CN109850915B - RUB-50 molecular sieve synthesized by Y molecular sieve crystal transformation and method thereof - Google Patents
RUB-50 molecular sieve synthesized by Y molecular sieve crystal transformation and method thereof Download PDFInfo
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- CN109850915B CN109850915B CN201910247183.XA CN201910247183A CN109850915B CN 109850915 B CN109850915 B CN 109850915B CN 201910247183 A CN201910247183 A CN 201910247183A CN 109850915 B CN109850915 B CN 109850915B
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Abstract
The invention discloses an RUB-50 molecular sieve synthesized by Y molecular sieve crystal transformation and a method thereof. The method specifically comprises the following steps: adding the Y molecular sieve into the aqueous solution of the template agent, adding sodium hydroxide, and uniformly stirring to obtain a mixed solution; and transferring the mixed solution into a reaction kettle for crystallization reaction, and obtaining the RUB-50 molecular sieve after the reaction is finished. The RUB-50 molecular sieve prepared by the invention has the grain size of 0.3-1.0 micron and the purity of more than 99.9 percent. The invention has the advantages of high purity of the RUB-50 molecular sieve, high crystallinity, high production efficiency, low energy consumption and the like.
Description
Technical Field
The invention belongs to the technical field of molecular sieves, and particularly relates to an RUB-50 molecular sieve synthesized by Y molecular sieve crystal transformation and a method thereof.
Background
A zeolitic molecular sieve is a microporous crystalline material having a framework structure. Due to the characteristics of the structure and the performance, the catalyst is widely applied to various fields such as catalysis, adsorption, ion exchange and the like. The eight-membered ring small pore molecular sieve has lower framework density, larger micropore volume and higher adsorption capacity, and the characteristics enable the molecular sieve to be used for selective catalytic reduction (NH) of ammonia3SCR) and the like, and has excellent catalytic activity and selectivity.
The RUB-50 molecular sieve, one of LEV molecular sieves, is a typical eight-membered ring molecular sieve, and is synthesized by Hermann Gies group by first crystallizing dimethyl diethyl ammonium hydroxide (DMDEAOH) at 150-175 deg.C for 14 days using a template. Chinese patent CN105283417A discloses a preparation method of LEV type molecular sieve, which is prepared by reacting raw materials of silicon dioxide, sodium aluminate, amantadine and sodium hydroxide in an autoclave, the reaction time is about 10 days, and RUB-50 is not clearly screened. Therefore, the method has the defects of low efficiency of synthesizing the RUB-50 molecular sieve and overlong synthesis time. There is no report on a route for rapidly synthesizing RUB-50 in a relatively short time.
Research reports that LEV molecular sieve is synthesized by taking RUB-50 as seed crystal, but the product is not RUB-50 molecular sieve and crystal transformation occurs.
In summary, the invention develops an RUB-50 molecular sieve synthesized by Y molecular sieve crystal transformation and a method thereof aiming at the defects and market demands of the existing RUB-50 molecular sieve preparation method, and the advantages of rapidly synthesizing the RUB-50 molecular sieve by adopting Y molecular sieve crystal transformation are mainly reflected in that: (1) the experimental operation time is greatly shortened, and the production steps are accelerated; (2) the synthesis temperature is reduced, so that the synthesis route is more energy-saving. Under the current big situation of energy conservation and emission reduction, the realization of the route has important social benefits and better industrial application prospect.
Disclosure of Invention
The invention aims to provide an RUB-50 molecular sieve synthesized by Y molecular sieve crystal transformation and a method thereof. The RUB-50 molecular sieve has the advantages of high purity, high crystallinity, high production efficiency, low energy consumption and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for synthesizing an RUB-50 molecular sieve by Y molecular sieve crystal transformation comprises the following steps:
(1) adding a Y molecular sieve into a water solution of a template agent, adding sodium hydroxide, and uniformly stirring to obtain a mixed solution;
(2) and transferring the mixed solution into a reaction kettle for crystallization reaction, and obtaining the RUB-50 molecular sieve after the reaction is finished.
In the method, the Y molecular sieve provides a silicon source and an aluminum source required by a system, and the sodium hydroxide provides a sodium source required by the system.
Further, the Y molecular sieve is a USY molecular sieve.
Further, the purity of the Y molecular sieve is more than 99%.
Further, the template agent is dimethyl diethyl ammonium hydroxide.
Further, the amounts of the Y molecular sieve, the template and the sodium hydroxide are controlled to ensure that SiO is in molar ratio in the reaction system2:Al2O3:Na2O:(DMDEA)2O:H2The range of O is 1: 0.02-0.07: 0.068-0.106: 0.206-0.255: 13.
