CN111252782B - Synthetic method of Beta molecular sieve with low silicon-aluminum ratio - Google Patents
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Abstract
The application discloses a synthesis method of a Beta molecular sieve with a low silicon-aluminum ratio, which is characterized by comprising the following steps: 1) crystallizing a mixture A containing a silicon source, an aluminum source, a template agent R and water at 80-300 ℃ for 5-72 hours to obtain a mixture B; the template agent R is selected from at least one of organic amines; 2) adding an aluminum source and water into the mixture B to obtain a mixture C; 3) crystallizing the mixture C at 80-300 ℃ for 5-72 h, separating, and roasting at 500-800 ℃ for 5-36 h to obtain the Beta molecular sieve with the low silicon-aluminum ratio.
Description
Technical Field
The application relates to a synthesis method of a Beta molecular sieve with a low silicon-aluminum ratio, belonging to the field of molecular sieve synthesis.
Background
Beta molecular sieve is a molecular sieve with three-dimensional structure and twelve-membered ring cross structure, and is widely applied to alkane isomerization, NH due to large specific surface, unique mechanism and good hydrothermal stability 3 The catalyst is an important industrial molecular sieve catalyst in petroleum refining and fine chemical catalytic reactions such as oxidative degradation, VOC oxidation, aromatic hydrocarbon alkylation and the like.
Huang et al (Huang Gang, Ji Peng, Xu Hao, et a1.Microporous and Mesoporous Materials,2017,248:30-39.) rapidly prepared a hierarchical pore Beta molecular sieve by using lamellar H-type hydrosilicon she stone as a silicon source and performing hydrothermal crystallization at a high temperature of 170 ℃ for 0-24 hours. However, the preparation process of the silicon source (H-type hydrosilicon she stone) required by the preparation method is complex, and the preparation process has high crystallization temperature, low product yield and is very easy to generate mordenite and other mixed crystals. Zhang et al (Zhang Haiyan, Xie Bin, Meng Xiangju, et al Microporous and Mesoporous Materials,2013,180:123-129) used a Beta molecular sieve as a seed crystal to prepare a high-purity phase Beta molecular sieve in a template-free system. However, the method needs to prepare the Beta molecular sieve with high quality in advance as the seed crystal, and has long crystallization time and low product yield.
In summary, the synthesis method of Beta molecular sieve reported at present still has some problems: such as high cost, complex preparation process, low preparation reproducibility, low product yield and the like, and limits the industrial production to a certain extent. Therefore, a preparation method of the Beta molecular sieve with simple operation and low cost is urgently needed to be developed.
When the molecular sieve acts in the acid catalysis reaction process, the catalytic performance of the molecular sieve is closely related to acidity. The more molecular sieve acid, the higher the catalyst activity and the lower the temperature required to achieve the target conversion. However, the silicon-aluminum ratio of the Beta molecular sieve synthesized by the conventional synthesis method is higher than 20, so that the Beta molecular sieve with a large acid content can be synthesized at low cost, and the further application of the molecular sieve in acid catalytic reaction can be expanded.
Disclosure of Invention
According to one aspect of the application, a method for synthesizing a low silica to alumina ratio Beta molecular sieve is provided.
The synthesis method of the Beta molecular sieve with the low silicon-aluminum ratio is characterized by comprising the following steps of:
1) crystallizing a mixture A containing a silicon source, an aluminum source, a template agent R and water at 80-300 ℃ for 5-72 hours to obtain a mixture B; the template agent R is selected from at least one of organic amines;
2) adding an aluminum source and water into the mixture B to obtain a mixture C;
3) crystallizing the mixture C at 80-300 ℃ for 5-72 h, separating, and roasting at 500-800 ℃ for 5-36 h to obtain the Beta molecular sieve with the low silicon-aluminum ratio.
Optionally, the silicon source is selected from at least one of silica sol, water glass, white carbon black and tetraethoxysilane;
the aluminum source is at least one selected from aluminum isopropoxide, sodium metaaluminate, pseudo-boehmite, aluminum sulfate and aluminum nitrate;
the organic amine is selected from at least one of tetraethylammonium hydroxide, tetraethylammonium bromide, tetraethylammonium chloride, methyltriethylammonium bromide and methyltriethylammonium chloride.
