CN105540608B - A kind of Y Beta composite molecular screens of pair of meso-hole structure and preparation method thereof - Google Patents
A kind of Y Beta composite molecular screens of pair of meso-hole structure and preparation method thereof Download PDFInfo
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Abstract
The invention discloses Y Beta composite molecular screens of a kind of pair of meso-hole structure and preparation method thereof.Y Beta composite molecular screens have 3 5nm and 7 ~ 10nm two kinds of meso-hole structures, aperture accounts for the 20% ~ 50% of total pore volume for 3 ~ 5nm mesoporous pore volume, aperture accounts for the 15% ~ 40% of total pore volume for 7 ~ 10nm pore volume, and silica is 7 ~ 25 with alumina molar ratio, and specific surface area is 480 ~ 780m2/ g, total pore volume is 0.39 ~ 0.70ml/g, and average pore size is 1.7 ~ 3.8nm.Preparation method includes following content：（1）Inorganic base, organic base are dissolved in water formation mixed solution；（2）Hydrogen Y Beta composite molecular screens are added into mixed solution, then constant temperature processing is filtered, washs, dries and be calcined, product of roasting carries out ammonium exchange, obtains the Y Beta composite molecular screens of double meso-hole structures.The Y Beta composite molecular screens of double meso-hole structures of the invention can provide more reaction compartments for macromolecular, improve the catalytic performance of composite molecular screen.
Description
Technical field
The present invention relates to a kind of Y-Beta composite molecular screens with double meso-hole structures and preparation method thereof.
Background technology
Y type molecular sieve be as formed by octahedral molecular sieve cage is mutually communicated by twelve-ring along three crystalline axis directions,
It is a kind of excellent catalyst activity component, cracking activity is high, selectivity is good, the discovery of Y type molecular sieve and using in catalysis neck
Domain has epoch-making meaning.High silica alumina ratio Y type molecular sieve（The mol ratio of silica and aluminum oxide is more than 4.3）Because it has
Good hydrothermal stability and absolute acid stability, by it is modified as a kind of catalysis material PETROLEUM PROCESSING catalytic cracking with
And played irreplaceable effect during being hydrocracked etc..
All the time, the modification work on Y type molecular sieve has obtained the extensive concern of numerous scientific research personnel.Y type molecules
The study on the modification of sieve is mainly to be modified to carry out desiliconization dealuminzation by conventional acid, alkali and hydro-thermal process, while producing a large amount of
Secondary mesopore structure.The a large amount of secondary pores produced are conducive to the reaction and diffusion of macromolecular.Current modified method is mainly
First pass through and acid treatment carried out after the hydro-thermal process of certain temperature, dealuminzation not only has been carried out to molecular sieve, hydrothermal stability is improved,
Substantial amounts of secondary pore structure can be produced simultaneously.But molecular sieve secondary pore prepared by this method is concentrated mainly on surface and number
Amount is limited, and the quantity for wanting to improve secondary pore is accomplished by advanced treating molecular sieve, and this can cause the excessive dealuminzation of molecular sieve, molecular sieve
Acid amount reduction can not meet requirement.
In recent years, huge progress is achieved by the research of aqueous slkali desiliconization, by further being carried out after pickling at alkali
Reason can greatly increase the amount of secondary pore, while the acid amount of molecular sieve can also be improved, solve what original advanced treating was brought
The problem of acid amount is not enough.But the aperture of secondary pore structure is concentrated mainly on 3 ~ 5nm, two rings and the virtue of the above still can not be handled
Hydrocarbon macromolecular, therefore it is a critically important direction of scientific rersearch to prepare the molecular sieve with bigger secondary pore structure.
CN201110217562.8 discloses a kind of Y-Beta composite molecular screens with regular meso-hole structure and its synthesis
Method, the composite molecular screen has a Y type molecular sieve crystalline phase and Beta molecular sieve crystalline phases simultaneously, mesoporous integrated distribution 2~4nm it
Between.
