CN117105239B - Preparation method of TON type zeolite molecular sieve - Google Patents
Preparation method of TON type zeolite molecular sieveInfo
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- CN117105239B CN117105239B CN202311080750.XA CN202311080750A CN117105239B CN 117105239 B CN117105239 B CN 117105239B CN 202311080750 A CN202311080750 A CN 202311080750A CN 117105239 B CN117105239 B CN 117105239B
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- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/04—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
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Abstract
The invention belongs to the technical field of molecular sieve preparation, and particularly relates to a preparation method of a TON type zeolite molecular sieve. The method comprises the steps of mixing a silicon source, an inorganic alkali metal compound, water and an organic template agent to obtain an aqueous phase solution, mixing an aluminum source and an organic solvent to obtain an organic phase solution, mixing the aqueous phase solution and the organic phase solution, and carrying out dynamic hydrothermal reaction on the obtained gel to obtain the TON type zeolite molecular sieve. According to the invention, a phase transfer method is adopted, a silicon source and an aluminum source are respectively dissolved in a water phase and an organic phase, and when the aluminum source raw material in the organic phase is slowly transferred to the water phase, the growth process of zeolite crystals is limited, so that the appearance of the nano-sheet is obtained. In conclusion, the TON type zeolite synthesized by the preparation method through the phase transfer method has the advantages of nano-plate morphology, wide silicon-aluminum ratio, high crystallization degree and short synthesis time.
Description
Technical Field
The invention belongs to the technical field of molecular sieve preparation, and particularly relates to a preparation method of a TON type zeolite molecular sieve.
Background
Zeolite is an inorganic microporous material with regular and uniform pore canal structure, and has wide application in the fields of adsorption, catalysis, ion exchange and the like. Wherein, the TON type zeolite has a one-dimensional ten-membered ring pore canal structure, and the pore canal size is aboutThe size is slightly smaller than ZSM-5 and ZSM-11. Because of its strong shape selectivity, TON-type zeolite has wide application in industry, such as alkane isomerization, propylene oligomerization, petroleum dewaxing, etc.
Document "Wang Y,Wang X,Wu Q,et al.Seed-directed and organotemplate-free synthesis ofTON zeolite[J].Catalysis Today,2014,226:103-108." discloses a method for dynamic synthesis of high-silicon TON-type zeolite under hydrothermal conditions without an organic template agent only under seed crystal guiding. A method for synthesizing extremely high silicon (Si/al=100) TON-type zeolite under hydrothermal conditions is disclosed in document "Yi Luo,WeiminYang,et al.Synthesis and crystal growthmechanism ofZSM-22zeolite nanosheets.CrystEngComm,2016,18,5611.". The TON type molecular sieve obtained by the preparation methods reported in the two documents has higher silicon-aluminum ratio (Si/Al > 30), causes fewer acid sites and is not beneficial to the catalytic reaction.
Chinese patent CN111422881a discloses a method for synthesizing low silicon TON type zeolite using an organic structure directing agent, which comprises preparing a gel containing a silicon source, an aluminum source, an organic template agent, a halogen compound, a base and water, then dynamically hydrothermally reacting the gel in an autoclave reactor under autogenous pressure, and then separating to obtain a zeolite product having TON topology. The low-silicon TON zeolite prepared by the method has increased acid reaction sites, but the prepared molecular sieve is a micron-sized large-particle crystal, and the molecular sieve has overlarge particle size, cannot be fully contacted with reactants, and is unfavorable for the catalytic reaction.
Disclosure of Invention
The invention aims to provide a preparation method of a TON type zeolite molecular sieve, and the TON type zeolite molecular sieve obtained by the preparation method has the characteristics of nanosheet morphology, high crystallization degree and wide silicon-aluminum ratio.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of TON type zeolite molecular sieve, comprising the following steps:
mixing a silicon source, an inorganic alkali metal compound, water and an organic template agent to obtain an aqueous phase solution;
Mixing an aluminum source with an organic solvent to obtain an organic phase solution;
And mixing the aqueous phase solution and the organic phase solution, and carrying out dynamic hydrothermal reaction on the obtained gel to obtain the TON type zeolite molecular sieve.