Optionally, the molar ratio SiO of the silicon source, the aluminum source, the template agent R and the water in the mixture A 2 :Al 2 O 3 : template agent R: h 2 O＝1:0～0.0125:0.20～0.50:5～40；
Wherein the mole number of the silicon source is SiO 2 The number of moles of (a);the mole number of the aluminum source is Al 2 O 3 The number of moles of (a); the mole number of the template agent R is calculated by the mole number of the template agent R; the moles of water are on their own.
Optionally, SiO in the mixture A 2 :Al 2 O 3 Organic amine H 2 The preferable molar ratio of O is 1:0.005-0.0125:0.25-0.40: 8-20.
Optionally, the mixture A in the step 1) is crystallized at 100-200 ℃ for 10-48 h.
Optionally, the upper limit of the temperature for crystallization of the mixture a in step 1) is selected from 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 160 ℃, 170 ℃,180 ℃, 190 ℃, 200 ℃, 250 ℃ or 300 ℃; the lower limit is selected from 80 deg.C, 100 deg.C, 110 deg.C, 120 deg.C, 130 deg.C, 140 deg.C, 160 deg.C, 170 deg.C, 180 deg.C, 190 deg.C, 200 deg.C or 250 deg.C.
Optionally, the upper limit of the time for crystallization of the mixture a in step 1) is selected from 12h, 18h, 24h, 30h, 36h, 40h or 48 h; the lower limit is selected from 10h, 12h, 18h, 24h, 30h, 36h or 40 h.
Optionally, the molar ratio SiO of the silicon source, the aluminum source, the template agent R and the water in the mixture C 2 :Al 2 O 3 : template agent R: h 2 O＝1:0.017～0.5:0.20～0.50:5～40。
Optionally, SiO in the mixture C 2 :Al 2 O 3 Organic amine H 2 The preferable molar ratio of O is 1:0.018-0.3:0.25-0.40: 8-30.
Optionally, crystallizing the mixture C in the step 3) at 100-200 ℃ for 12-72 h.
Optionally, the upper limit of the temperature of crystallization of the mixture C in step 3) is selected from 110 ℃, 120 ℃, 130 ℃, 140 ℃, 160 ℃, 170 ℃,180 ℃, 190 ℃ or 200 ℃; the lower limit is selected from 100 deg.C, 110 deg.C, 120 deg.C, 130 deg.C, 140 deg.C, 160 deg.C, 170 deg.C, 180 deg.C or 190 deg.C.
Optionally, the upper limit of the time for crystallization of the mixture C in step 3) is selected from 10h, 12h, 18h, 24h, 30h, 36h, 40h, 48h, 54h, 60h, 64h, 72 h; the lower limit is selected from 5h, 10h, 12h, 18h, 24h, 30h, 36h, 40h, 48h, 54h, 60h or 64 h.
Optionally, the roasting in the step 3) is carried out at 550-700 ℃ for 12-24 h.
Optionally, the upper limit of the temperature of the roasting in step 3) is selected from 600 ℃, 650 ℃ or 700 ℃; the lower limit is selected from 550 ℃, 600 ℃ or 650 ℃.
Optionally, the upper limit of the time for the calcination in step 3) is selected from 18h, 20h or 24 h; the lower limit is selected from 12h, 18h or 20 h.
Optionally, the low silicon to aluminum Beta molecular sieve has a silicon to aluminum atomic mole ratio of Si/Al of less than 30.