The content of the invention
In view of the shortcomings of the prior art, the Y-Beta composite molecular screens of a kind of pair of meso-hole structure of present invention offer and its preparation
Method.Y-Beta composite molecular screens of the present invention have 3-5nm and 7 ~ 10nm two kinds of meso-hole structures, can be provided more for macromolecular
Many reaction compartments, improve the catalytic performance of composite molecular screen.
The Y-Beta composite molecular screens of double meso-hole structures of the present invention, with following property：Y-Beta compound molecule sifter device
There are 3 ~ 5nm and 7 ~ 10nm two kinds of meso-hole structures distribution, wherein aperture accounts for the 20% ~ 50% of total pore volume for 3 ~ 5nm mesoporous pore volume, excellent
30% ~ 45% is selected, aperture accounts for the 15% ~ 40% of total pore volume, preferably 20% ~ 35% for 7 ~ 10nm pore volume；Silica rubs with aluminum oxide
You are than being 7 ~ 25, preferably 9 ~ 18；Specific surface area is 480 ~ 780m2/ g, preferably 500 ~ 750m2/g；Total pore volume is 0.39 ~ 0.70ml/
G, preferably 0.42 ~ 0.66ml/g；Average pore size is 1.7 ~ 3.8nm, preferably 2.2 ~ 3.5nm.
The preparation method of the Y-Beta composite molecular screens of double meso-hole structures of the present invention, including following content：
（1）Inorganic base, organic base are dissolved in water formation mixed solution；
（2）Hydrogen Y-Beta composite molecular screens are added into mixed solution, constant temperature is handled 0.5 ~ 3 hour at 50 ~ 90 DEG C,
Then filter, wash, dry and be calcined, product of roasting carries out ammonium exchange, obtain double mesoporous Y-Beta composite molecular screens.
In the inventive method, step（1）Described inorganic base is sodium hydroxide and/or potassium hydroxide, preferred sodium hydroxide,
The concentration of inorganic base is 0.35 ~ 0.80mol/L, preferably 0.45 ~ 0.65mol/L in mixed solution.
In the inventive method, step（1）Described organic base is tetraethyl ammonium hydroxide, TPAOH or four fourths
In one or more in base ammonium hydroxide, mixed solution the concentration of organic base be 0.08 ~ 0.20mol/L, preferably 0.10 ~
0.15mol/L。
In the inventive method, step（1）Tetraethyl ammonium halide, tetrapropyl ammonium halide or tetrabutyl halogen can also be directly added into
Change ammonium etc. and generate the organic bases such as tetraethyl ammonium hydroxide, TPAOH or TBAH with inorganic base reaction.
In the inventive method, step（2）Described Hydrogen Y-Beta composite molecular screens silica/alumina molar ratio be 7 ~
25, preferably 10 ~ 18, specific surface area is 650 ~ 800m2/ g, preferably 710 ~ 780m2/ g, mesoporous integrated distribution is between 2 ~ 4nm, hole
Footpath is that the mesoporous pore volume between 2 ~ 4nm accounts for Y molecular sieve in the 85% ~ 97% of total mesoporous pore volume, Hydrogen Y-Beta composite molecular screens
Weight content is 20% ~ 80%, and the those skilled in the art that are prepared as of Hydrogen Y-Beta composite molecular screens know.
In the inventive method, step（2）Water quality in the addition and mixed solution of middle Hydrogen Y-Beta composite molecular screens
Amount is than being 1：5~1：20, preferably 1：7.5~1：15.
In the inventive method, step（2）Middle washing to filtrate pH value is less than 9；Drying condition is under the conditions of 80 ~ 120 DEG C
Dry 6 ~ 24 hours；Roasting condition is roasting 2 ~ 12 hours under the conditions of 450 ~ 650 DEG C.
