CN113371729B - Modification method of all-silicon Beta molecular sieve containing three-membered ring - Google Patents
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Abstract
The invention provides a modification method of an all-silicon Beta molecular sieve containing three-membered rings and Lewis acid, belonging to the field of petrochemical industry. Firstly, using a Beta molecular sieve with the Si/Al ratio higher than 10 as raw powder, carrying out continuous overtime treatment on the Beta molecular sieve by using a nitric acid solution, then carrying out complete dealumination treatment, utilizing deionized water to balance the dealumination thickness Beta molecular sieve with acid and alkali to obtain an all-silicon Beta molecular sieve, then drying, feeding the dried all-silicon Beta molecular sieve into a muffle furnace for roasting, and finally obtaining the all-silicon Beta molecular sieve containing a three-membered ring and Lewis acid. The method avoids the use of a fluorine-containing mineralizer in-situ synthesis, and is green and environment-friendly; the obtained all-silicon Si-Beta molecular sieve contains a three-membered ring structure and an effective Lewis acid site, can be used for olefin isomerization reaction, and has the advantages of simple whole step, quick preparation, environmental protection and the like.
Description
Technical Field
The invention relates to a modification method of an all-silicon Beta molecular sieve containing three-membered rings, belonging to the field of petrochemical industry.
Background
Molecular sieves are widely used in the petrochemical industry due to their tunable acid properties and unique pore structures, where the acid properties of molecular sieves essentially determine their application and catalytic performance. The acidity modulation of the molecular sieve is not easy to control, and the molecular sieve only containing Lewis acid is difficult to obtain. The Lewis acid in the molecular sieve is mainly derived from non-framework aluminum species, but the molecular sieve cannot only have the non-framework aluminum species, and generally has both framework aluminum species and non-framework aluminum species, so that the general molecular sieve has both framework aluminum species and non-framework aluminum species
Acids and Lewis acids. Only present in the molecular sieve
The presence of acids or only Lewis acids is difficult to achieve.
Most molecular sieves do not contain a three-membered ring structure, a montmorillonoid, etc. (study of stacking fault structure of beta-zeolite [ J ]]Physicochemical journal, 1996, 12 (8): 727-734.) report that only twelve-membered rings formed by four-, five-and six-membered rings are present in the Beta zeolite. These rings are generally stable and generally cannot be opened. The three-membered ring has strong tension and is unstable and can be opened under the action of the probe molecules. For example, C.Jeffrey Brinker (Haiyuann Zhang, Darren R.Dunphy, Xingmao Jiang [ J ]]Journal of American Chemistry society.2012,134,15790-15804) reports SiO2The three-membered ring formed in the step (a) can be opened under the action of water molecules to form a Lewis acid site Si+And active oxygen sites.
The Beta molecular sieve of all silicon is also not easy to be obtained by an in-situ synthesis method, hydrofluoric acid is generally required to be used as a mineralizer in the in-situ synthesis, and the synthesis process is not green and is not beneficial to environmental protection. CN111333082A and CN105800624A disclose methods for synthesizing all-silicon Beta molecular sieves, which use fluoric mineralizers in the in-situ synthesis process of all-silicon Beta molecular sieves, and have harsh synthesis conditions and cannot meet the requirements of environmental protection.
Disclosure of Invention
Aiming at the defects of the prior art, the method for modifying the all-silicon Beta molecular sieve containing the three-membered ring is simple in step, the all-silicon Si-Beta molecular sieve obtained after modification contains a rare three-membered ring structure, and an active site for catalyzing isomerization of low-carbon olefin is formed after the all-silicon Si-Beta molecular sieve is opened under the action of probe molecules.
In order to realize the technical purpose, the invention discloses a method for modifying a three-membered ring-containing all-silicon Beta molecular sieve, which comprises the steps of firstly adding the Beta molecular sieve into a nitric acid solution, then carrying out complete dealumination treatment on the Beta molecular sieve by continuous heating and stirring to obtain a completely dealuminated Si-Beta molecular sieve, then washing the completely dealuminated Si-Beta molecular sieve by using deionized water until the acid-base balance is achieved, carrying out drying treatment on the acid-base balanced Si-Beta molecular sieve, and finally placing the dried Si-Beta molecular sieve in a muffle furnace for high-temperature roasting in an air environment to obtain the all-silicon Beta molecular sieve containing a three-membered ring structure and an effective Lewis acid site.
