CN115304079A - Preparation method and application of morphology-adjustable ZSM-5 molecular sieve - Google Patents
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
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Abstract
The invention provides a novel preparation method of a morphology-adjustable ZSM-5 molecular sieve, which is applied to the field of VOCs adsorption and comprises the following steps: s1, preparing two different organic templates, namely R1 and R2, wherein at least one of R1 and R2 is alkaline organic amine; s2, crystallizing; s3, filtering and washing; s4, drying; s5, roasting; and S6, crushing. And (3) adjusting the molar ratio of the R1 to the R2 according to the shape of the required finished product, thus obtaining the finished product with the required shape. The preparation method uses two organic templates, on one hand, the molecular sieves with different shapes are obtained by adjusting the proportion of the two organic templates, and on the other hand, at least one alkaline organic amine is contained in the organic templates, so that the use of inorganic alkali is reduced, the exchange and roasting processes in the traditional production process are saved, the process flow is shortened, the generation of ammonia nitrogen wastewater is avoided, and the production cost is reduced.
Description
Technical Field
The invention relates to the field of preparation of ZSM-5 molecular sieves, in particular to a preparation method and application of a morphology-adjustable ZSM-5 molecular sieve.
Background
Molecular sieves are a class of adsorbents or membranes having uniform micropores and composed primarily of silicon, aluminum, oxygen, and other metal cations, and having pore sizes comparable to the size of a typical molecule, and are designed to screen a variety of fluid molecules according to their effective pore sizes. The zeolite molecular sieve is a natural and artificially synthesized crystalline aluminosilicate with the molecular sieve effect. ZSM-5 zeolite has wide application in the fields of petrochemical industry, fine chemical industry and the like, such as adsorption of VOCs, due to unique and uniform pore structure, larger specific surface area, adjustable acidity and higher hydrothermal stability.
The hydrothermal synthesis method is a common method for synthesizing ZSM-5 molecular sieves at present, crystals grow in a hydrothermal system, insoluble or indissolvable substances are dissolved by utilizing the high-temperature and high-pressure conditions in a crystallization kettle, and the crystallization process is long when a certain saturation degree is reached. The synthesis process generally comprises the steps of mixing certain amounts of silicon sources and aluminum sources according to a certain sequence and proportion. The organic template agent can play the roles of structure guiding, framework charge balancing, framework space filling and the like in zeolite synthesis. The application of the molecular sieve requires precise control of the morphology of molecular sieve crystals, and a large amount of different single-kind organic templates or certain specific-kind additives are required for preparing the molecular sieves with different morphologies, which causes the large amount of the templates and the complex wastewater components after the additives are used, difficult to treat and environment-friendly; on the other hand, a synthesized ZSM-5 molecular sieve system is alkaline, and an alkaline environment can not only depolymerize a silicon source and an aluminum source of the system to form rich nucleation units, so that the growth of crystal nuclei is effectively prevented in a nucleation stage, the size of crystal grains is reduced, and the occurrence of crystal transformation can be avoided.
In summary, the problems currently existing include: firstly, a large amount of organic template agents or additives are needed for preparing the molecular sieves with different morphologies, so that the template agents are used in a large amount, and the wastewater after the additives are used is complex in components, difficult to treat and environment-friendly; secondly, a large amount of inorganic base is used, and an exchange procedure is needed to remove non-active alkali metal ions, so that the difficulty and the cost of treatment are increased.
Disclosure of Invention
In order to prepare ZSM-5 molecular sieves with different morphologies, reduce production procedures and reduce cost, the invention provides a preparation method of a ZSM-5 molecular sieve with an adjustable morphology.
The specific scheme is as follows:
a preparation method of a morphology-adjustable ZSM-5 molecular sieve comprises the following steps:
s1, preparing two different organic templates, namely R1 and R2, wherein at least one of R1 and R2 is alkaline organic amine, and products with different appearances can be obtained by adjusting different proportions of R1 and R2;
s2, crystallization: under the condition of stirring, preparing water, a silicon source, an aluminum source, an organic template R1, an organic template R2, inorganic base and seed crystals into uniform suspension in proportion, heating to 110-160 ℃, keeping the temperature for 22-26h, adding the seed crystals in the formula to facilitate the synthesis of the ZSM-5 molecular sieve, and simultaneously avoiding the generation of mixed crystals, wherein the seed crystals can play a role in refining crystal grains;
s3, filtering and washing: cooling the crystallized slurry, vacuum filtering to remove the mother liquor, and then adding water to wash until the pH value is less than 8;
s4, drying: drying at 110-130 deg.C;
s5, roasting: heating to over 500 deg.c for roasting;
s6, crushing: and crushing the roasted massive materials into powder to obtain the finished product.