Optionally, the acid content of the low silicon-aluminum ratio Beta molecular sieve is 0.69-4.10 mmol (NH) 3 )/g。
Specifically, the preparation method of the low-silica-alumina ratio molecular sieve comprises the following steps:
1) preparation of the precursor mixture: mixing silicon source, aluminum source, organic amine and water according to a certain proportion, stirring the mixture evenly to form a precursor mixture A, wherein SiO in the precursor mixture A 2 :Al 2 O 3 Organic amine H 2 The molar ratio of O is 1:0-0.0125:0.20-0.50:5-40 (the silicon source and the aluminum source are calculated according to the oxide forms);
2) heating and crystallizing the prepared precursor mixture A at the temperature of 80-300 ℃ for 5-72 h, and cooling to room temperature to obtain a mixture B;
3) adding a certain amount of aluminum source and water into the mixture B, and stirring the mixture B uniformly to obtain a mixture C, wherein SiO in the mixture C 2 :Al 2 O 3 Organic amine H 2 The molar ratio of O is 1:0.017-0.5:0.20-0.50:5-40 (the silicon source and the aluminum source are calculated according to the oxide forms);
4) heating and crystallizing the mixture C at the temperature of 80-300 ℃ for 5-100 h;
5) and after crystallization is finished, cooling the mixture to room temperature, filtering, washing and drying, and roasting at 500-800 ℃ for 5-36 h to obtain the solid Beta molecular sieve with low silica-alumina ratio.
The silicon source in the step 1) is one or more than two of silica sol, water glass, white carbon black and tetraethoxysilane; the aluminum source is one or more than two of aluminum isopropoxide, sodium metaaluminate, pseudo-boehmite, aluminum sulfate and aluminum nitrate; the organic amine is one or more of tetraethyl ammonium hydroxide, tetraethyl ammonium bromide, tetraethyl ammonium chloride, methyltriethylammonium bromide and methyltriethylammonium chloride.
SiO in the mixture A in the step 1) above 2 :Al 2 O 3 Organic amine H 2 The preferred molar ratio of O is 1:0.005-0.0125:0.25-0.40: 8-20.
The preferable crystallization temperature of the mixture A in the step 2) is 100-200 ℃; the preferred crystallization time is 10h to 48 h.
SiO in the mixture C in the step 3) 2 :Al 2 O 3 Organic amine H 2 The preferred molar ratio of O is 1:0.018-0.3:0.25-0.40: 8-30.
The preferable crystallization temperature of the mixture C in the step 4) is 100-200 ℃; the preferred crystallization time is 12h to 72 h.
The preferred roasting temperature in the step 5) is 550-700 ℃; the preferred calcination time is 12h to 24 h.
The silicon source, the aluminum source and the template agent are crystallized at a certain temperature for a certain time to generate the low-crystallinity Beta molecular sieve, and at the moment, the system contains the low-crystallinity Beta molecular sieve, silicon-aluminum amorphous substances, the template agent and water. After an aluminum source is added into the system, the Beta molecular sieve with low crystallinity plays a role of seed crystal, in the crystallization process at a certain temperature, the added aluminum source can enter the molecular sieve more easily under the action of the seed crystal, so that more aluminum enters a molecular sieve framework, and the Beta molecular sieve with low silicon-aluminum ratio is prepared after crystallization is finished.
The beneficial effects that this application can produce include:
1) the application provides a new method for synthesizing a Beta molecular sieve with a low silicon-aluminum ratio;
2) the Beta molecular sieve provided by the application has more acid content;
3) the synthesis method provided by the application has low cost, only needs commercial template agent for synthesis, is simple and convenient to operate, and has strong economy.
Drawings
FIG. 1 is an XRD spectrum of the synthesized Beta molecular sieve of comparative example 1.
FIG. 2 shows NH of Beta molecular sieve synthesized in comparative example 1 3 -TPD spectrum.
Fig. 3 is an XRD spectrum of the MTW-type molecular sieve synthesized in comparative example 2.
FIG. 4 is an XRD spectrum of the synthesized Beta molecular sieve of example 1 of the present invention.
FIG. 5 shows NH of Beta molecular sieve synthesized in example 1 of the present invention 3 -TPD spectrum.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
The raw materials in the examples of the present application were purchased commercially unless otherwise specified.
The analysis method in the examples of the present application is as follows:
x-ray powder diffraction phase analysis (XRD) an X' Pert PRO X-ray diffractometer from pananace (PANalytical) of the netherlands, Cu target, K α radiation source (λ ═ 0.15418nm), voltage 40KV, current 40mA were used.