The method comprises the following specific steps:
step 1, placing a Beta molecular sieve with a Si/Al ratio higher than 10 in a container filled with a nitric acid solution, uniformly mixing, continuously stirring the Beta molecular sieve for 12 hours at a temperature of between 50 and 200 ℃, and performing condensation reflux assistance by using a condensing tube arranged above the container to obtain the completely dealuminized Si-Beta molecular sieve;
step 2, washing the completely dealuminized Si-Beta molecular sieve for multiple times by using ionized water until the PH of the obtained supernatant after centrifugation is approximately equal to 7;
step 3, drying the Si-Beta molecular sieve obtained in the step 2 at the temperature of 60-150 ℃ for 12 hours;
and 4, roasting the Si-Beta molecular sieve obtained in the step 3 at the temperature of 350-650 ℃ in the air environment of a muffle furnace for 4-8 hours to finally obtain the all-silicon Beta molecular sieve containing the three-membered ring structure, wherein the three-membered ring contained in the all-silicon Beta molecular sieve forms a Lewis acid site after being opened under the action of probe molecules.
Further, the concentration of the nitric acid solution is 8-15 mol/L.
Further, the specific surface area of the Beta molecular sieve added into the nitric acid solution is 300-600m2Per g, pore volume of 0.05-0.2cm3/g。
Further, the all-silicon Beta molecular sieve with the ternary ring structure obtained in the step 4 has a BEA topological structure, a complete framework and a characteristic diffraction peak in an XRD spectrogram.
Further, the specific surface area of the all-silicon Beta molecular sieve of the ternary ring structure obtained in the step 4 is 300-600m2Per g, pore volume of 0.05-0.2cm3/g。
Further, the all-silicon Beta molecular sieve with the ternary ring structure obtained in the step 4 exists at 607cm in a Raman spectrum-1Characteristic peak of wave number.
Further, the all-silicon Beta molecular sieve with the ternary ring structure obtained in the step 4 contains Lewis acid, and the pyridine-infrared characterization result spectrogram of the all-silicon Beta molecular sieve with the ternary ring structure contains 1460-1440 cm-1Characteristic peak of wave number.
Has the advantages that:
the modified all-silicon Si-Beta molecular sieve is obtained by a dealumination method, and the process is simple and feasible, and is green and environment-friendly;
after the Si-Beta molecular sieve of the all-silicon is roasted at high temperature, the defect sites are dehydrated and reconstructed to form three-membered rings, the number of the defect sites is greatly reduced, so that the structure of the Si-Beta molecular sieve is more regular, and the specific surface area and the volume of micropores are close to those of the Beta molecular sieve;
the generated all-silicon Si-Beta molecular sieve contains a three-membered ring structure which is rare in common molecular sieves, and the three-membered ring is opened to form a Lewis acid site Si+And active oxygen sites, the Si-Beta molecular sieve has obvious Lewis acid property;
the weak Lewis acidity of the generated all-silicon Si-Beta molecular sieve can catalyze the isomerization reaction of low-carbon olefin, such as the isomerization reaction of butylene;
the modified all-silicon molecular sieve Si-Beta contains a three-membered ring, and the three-membered ring is opened under the action of the probe molecule to form a Lewis acid site. The molecular sieve only contains weak Lewis acid and is suitable for isomerization reaction of low-carbon olefin.
The generated all-silicon Si-Beta molecular sieve has a complete pore channel structure, the defect sites generated by dealumination are greatly reduced after roasting, the difference between the volume and the surface area of the micropores and the raw powder of the Beta molecular sieve is small, the use of non-green raw materials in the in-situ synthesis process is effectively reduced, and the environment protection is facilitated.
Drawings
FIG. 1 is an X-ray diffraction XRD spectrum of the all-silicon Beta molecular sieve of comparative example 1;
FIG. 2 is an XRD spectrum of an all-silicon Si-Beta molecular sieve in example 1 of the present invention;
FIG. 3 is an XRD spectrum of an all-silicon Si-Beta molecular sieve in example 3 of the present invention;
FIG. 4 is an XRD spectrum of an all-silicon Si-Beta molecular sieve in example 4 of the present invention;
FIG. 5 is an XRD spectrum of an all-silicon Si-Beta molecular sieve in example 4 of the present invention;
FIG. 6 is a Raman spectrum of an all-silicon Si-Beta molecular sieve in example 3 of the present invention;
FIG. 7 is a pyridine-IR spectrum of the all-silicon Si-Beta molecular sieve after adsorbing pyridine molecules and after desorption at different temperatures in example 3 of the present invention.
FIG. 8 is a SEM image of the all-silicon Si-Beta molecular sieve of example 3.