Preferably, water, a silicon source, an aluminum source, an organic template agent R1, an organic template agent R2, inorganic base and seed crystal are prepared into uniform suspension in S2 according to a proportion, so that the silicon-aluminum gel meets the requirement that SiO2 (0-0.0025) Al 2 O 3 X R1 (0.1-x) R2 (0.005-0.015) R3 (13-20) H2O (0.5-2%) crystal seed, R3 is sodium oxideOr potassium oxide, the seed crystal is calculated according to the mass proportion, and the rest is calculated according to the molar proportion.
Preferably, R1 is ethylamine, and R2 is 1,6 hexamethylene diamine or tetrapropylammonium bromide.
Preferably, the seed crystal in S2 is ZSM-5 molecular sieve after roasting and demoulding.
Preferably, the silicon source in S2 is one or a mixture of two of silica sol and silica gel; the aluminum source is one or a mixture of more of sodium metaaluminate, pseudo-boehmite and aluminum sulfate; the inorganic base is one or a mixture of sodium hydroxide and potassium hydroxide.
Preferably, the cooling manner in S3 is water quenching or natural cooling.
Preferably, the equipment used in the filtering and washing step is a Buchner funnel, the equipment used in the roasting step is a muffle furnace, and the crushing is carried out by a mechanical crushing process.
Preferably, the morphology of the desired finished product includes spheroidal, columnar, and platelet-like.
A ZSM-5 molecular sieve with adjustable morphology is applied to the field of adsorption of VOCs, and has water adsorption capacity of less than or equal to 2.5%, toluene adsorption capacity of more than or equal to 10.5% and xylene adsorption capacity of more than or equal to 5.1%.
Has the advantages that:
(1) The invention provides a preparation method of a morphology-adjustable ZSM-5 molecular sieve, wherein two organic template agents are used in a formula, products with different morphologies can be obtained by adjusting the proportion of the two organic template agents, the application scene of the molecular sieve can be met more flexibly, and when the ZSM-5 molecular sieve is applied to the field of VOCs adsorption, the adsorption capacity of water is less than or equal to 2.5%, the adsorption capacity of toluene is more than or equal to 10.5%, the adsorption capacity of xylene is more than or equal to 5.1%, and the products with different morphologies have little difference.
(2) The invention provides a preparation method of a morphology-adjustable ZSM-5 molecular sieve, which comprises two organic templates, wherein one of the two organic templates is alkaline organic amine, on one hand, the organic amine has the characteristic of low boiling point so as to be convenient for recycling, on the other hand, the alkaline organic amine can reduce the use of inorganic alkali, finally, alkali metal elements remained in a system can be removed by a washing procedure, the rest part is less than 0.15%, the procedures of exchange and roasting are reduced, the process flow is shortened, the generation of ammonia nitrogen wastewater is avoided, and the production cost is reduced.
(3) The preparation method is flexible and simple to operate, greatly reduces the procedures of treating wastewater compared with the traditional process, improves the production efficiency and reduces the enterprise cost.
Drawings
FIG. 1 is an SEM picture of the ZSM-5 molecular sieve prepared in example 1.
FIG. 2 is an SEM picture of the ZSM-5 molecular sieve prepared in example 2.
FIG. 3 is an SEM picture of the ZSM-5 molecular sieve prepared in example 3.
FIG. 4 is an XRD pattern of the ZSM-5 molecular sieve prepared in the example.
Detailed Description
For the purpose of enhancing the understanding of the present invention, the present invention will be further described in detail with reference to the following examples and the accompanying drawings, which are only used for explaining the present invention and are not to be construed as limiting the scope of the present invention.
