CN102441424A - Y/ZSM-12 composite molecular sieve and preparation method thereof - Google Patents
Y/ZSM-12 composite molecular sieve and preparation method thereof Download PDFInfo
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- CN102441424A CN102441424A CN2010105091973A CN201010509197A CN102441424A CN 102441424 A CN102441424 A CN 102441424A CN 2010105091973 A CN2010105091973 A CN 2010105091973A CN 201010509197 A CN201010509197 A CN 201010509197A CN 102441424 A CN102441424 A CN 102441424A
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Abstract
The invention relates to a Y/ZSM-12 composite molecular sieve and a preparation method thereof. The composite molecular sieve is provided with a Y molecular sieve crystal phase and a ZSM-12 molecular sieve crystal phase. The preparation method for the composite molecular sieve includes the following steps: Y-type molecular sieve powder is added into solution containing sodium hydroxide and tetraethylammonium bromide, a silicon source is added, a reaction mixture gel system is obtained after uniform stirring, the molar ratio of the mixture of the reaction mixture gel system is (1.16 to 1.21) Na2O:(9.0 to 11.0) SiO2:(2.20 to 2.30) TEABr:Al2O3:(135 to 150) H2O, the reaction mixture is crystallized under a hermetic condition and at the temperature of 130 DEG C to 150 DEG C for 4 to 7 days, and thereby the Y/ZSM-12 composite molecular sieve is obtained. The composite molecular sieve provided by the invention is a new product, and can be used in a variety of catalytic processes.
Description
Technical field
The present invention relates to a kind of composite molecular screen and synthetic technology thereof, specifically is exactly simultaneously Y zeolite, ZSM-12 molecular sieve crystalline phase to be synthesized in a kind of composite molecular screen.
Background technology
Y zeolite is connected each other along three crystalline axis direction through twelve-ring by octahedral zeolite cage and forms, and is a kind of good catalyst activity component, and not only cracking activity is high, and selectivity is good.Therefore the invention of Y zeolite has epoch making significance at catalytic field.Because the high silica alumina ratio Y zeolite has good hydrothermal stability and absolute acid stability, so it has obtained using widely in chemical industry as a kind of catalysis material.
Breadboard Rosinski of U.S. Mobil in 1973 and Rubin have synthesized the ZSM-12 molecular sieve first, and its structure type is the MTW type, have the non-intersection of the one-dimensional linear duct that twelve-ring constitutes, and the aperture is 0.57 * 0.61nm, belongs to high silicon class zeolite.This duct size between mesopore and large pore molecular sieve can realize the shape selective catalysis of most of organic molecules is transformed effectively, in reactions such as alkylating aromatic hydrocarbon, isomerization, shows excellent catalytic performance, and application prospect is very wide.
Above-mentioned high silica alumina ratio Y zeolite and the ZSM-12 molecular sieve of showing all has application widely at the petrochemical industry catalytic field.
Composite molecular screen is in a kind of product, to contain two kinds of molecular crystal phase structures; And two kinds of molecular sieve crystal phase structures are what to be organically combined to one; Rather than mechanical mixture; A large amount of experiments show that the mechanical mixture product of compound molecule sieve ratio monocrystalline phase molecule sieve or two kinds of crystalline phase molecular sieves has tangible performance advantage at numerous catalytic fields, become the synthetic hot research fields of molecular sieve.But prior art still fails to synthesize Y zeolite, the composite molecular screen product of two kinds of crystalline phases of ZSM-12 molecular sieve in a kind of product.
Summary of the invention
The present invention provides a kind of Y/ZSM-12 composite molecular screen and preparation method thereof, for catalytic field provides a kind of new catalytic material.
Y/ZSM-12 composite molecular screen of the present invention has Y molecular sieve crystalline phase and ZSM-12 molecular sieve crystalline phase.
It is following that Y/ZSM-12 composite molecular screen of the present invention prepares process: the Y zeolite powder is added contain in the solution of NaOH (NaOH) and template; Add the silicon source; Stirring obtains the reaction mixture gel system, and the mol ratio of reaction mixture gel system mixture is: (1.16-1.21) Na
2O: (9.0-11.0) SiO
2: (2.20-2.30) template: Al
2O
3: (135-150) H
2O, reactant mixture in confined conditions in 130 ℃-150 ℃ following crystallization 4-7 days, obtain the Y/ZSM-12 composite molecular screen.