Detailed Description
Embodiments of the present application are further described below with reference to the accompanying drawings:
the invention relates to a modification method of a three-membered ring-containing all-silicon Beta molecular sieve, which comprises the steps of firstly adding the Beta molecular sieve into a nitric acid solution, then carrying out complete dealumination treatment on the Beta molecular sieve by continuous heating and stirring to obtain a completely dealuminated Si-Beta molecular sieve, then washing the completely dealuminated Si-Beta molecular sieve by using deionized water until the acid-base balance is achieved, carrying out drying treatment on the acid-base balanced Si-Beta molecular sieve, and finally placing the dried Si-Beta molecular sieve in a muffle furnace for high-temperature roasting in an air environment to obtain the all-silicon Beta molecular sieve containing a ternary ring structure and an effective Lewis acid site.
The method comprises the following specific steps:
step 1, placing a Beta molecular sieve with a Si/Al ratio higher than 10 in a container filled with a nitric acid solution, uniformly mixing, continuously stirring the Beta molecular sieve for 12 hours at a temperature of between 50 and 200 ℃, and performing condensation reflux assistance by using a condensing tube arranged above the container to obtain the completely dealuminized Si-Beta molecular sieve; the concentration of the nitric acid solution is 8-15 mol/L; the specific surface area of the Beta molecular sieve is 300-600m2Per g, pore volume of 0.05-0.2cm3/g
Step 2, washing the completely dealuminized Si-Beta molecular sieve for multiple times by using ionized water until the PH of the obtained supernatant after centrifugation is approximately equal to 7;
step 3, drying the Si-Beta molecular sieve obtained in the step 2 at the temperature of 60-150 ℃ for 12 hours;
step 4, roasting the Si-Beta molecular sieve obtained in the step 3 for 4-8 hours at the temperature of 350-650 ℃ in the air environment of a muffle furnace, and finallyFinally obtaining the all-silicon Beta molecular sieve containing the ternary ring structure, wherein the three-membered ring contained in the all-silicon Beta molecular sieve can form a Lewis acid site after being opened under the action of probe molecules, and the specific surface area of the all-silicon Beta molecular sieve containing the ternary ring structure is 300-600m2Per g, pore volume of 0.05-0.2cm3(g), as shown in FIG. 6, there is 607cm in the Raman spectrum-1Characteristic peak of wave number; the all-silicon Beta molecular sieve has a BEA topological structure and a complete skeleton, has a characteristic diffraction peak in an XRD spectrogram, also contains Lewis acid, and has a pyridine-infrared characterization result spectrogram of 1460-1440 cm as shown in figure 7-1Characteristic peak of wave number.
The model of an X-Ray diffractometer used for XRD test of the all-silicon Si-Beta molecular sieve is a Brucker X-Ray diffractometer, the test voltage is 30kV, the test current is 10mA, and the test range is 5-50 degrees. The determination method comprises the following steps: the dried, milled and dispersed sample was placed in the test window and after the sample was scraped flat with a glass slide, it was scanned in the instrument.
The specific surface area measurement was performed on a low-temperature argon physical adsorption apparatus (AutosorbiQ), the total surface area was measured by the BET method, and the micropore volume was calculated by the t-plot method.
The determination of the three-membered ring is characterized by Raman spectroscopy, using a LabRAM HR800 system and a light source with a wavelength of 325 nm.
pyridine-Infrared experiments were carried out on a VERTEX 70 Infrared spectrometer with a resolution of 2cm, from Bruker, Germany-1。
The all-silicon Beta molecular sieve is obtained by in-situ synthesis according to an X-ray diffraction (XRD) spectrogram of the all-silicon Beta molecular sieve shown in figure 1.
Example 1
As shown in fig. 2, 630 g nitric acid (mass fraction 65% -68%) is weighed into a 500ml volumetric flask, and then deionized water is added to the volume of 500ml to obtain a nitric acid solution, which is denoted as solution a. Weighing 25g of Beta molecular sieve raw powder (Si/Al is 10.6), uniformly mixing the raw powder with the solution A, transferring the mixture into a round-bottom flask, placing the round-bottom flask into an oil bath pot, heating the mixture by the oil bath pot at the temperature of 100 ℃, the heating rate of 1 ℃/min, the heating time of 12 hours, placing a magneton at the bottom of the round-bottom flask for stirring, and setting a serpentine condenser pipe at an outlet at the top of the round-bottom flask for condensation reflux to obtain the dealuminized and modified all-silicon Beta molecular sieve Si-Beta. The Si-Beta is washed by deionized water for a plurality of times until the PH of the supernatant obtained after centrifugation is approximately equal to 7. And (3) placing the washed Si-Beta molecular sieve in an oven, and drying for 12 hours at 80 ℃. And (3) placing the dried Si-Beta molecular sieve in a muffle furnace, roasting for 6 hours at 350 ℃ in air, and heating at the rate of 1 ℃/min.
