CN105540608A - Y-Beta composite molecular sieve having double mesoporous structure, and preparation method thereof - Google Patents
Y-Beta composite molecular sieve having double mesoporous structure, and preparation method thereof Download PDFInfo
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- CN105540608A CN105540608A CN201410603843.0A CN201410603843A CN105540608A CN 105540608 A CN105540608 A CN 105540608A CN 201410603843 A CN201410603843 A CN 201410603843A CN 105540608 A CN105540608 A CN 105540608A
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Abstract
The present invention discloses a Y-Beta composite molecular sieve having a double mesoporous structure, and a preparation method thereof. The Y-Beta composite molecular sieve has two mesoporous structures such as 3-5 nm mesopores and 7-10 nm mesopores, wherein the pore volume of the mesopores with the pore size of 3-5 nm accounts for 20-50% of the total pore volume, the pore volume of the mesopores with the pore size of 7-10 nm accounts for 15-40% of the total pore volume, a molar ratio of silica to alumina is 7-25, a specific surface area is 480-780 m<2>/g, the total pore volume is 0.39-0.70 ml/g, and the average pore size is 1.7-3.8 nm. The preparation method comprises: (1) dissolving an inorganic alkali and an organic alkali in water to form a mixed solution; and (2) adding a hydrogen type Y-Beta composite molecular sieve to the mixed solution, carrying out a constant temperature treatment, filtering, washing, drying, calcining, and carrying out ammonium exchange on the calcined product to obtain the Y-Beta composite molecular sieve having the double mesoporous structure. The Y-Beta composite molecular sieve of the present invention can provide more reaction spaces for macromolecules so as to improve the catalytic performance of the composite molecular sieve.
Description
Technical field
The present invention relates to a kind of Y-Beta composite molecular screen with two meso-hole structure and preparation method thereof.
Background technology
Y zeolite is mutually through and formed along three crystalline axis direction by twelve-ring by octahedral molecular sieve cage, it is a kind of excellent catalyst activity component, cracking activity is high, and selectivity is good, the discovery of Y zeolite and be used in catalytic field and have epoch-making meaning.High silica alumina ratio Y zeolite (mol ratio of silicon oxide and aluminum oxide is more than 4.3) has good hydrothermal stability and acid acceptance because of it, through modified as the process such as catalytic cracking and hydrocracking of a kind of catalytic material in refining of petroleum in played irreplaceable effect.
All the time, the extensive concern of numerous scientific research personnel is obtained about the modification work of Y zeolite.The study on the modification of Y zeolite mainly carries out desiliconization dealuminzation by the acid of routine, alkali and hydrothermal treatment consists modification, produces a large amount of secondary mesopore structures simultaneously.The a large amount of secondary pores produced are conducive to macromolecular reaction and diffusion.Current modified method mainly first by carrying out acid treatment after the hydrothermal treatment consists of certain temperature, not only having carried out dealuminzation to molecular sieve, having improve hydrothermal stability, can produce a large amount of secondary pore structures simultaneously.But molecular sieve secondary pore prepared by the method mainly concentrates on surface and limited amount, the quantity wanting to improve secondary pore just needs advanced treatment molecular sieve, and this can cause the excessive dealuminzation of molecular sieve, and the acid amount of molecular sieve reduces and cannot meet the demands.
In recent years, huge progress is achieved by the research of alkaline solution desiliconization, by carrying out the amount that alkaline purification can increase secondary pore greatly after pickling further, the acid amount of molecular sieve can also be improved simultaneously, solve the problem of the sour quantity not sufficient that original advanced treatment is brought.But the aperture of secondary pore structure mainly concentrates on 3 ~ 5nm, still cannot process two rings and above aromatic hydrocarbons macromole, the molecular sieve that therefore preparation has a larger secondary pore structure is a very important direction of scientific rersearch.