In the inventive method, step（3）Middle ammonium exchange times are at least 2 times, exchange temperature be 60 ~ 110 DEG C, preferably 80 ~
100℃；The liquid-solid ratio of exchange process（ml/g）For 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 preferably ammonium salt is ammonium nitrate, and the concentration of ammonium salt is
0.5 ~ 3mol/L, preferably 1 ~ 2mol/L.
The inventive method is handled Y-Beta composite molecular screens using mixed ammonium/alkali solutions, unformed in molecular sieve
Silica reacts the sodium metasilicate that generation is dissolved in water with sodium hydroxide, so as to effectively deviate from amorphous silica, while may be used also
Reacted with the framework silica with defective bit in duct and generate the sodium metasilicate for being dissolved in water, part skeleton dioxy can be taken off
SiClx, so that the mesoporous meso-hole structure for expanding to 3 ~ 5nm of 2 original ~ 4nm of Y-Beta composite molecular screens.Organic base just from
Son changes the bond energy of skeleton Al-O-Si keys so that partial oxidation silicon easily deviates from skeleton, makes the portion in composite molecular screen
The mesoporous of 3 ~ 5nm or so is divided to run through the mesoporous pore structure for forming 7 ~ 10nm or so.Double mesoporous Y-Beta prepared by this method
Composite molecular screen can be used to prepare catalyst directly as acid carrier.Compared to more traditional method of modifying, prepared by the present invention
Double mesoporous Y-Beta composite molecular screens there is 3 ~ 5nm and 7 ~ 10nm two kinds of meso-hole structures distribution, while during alkali process
Reduce the silica alumina ratio of molecular sieve, substantially increase molecular sieve acid amount, therefore this method prepare molecular sieve have it is excellent
Catalytic activity, diffusion and anti-carbon deposition ability.
Brief description of the drawings
Fig. 1 is the graph of pore diameter distribution of double mesoporous Y-Beta composite molecular screens prepared by embodiment 1.
Fig. 2 is the XRD diffraction patterns of double mesoporous Y-Beta composite molecular screens prepared by embodiment 1.
Embodiment
The preparation process of the present invention is further illustrated with reference to embodiment, but following examples are not constituted to present invention side
The limitation of method.The Hydrogen Y-Beta composite molecular screens that there is following property using adding in preparation process：Silica/alumina
Mol ratio is 20.6, and specific surface area is 723m2/ g, aperture accounts for the 90% of total mesoporous pore volume, Hydrogen Y- for 2 ~ 4nm mesoporous pore volume
The weight content of Y type molecular sieve component is 50% in Beta composite molecular screens.
Wherein Hydrogen Y-Beta composite molecular screens preparation method is as follows：By Y-Beta composite molecular screens and 1.5mol/L nitre
Sour ammonium is mixed according to the ratio of liquid-solid ratio 15ml water/g molecular sieves, and constant temperature is stirred 1.5 hours under the conditions of bath temperature is 85 DEG C,
Then suction filtration；Repeat said process once.Then dried 12 hours under the conditions of 110 DEG C.Then in 0.2MPa vapor bar
Under part, 600 DEG C of constant temperature calcinings 5 hours.Finally using 1.0mol/L ammonium nitrate solution according to liquid-solid ratio 5ml water/g molecular sieves
Ratio is mixed, and constant temperature is stirred 1.5 hours under the conditions of bath temperature is 85 DEG C, and then suction filtration, dries 12 small under the conditions of 110 DEG C
When obtain Hydrogen Y-Beta composite molecular screens.