Preferably, the organic template is tetramethylene bis- (1-methylimidazole) hydroxide.
Preferably, the silicon source comprises one or more of sodium silicate, white carbon black, water glass and silica sol.
Preferably, the inorganic alkali metal compound includes one or more of sodium carbonate, potassium carbonate, sodium hydroxide and potassium hydroxide.
Preferably, the aluminum source comprises one or more of sodium aluminate, pseudo-boehmite, aluminum hydroxide, aluminum chloride, aluminum nitrate, aluminum sulfate, and aluminum isopropoxide.
Preferably, the mass of the silicon source is calculated by silicon dioxide, the mass of the aluminum source is calculated by aluminum oxide, the mass of the inorganic alkali metal compound is calculated by alkali metal oxide, the molar ratio of the inorganic alkali metal compound to the silicon source in the gel is 0.049-0.169:1, the molar ratio of the organic template agent to the silicon source is 0.024-0.084:1, and the molar ratio of the aluminum source to the silicon source is 0.007-0.084:1.
Preferably, the organic solvent is toluene, the mass of the silicon source is calculated by silicon dioxide, the molar ratio of water to the silicon source in the gel is 8-29:1, and the molar ratio of the organic solvent to the silicon source is 0.54-1.8:1.
Preferably, the temperature of the dynamic hydrothermal reaction is 130-200 ℃, the heat preservation time is 10-8 d, the dynamic hydrothermal reaction is carried out under the stirring condition, and the stirring rotating speed is 10-100 rpm.
The TON type zeolite molecular sieve prepared by the preparation method provided by the technical scheme is nanosheets in morphology, and the silicon-aluminum ratio is 10-60.
Preferably, the TON type zeolite molecular sieve with the appearance of the nano sheet has the thickness of 10-100 nm.
The invention provides a preparation method of a TON type zeolite molecular sieve, which comprises the following steps of mixing a silicon source, an inorganic alkali metal compound, water and an organic template agent to obtain an aqueous phase solution, mixing an aluminum source and an organic solvent to obtain an organic phase solution, mixing the aqueous phase solution and the organic phase solution, and carrying out dynamic hydrothermal reaction on the obtained gel to obtain the TON type zeolite molecular sieve. According to the invention, a phase transfer method is adopted, a silicon source and an aluminum source are respectively dissolved in a water phase and an organic phase, and when the aluminum source raw material in the organic phase is slowly transferred to the water phase, the growth process of zeolite crystals is limited, so that the appearance of the nano-sheet is obtained. Compared with the existing zeolite crystallization process comprising a crystal nucleation process and a crystal growth process, the method adopts a phase transfer process, utilizes an aluminum source in an organic phase to slowly transfer into an aqueous phase, has longer nucleation process, consumes most aluminosilicate in the nucleation process, and causes the growth process to lack raw materials, so that the growth process is limited, and the crystal size is smaller. Therefore, the preparation method provided by the invention avoids that the silicon source and the aluminum source are directly contacted to form large-particle colloid particles, thereby avoiding that the large-particle colloid particles are directly converted into large-particle zeolite crystals. Meanwhile, the crystallization degree of TON type zeolite is further improved by a phase transfer method. In conclusion, the TON type zeolite synthesized by the preparation method through the phase transfer method has the advantages of nano-plate morphology, wide silicon-aluminum ratio, high crystallization degree and short synthesis time.
Drawings
FIG. 1 is an XRD spectrum of TON-type zeolite prepared in examples 1-3;
FIG. 2 is a scanning electron microscope image of TON-type zeolite H1 prepared in example 1;
FIG. 3 is a scanning electron microscope image of TON-type zeolite H2 prepared in example 2;
FIG. 4 is a scanning electron microscope image of TON-type zeolite H3 prepared in example 3;
FIG. 5 is a scanning electron microscope image of TON-type zeolite H4 prepared in comparative example 1;
FIG. 6 is a scanning electron microscope image of TON-type zeolite H5 prepared in comparative example 2;
FIG. 7 is a scanning electron microscope image of TON-type zeolite H6 prepared in comparative example 3;
FIG. 8 is a scanning electron microscope image of TON-type zeolite H8 prepared in comparative example 5;
Fig. 9 is an XRD contrast pattern of the products prepared in examples and comparative examples.
