CN108975353B - Hierarchical porous EU-1 molecular sieve and preparation method thereof - Google Patents
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Abstract
The invention discloses a hierarchical porous EU-1 molecular sieve and a preparation method thereof, wherein EU-1 molecular sieve raw powder with the molar ratio of silicon oxide to aluminum oxide of 20-200 is placed in an inorganic base and imidazole organic base compound mixed alkaline solution, the EU-1 molecular sieve raw powder is treated for 10-60min at room temperature according to the solid/liquid mass ratio of 1 (10-50), then acid is added to adjust the pH value to be neutral, a sample is filtered, washed and dried, and is refluxed with an acid solution with the concentration of 0.01-0.5mol/L for 0.5-12 h at the temperature of 80-120 ℃ according to the mass ratio of 1 (10-50), and the hierarchical porous EU-1 molecular sieve is obtained after filtering, washing and drying. The hierarchical porous EU-1 molecular sieve provided by the invention has good reaction molecular diffusion performance and has good application prospect when being used as a catalyst carrier.
Description
Technical Field
The invention relates to a hierarchical pore EU-1 molecular sieve and a preparation method thereof, which are a post-treatment method of the EU-1 molecular sieve and belong to the field of inorganic material synthesis.
Background
The EUO type topological structure molecular sieve crystal structure is provided with a one-dimensional ten-membered ring channel with the diameter of 0.54nm multiplied by 0.41nm in the [100] direction, and two sides of the ten-membered ring channel are also provided with a twelve-membered ring side pocket with the depth of 0.81nm multiplied by 0.68nm multiplied by 0.58 nm. EU-1, ZSM-50 and TPZ-3 molecular sieves all have EUO type topological structures, wherein the EU-1 molecular sieve is a relatively wide molecular sieve researched in recent years, and due to the special pore channel structure and the acidic characteristic of the EUO type molecular sieve, the EUO type molecular sieve is used as a bifunctional catalyst prepared from an acidic component of a carbon octaarene isomerization catalyst, has good activity and selectivity in the carbon octaarene hydroisomerization and benzene isopropylation catalytic reaction, and is known as the first choice of a new generation of xylene isomerization catalytic materials.
US4537754 discloses a hydrothermal crystallization synthesis method of EU-1 type molecular sieve, using alkylated derivative of polymethylene α -omega-diamine ion or its precursor as template agent, uniformly mixing silica-alumina source, alkali metal, template agent and seed crystal, then making hydrothermal crystallization to obtain the invented EUO type molecular sieve, US65144479 discloses a hydrothermal synthesis method of EUO type molecular sieve, uniformly mixing silica-alumina source, alkali metal, template agent and seed crystal, then making hydrothermal treatment, and adopting ultrasonic treatment to reduce grain size, and the obtained grain size is less than 5 micrometers, and Lixiafeng etc. (same or heterogeneous seed crystal effect in EU-1 molecular sieve synthesis, journal of Petroleum institute (Petroleum processing) 2006: 93-95) investigates same or heterogeneous seed crystal effect in EU-1 molecular sieve synthesis.The addition of the homogeneous seed crystal can improve the crystallinity of the product and shorten the crystallization time to 1-2 days. The obtained EU-1 molecular sieve was oval in shape and 2.0. mu. m.times.1.0. mu.m in size. Liaofeng et al (Rapid synthesis and characterization of EU-1 molecular sieves, petrochemical, 2007,36(8):794-2-Na2O-Al2O3-SiO2-H2The hydrothermal synthesis time can be shortened to 28 hours by the method for quickly synthesizing the EU-1 molecular sieve with high crystallinity in the O system. The EU-1 molecular sieve obtained by the method is an aggregate with the particle size of 1-5 mu m, and is formed by aggregating sub-particles with the particle size of 0.3-0.8 mu m. The US6377063 patent discloses a process for the synthesis of molecular sieves with EUO structure, using as structure directing agent at least one alkylated derivative of methylenediamine ions which is safer and cheaper than the templating agents or precursors of templating agents disclosed in the prior art, reducing the production costs and being safer and more environmentally friendly.