CN201110217562.8 discloses a kind of Y-Beta composite molecular screen and the synthetic method thereof with regular meso-hole structure, and this composite molecular screen has Y zeolite crystalline phase and Beta molecular sieve crystalline phase simultaneously, and mesoporous integrated distribution is between 2 ~ 4nm.
Summary of the invention
For the deficiencies in the prior art, Y-Beta composite molecular screen that the invention provides a kind of pair of meso-hole structure and preparation method thereof.Y-Beta composite molecular screen of the present invention has two kinds of meso-hole structures of 3-5nm and 7 ~ 10nm, can provide more reaction compartment, improve the catalytic performance of composite molecular screen for macromole.
The Y-Beta composite molecular screen of of the present invention pair of meso-hole structure, there is following character: Y-Beta composite molecular screen has 3 ~ 5nm and 7 ~ 10nm, two kinds of meso-hole structure distributions, its mesoporous is that the mesoporous pore volume of 3 ~ 5nm accounts for 20% ~ 50% of total pore volume, preferably 30% ~ 45%, aperture is that the pore volume of 7 ~ 10nm accounts for 15% ~ 40% of total pore volume, preferably 20% ~ 35%; Silicon oxide and alumina molar ratio are 7 ~ 25, preferably 9 ~ 18; Specific surface area is 480 ~ 780m
2/ g, preferably 500 ~ 750m
2/ g; Total pore volume is 0.39 ~ 0.70ml/g, preferably 0.42 ~ 0.66ml/g; Mean pore size is 1.7 ~ 3.8nm, preferably 2.2 ~ 3.5nm.
The preparation method of the Y-Beta composite molecular screen of of the present invention pair of meso-hole structure, comprises following content:
(1) by mineral alkali, the water-soluble formation mixing solutions of organic bases;
(2) in mixing solutions, add Hydrogen Y-Beta composite molecular screen, constant temperature process 0.5 ~ 3 hour at 50 ~ 90 DEG C, then filter, wash, dry and roasting, product of roasting carries out ammonium exchange, obtains two mesoporous Y-Beta composite molecular screen.
In the inventive method, the mineral alkali described in step (1) is sodium hydroxide and/or potassium hydroxide, preferred sodium hydroxide, and in mixing solutions, inorganic paper mill wastewater is 0.35 ~ 0.80mol/L, preferably 0.45 ~ 0.65mol/L.
In the inventive method, the organic bases described in step (1) is one or more in tetraethyl ammonium hydroxide, TPAOH or TBAH, and in mixing solutions, organic paper mill wastewater is 0.08 ~ 0.20mol/L, preferably 0.10 ~ 0.15mol/L.
In the inventive method, step (1) also directly can add tetraethyl-ammonium halide, tetrapropyl ammonium halide or tetrabutyl ammonium halide etc. and react with mineral alkali organic basess such as generating tetraethyl ammonium hydroxide, TPAOH or TBAH.
In the inventive method, the Hydrogen Y-Beta composite molecular screen silica/alumina molar ratio described in step (2) is 7 ~ 25, preferably 10 ~ 18, and specific surface area is 650 ~ 800m
2/ g, preferably 710 ~ 780m
2/ g, mesoporous integrated distribution is between 2 ~ 4nm, aperture is the weight content that the mesoporous pore volume between 2 ~ 4nm accounts for Y molecular sieve in 85% ~ 97%, Hydrogen Y-Beta composite molecular screen of total mesoporous pore volume is 20% ~ 80%, and the those skilled in the art that are prepared as of Hydrogen Y-Beta composite molecular screen know.
In the inventive method, in step (2), the add-on of Hydrogen Y-Beta composite molecular screen and the quality in mixing solutions are than being 1:5 ~ 1:20, preferred 1:7.5 ~ 1:15.
In the inventive method, in step (2), washing to filtrate pH value is less than 9; Drying conditions is under 80 ~ 120 DEG C of conditions dry 6 ~ 24 hours; Roasting condition is roasting 2 ~ 12 hours under 450 ~ 650 DEG C of conditions.