Embodiment 1
Sodium hydroxide and water are mixed, while being heated to 60 DEG C, Ran Houjia using water-bath mode under agitation
Enter TPAOH, be eventually adding Y-Beta composite molecular screens, continue constant temperature and stir 2 hours, cooling, suction filtration is small to pH value
In 9, dried under the conditions of 110 DEG C 12 hours, 4 hours abjection residual organic matters are finally calcined under the conditions of 550 DEG C.Finally by alkali
Y-Beta composite molecular screens carry out ammonium exchange after processing, obtain double mesoporous Y-Beta composite molecular screens.Sodium hydroxide solution it is dense
Spend for 0.48mol/L, concentration of the TPAOH in sodium hydroxide solution is 0.12mol/L, water and molecular sieve matter
Amount is than being 8.Double mesoporous Y-Beta composite molecular screens specific natures are as shown in table 1.
Embodiment 2
Sodium hydroxide and water are mixed, while being heated to 75 DEG C, Ran Houjia using water-bath mode under agitation
Enter TBAH, be eventually adding Y-Beta composite molecular screens, continue constant temperature and stir 1.5 hours, cooling, suction filtration to pH value
Less than 9, dried under the conditions of 110 DEG C 24 hours, 5 hours abjection residual organic matters are finally calcined under the conditions of 500 DEG C.Finally will
Y-Beta composite molecular screens after alkali process carry out ammonium exchange, obtain double mesoporous Y-Beta composite molecular screens.Sodium hydroxide solution
Concentration be 0.49mol/L, concentration of the TBAH in sodium hydroxide solution be 0.12mol/L, water and molecular sieve
Mass ratio be 11.Double mesoporous Y-Beta composite molecular screens specific natures are as shown in table 1.
Embodiment 3
Sodium hydroxide and water are mixed, while being heated to 65 DEG C, Ran Houjia using water-bath mode under agitation
Enter tetraethyl ammonium hydroxide, be eventually adding Y-Beta composite molecular screens, continue constant temperature and stir 2 hours, cooling, suction filtration is small to pH value
In 9, dried under the conditions of 90 DEG C 18 hours, 6 hours abjection residual organic matters are finally calcined under the conditions of 540 DEG C.Finally by alkali
Y-Beta composite molecular screens after processing carry out ammonium exchange, obtain double mesoporous Y-Beta composite molecular screens.Sodium hydroxide solution
Concentration is 0.60mol/L, and concentration of the tetraethyl ammonium hydroxide in sodium hydroxide solution is 0.11mol/L, water and molecular sieve
Mass ratio is 9.Double mesoporous Y-Beta composite molecular screens specific natures are as shown in table 1.
Embodiment 4
Sodium hydroxide and water are mixed, while being heated to 65 DEG C, Ran Houjia using water-bath mode under agitation
Enter TBAH, be eventually adding Y-Beta composite molecular screens, continue constant temperature and stir 1.5 hours, cooling, suction filtration to pH value
Less than 9, dried under the conditions of 105 DEG C 18 hours, 8 hours abjection residual organic matters are finally calcined under the conditions of 500 DEG C.Finally will
Y-Beta composite molecular screens after alkali process carry out ammonium exchange, obtain double mesoporous Y-Beta composite molecular screens.Sodium hydroxide solution
Concentration be 0.52mol/L, concentration of the TBAH in sodium hydroxide solution be 0.13mol/L, water and molecular sieve
Mass ratio be 8.5.Double mesoporous Y-Beta composite molecular screens specific natures are as shown in table 1.
Embodiment 5
Sodium hydroxide and water are mixed, while being heated to 73 DEG C, Ran Houjia using water-bath mode under agitation
Enter TPAOH, be eventually adding Y-Beta composite molecular screens, continue constant temperature and stir 2 hours, cooling, suction filtration is small to pH value
In 9, dried under the conditions of 95 DEG C 12 hours, 4 hours abjection residual organic matters are finally calcined under the conditions of 600 DEG C.Finally by alkali
Y-Beta composite molecular screens after processing carry out ammonium exchange, obtain double mesoporous Y-Beta composite molecular screens.Sodium hydroxide solution
Concentration is 0.55mol/L, and concentration of the TPAOH in sodium hydroxide solution is 0.14mol/L, water and molecular sieve
Mass ratio is 11.Double mesoporous Y-Beta composite molecular screens specific natures are as shown in table 1.