The preparation method of the molecular sieve with the EUO structure disclosed by the above documents mainly comprises a traditional hydrothermal method and a solid-phase in-situ method, but the molecular sieve has basically consistent structure, generally larger particle size which is in micron order, is easy to generate mixed crystals, has serious limitation on the catalytic life of the molecular sieve, and the product yield needs to be improved. The molecular sieve with the multilevel pore channel EUO structure shortens the molecular diffusion distance, so that reaction products are easier to diffuse from active sites to the outer surface, the formation of coking is inhibited, and the service life of the catalyst is prolonged.
Aiming at the defects of the prior art, the invention provides a method for desiliconizing an EU-1 molecular sieve under an alkaline condition and dealuminizing under an acidic condition to obtain a multi-stage pore structure and restore the silicon/aluminum ratio to the original level so as to meet the requirements of mass transfer and hydrothermal stability of a molecular sieve catalyst.
Disclosure of Invention
The invention aims to solve the problems of low diffusion efficiency and poor hydrothermal stability of reactant molecules on an EU-1 molecular sieve, which result in high inactivation speed of catalytic reaction, and provides a preparation method of a hierarchical pore EU-1 molecular sieve material.
Usually, a mesoporous molecular sieve is obtained in a top-down mode, Si in a skeleton structure is dissolved by alkali to create a mesoporous, the mode is simple to operate and low in price, and when the high-silicon aluminum molecular sieve is treated, the structure is unstable under a hydrothermal condition and even collapses. When the molecular sieve is treated by inorganic base, the yield is low and the mesopores are large; and when the organic alkali is adopted for treatment, the yield is high and the mesopores are small. According to the invention, the imidazole monocyclic compound organic base is added while inorganic base treatment is carried out, so that silicon hydroxyl vacancy remained after inorganic base treatment can be occupied, steric hindrance effect is formed, excessive dissolution of Si-O structure in the molecular sieve is slowed down, the relative crystallinity retention degree of the molecular sieve is improved, and a proper mesoporous structure can be generated.
The invention provides an EU-1 molecular sieve with the silica-alumina ratio of 20-200, the silica-alumina ratio in the range enables a desilication method to obtain intracrystalline mesopores and keeps the most appropriate range of Al centers, and for EU-1 zeolite with a higher silica-alumina ratio, alkali treatment can cause large amount of desilication without selectivity to generate partial macropores with an amorphous structure, so that the relative crystallinity of the molecular sieve is greatly reduced.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a preparation method of a hierarchical porous EU-1 molecular sieve comprises the following steps: silicon oxide prepared by a conventional method: putting EU-1 molecular sieve raw powder with the molar ratio of aluminum oxide of 20-200 into a mixed alkaline solution formed by an inorganic alkaline solution and an imidazole organic alkaline compound, and carrying out alkaline treatment for 10-60min at room temperature; adding acid into the system to adjust the pH value to be neutral, filtering out solid, washing the solid to be neutral by deionized water, and drying; and placing the dried solid in an acid solution for reflux treatment, filtering out a solid product, and drying the solid product after deionized and washed to be neutral to obtain the hierarchical porous EU-1 molecular sieve.
In the above technical scheme, the inorganic alkali solution is an aqueous solution of inorganic alkali, and the inorganic alkali is NaOH or Na2CO3、NaHCO3、LiOH、KOH、K2CO3、KHCO3Any one, two or more of them are mixed in any proportion to form a mixture.
In the technical scheme, the concentration of the inorganic alkali in the inorganic alkali solution is 0.05-5.0 mol/L, preferably 0.05-1.0 mol/L.