In the inventive method, in step (3), ammonium exchange times is at least 2 times, and exchange temperature is 60 ~ 110 DEG C, preferably 80 ~ 100 DEG C; The liquid-solid ratio (ml/g) of exchange process is 5 ~ 30, preferably 10 ~ 20; Each swap time is 0.5 ~ 2.0 hour, preferably 1 ~ 1.5 hour; The ammonium salt of ammonium clearing house is ammonium chloride, ammonium sulfate or ammonium nitrate, and preferred ammonium salt is ammonium nitrate, and the concentration of ammonium salt is 0.5 ~ 3mol/L, is preferably 1 ~ 2mol/L.
The inventive method adopts mixed ammonium/alkali solutions to process Y-Beta composite molecular screen, amorphous silica in molecular sieve and sodium hydroxide react and generate water-soluble water glass, thus effectively deviate from amorphous silica, can also react with the framework silica of defective bit in duct simultaneously and generate water-soluble water glass, part framework silica can be taken off, thus make the mesoporous meso-hole structure expanding to 3 ~ 5nm of 2 original ~ 4nm of Y-Beta composite molecular screen.Organic bases positive ion changes the bond energy of skeleton Al-O-Si key, makes partial oxidation silicon deviate from skeleton easily, makes the mesoporous mesoporous pore structure running through formation about 7 ~ 10nm of part about the 3 ~ 5nm in composite molecular screen.The two mesoporous Y-Beta composite molecular screen prepared of present method can directly as acid carrier for the preparation of catalyzer.To compare traditional method of modifying, two mesoporous Y-Beta composite molecular screen prepared by the present invention has 3 ~ 5nm and 7 ~ 10nm, two kinds of meso-hole structure distributions, in alkaline purification process, reduce the silica alumina ratio of molecular sieve simultaneously, substantially increase the acid amount of molecular sieve, the molecular sieve that therefore prepared by present method has excellent catalytic activity, diffusion and anti-carbon deposition ability.
Accompanying drawing explanation
Fig. 1 is the graph of pore diameter distribution of two mesoporous Y-Beta composite molecular screen prepared by embodiment 1.
Fig. 2 is the XRD diffractogram of two mesoporous Y-Beta composite molecular screen prepared by embodiment 1.
Embodiment
Further illustrate preparation process of the present invention below in conjunction with embodiment, but following examples do not form the restriction to the inventive method.All adopt in preparation process and add the Hydrogen Y-Beta composite molecular screen with following character: silica/alumina molar ratio is 20.6, and specific surface area is 723m
2/ g, aperture is the weight content that the mesoporous pore volume of 2 ~ 4nm accounts for Y zeolite component in 90%, Hydrogen Y-Beta composite molecular screen of total mesoporous pore volume is 50%.
Wherein Hydrogen Y-Beta composite molecular screen preparation method is as follows: mixed according to the ratio of liquid-solid ratio 15ml water/g molecular sieve with the ammonium nitrate of 1.5mol/L by Y-Beta composite molecular screen, under bath temperature is 85 DEG C of conditions, constant temperature stirs 1.5 hours, then suction filtration; Repeat said process once.Then under 110 DEG C of conditions dry 12 hours.Then under the water vapor conditions of 0.2MPa, 600 DEG C of constant temperature calcinings 5 hours.Finally adopt the ammonium nitrate solution of 1.0mol/L to mix according to the ratio of liquid-solid ratio 5ml water/g molecular sieve, under bath temperature is 85 DEG C of conditions, constant temperature stirs 1.5 hours, then suction filtration, and under 110 DEG C of conditions, drying obtains Hydrogen Y-Beta composite molecular screen for 12 hours.