Detailed Description
The invention provides a preparation method of TON type zeolite molecular sieve, comprising the following steps:
mixing a silicon source, an inorganic alkali metal compound, water and an organic template agent to obtain an aqueous phase solution;
Mixing an aluminum source with an organic solvent to obtain an organic phase solution;
And mixing the aqueous phase solution and the organic phase solution, and carrying out dynamic hydrothermal reaction on the obtained gel to obtain the TON type zeolite molecular sieve.
In the present invention, all preparation materials/components are commercially available products well known to those skilled in the art unless specified otherwise.
The invention mixes the silicon source, inorganic alkali metal compound, water and organic template agent (marked as first mixing) to obtain aqueous phase solution.
In the present invention, the silicon source preferably includes one or more of sodium silicate, white carbon black, water glass, and silica sol, and more preferably silica sol. In the invention, the mass content of SiO 2 in the silica sol is preferably 30-40%, more preferably 40%. The counter cation in the silica sol is preferably an ammonium ion. The inorganic alkali metal compound preferably includes one or more of sodium carbonate, potassium carbonate, sodium hydroxide and potassium hydroxide, more preferably sodium hydroxide. The water is preferably deionized or distilled water. The organic template is preferably tetramethylenebis- (1-methylimidazole) hydroxide. In a specific embodiment of the present invention, the first mixing is preferably performed in the form of an aqueous solution of tetramethylene bis- (1-methylimidazole) hydroxide, and the mass concentration of the aqueous solution of tetramethylene bis- (1-methylimidazole) hydroxide is preferably 10 to 17%, more preferably 12%. In a specific embodiment of the present invention, the aqueous tetramethylene bis- (1-methylimidazole) hydroxide solution is preferably available from Kent catalytic materials Co.
In the present invention, the first mixing is preferably performed in a closed vessel, the temperature of the first mixing is preferably room temperature, and the first mixing is preferably performed under stirring conditions, and the specific embodiment of the stirring is not particularly limited.
The present invention mixes the aluminum source with the organic solvent (denoted as a second mix) to obtain an organic phase solution.
In the present invention, the aluminum source preferably includes one or more of sodium aluminate, pseudo-boehmite, aluminum hydroxide, aluminum chloride, aluminum nitrate, aluminum sulfate, and aluminum isopropoxide, and more preferably aluminum isopropoxide. The organic solvent is toluene.
In the present invention, the second mixing is preferably performed in a closed vessel, the temperature of the second mixing is preferably room temperature, and the second mixing is preferably performed under stirring conditions, and the specific embodiment of the stirring is not particularly limited.
After the aqueous phase solution and the organic phase solution are obtained, the aqueous phase solution and the organic phase solution are mixed (marked as third mixing), and the obtained gel is subjected to dynamic hydrothermal reaction to obtain the TON type zeolite molecular sieve.
In the invention, the mass of the silicon source is calculated as silicon dioxide, the mass of the aluminum source is calculated as aluminum oxide, the mass of the inorganic alkali metal compound is calculated as alkali metal oxide, and the molar ratio of the inorganic alkali metal compound to the silicon source in the gel is preferably 0.049-0.169:1, more preferably 0.05-0.16:1, even more preferably 0.055-0.15:1, and most preferably 0.06-0.13:1. The molar ratio of the organic template to the silicon source is preferably 0.024 to 0.084:1, more preferably 0.025 to 0.08:1, even more preferably 0.028 to 0.075:1, and most preferably 0.03 to 0.07:1. The molar ratio of the aluminum source to the silicon source is preferably 0.007 to 0.084:1, more preferably 0.008 to 0.08:1, still more preferably 0.009 to 0.07:1, and most preferably 0.01 to 0.06:1. The molar ratio of water to silicon source is preferably 8 to 29:1, more preferably 10 to 27:1, and even more preferably 12 to 25:1. The molar ratio of the organic solvent to the silicon source is preferably 0.54 to 1.8:1, more preferably 0.55 to 1.7:1, and still more preferably 0.6 to 1.6:1.