In the above technical scheme, the imidazole-based organic base compound is imidazole, methimazole, 1, 3-dimethylimidazolidinone, N-methylimidazole, 2-methylimidazole, 4-methylimidazole, 5-chloro-1-methylimidazole, 2, 4-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-ethylimidazole, 1-vinylimidazole, 1, 2-dimethylimidazole, 1-acetylimidazole, 4-formylimidazole, 1-formylimidazole, N-butylimidazole, 1-isopropylimidazole, 4-aminoimidazole, N-ethylimidazole, 2-aminoimidazole, 2-formylimidazole, 4-chloromethylimidazole, 2-methyl-4-ethylimidazole, thiopropionic acid, or, Any one, two or more than two of N-allyl imidazole, 1-propyl imidazole, 2-isopropyl imidazole, 2-butyl imidazole, 2-propyl imidazole and 2-ethyl-4-formyl imidazole are mixed in any proportion to form a mixture.
In the technical scheme, the solid-liquid mass ratio of EU-1 molecular sieve raw powder to mixed alkaline solution is 1: (10-50) imidazole organic alkali compound and SiO in EU-1 molecular sieve raw powder2The molar ratio of (0.01-0.06): 1.
in the technical scheme, the acid for adjusting the pH is any one or a mixture of two or more of citric acid, oxalic acid, succinic acid, glutaric acid, acetic acid, formic acid, propionic acid, nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid, tartaric acid, malic acid and succinic acid in any proportion, and the concentration of the acid is 0.01-0.5 mol/L.
In the technical scheme, the solid is washed to be neutral by deionized water and then dried, the drying temperature is 100-130 ℃, and the drying time is 2-24 h.
In the above technical scheme, the acid solution for reflux is an aqueous solution of an acid, the acid is a mixture of any one, two or more of citric acid, oxalic acid, succinic acid, glutaric acid, acetic acid, formic acid, propionic acid, nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid, tartaric acid, malic acid and succinic acid mixed in any proportion, and the concentration of the acid in the acid solution is 0.01-0.5 mol/L.
In the technical scheme, the dried solid is placed in an acid solution for reflux treatment, and the solid-liquid mass ratio of the solid to the acid solution is 1: (10-50).
In the technical scheme, the temperature of the reflux treatment is 80-120 ℃, and the treatment time is 0.5-12 h.
In the technical scheme, the solid product is dried after being deionized and washed to be neutral, the drying temperature is 100-130 ℃, and the drying time is 2-24 h.
Compared with the existing EU-1 molecular sieve synthesis method, the method has the following characteristics:
(1) the EUO molecular sieve synthesized by the invention has a micropore-mesopore multilevel pore channel structure, is beneficial to the diffusion of reactant molecules on the catalyst active site, increases the external specific surface area, improves the diffusion performance of the molecular sieve and further improves the catalytic activity.
(2) In the method, the mesopores of the EU-1 molecular sieve obtained by inorganic base treatment can be filled with imidazole monocyclic compounds and can be used as a protective agent to effectively relieve the silicon dissolving rate, so that the mesopores with uniform size are produced, the solid yield of the product can be greatly improved, secondary mesopores are produced, the mesopore volume is increased, and the micropore volume can be greatly reserved.
Drawings
FIG. 1 is an X-ray diffraction (XRD) pattern of the molecular sieve prepared in comparative example 1 of the present invention.
FIG. 2 is an X-ray diffraction (XRD) pattern of the molecular sieve prepared in example 1 of the present invention.
Fig. 3 is a Scanning Electron Microscope (SEM) photograph of the molecular sieve prepared in comparative example 1 of the present invention.
FIG. 4 is a Scanning Electron Microscope (SEM) photograph of the molecular sieve prepared in example 2 of the present invention.