Comparative example 1
Weighing 0.08g of sodium metaaluminate and 6.48g of tetraethyl ammonium hydroxide, adding 3.90g of water, fully stirring, adding 6.6g of 40% silica sol, uniformly stirring, transferring the mixed solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining, putting the stainless steel reaction kettle into a 160 ℃ oven, crystallizing for 5 days, cooling to room temperature, washing with deionized water for 3 times, drying in a 120 ℃ oven, and roasting at 550 ℃ for 12 hours to obtain the Beta molecular sieve. Its XRD spectrum is shown in figure 1; NH 3 The TPD diagram is shown in figure 2. The Si/Al and acid content characterization results of the Beta molecular sieve are summarized in Table 1.
Comparative example 2
Weighing 0.13g of sodium metaaluminate and 6.48g of tetraethyl ammonium hydroxide, adding 3.90g of water, fully stirring, adding 6.6g of 40% silica sol, uniformly stirring, transferring the mixed solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining, putting the stainless steel reaction kettle into a 160 ℃ oven, crystallizing for 5 days, cooling to room temperature, washing with deionized water for 3 times, drying in a 120 ℃ oven, and roasting at 550 ℃ for 12 hours to prepare the MTW type molecular sieve. The XRD spectrum is shown in figure 3. The Si/Al and acid content characterization results of the obtained MTW type molecular sieve are summarized in Table 1.
Comparative example 3
Weighing 0.27g of sodium metaaluminate and 6.48g of tetraethyl ammonium hydroxide, adding 3.90g of water, fully stirring, adding 6.6g of 40% silica sol, uniformly stirring, transferring the mixed solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining, putting the stainless steel reaction kettle into a 160 ℃ oven, crystallizing for 5 days, cooling to room temperature, washing for 3 times by using deionized water, drying in a 120 ℃ oven, and roasting at 550 ℃ for 12 hours to obtain the MTW type molecular sieve. The Si/Al and acid content characterization results of the obtained MTW type molecular sieve are summarized in Table 1.
Comparative example 4
Weighing 0.80g of sodium metaaluminate and 6.48g of tetraethyl ammonium hydroxide, adding 3.90g of water, fully stirring, adding 6.6g of 40% silica sol, uniformly stirring, transferring the mixed solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining, putting the stainless steel reaction kettle into a 160 ℃ oven, crystallizing for 5 days, cooling to room temperature, washing for 3 times by using deionized water, drying in a 120 ℃ oven, and roasting at 550 ℃ for 12 hours to obtain the MTW type molecular sieve. The Si/Al and acid content characterization results of the obtained MTW type molecular sieve are summarized in Table 1.
Example 1
0.08g of sodium metaaluminate and 6.48g of 25% tetraethylammonium hydroxide solution are weighed, mixed fully, 6.6g of 40% silica sol solution is added, and then the mixture is stirred uniformly. Transferring the mixed solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining, heating to 160 ℃, keeping for 1 day, cooling to room temperature, taking out, adding 0.05g of sodium metaaluminate and 3.9g of water, uniformly stirring, transferring the mixed solution into the stainless steel reaction kettle with the polytetrafluoroethylene lining, heating to 160 ℃, keeping for 2 days, cooling to room temperature, washing for 3 times with deionized water, drying in a 120 ℃ oven, and roasting at 550 ℃ for 12 hours to obtain the Beta molecular sieve. Its XRD spectrum is as shown in figure 4; NH (NH) 3 The TPD diagram is shown in figure 5. The Si/Al and acid content characterization results of the Beta molecular sieve are summarized in Table 1.
Example 2
0.08g of sodium metaaluminate and 7g of 25% tetraethylammonium hydroxide solution are weighed, fully mixed, added with 6.6g of 40% silica sol solution and stirred uniformly. Transferring the mixed solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining, heating to 170 ℃ for 1 day, cooling to room temperature, adding 0.12g of sodium metaaluminate and 3.9g of water, uniformly stirring, transferring the mixed solution into the stainless steel reaction kettle with the polytetrafluoroethylene lining, heating to 170 ℃ for 2 days, cooling to room temperature, washing with deionized water for 3 times, drying in a 120 ℃ oven, and roasting at 550 ℃ for 12 hours to obtain the Beta molecular sieve. The Si/Al and acid content characterization results of the Beta molecular sieve are summarized in Table 1.
