an oven at 190 °C for hydrothermal crystallization reaction for 48 h. After the crystallization is completed, cool the synthesis kettle to room temperature. The obtained product is filtered and washed, and placed in an oven at 90 °C to dry overnight to obtain the product SAPO-15 molecular sieve. The molar ratio of each material in the system is Al 2 O 3 :H 2 O:P 2 O 5 :SiO 2 :NH 4 + :R = 1.0:41.3:0.87:0.76:0.75:1.48.
[0075] The crystallinity of the prepared SAPO-15 zeolite molecular sieve is shown in Table 1.
[0076] Experimental Example 9 - Experimental Example 13
[0077] The preparation method of the products in Examples 9 - 13 is the same as that in Example 1, except that the crystallization reaction temperature is different.
[0078] The crystallization reaction temperature of Example 9 is 180 °C.
[0079] The crystallization reaction temperature of Example 10 is 190 °C (the same as Example 1).
[0080] The crystallization reaction temperature of Example 11 is 200 °C.
[0081] The crystallization reaction temperature of Example 12 is 210 °C.
[0082] The crystallization reaction temperature of Example 13 is 220 °C.
[0083] The crystallinity of the prepared SAPO-15 zeolite molecular sieve is shown in Table 1.
[0084] Examples 14 - 18
[0085] The preparation method of the products in Examples 14 - 18 is the same as that in Example 11, except that the crystallization reaction time is different.
[0086] The crystallization reaction time of Example 14 is 24 h.
[0087] The crystallization reaction time of Example 15 is 36 h.
[0088] The crystallization reaction time of Example 16 is 48 h (the same as Example 11).
[0089] The crystallization reaction time of Example 17 was 60 h.
[0090] The crystallization reaction time of Example 18 was 72 h.
[0091] The crystallinity of the prepared SAPO-15 zeolite molecular sieve is shown in Table 1.
[0092] Calculation method of crystallinity: The crystallinity was tested using an X-ray diffractometer. The calculation formula is: crystallinity = (diffraction peak intensity / total intensity) * 100%, and data processing was carried out using jade software. The reaction parameters and specific crystallinity data of the above examples are shown in Table 1.
[0093] Table 1 Reaction parameters and crystallinity of examples
[0094]
[0095] As can be seen from Table 1, in Examples 4-8, by adjusting the pH range, it was found that the acidity and alkalinity of the system had no effect on the synthesis of SAPO-15 zeolite molecular sieve. In Example 2, using water glass as the silicon source, the crystallinity of the synthesized SAPO-15 zeolite molecular sieve was relatively low, less than 50%.
[0096] In Examples 10-13 and Examples 16-17, under the condition that the molar ratio of each raw material input was Al 2 O 3 :H 2 O:P 2 O 5 :SiO 2 :NH 4 + :R = 1.0:41.3:0.87:0.76:0.75:1.48, and the crystallization reaction was carried out at 190 - 220 °C for 48 - 60 h, a ping-pong flower-like SAPO-15 zeolite molecular sieve could be obtained, and the crystallinity of the SAPO-15 zeolite molecular sieve was all above 80%. Among them, Example 11 was the best reaction condition.
[0097] The SEM scanning electron micrograph of the SAPO-15 zeolite molecular sieve of Example 11 is as Figures 5 - 8 shown. As can be Figures 5 - 8 seen, the ping-pong flower-like SAPO-15 zeolite molecular sieve was prepared by the method of the present invention.
[0098] Application Example 1
[0099] The ping-pong flower-like SAPO-15 zeolite molecular sieve of Example 11 above was applied to the reaction of hydrogenation of carbon dioxide to methanol.
[0100] Using a chrysanthemum-like SAPO-15 zeolite molecular sieve as a carrier to load a transition metal to prepare a catalyst, the specific preparation process is as follows: Weigh a certain amount of pseudoboehmite and dissolve it in deionized water. After stirring evenly, add a certain amount of 85% wt phosphoric acid solution and tetraethyl orthosilicate in sequence, stir evenly, add morpholine, and then stir evenly again, and add ammonium chloride. Perform hydrothermal crystallization reaction at 200 °C for 48 h, and the system composition is Al 2 O 3 :H 2 O:P 2 O 5 :SiO 2 :NH 4 + :R = 1.0:41.3:0.87:(0.73 - 0.79):0.76:1.48. After filtering, washing, and drying the product obtained from the reaction, the SAPO-15 zeolite molecular sieve powder sample is obtained. Measure its water intake rate to be 6. The corresponding catalyst is prepared by the equal-volume impregnation method. Select metal nitrate as the precursor, calculate the mass of the required metal nitrate according to 5% of the total mass of the catalyst, and prepare a solution based on the measured water intake rate, and evenly drop it onto the surface of the zeolite molecular sieve. Subsequently, place it in the air and dry for 12 h, then dry at 100 °C for 12 h, and the required metal-loaded zeolite molecular sieve catalyst is obtained after calcination.