The preparation method provided by the invention can realize that the silicon source and the aluminum source reach proper contact speed in the phase transfer process by controlling the silicon source, the aluminum source, the inorganic alkali metal compound, the organic template agent, the water and the organic solvent within the molar ratio range, and the zeolite crystal grows into a two-dimensional structure under the control of the organic phase and the water phase, so that the appearance of the nano sheet is obtained.
In the present invention, the third mixing is preferably performed in a reaction vessel with a polytetrafluoroethylene liner.
In the present invention, the dynamic hydrothermal reaction is preferably carried out in a reactor with polytetrafluoroethylene lining. The temperature of the dynamic hydrothermal reaction is preferably 130 to 200 ℃, more preferably 150 to 180 ℃, and even more preferably 150 to 170 ℃. The holding time is preferably 10h to 8d, more preferably 12h to 6d, still more preferably 1 to 5d, and particularly preferably 15h, 72h or 120h. The dynamic hydrothermal reaction is preferably carried out under stirring, and the stirring speed is preferably 10 to 100rpm, more preferably 20 to 90rpm, still more preferably 30 to 80rpm, and particularly preferably 60rpm or 80rpm.
The TON type zeolite molecular sieve prepared by the preparation method provided by the technical scheme is nanosheets in morphology, and the silicon-aluminum ratio is 10-60.
In the invention, the thickness of the TON type zeolite molecular sieve with the nano-sheet morphology is preferably 10-100 nm, more preferably 10-80 nm, and further preferably 20-60 nm. The TON type zeolite molecular sieve prepared by the invention has the shape of nano-sheets, is beneficial to increasing the contact area during the catalytic reaction and improving the efficiency of the catalytic reaction.
The silicon-aluminum ratio of the TON type zeolite molecular sieve prepared by the method is 10-60. In the specific embodiment of the invention, the TON type zeolite molecular sieve has a silicon-aluminum ratio of 10 to 30 or 60. According to the preparation method provided by the invention, the TON type zeolite molecular sieve with flexibly controlled silicon-aluminum ratio can be obtained according to the quality of the added aluminum source.
The technical solutions provided by the present invention are described in detail below in conjunction with examples for further illustrating the present invention, but they should not be construed as limiting the scope of the present invention.
Example 1
0.0614G of sodium hydroxide, 1.201mL of distilled water, 0.908mL of a 12% by mass concentration tetramethylene bis (1-methylimidazole) aqueous solution (available from Kent catalytic materials Co., ltd.) and 1.165g of silica sol (wherein the balance cation is ammonium ion and SiO 2 mass is 0.4660 g) were added into a reaction vessel, and stirred uniformly under closed and room temperature conditions to obtain a phase transfer reaction solution A-1;
0.068g of aluminum isopropoxide and 0.88g of toluene are added into a reaction vessel, and the mixture is stirred uniformly under the conditions of sealing and room temperature to obtain a phase transfer reaction liquid B-1.
The phase transfer reaction liquid A-1 and the phase transfer reaction liquid B-1 are sequentially filled into a reaction kettle with a polytetrafluoroethylene lining, and are dynamically crystallized for 15 hours at the rotation speed of 60rpm under the condition of 170 ℃.
After the hydrothermal reaction is completed, solid-liquid separation is performed by using a centrifugal device, and after the solid product is washed by water, the solid product is dried in a 75 ℃ oven for 12 hours, so that the product is obtained and is marked as H1.
The crystallinity and silicon to aluminum ratio (Si/Al) of H1 were determined and are shown in Table 1. The crystallinity of H1 is calculated by XRD diffraction data, the calculation method is a conventional method in the field, the silicon-aluminum ratio (Si/Al) is calculated by atomic emission spectrum (ICP) data, and the calculation method is a conventional method in the field.