Example 3
0.08g of sodium metaaluminate and 7.5g of 25 percent tetraethylammonium hydroxide solution are weighed, fully mixed, added with 6.6g of 40 percent silica sol solution and stirred evenly. Transferring the mixed solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining, heating to 170 ℃, keeping for 1 day, cooling to room temperature, adding 0.32g of sodium metaaluminate and 3.9g of water, uniformly stirring, transferring the mixed solution into the stainless steel reaction kettle with the polytetrafluoroethylene lining, heating to 170 ℃, keeping for 2 days, cooling to room temperature, washing for 3 times by deionized water, drying in a 120 ℃ oven, and roasting at 550 ℃ for 12 hours to obtain the Beta molecular sieve. The Si/Al and acid content characterization results of the Beta molecular sieve are summarized in Table 1.
Example 4
0.08g of sodium metaaluminate and 7g of 25% tetraethylammonium hydroxide solution are weighed, fully mixed, added with 6.6g of 40% silica sol solution and stirred uniformly. Transferring the mixed solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining, heating to 170 ℃, keeping for 1 day, cooling to room temperature, adding 0.72g of sodium metaaluminate and 3.9g of water, uniformly stirring, transferring the mixed solution into the stainless steel reaction kettle with the polytetrafluoroethylene lining, heating to 170 ℃, keeping for 2 days, cooling to room temperature, washing for 3 times by deionized water, drying in a 120 ℃ oven, and roasting at 550 ℃ for 12 hours to obtain the Beta molecular sieve. The Si/Al and acid content characterization results of the Beta molecular sieve are summarized in Table 1.
Example 5
0.08g of sodium metaaluminate and 8g of 25 percent tetraethylammonium hydroxide solution are weighed, fully mixed, added with 6.6g of 40 percent silica sol solution and stirred evenly. Transferring the mixed solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining, heating to 160 ℃, keeping for 2 days, cooling to room temperature, adding 0.32g of sodium metaaluminate and 3.9g of water, uniformly stirring, transferring the mixed solution into the stainless steel reaction kettle with the polytetrafluoroethylene lining, heating to 170 ℃, keeping for 3 days, cooling to room temperature, washing for 3 times by deionized water, drying in a 120 ℃ oven, and roasting at 550 ℃ for 12 hours to obtain the Beta molecular sieve. The Si/Al and acid content characterization results of the Beta molecular sieve are summarized in Table 1.
Example 6
0.08g of sodium metaaluminate, 0.08g of sodium hydroxide and 7g of 25% tetraethylammonium bromide solution are weighed, fully mixed, added with 6.6g of 40% silica sol solution and stirred uniformly. Transferring the mixed solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining, heating to 160 ℃, keeping for 2 days, cooling to room temperature, adding 0.32g of sodium metaaluminate and 3.9g of water, uniformly stirring, transferring the mixed solution into the stainless steel reaction kettle with the polytetrafluoroethylene lining, heating to 170 ℃, keeping for 3 days, cooling to room temperature, washing for 3 times by deionized water, drying in a 120 ℃ oven, and roasting at 550 ℃ for 12 hours to obtain the Beta molecular sieve. The Si/Al and acid content characterization results of the Beta molecular sieve are summarized in Table 1.
Example 7
0.08g of sodium metaaluminate, 0.08g of sodium hydroxide and 7g of 25 percent tetraethylammonium bromide solution are weighed, fully mixed, added with 6.6g of 40 percent silica sol solution and stirred evenly. Transferring the mixed solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining, heating to 160 ℃, keeping for 2 days, cooling to room temperature, adding 0.60g of aluminum sulfate and 3.9g of water, uniformly stirring, transferring the mixed solution into the stainless steel reaction kettle with the polytetrafluoroethylene lining, heating to 170 ℃, keeping for 3 days, cooling to room temperature, washing for 3 times with deionized water, drying in a 120 ℃ oven, and roasting at 550 ℃ for 12 hours to obtain the Beta molecular sieve. The Si/Al and acid content characterization results of the Beta molecular sieve are summarized in Table 1.