Example 1
A preparation method of a morphology-adjustable ZSM-5 molecular sieve comprises the following specific steps:
adding 16.4g of water into a 100mL reaction kettle, starting stirring, respectively weighing and adding 0.21g of sodium hydroxide, 0.04g of sodium metaaluminate, 0.27g of an ethylamine solution R1, 4.1g of tetrapropylammonium bromide R2 (R1: R2= 1:4), 0.12g of seed crystal and 40g of silica sol, stirring at normal temperature for 30 minutes, stopping stirring, sealing the reaction kettle, filling the reaction kettle into a homogeneous reactor, crystallizing at 160 ℃ for 24 hours, naturally cooling, performing suction filtration washing until the pH is neutral, drying at 120 ℃ for 12 hours, and then roasting at 550 ℃ for 4 hours to obtain the final ZSM-5 product.
The ZSM-5 molecular sieve prepared in example 1 was analyzed by scanning electron microscope to observe the morphology, grain size and degree of dispersion of the molecular sieve crystals, the results of which are shown in FIG. 1.
Example 2
A preparation method of a morphology-adjustable ZSM-5 molecular sieve comprises the following specific steps:
adding 19.8g of water into a 100mL reaction kettle, starting stirring, respectively weighing and adding 0.14g of sodium hydroxide, 0.12g of aluminum sulfate, 0.66g of ethylamine solution R1, 2.53g of tetrapropylammonium bromide R2 (R1: R2= 1:1), 0.18g of seed crystal and 40g of silica sol, stirring at normal temperature for 30 minutes, stopping stirring, sealing the reaction kettle, filling the reaction kettle into a homogeneous reactor, crystallizing for 24 hours at 160 ℃, naturally cooling, performing suction filtration washing until the pH is neutral, drying for 12 hours at 120 ℃, and then roasting for 4 hours at 550 ℃ to obtain the final ZSM-5 product.
The ZSM-5 molecular sieve prepared in example 2 was analyzed by scanning electron microscope, and the morphology, the grain size and the degree of dispersion of the molecular sieve crystals were observed, the results of which are shown in FIG. 2.
Example 3
A preparation method of a morphology-adjustable ZSM-5 molecular sieve comprises the following specific steps:
adding 54.7g of water into a 100mL reaction kettle, starting stirring, respectively weighing and adding 0.06g of sodium hydroxide, 204g of pseudo-boehmite, 1.25g of ethylamine solution R1, 0.11g of 1,6 hexamethylenediamine R2 (R1: R2= 19).
The ZSM-5 molecular sieve prepared in example 3 was analyzed by scanning electron microscope, and the morphology, the grain size and the degree of dispersion of the molecular sieve crystals were observed, the results of which are shown in FIG. 3.
From the graphs of FIGS. 1-3, ZSM-5 molecular sieves with different shapes and sizes can be obtained by adjusting the ratio of the two organic templates.
XRD analysis of the molecular sieves prepared in the above examples is shown in FIG. 4.
The ZSM-5 molecular sieve prepared by the embodiment has a topological structure of MFI; relative crystallinity is greater than or equal to 90%; the mass fraction of inorganic alkali metal in the system is less than or equal to 0.15 percent.
As a further improvement, the above-mentioned is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a morphology-adjustable ZSM-5 molecular sieve is characterized by comprising the following steps:
s1, preparing two different organic templates which are respectively named as R1 and R2, wherein at least one of R1 and R2 is alkaline organic amine;
s2, crystallization: under the condition of stirring, preparing water, a silicon source, an aluminum source, an organic template agent R1, an organic template agent R2, inorganic base and seed crystal into uniform suspension in proportion, heating to 110-160 ℃, and keeping the temperature for 22-26h;
s3, filtering and washing: cooling the crystallized slurry, vacuum filtering to remove the mother liquor, and then adding water to wash until the pH value is less than 8;
s4, drying: drying at 110-130 deg.C;
s5, roasting: heating to over 500 deg.c for roasting;
s6, crushing: and crushing the roasted massive materials into powder to obtain the finished product.
2. The preparation method of the ZSM-5 molecular sieve with the adjustable morphology as claimed in claim 1, wherein the S2 is prepared by mixing water, a silicon source, an aluminum source, an organic template R1, an organic template R2, an inorganic base and a seed crystal into a uniform suspension in proportion so that the silica-alumina gel meets SiO 2 :(0～0.0025)Al 2 O 3 :xR1:(0.1-x)R2:(0.005～0.015)R3:(13～20)H 2 O (0.5-2%) crystal seed, R3 is sodium oxide or potassium oxide, the crystal seed is calculated according to mass ratio, and the rest is calculated according to molar ratio.