Example 2
As shown in fig. 3, 630 g nitric acid (mass fraction 65% -68%) is weighed into a 500ml volumetric flask, and then deionized water is added to the volume of 500ml to obtain a nitric acid solution, which is denoted as solution a. Weighing 25g of Beta molecular sieve raw powder (Si/Al is 10.6) and A solution, uniformly mixing the Beta molecular sieve raw powder and the A solution, transferring the mixture into a round-bottom flask, placing the round-bottom flask into an oil bath pot, heating the mixture by the oil bath pot at the temperature of 100 ℃, the heating rate of 1 ℃/min, the heating time of 12 hours, placing a magneton at the bottom of the round-bottom flask for stirring, and setting a serpentine condenser pipe at an outlet at the top of the round-bottom flask for condensation reflux to obtain the dealuminized and modified all-silicon Beta molecular sieve Si-Beta. The Si-Beta is washed by deionized water for a plurality of times until the PH of the supernatant obtained after centrifugation is approximately equal to 7. And (3) placing the washed Si-Beta molecular sieve in an oven, and drying for 12 hours at 80 ℃. The dried Si-Beta molecular sieve is placed in a muffle furnace and is roasted for 6 hours in air at the temperature of 450 ℃, the heating rate is 1 ℃/min, and the Raman spectrum of the obtained all-silicon Si-Beta molecular sieve is shown in figure 6.
Example 3
If shown in FIG. 4, 630 g of nitric acid (65-68 wt%) is weighed into a 500ml volumetric flask, and then deionized water is added to the volume of 500ml to obtain a nitric acid solution, which is marked as solution A. Weighing 25g of Beta molecular sieve raw powder (Si/Al is 10.6) and A solution, uniformly mixing the Beta molecular sieve raw powder and the A solution, transferring the mixture into a round-bottom flask, placing the round-bottom flask into an oil bath pot, heating the mixture by the oil bath pot at the temperature of 100 ℃, the heating rate of 1 ℃/min, the heating time of 12 hours, placing a magneton at the bottom of the round-bottom flask for stirring, and setting a serpentine condenser pipe at an outlet at the top of the round-bottom flask for condensation reflux to obtain the dealuminized and modified all-silicon Beta molecular sieve Si-Beta. The Si-Beta is washed by deionized water for a plurality of times until the PH of the supernatant obtained after centrifugation is approximately equal to 7. And (3) placing the washed Si-Beta molecular sieve in an oven, and drying for 12 hours at 80 ℃. And (3) placing the dried Si-Beta molecular sieve in a muffle furnace, roasting for 6 hours at 550 ℃ in air, and heating at the rate of 1 ℃/min to finally obtain the all-silicon Si-Beta molecular sieve, wherein a scanning electron microscope picture SEM of the all-silicon Si-Beta molecular sieve is shown in FIG. 8.
Example 4
As shown in fig. 5, 630 g nitric acid (mass fraction 65% -68%) is weighed into a 500ml volumetric flask, and then deionized water is added to the volume of 500ml to obtain a nitric acid solution, which is denoted as solution a. Weighing 25g of Beta molecular sieve raw powder (Si/Al is 10.6) and A solution, uniformly mixing the Beta molecular sieve raw powder and the A solution, transferring the mixture into a round-bottom flask, placing the round-bottom flask into an oil bath pot, heating the mixture by the oil bath pot at the temperature of 100 ℃, the heating rate of 1 ℃/min, the heating time of 12 hours, placing a magneton at the bottom of the round-bottom flask for stirring, and setting a serpentine condenser pipe at an outlet at the top of the round-bottom flask for condensation reflux to obtain the dealuminized and modified all-silicon Beta molecular sieve Si-Beta. The Si-Beta is washed by deionized water for a plurality of times until the PH of the supernatant obtained after centrifugation is approximately equal to 7. And (3) placing the washed Si-Beta molecular sieve in an oven, and drying for 12 hours at 80 ℃. And (3) placing the dried Si-Beta molecular sieve in a muffle furnace, roasting for 6 hours at 650 ℃ in air, and heating at the rate of 1 ℃/min.