Detailed Description
The following detailed description of the embodiments of the present invention is provided, but the present invention is not limited to the following descriptions:
the products in the examples and the comparative examples of the present invention were characterized and analyzed for specific surface area, pore volume and average pore diameter by using a Micromeritics ASAP 2020 nitrogen physical adsorption apparatus. The pretreatment method of the sample before analysis was as follows: and (3) vacuumizing the molecular sieve sample at normal temperature, treating at 130 ℃ for 2h when the vacuum condition is achieved, and then treating at 350 ℃ for 2 h.
Comparative example 1:
EU-1 molecular sieves were synthesized according to the example of patent CN 201610102491: 393.3g of deionized water and 0.18g of sodium hydroxide (NaOH: 96%), 82.32g of hexamethonium bromide (HMBr 2: 99%), 97.96g of white carbon black (SiO 2: 92%), 9.09g of sodium metaaluminate (Al)2O337.4 wt%, Na 2O%: 29.22%), stirred for 2h, placed in a reaction vessel for aging: the aging temperature is 80 ℃, and the aging time is 24 h. Crystallizing at 170 ℃ for 60 hours, performing suction filtration, washing, drying at 120 ℃ for 12 hours, heating to 550 ℃ and roasting for 4 hours, wherein the obtained sample is an EU-1 phase shown by characterization and analysis of XRD (figure 1), the relative crystallinity is 95%, the silicon-aluminum ratio is 45 by XRF analysis, and the grain size analysis is 2-4 mu m. FIG. 3 illustrates the conventional method for obtaining large-sized grain morphology.
Example 1:
the EU-1 molecular sieve in the comparative example 1 is used as raw powder, the raw powder is placed in a mixed alkaline solution formed by 0.08mol/L NaOH and imidazole, the alkali treatment is carried out for 10min at room temperature, the solid-liquid mass ratio is 1:20, and the imidazole and the SiO in the EU-1 molecular sieve raw powder are mixed according to the weight ratio of 1:202Is 0.02: 1. then adding nitric acid with the concentration of 0.2mol/L into the system to adjust the pH value to be neutral, filtering out solid, washing the solid to be neutral by deionized water, and drying the solid for 12 hours at 120 ℃; placing the dried solid in 0.5mol/L citric acid solution, and performing reflux treatment at 120 ℃ for 10h, wherein the solid-liquid mass ratio is 1: 10; and then filtering out a solid product, and drying the solid product at 120 ℃ for 12h after the solid product is deionized and washed to be neutral to obtain the hierarchical porous EU-1 molecular sieve. Fig. 2 illustrates the resulting product as an EUO topology phase and fig. 4 illustrates the hierarchical pore molecular sieve morphology.
Examples 2 to 8:
examples 2 to 8 were prepared in substantially the same manner as in example 1, except that various parameters such as the kind of the inorganic base solution, the kind of the piperidine compound, the treatment time of the molecular sieve in the base solution, the kind of the acid, the acid concentration, the mass ratio of the solid to the acid solution, the reflux temperature and the reflux time were varied as shown in tables 1 and 2; the results of nitrogen physical adsorption show that the samples obtained in examples 1 to 8 all have mesoporous structures, and the mesoporous pore size distribution, the average pore size, and the mesoporous pore volume are shown in table 3:
TABLE 1
TABLE 2
*: the product solid yield is equal to the product mass of the hierarchical porous EU-1 molecular sieve/the initial EU-1 molecular sieve mass multiplied by 100 percent
TABLE 3
As can be seen from Table 3, the molecular sieve synthesized by the example of the present invention has two mesoporous structures with different sizes, and forms a hierarchical pore structure EU-1 molecular sieve with the original micropores of the molecular sieve. In addition, the embodiment sample can keep larger micropore volume, and obtain the mesopore volume which is obviously larger than that of the comparative sample, which shows that the invention has excellent hierarchical pore structure characteristics, is suitable for reducing the diffusion resistance of reaction molecules, increasing the kinetic reaction rate and reducing the carbon deposition inactivation probability of the molecular sieve catalyst.