3. The method for preparing a morphology-adjustable ZSM-5 molecular sieve according to claim 1, wherein R1 is ethylamine and R2 is one of 1,6 hexanediamine and tetrapropylammonium bromide.
4. The preparation method of the ZSM-5 molecular sieve with adjustable morphology as claimed in claim 1, wherein the seed crystal in the S2 is the ZSM-5 molecular sieve after calcination and demoulding.
5. The preparation method of the ZSM-5 molecular sieve with adjustable morphology as claimed in claim 1, wherein the silicon source in S2 is one or a mixture of two of silica sol and silica gel; the aluminum source is one or a mixture of more of sodium metaaluminate, pseudo-boehmite and aluminum sulfate; the inorganic base is one or a mixture of sodium hydroxide and potassium hydroxide.
6. The method for preparing the morphology-adjustable ZSM-5 molecular sieve according to claim 1, wherein the cooling manner in the S3 is water quenching or natural cooling.
7. The method for preparing the morphology-adjustable ZSM-5 molecular sieve according to claim 1, wherein the equipment used in the filtering and washing step is a Buchner funnel, the equipment used in the roasting step is a muffle furnace, and the crushing is performed by a mechanical crushing process.
8. The preparation method of the ZSM-5 molecular sieve with the adjustable morphology as claimed in claim 1, wherein the morphology of the required finished product includes sphere-like shape, column-like shape and sheet-like shape, and the required finished product can be obtained by adjusting different ratios of R1 and R2 in the crystallization process.
9. The ZSM-5 molecular sieve with adjustable morphology, prepared by the preparation method according to any one of claims 1 to 8.
10. The ZSM-5 molecular sieve with the adjustable morphology according to claim 9, which is applied to the field of adsorption of VOCs, and is characterized in that the water adsorption capacity is less than or equal to 2.5%, the toluene adsorption capacity is greater than or equal to 10.5%, and the xylene adsorption capacity is greater than or equal to 5.1%.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1970361A1 (en) * | 2007-03-13 | 2008-09-17 | Total Petrochemicals Research Feluy | MTO process based on MeAPO molecular sieves combined with an OCP process to make olefins |
| CN105883849A (en) * | 2016-07-04 | 2016-08-24 | 山西大同大学 | Synthesis method of appearance-controllable ZSM-5 molecular sieve |
| CN106348312A (en) * | 2016-11-04 | 2017-01-25 | 中国科学院上海高等研究院 | Inorganic synthesis method for regulating morphology of ZSM-5 molecular sieve |
| CN106745056A (en) * | 2017-01-17 | 2017-05-31 | 大连理工大学 | A kind of method of the regulation Molecular Sieve Morphologies of ZSM 5 |
| CN112678844A (en) * | 2019-10-18 | 2021-04-20 | 中国石油化工股份有限公司 | Method for regulating morphology of molecular sieve |
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- 2022-07-18 CN CN202210838890.8A patent/CN115304079A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1970361A1 (en) * | 2007-03-13 | 2008-09-17 | Total Petrochemicals Research Feluy | MTO process based on MeAPO molecular sieves combined with an OCP process to make olefins |
| CN105883849A (en) * | 2016-07-04 | 2016-08-24 | 山西大同大学 | Synthesis method of appearance-controllable ZSM-5 molecular sieve |
| CN106348312A (en) * | 2016-11-04 | 2017-01-25 | 中国科学院上海高等研究院 | Inorganic synthesis method for regulating morphology of ZSM-5 molecular sieve |
| CN106745056A (en) * | 2017-01-17 | 2017-05-31 | 大连理工大学 | A kind of method of the regulation Molecular Sieve Morphologies of ZSM 5 |
| CN112678844A (en) * | 2019-10-18 | 2021-04-20 | 中国石油化工股份有限公司 | Method for regulating morphology of molecular sieve |
Non-Patent Citations (1)
| Title |
|---|
| 朱鹏: "不同形貌ZSM-5分子筛的调控合成与催化性能研究", 中国优秀硕士学位论文全文数据库, pages 189 * |
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