[0101] The 5% Zr / SAPO-15, 5% Co / SAPO-15, 5% Zn / SAPO-15, 5% Cu / SAPO-15, 5% Ni / SAPO-15, 5% Fe / SAPO-15, 5% Zr-5% Cu / SAPO-15, 5% Co-5% Cu / SAPO-15, 5% Zn-5% Cu / SAPO-15, 5% Ni-5% Cu / SAPO-15, 5% Fe-5% Cu / SAPO-15 catalysts were prepared respectively according to the aforementioned method, and the catalytic activity of the series of SAPO-15 zeolite molecular sieve catalysts for the hydrogenation of CO 2 to methanol was tested as Figure 9 shown. As Figure 9 can be seen, the CO 2 conversion rate on 5% Cu / SAPO-15 is the highest (21.73%), and the selectivity of the target product methanol is the best (95.97%).
[0102] The above is only a preferred specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Any person skilled in the art within the technical scope disclosed by the present invention, according to the technical solution of the present invention and its inventive concept, makes equivalent substitutions or changes, and should be covered by the protection scope of the present invention.
Claims
1. A method for preparing a ping-pong chrysanthemum-like SAPO-15 zeolite molecular sieve, characterized in that: The following steps are involved: (1) Add aluminum source, phosphorus source, silicon source, organic amine structure directing agent and inorganic structure directing agent to water in sequence, stir evenly after adding each raw material and then add other raw materials; (2) After all the raw materials are added, continue stirring for several hours; (3) crystallizing the mixture at 190-220° C. for 48-60 hours; (4) After the crystallization reaction is completed, the ping-pong-like SAPO-15 zeolite molecular sieve is obtained by filtration and washing; Wherein, the inorganic structure directing agent is an inorganic compound of ammonium salt or ammonia water, and R represents an organic amine structure directing agent; The aluminum source is measured in Al2O3, the phosphorus source is measured in P2O5, the silicon source is measured in SiO2, and the inorganic structure directing agent is measured in NH4 + Metering, the molar ratio of each raw material is Al2O3:H2O:P2O5:SiO2:NH4 + :R=1.0:41.3:0.87:(0.73-0.79):(0.75-1.3):1.
48.
2. The method for preparing a ping-pong chrysanthemum-like SAPO-15 zeolite molecular sieve according to claim 1, characterized in that: The aluminum source is pseudo-boehmite.
3. The method for preparing a ping-pong chrysanthemum-like SAPO-15 zeolite molecular sieve according to claim 1, characterized in that: The phosphorus source is an 85% wt phosphoric acid aqueous solution.
4. The method for preparing a ping-pong chrysanthemum-like SAPO-15 zeolite molecular sieve according to claim 1, characterized in that: The silicon source is tetraethyl silicate.
5. The method for preparing a ping-pong chrysanthemum-like SAPO-15 zeolite molecular sieve according to claim 1, characterized in that: The inorganic structure directing agent is ammonium chloride.
6. The method for preparing a ping-pong chrysanthemum-like SAPO-15 zeolite molecular sieve according to claim 1, characterized in that: The organic amine structure directing agent is morpholine.
7. The method for preparing a ping-pong chrysanthemum-like SAPO-15 zeolite molecular sieve according to claim 1, characterized in that: After the crystallization reaction is completed, the product is washed with water and dried.
8. Application of a ping-pong chrysanthemum-like SAPO-15 zeolite molecular sieve in the hydrogenation of carbon oxides to prepare alcohol compounds, characterized in that: The ping-pong-like SAPO-15 zeolite molecular sieve is loaded with transition metal or transition metal oxide to prepare a catalyst for use.
9. The use according to claim 8, characterized in that: The transition metal is one or more of Zr, Ni, Co, Zn, Cu, and Fe.
10. The use according to claim 8, characterized in that: The transition metal is a metal containing Cu or a metal oxide containing Cu.
11. A ping-pong chrysanthemum-like SAPO-15 zeolite molecular sieve, characterized in that: The method is obtained by the preparation method according to any one of claims 1 to 7.
12. A catalyst, characterized in that It comprises the ping-pong-like SAPO-15 zeolite molecular sieve as described in claim 11 and a transition metal or a transition metal oxide.
13. The catalyst according to claim 12, characterized in that The transition metal is one or more of Zr, Ni, Co, Zn, Cu, and Fe.
14. The catalyst according to claim 12, characterized in that The transition metal is a metal containing Cu or a metal oxide containing Cu.