The above examples are only for illustrating the technical concept and features of the present invention, and are not intended to limit the scope of the present invention. All equivalent changes or modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (10)
1. A preparation method of a hierarchical porous EU-1 molecular sieve is characterized by comprising the following steps: silicon oxide prepared by a conventional method: putting EU-1 molecular sieve raw powder with the molar ratio of aluminum oxide of 20-200 into a mixed alkaline solution formed by an inorganic alkaline solution and an imidazole organic alkaline compound, and carrying out alkaline treatment for 10-60min at room temperature; adding acid into the system to adjust the pH value to be neutral, filtering out solid, washing the solid to be neutral by deionized water, and drying; placing the dried solid in an acid solution for reflux treatment, filtering out a solid product, deionizing and washing the solid product to be neutral, and drying to obtain the hierarchical porous EU-1 molecular sieve;
the imidazole organic alkali compound is imidazole, methimazole, 1, 3-dimethyl imidazolone, N-methylimidazole, 2-methylimidazole, 4-methylimidazole, 5-chloro-1-methylimidazole, 2, 4-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-ethylimidazole, 1-vinylimidazole, 1, 2-dimethylimidazole, 1-acetylimidazole, 4-formylimidazole, 1-formylimidazole, N-butylimidazole, 1-isopropylimidazole, 4-aminoimidazole, N-ethylimidazole, 2-aminoimidazole, 2-formylimidazole, 4-chloromethylimidazole, 2-methyl-4-ethylimidazole, N-allylimidazole, N-methylimidazole, Any one, two or more than two of 1-propyl imidazole, 2-isopropyl imidazole, 2-butyl imidazole, 2-propyl imidazole and 2-ethyl-4-formyl imidazole are mixed in any proportion to form a mixture.
2. The method according to claim 1, wherein the inorganic alkali solution is an aqueous solution of an inorganic alkali such as NaOH or Na2CO3、NaHCO3、LiOH、KOH、K2CO3、KHCO3Any one, two or more of them are mixed in any proportion to form a mixture.
3. The method according to claim 1, wherein the inorganic base solution has a concentration of 0.05 to 5.0 mol/L.
4. The preparation method of claim 1, wherein the solid-liquid mass ratio of the EU-1 molecular sieve raw powder to the mixed alkaline solution is 1: (10-50) imidazole organic alkali compound and SiO in EU-1 molecular sieve raw powder2The molar ratio of (0.01-0.06): 1.
5. the method according to claim 1, wherein the acid for adjusting pH is a mixture of one, two or more selected from the group consisting of citric acid, oxalic acid, succinic acid, glutaric acid, acetic acid, formic acid, propionic acid, nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid, tartaric acid, malic acid and succinic acid, and the concentration of the acid is 0.01 to 0.5 mol/L.
6. The method as claimed in claim 1, wherein the solid is washed to neutrality with deionized water and then dried at a temperature of 100 ℃ and 130 ℃ for a time of 12-48 h.
7. The method according to claim 1, wherein the acid solution for reflux is an aqueous acid solution, the acid is a mixture of one, two or more selected from the group consisting of citric acid, oxalic acid, succinic acid, glutaric acid, acetic acid, formic acid, propionic acid, nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid, tartaric acid, malic acid and succinic acid, and the concentration of the acid in the acid solution is 0.01 to 0.5 mol/L.
8. The preparation method according to claim 1, wherein the dried solid is placed in an acid solution for reflux treatment, and the solid-liquid mass ratio of the solid to the acid solution is 1: (10-50).
9. The method according to claim 1, wherein the temperature of the reflux treatment is 80 to 120 ℃ and the treatment time is 0.5 to 12 hours.
10. The method as claimed in claim 1, wherein the solid product is dried after being washed to neutrality by deionization at a temperature of 100 ℃ and a temperature of 130 ℃ for a time of 12-48 h.
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