TON (Si/al=10) in fig. 1 is an X-ray diffraction pattern of H1, and H1 is a zeolite having a TON structure as compared with a standard diffraction pattern published by the international zeolite association. FIG. 2 is a scanning electron microscope image of H1, H1 is a nano-sheet structure, and the thickness of the sheet layer is 10nm.
Example 2
0.0620G of sodium hydroxide, 1.220mL of distilled water, 0.916mL of a 12% aqueous solution of tetramethylene bis (1-methylimidazole) hydroxide (available from Kent catalytic materials Co., ltd.), 1.180g of silica sol (wherein the balancing cation is ammonium ion and SiO 2 mass is 0.4660 g) were added to a reaction vessel, and stirred uniformly under closed and room temperature conditions to obtain a phase transfer reaction solution A-2;
0.043g of aluminum isopropoxide and 0.87g of toluene were added to a reaction vessel, and the mixture was stirred uniformly under the conditions of sealing and room temperature to obtain a phase transfer reaction liquid B-2.
The phase transfer reaction liquid A-2 and the phase transfer reaction liquid B-2 are sequentially filled into a reaction kettle with a polytetrafluoroethylene lining, and are dynamically crystallized for 72 hours at a rotation speed of 80rpm under the condition of 170 ℃.
After the hydrothermal reaction is completed, solid-liquid separation is performed by using a centrifugal device, and after the solid product is washed with water, the solid product is dried in a 100 ℃ oven for 6 hours, so that the product is obtained and is marked as H2.
The crystallinity and silicon to aluminum ratio (Si/Al) of H2 were determined and are shown in Table 1.
TON (Si/al=30) in fig. 1 is an X-ray diffraction pattern of H2, and H2 is a zeolite having a TON structure as compared with a standard diffraction pattern published by the international zeolite association. FIG. 3 is a scanning electron microscope image of H2, H2 is a nano-sheet structure, and the thickness of the sheet layer is 20nm.
Example 3
0.0614G of sodium hydroxide, 1.923mL of distilled water, 0.900mL of a 12% by mass concentration tetramethylene bis (1-methylimidazole) aqueous solution (purchased from Kent catalytic materials Co., ltd.) and 1.174g of silica sol (wherein the balance cation is ammonium ion and the mass of SiO 2 is 0.4660 g) were added to a reaction vessel, and stirred uniformly under closed and room temperature conditions to obtain a phase transfer reaction solution A-3;
0.023g of aluminum isopropoxide and 0.90g of toluene were added to a reaction vessel, and the mixture was stirred uniformly under the conditions of sealing and room temperature to obtain a phase transfer reaction liquid B-3.
The phase transfer reaction liquid A-3 and the phase transfer reaction liquid B-3 are sequentially filled into a reaction kettle with a polytetrafluoroethylene lining, and are dynamically crystallized for 120 hours at the rotation speed of 60rpm under the condition of 170 ℃.
After the hydrothermal reaction is completed, solid-liquid separation is performed by using a centrifugal device, and after the solid product is washed with water, the solid product is dried in a 120 ℃ oven for 3 hours, so that the product is obtained and is marked as H3.
The crystallinity and silicon to aluminum ratio (Si/Al) of H3 were determined and are shown in Table 1.
TON (Si/al=60) in fig. 1 is an X-ray diffraction pattern of H3, and H3 is a zeolite having a TON structure as compared with a standard diffraction pattern published by the international zeolite association. FIG. 4 is a scanning electron microscope image of H3, H3 is a nano-sheet structure, and the thickness of the sheet layer is 20nm.
Comparative example 1
Synthesized according to the method of example 2 disclosed in chinese patent CN111422881a, the resulting product is designated H4.
The crystallinity and silicon to aluminum ratio (Si/Al) of H4 were determined and are shown in Table 1. FIG. 5 is a scanning electron microscope image of H4, H4 is a spindle-shaped structure, and the particle size is 2-5 μm.
Comparative example 2
The TON-type zeolite (purchased from Dalian corporation) synthesized by the conventional method was ground into powder, dispersed in distilled water, stirred for 4 hours, and then solid-liquid separated by using a centrifuge, and the solid product was dried in an oven at 100℃for 4 hours to obtain a product, which was designated as H5. The crystallinity and silicon to aluminum ratio (Si/Al) of H5 were determined and are shown in Table 1. FIG. 6 is a scanning electron microscope image of H5, H5 is a rod-like structure, and the length is 5 μm.