Comparative example 1
Be the same as Example 5 is simply added without TPAOH.Double mesoporous Y-Beta composite molecular screens specific nature such as tables 1
It is shown.
The Y-Beta composite molecular screen properties of 1 pair of meso-hole structure of table.
Claims (7)
1. the Y-Beta composite molecular screens of a kind of pair of meso-hole structure, it is characterised in that：Y-Beta composite molecular screens have 3 ~ 5nm and
The distribution of 7 ~ 10nm, two kinds of meso-hole structures, wherein aperture account for the 20% ~ 50% of total pore volume for 3 ~ 5nm mesoporous pore volume, and aperture is 7 ~
10nm pore volume accounts for the 15% ~ 40% of total pore volume.
2. according to the Y-Beta composite molecular screens described in claim 1, it is characterised in that：Total pore volume is 0.39 ~ 0.70ml/g, is put down
Equal aperture is 1.7 ~ 3.8nm；Silica is 7 ~ 25 with alumina molar ratio, and specific surface area is 480 ~ 780m2/g。
3. the preparation method of the Y-Beta composite molecular screens described in a kind of claim 1 or 2, it is characterised in that in following
Hold：（1）Inorganic base, organic base are dissolved in water formation mixed solution；（2）Hydrogen Y-Beta compound molecules are added into mixed solution
Sieve, constant temperature is handled 0.5 ~ 3 hour at 50 ~ 90 DEG C, is then filtered, washs, dries and is calcined, product of roasting carries out ammonium exchange,
Obtain the Y-Beta composite molecular screens of double meso-hole structures；Step（1）Described inorganic base be sodium hydroxide and/or potassium hydroxide,
The concentration of inorganic base is 0.35 ~ 0.80mol/L in mixed solution；Step（1）Described organic base is tetraethyl ammonium hydroxide, four
In one or more in propyl group ammonium hydroxide or TBAH, mixed solution the concentration of organic base be 0.08 ~
0.20mol/L；Step（2）Described Hydrogen Y-Beta composite molecular screens silica/alumina molar ratio is 7 ~ 25, specific surface area
For 650 ~ 800m2/ g, aperture is that the mesoporous pore volume between 2 ~ 4nm accounts for the 85%~97% of total mesoporous pore volume, and Hydrogen Y-Beta is combined
The weight content of Y molecular sieve is 20%~80% in molecular sieve.
4. in accordance with the method for claim 3, it is characterised in that：Step（2）The addition of middle Hydrogen Y-Beta composite molecular screens
Amount is 1 with the water quality ratio in mixed solution：5~1：20.
5. in accordance with the method for claim 3, it is characterised in that：Step（2）Middle washing to filtrate pH value is less than 9.
6. in accordance with the method for claim 3, it is characterised in that：Drying condition is small to dry 6 ~ 24 under the conditions of 80 ~ 120 DEG C
When.
7. in accordance with the method for claim 3, it is characterised in that：Roasting condition is small for roasting 2 ~ 12 under the conditions of 450 ~ 650 DEG C
When.
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| CN107344114B (en) * | 2016-05-05 | 2020-02-14 | 中国石油化工股份有限公司 | Modified Y/ZSM-48 composite molecular sieve and preparation method and application thereof |
| CN107973310B (en) * | 2016-10-21 | 2019-11-15 | 中国石油化工股份有限公司 | A kind of Y molecular sieve and preparation method thereof containing rare earth |
| CN106986353B (en) * | 2017-04-28 | 2019-01-11 | 长乐净能新材料科技有限公司 | A kind of nanometer of Pr, Ce-Y/Beta modified molecular screen and its application |
| CN109775718A (en) * | 2017-11-14 | 2019-05-21 | 中国石油化工股份有限公司 | A kind of modified Y-Y isomorphous molecular sieve and its preparation method and application |
| 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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