Further, the mass concentration of the aqueous solution of the template agent is 20%.
Further, the temperature of the crystallization reaction is 140-160 ℃, and the time is 3-6 days.
Further, the crystallization reaction also comprises the steps of suction filtration and drying.
The invention also provides the RUB-50 molecular sieve synthesized by the method, wherein the grain size of the RUB-50 molecular sieve is 0.3-1.0 micron.
Further, the purity of the RUB-50 molecular sieve is more than 99.9 percent.
Compared with the prior art, the invention has the beneficial effects that:
1. the method utilizes the Y molecular sieve, especially the USY molecular sieve as the raw material to quickly synthesize the RUB-50 molecular sieve, shortens the synthesis time, reduces the synthesis temperature, and is more favorable for the industrial production of the RUB-50 molecular sieve.
2. Compared with the prior art, the RUB-50 molecular sieve obtained by the USY crystal transformation method has the advantages of good purity, high crystallinity and uniform dispersion, and the grain size is about 0.3-1.0 micron.
3. The product of the invention not only maintains good crystallinity and purity, but also has equivalent catalytic activity.
Drawings
FIG. 1: XRD pattern of ultrastable Y molecular sieve.
FIG. 2: XRD pattern of RUB-50 product synthesized by ultra-stable Y molecular sieve crystal transformation.
FIG. 3: scanning electron microscope photo of the RUB-50 product synthesized by ultra-stable Y molecular sieve crystal transformation.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the described embodiments of the invention without any inventive step, are within the scope of protection of the invention.
Unless defined otherwise, technical or scientific terms used herein shall have the ordinary meaning as understood by one of ordinary skill in the art to which this invention belongs.
Example 1: synthesis of RUB-50 molecular sieve by USY crystal transformation
The specific method comprises the following steps: first 1.2g of USY (Si/Al ═ 15) molecular sieve was added to 5.2g of 20% DMDEAOH solution,then 0.11g NaOH was added, and stirring was continued until the solution became homogeneous, and SiO in the obtained gel2:Al2O3:Na2O:(DMDEA)2O:H2The molar ratio of O is 1:0.03:0.068:0.255: 13. Then adding the reaction raw materials into a polytetrafluoroethylene stainless steel reaction kettle, crystallizing for 6 days at a static temperature of 140 ℃ to obtain complete crystallization, and performing suction filtration and drying on a product to obtain the product.
FIG. 1 shows the XRD pattern of USY, showing that the raw materials have high purity.
FIG. 2 is an XRD spectrum of an RUB-50 molecular sieve synthesized by USY crystal transformation, and the spectrum shows that the product has a typical RUB-50 zeolite molecular sieve structure, and a sample has higher crystallinity.
FIG. 3 is an SEM image of a RUB-50 molecular sieve product synthesized by USY transcrystallization, wherein diamond-shaped small blocks can be seen from the image, and the grain size is about 0.3-1.0 micron. Is consistent with the appearance of RUB-50 reported in the literature.
Example 2: synthesis of RUB-50 under relatively high temperature conditions
Firstly, 1.2g of USY (Si/Al ═ 15) molecular sieve is added into 5.2g of 20% DMDEAH solution, then 0.11g of NaOH is added, stirring is continued until the solution becomes homogeneous, and SiO in the obtained gel2:Al2O3：Na2O：(DMDEA)2O：H2The molar ratio of O is 1:0.03:0.068:0.255: 13. Then adding the reaction raw materials into a polytetrafluoroethylene stainless steel reaction kettle, crystallizing for 3 days at the static temperature of 160 ℃, completely crystallizing, filtering the product, and drying to obtain the product.
Example 3: synthesis of RUB-50 under relatively high alkaline conditions
Firstly, 1.2g of USY (Si/Al ═ 15) molecular sieve is added into 5.2g of 20% DMDEAH solution, then 0.17g of NaOH is added, stirring is continued until the solution becomes homogeneous, and SiO in the obtained gel2:Al2O3：Na2O：(DMDEA)2O：H2The molar ratio of O is 1:0.03:0.106:0.255: 13. Then adding the reaction raw materials into a polytetrafluoroethylene stainless steel reaction kettle, crystallizing for 6 days at a static temperature of 140 ℃ to obtain complete crystallization, and performing suction filtration and drying on a product to obtain the product.