Comparative example 3
In comparison with example 2, comparative product, designated H6, was prepared in the same manner as in example 2 except that 0.87g of toluene was not added in comparative example 3. The crystallinity and silicon to aluminum ratio (Si/Al) of H6 were determined and are shown in Table 1. FIG. 7 is a scanning electron microscope image of H6, H6 is a spindle structure, and the particle size is 2-5 μm.
Comparative example 4
In comparison with example 2, comparative example 4 was prepared by the same procedure as in example 2 except that 0.916mL of an aqueous solution of tetramethylene bis (1-methylimidazole) hydroxide having a mass concentration of 12% was not added, and the resultant product was designated as H7. From the PXRD plot of H7 (FIG. 9), H7 is not a TON-type zeolite.
Comparative example 5
In comparison with example 2, comparative product, designated as H8, was prepared in the same manner as in example 2 except that static crystallization (no stirring, static condition) was used instead of dynamic crystallization in comparative example 5. The crystallinity and silicon to aluminum ratio (Si/Al) of H8 were determined and are shown in Table 1. FIG. 8 is a scanning electron microscope image of H8, H8 is a spindle structure, and the particle size is 2-5 μm.
Comparative example 6
In comparison with example 2, comparative product, designated as H9, was prepared by crystallizing at 120℃in comparative example 6 in the same manner as in example 2. From the PXRD pattern of H9 (fig. 9), H9 is not pure TON-type zeolite.
Comparative example 7
In comparative example 7, the crystallization time was 8H, and the other procedures were the same as in example 2, to prepare a comparative product, designated as H10. From the PXRD plot of H10 (FIG. 9), H10 is not a pure TON-type zeolite.
Table 1 shows the results of the Si/Al ratio measurement of the products prepared in examples and comparative examples.
Table 1 results of determination of silicon to aluminum ratio of products prepared in examples and comparative examples
| Product(s) | H1 | H2 | H3 | H4 | H5 | H6 | H7 | H8 | H9 | H10 |
| Si/Al | 9.3 | 28.0 | 58.3 | 22.3 | 35.0 | 29.1 | - | 27.8 | - | - |
As can be seen from the data in Table 1, in the embodiments 1 to 3, TON type zeolite molecular sieves with silicon-aluminum ratios of 9.3, 28 or 58.3 can be obtained by adjusting the mass of the added aluminum source, so that the preparation method provided by the invention can flexibly adjust and control the silicon-aluminum ratio of the TON type zeolite molecular sieves.
Although the foregoing embodiments have been described in some, but not all embodiments of the invention, other embodiments may be obtained according to the present embodiments without departing from the scope of the invention.
Claims (4)
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85104941A (en) * | 1984-12-19 | 1987-01-07 | 美孚石油公司 | Synthesizing of Silicophosphoaluminaand |
| CN111422881A (en) * | 2020-04-10 | 2020-07-17 | 吉林大学 | TON type zeolite molecular sieve and preparation method thereof |
| CN114436286A (en) * | 2020-10-19 | 2022-05-06 | 中国石油化工股份有限公司 | Molecular sieve with TON structure and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| ZA849733B (en) * | 1983-12-19 | 1986-07-30 | Mobil Oil Corp | Crystalline silicophospholuminate |
| CN110526260B (en) * | 2019-09-30 | 2021-07-27 | 中国石油大学(北京) | A kind of method for synthesizing aluminosilicate molecular sieve by seed method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85104941A (en) * | 1984-12-19 | 1987-01-07 | 美孚石油公司 | Synthesizing of Silicophosphoaluminaand |
| CN111422881A (en) * | 2020-04-10 | 2020-07-17 | 吉林大学 | TON type zeolite molecular sieve and preparation method thereof |
| CN114436286A (en) * | 2020-10-19 | 2022-05-06 | 中国石油化工股份有限公司 | Molecular sieve with TON structure and preparation method and application thereof |
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