Example 8
0.08g of sodium metaaluminate, 0.08g of sodium hydroxide and 8g of 25% tetraethylammonium bromide solution are weighed, fully mixed, added with 6.6g of 40% silica sol solution and stirred uniformly. Transferring the mixed solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining, heating to 160 ℃, keeping for 2 days, cooling to room temperature, adding 0.66g of aluminum nitrate and 3.9g of water, uniformly stirring, transferring the mixed solution into the stainless steel reaction kettle with the polytetrafluoroethylene lining, heating to 170 ℃, keeping for 3 days, cooling to room temperature, washing for 3 times with deionized water, drying in a 120 ℃ oven, and roasting at 550 ℃ for 12 hours to obtain the Beta molecular sieve. The Si/Al and acid content characterization results of the Beta molecular sieve are summarized in Table 1.
The XRD patterns of the Beta molecular sieves prepared in examples 2 to 8 are similar to those of FIG. 4.
TABLE 1 characterization results of crystal form, Si/Al and acid amount of the obtained molecular sieve in comparative example and example
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (5)
1. A synthetic method of a Beta molecular sieve with a low silicon-aluminum ratio is characterized by comprising the following steps:
1) crystallizing a mixture A containing a silicon source, an aluminum source, a template agent R and water at 80-300 ℃ for 5-72 hours to obtain a mixture B; the template agent R is selected from at least one of organic amines;
2) adding an aluminum source and water into the mixture B to obtain a mixture C;
3) crystallizing the mixture C at 80-300 ℃ for 5-72 h, separating, and roasting at 500-800 ℃ for 5-36 h to obtain the Beta molecular sieve with the low silicon-aluminum ratio;
the organic amine is selected from at least one of tetraethylammonium hydroxide, tetraethylammonium bromide, tetraethylammonium chloride, methyltriethylammonium bromide and methyltriethylammonium chloride;
SiO in the mixture A 2 :Al 2 O 3 Organic amine H 2 The molar ratio of O is 1:0.005-0.0125:0.25-0.40: 8-20;
wherein the mole number of the silicon source is SiO 2 In moles; the mole number of the aluminum source is Al 2 O 3 In moles; the mole number of the template agent R is calculated by the mole number of the template agent R; the moles of water are on their own;
SiO in the mixture C 2 :Al 2 O 3 Organic amine H 2 The molar ratio of O is 1:0.018-0.3:0.25-0.40: 8-30;
the low silicon-aluminum ratio Beta molecular sieve has a silicon-aluminum atom molar ratio Si/Al lower than 30;
the acid content of the Beta molecular sieve with the low silicon-aluminum ratio is 0.69-4.10 mmol (NH) 3 )/g。
2. The method according to claim 1, wherein the silicon source is selected from at least one of silica sol, water glass, white carbon black and tetraethoxysilane;
the aluminum source is at least one selected from aluminum isopropoxide, sodium metaaluminate, pseudo-boehmite, aluminum sulfate and aluminum nitrate.
3. The method as claimed in claim 1, wherein the mixture A is crystallized at 100-200 ℃ for 10-48 h in the step 1).
4. The method as claimed in claim 1, wherein the mixture C is crystallized at 100-200 ℃ for 12-72 h in the step 3).
5. The method as claimed in claim 1, wherein the roasting in step 3) is carried out at 550 to 700 ℃ for 12 to 24 hours.
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| CN101205072A (en) * | 2006-12-18 | 2008-06-25 | 中国石油化工股份有限公司 | Method for synthesizing low silica-alumina ratio beta zeolite |
| CN102910646A (en) * | 2011-08-01 | 2013-02-06 | 中国石油化工股份有限公司 | Gradient acid distributed ZSM-5 molecular sieve and preparation method thereof |
| CN103880037A (en) * | 2012-12-20 | 2014-06-25 | 中国石油化工股份有限公司 | ZSM-5 molecular sieve and preparation method thereof |
| CN105621439A (en) * | 2014-10-30 | 2016-06-01 | 中国石油化工股份有限公司 | Synthetic method of Beta zeolite |
| CN105967202A (en) * | 2016-05-03 | 2016-09-28 | 太原理工大学 | Synthetic method of ZSM-48 molecular sieve with low silica-alumina ratio |
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