Example 4: synthesis of RUB-50 under relatively low base conditions
Firstly, 1.2g of USY (Si/Al ═ 15) molecular sieve is added into 5.2g of 20% DMDEAH solution, then 0.05g of NaOH is added, stirring is continued until the solution becomes homogeneous, and SiO in the obtained gel2:Al2O3：Na2O：(DMDEA)2O：H2The molar ratio of O is 1:0.03:0.031:0.255: 13. Then adding the reaction raw materials into a polytetrafluoroethylene stainless steel reaction kettle, crystallizing for 6 days at a static temperature of 140 ℃ to obtain complete crystallization, and performing suction filtration and drying on a product to obtain the product.
Example 5: synthesis of RUB-50 under relatively high silicon conditions
Firstly, 1.2g of USY (Si/Al-25) molecular sieve is added into 5.2g of 20% DMDEAOH solution, then 0.11g of NaOH is added, stirring is continued until the solution becomes uniform, and SiO in the obtained gel2:Al2O3：Na2O：(DMDEA)2O：H2The molar ratio of O is 1:0.02:0.068:0.255: 13. Then adding the reaction raw materials into a polytetrafluoroethylene stainless steel reaction kettle, crystallizing for 6 days at a static temperature of 140 ℃ to obtain complete crystallization, and performing suction filtration and drying on a product to obtain the product.
Example 6: synthesis of RUB-50 under relatively low silicon conditions
Firstly, 1.2g of USY (Si/Al ═ 7) molecular sieve is added into 5.2g of 20% DMDEAH solution, then 0.11g of NaOH is added, stirring is continued until the solution becomes homogeneous, and SiO in the obtained gel2:Al2O3：Na2O：(DMDEA)2O：H2The molar ratio of O is 1:0.07:0.068:0.255: 13. Then adding the reaction raw materials into a polytetrafluoroethylene stainless steel reaction kettle, crystallizing for 6 days at a static temperature of 140 ℃ to obtain complete crystallization, and performing suction filtration and drying on a product to obtain the product.
Example 7: synthesis of RUB-50 with relatively little template
Firstly, 1.2g of USY (Si/Al ═ 15) molecular sieve is added into 4.2g of 20% DMDEAH solution, then 0.11g of NaOH and 0.8g of deionized water are added, stirring is continued until the solution becomes uniform, and SiO in the obtained gel2:Al2O3：Na2O：(DMDEA)2O：H2The molar ratio of O is 1:0.07:0.068:0.206: 13. Then adding the reaction raw materials into a polytetrafluoroethylene stainless steel reaction kettle, crystallizing for 6 days at a static temperature of 140 ℃ to obtain complete crystallization, and performing suction filtration and drying on a product to obtain the product.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core ideas. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
Claims (8)
1. A method for synthesizing a RUB-50 molecular sieve by crystal transformation of a Y molecular sieve is characterized by comprising the following steps:
(1) adding the Y molecular sieve into the aqueous solution of the template agent, adding sodium hydroxide, and uniformly stirring to obtain a mixed solution;
(2) transferring the mixed solution into a reaction kettle for crystallization reaction to obtain the RUB-50 molecular sieve after the reaction is finished; controlling the amounts of the Y molecular sieve, the template agent and the sodium hydroxide to ensure that SiO is in molar ratio in the reaction system2 :Al2O3 :Na2O:(DMDEA)2O:H2The range of O is 1: 0.02-0.07: 0.068-0.106: 0.206-0.255: 13; the (DMDEA)2O is dimethyl diethyl ammonium hydroxide.
2. The method for synthesizing the RUB-50 molecular sieve by the crystal transformation of the Y molecular sieve according to claim 1, wherein the Y molecular sieve is a USY molecular sieve.
3. The method for synthesizing the RUB-50 molecular sieve by the crystal transformation of the Y molecular sieve as claimed in claim 1, wherein the purity of the Y molecular sieve is more than 99%.
4. The method for synthesizing the RUB-50 molecular sieve by the crystal transformation of the Y molecular sieve according to claim 1, wherein the mass concentration of the aqueous solution of the template agent is 20%.
5. The method for synthesizing the RUB-50 molecular sieve by carrying out crystal transformation on the Y molecular sieve according to claim 1, wherein the temperature of the crystallization reaction is 140-160 ℃ and the time is 3-6 days.
6. The method for synthesizing the RUB-50 molecular sieve by carrying out crystal transformation on the Y molecular sieve according to claim 1, wherein the crystallization reaction further comprises the steps of suction filtration and drying.
7. The RUB-50 molecular sieve synthesized according to any of claims 1 to 6, wherein the RUB-50 molecular sieve crystallite size is from 0.3 to 1.0 micron.
8. The RUB-50 molecular sieve of claim 7, wherein the RUB-50 molecular sieve has a purity of greater than 99.9%.
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