Evaluation of n-butene isomerization reaction
The Si-Beta molecular sieves obtained in examples 1 to 4 were subjected to tabletting, crushing and sieving treatments, respectively. And (3) taking a molecular sieve with 40-60 meshes for carrying out n-butene isomerization reaction evaluation. The reaction temperature is 350 ℃, and the mass space velocity is 6h-1The catalyst loading was 0.2 g.
The n-butene isomerization product selectivity is shown in Table 1.
TABLE 1 evaluation results of n-butene isomerization reaction
As can be seen from the reaction evaluation results, the Si-Beta molecular sieves modified in the examples 1 to 4 all show excellent catalytic performance in butene isomerization reaction, and can perform double bond isomerization reaction to generate cis-2-butene and trans-2-butene products, and simultaneously perform skeleton isomerization reaction to generate isobutene, and can also perform polymerization reaction to generate C5+, mainly C8.
Claims (7)
1. A modification method of a three-membered ring-containing all-silicon Beta molecular sieve is characterized by comprising the following steps: firstly, adding a Beta molecular sieve into a nitric acid solution, then carrying out complete dealumination treatment on the Beta molecular sieve by continuous heating and stirring to obtain a completely dealuminated Si-Beta molecular sieve, then washing the completely dealuminated Si-Beta molecular sieve by using deionized water until the acid-base balance is achieved, drying the acid-base balanced Si-Beta molecular sieve, and finally placing the dried Si-Beta molecular sieve in a muffle furnace for high-temperature roasting in an air environment to obtain the all-silicon Beta molecular sieve containing a ternary ring structure and an effective Lewis acid site;
the method comprises the following specific steps:
step 1, placing a Beta molecular sieve with a Si/Al ratio higher than 10 in a container filled with a nitric acid solution, uniformly mixing, continuously stirring the Beta molecular sieve for 12 hours at a temperature of between 50 and 200 ℃, and performing condensation reflux assistance by using a condensing tube arranged above the container to obtain the completely dealuminized Si-Beta molecular sieve;
step 2, washing the completely dealuminized Si-Beta molecular sieve for multiple times by using ionized water until the PH of the obtained supernatant after centrifugation is approximately equal to 7;
step 3, drying the Si-Beta molecular sieve obtained in the step 2 at the temperature of 60-150 ℃ for 12 hours;
and 4, roasting the Si-Beta molecular sieve obtained in the step 3 at the temperature of 350-650 ℃ in the air environment of a muffle furnace for 4-8 hours to finally obtain the all-silicon Beta molecular sieve containing the three-membered ring structure, wherein the three-membered ring contained in the all-silicon Beta molecular sieve forms a Lewis acid site after being opened under the action of probe molecules.
2. The process of modifying an all-silicon Beta molecular sieve containing a three-membered ring according to claim 1, wherein: the concentration of the nitric acid solution is 8-15 mol/L.
3. The process of modifying an all-silicon Beta molecular sieve containing a three-membered ring according to claim 1, wherein: the specific surface area of the Beta molecular sieve arranged in a container filled with the nitric acid solution is 300-600m2Per g, pore volume of 0.05-0.2cm3/g。
4. The process of modifying an all-silicon Beta molecular sieve containing a three-membered ring according to claim 1, wherein: the all-silicon Beta molecular sieve with the ternary ring structure obtained in the step 4 has a BEA topological structure, a complete framework and a characteristic diffraction peak in an XRD spectrogram.
5. The process of modifying an all-silicon Beta molecular sieve containing a three-membered ring according to claim 1, wherein: the specific surface area of the all-silicon Beta molecular sieve of the ternary ring structure obtained in the step 4 is 300-2Per g, pore volume of 0.05-0.2cm3/g。
6. The process of modifying an all-silicon Beta molecular sieve containing a three-membered ring according to claim 1, wherein: the all-silicon Beta molecular sieve with the ternary ring structure obtained in the step 4 exists at 607cm in a Raman spectrogram-1Characteristic peak of wave number.
7. The process of modifying an all-silicon Beta molecular sieve containing a three-membered ring according to claim 1, wherein: the all-silicon Beta molecular sieve with the ternary ring structure obtained in the step 4 contains Lewis acid, and the pyridine-infrared characterization result spectrogram of the all-silicon Beta molecular sieve is 1460-1440 cm-1Characteristic peak of wave number.
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| CN112174162A (en) * | 2020-10-13 | 2021-01-05 | 天津大学 | Method for preparing Silicalite-1 molecular sieve |
| CN112707409A (en) * | 2020-12-30 | 2021-04-27 | 中海油天津化工研究设计院有限公司 | Green preparation method of nano all-silicon Beta molecular sieve |
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