Embodiment 1
Sodium hydroxide and water are mixed, adopt water-bath mode to be heated to 60 DEG C under agitation simultaneously, then TPAOH is added, finally add Y-Beta composite molecular screen, continue constant temperature and stir 2 hours, cooling, suction filtration is less than 9 to pH value, drying 12 hours under 110 DEG C of conditions, finally under 550 DEG C of conditions, roasting deviates from residual organic matter in 4 hours.Finally Y-Beta composite molecular screen after alkaline purification is carried out ammonium exchange, obtain two mesoporous Y-Beta composite molecular screen.The concentration of sodium hydroxide solution is 0.48mol/L, and the concentration of TPAOH in sodium hydroxide solution is 0.12mol/L, and the mass ratio of water and molecular sieve is 8.Two mesoporous Y-Beta composite molecular screen specific nature is as shown in table 1.
Embodiment 2
Sodium hydroxide and water are mixed, adopt water-bath mode to be heated to 75 DEG C under agitation simultaneously, then TBAH is added, finally add Y-Beta composite molecular screen, continue constant temperature and stir 1.5 hours, cooling, suction filtration is less than 9 to pH value, drying 24 hours under 110 DEG C of conditions, finally under 500 DEG C of conditions, roasting deviates from residual organic matter in 5 hours.Finally the Y-Beta composite molecular screen after alkaline purification is carried out ammonium exchange, obtain two mesoporous Y-Beta composite molecular screen.The concentration of sodium hydroxide solution is 0.49mol/L, and the concentration of TBAH in sodium hydroxide solution is 0.12mol/L, and the mass ratio of water and molecular sieve is 11.Two mesoporous Y-Beta composite molecular screen specific nature is as shown in table 1.
Embodiment 3
Sodium hydroxide and water are mixed, adopt water-bath mode to be heated to 65 DEG C under agitation simultaneously, then tetraethyl ammonium hydroxide is added, finally add Y-Beta composite molecular screen, continue constant temperature and stir 2 hours, cooling, suction filtration is less than 9 to pH value, drying 18 hours under 90 DEG C of conditions, finally under 540 DEG C of conditions, roasting deviates from residual organic matter in 6 hours.Finally the Y-Beta composite molecular screen after alkaline purification is carried out ammonium exchange, obtain two mesoporous Y-Beta composite molecular screen.The concentration of sodium hydroxide solution is 0.60mol/L, and the concentration of tetraethyl ammonium hydroxide in sodium hydroxide solution is 0.11mol/L, and the mass ratio of water and molecular sieve is 9.Two mesoporous Y-Beta composite molecular screen specific nature is as shown in table 1.
Embodiment 4
Sodium hydroxide and water are mixed, adopt water-bath mode to be heated to 65 DEG C under agitation simultaneously, then TBAH is added, finally add Y-Beta composite molecular screen, continue constant temperature and stir 1.5 hours, cooling, suction filtration is less than 9 to pH value, drying 18 hours under 105 DEG C of conditions, finally under 500 DEG C of conditions, roasting deviates from residual organic matter in 8 hours.Finally the Y-Beta composite molecular screen after alkaline purification is carried out ammonium exchange, obtain two mesoporous Y-Beta composite molecular screen.The concentration of sodium hydroxide solution is 0.52mol/L, and the concentration of TBAH in sodium hydroxide solution is 0.13mol/L, and the mass ratio of water and molecular sieve is 8.5.Two mesoporous Y-Beta composite molecular screen specific nature is as shown in table 1.
Embodiment 5
Sodium hydroxide and water are mixed, adopt water-bath mode to be heated to 73 DEG C under agitation simultaneously, then TPAOH is added, finally add Y-Beta composite molecular screen, continue constant temperature and stir 2 hours, cooling, suction filtration is less than 9 to pH value, drying 12 hours under 95 DEG C of conditions, finally under 600 DEG C of conditions, roasting deviates from residual organic matter in 4 hours.Finally the Y-Beta composite molecular screen after alkaline purification is carried out ammonium exchange, obtain two mesoporous Y-Beta composite molecular screen.The concentration of sodium hydroxide solution is 0.55mol/L, and the concentration of TPAOH in sodium hydroxide solution is 0.14mol/L, and the mass ratio of water and molecular sieve is 11.Two mesoporous Y-Beta composite molecular screen specific nature is as shown in table 1.
Comparative example 1
Just TPAOH is not added with embodiment 5.Two mesoporous Y-Beta composite molecular screen specific nature is as shown in table 1.
The Y-Beta composite molecular screen character of table 1 pair meso-hole structure.
Claims (10)
1. the Y-Beta composite molecular screen of a two meso-hole structure, it is characterized in that: Y-Beta composite molecular screen has 3 ~ 5nm and 7 ~ 10nm, two kinds of meso-hole structure distributions, its mesoporous is that the mesoporous pore volume of 3 ~ 5nm accounts for 20% ~ 50% of total pore volume, and aperture is that the pore volume of 7 ~ 10nm accounts for 15% ~ 40% of total pore volume.
2. according to Y-Beta composite molecular screen according to claim 1, it is characterized in that: total pore volume is 0.39 ~ 0.70ml/g, and mean pore size is 1.7 ~ 3.8nm; Silicon oxide and alumina molar ratio are 7 ~ 25, and specific surface area is 480 ~ 780m
2/ g.
3. a preparation method for the Y-Beta composite molecular screen described in claim 1 or 2, is characterized in that comprising following content: (1) is by mineral alkali, the water-soluble formation mixing solutions of organic bases; (2) in mixing solutions, add Hydrogen Y-Beta composite molecular screen, constant temperature process 0.5 ~ 3 hour at 50 ~ 90 DEG C, then filter, wash, dry and roasting, product of roasting carries out ammonium exchange, obtains the Y-Beta composite molecular screen of two meso-hole structure.
4. in accordance with the method for claim 3, it is characterized in that: the mineral alkali described in step (1) is sodium hydroxide and/or potassium hydroxide, in mixing solutions, inorganic paper mill wastewater is 0.35 ~ 0.80mol/L.
5. in accordance with the method for claim 3, it is characterized in that: the organic bases described in step (1) is one or more in tetraethyl ammonium hydroxide, TPAOH or TBAH, in mixing solutions, organic paper mill wastewater is 0.08 ~ 0.20mol/L.
6. in accordance with the method for claim 3, it is characterized in that: the Hydrogen Y-Beta composite molecular screen silica/alumina molar ratio described in step (2) is 7 ~ 25, and specific surface area is 650 ~ 800m
2/ g, aperture is the weight content that the mesoporous pore volume between 2 ~ 4nm accounts for Y molecular sieve in 85% ~ 97%, Hydrogen Y-Beta composite molecular screen of total mesoporous pore volume is 20% ~ 80%.
7. in accordance with the method for claim 3, it is characterized in that: in step (2), the add-on of Hydrogen Y-Beta composite molecular screen and the quality in mixing solutions are than being 1:5 ~ 1:20.
8. in accordance with the method for claim 3, it is characterized in that: in step (2), washing to filtrate pH value is less than 9.
9. in accordance with the method for claim 3, it is characterized in that: drying conditions is under 80 ~ 120 DEG C of conditions dry 6 ~ 24 hours.
10. in accordance with the method for claim 3, it is characterized in that: roasting condition is roasting 2 ~ 12 hours under 450 ~ 650 DEG C of conditions.
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| CN115646539A (en) * | 2022-07-13 | 2023-01-31 | 中国科学院山西煤炭化学研究所 | Solid acid catalyst synthesized from long-chain alkylbenzene and preparation method thereof |
| CN115646539B (en) * | 2022-07-13 | 2024-04-23 | 中国科学院山西煤炭化学研究所 | Solid acid catalyst for synthesizing long-chain alkylbenzene and preparation method thereof |
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