The present invention utilizes Y zeolite to prepare gel rubber system as the suitable component of aluminium source adding; React under certain condition then and obtain final Y/ZSM-12 composite molecular screen; A kind of detailed process is following: take by weighing a certain amount of NaOH and template earlier, add a certain amount of distilled water then, use magnetic stirrer; NaOH and template are dissolved fully; Then the Y zeolite powder is added in the solution, the back that stirs adds the silicon source, and stirring obtains white synthesis reaction mixture gel rubber system.
Above-mentioned composite molecular screen is characterized in that, contains the crystalline phase of Y and two kinds of molecular sieves of ZSM-12 in the molecular sieve simultaneously.And the relative scale of Y zeolite and ZSM-12 can be come modulation through regulating synthesis condition; Relative amount as along with the prolongation ZSM-12 molecular sieve of crystallization time can increase; Along with the relative amount of the minimizing ZSM-12 molecular sieve of silicon source consumption can reduce etc., specifically can regulate on demand by those skilled in the art.
Above-mentioned composite molecular screen preparation method is characterized in that utilizing high-Si Y-type molecular sieve as the aluminium source, adopts a step hydro-thermal synthetic system to synthesize composite molecular screen.Described Y zeolite silica alumina ratio is 4.8-5.2 (a silica molecule mol ratio), can be selected from the synthetic sodium type Y molecular sieve of industry.
Among the above-mentioned composite molecular screen preparation method, the silicon source is selected from Ludox.Template can be tetraethylammonium bromide (TEABr) or tetraethyl ammonium hydroxide (TEAOH).
The advantage of composite molecular screen of the present invention and preparation method thereof is: through suitable proportioning raw materials; One step hydro-thermal synthetic system synthesize have Y zeolite, the composite molecular screen of two kinds of crystalline phases of ZSM-12 molecular sieve; Through regulating pore passage structure, acidity between them each other, can give full play to their catalysis characteristics each other.Experiment shows that composite molecular screen can be used for petroleum refining process such as hydrocracking, catalytic cracking, also can be used for some petrochemical industry catalytic process such as isomerization, and the serviceability of its some aspect is superior to the serviceability of dissimilar molecular sieve physical mixed.
Description of drawings
Fig. 1 is the composite molecular screen XRD diffraction pattern that exemplary embodiments 4 of the present invention is synthesized, and can find out that it is the composite molecular screen that contains Y zeolite, ZSM-12 molecular sieve.
The specific embodiment
The present invention utilizes high-Si Y-type molecular sieve as the synthetic composite molecular screen Y/ZSM-12 in aluminium source; The preparation method of composite molecular screen of the present invention adopts tetraethylammonium bromide or tetraethyl ammonium hydroxide as template, the method that adopts high silicon Y to synthesize through hydro-thermal for the aluminium source.
Further specify preparation process of the present invention below in conjunction with embodiment.
Take by weighing 0.65g NaOH and 10.4gTEABr and be dissolved in the 37.0ml deionized water, add 10.0gY type molecular sieve then while stirring, stir half an hour, add the 20.0ml Ludox again, move on in the closed stainless steel agitated reactor behind the stirring 2h.138 ℃ of following crystallization 5 days, obtain molecular sieve product, show that through analyzing molecular sieve product is the compound crystalline phase molecular sieve of Y/ZSM-12.
Synthetic material proportion: 1.18Na
2O: 10.5SiO
2: 2.25TEABr: Al
2O
3: 144H
2O.
Embodiment 2
Take by weighing 0.65g NaOH and 10.4gTEABr and be dissolved in the 37.0ml deionized water, add 10.0gY type molecular sieve then while stirring, stir half an hour, add the 20.0ml Ludox again, move on in the closed stainless steel agitated reactor behind the stirring 2h.139 ℃ of following crystallization 4.5 days, obtain molecular sieve product, show that through analyzing molecular sieve product is the compound crystalline phase molecular sieve of Y/ZSM-12.
Synthetic material proportion: 1.18Na
2O: 10.5SiO
2: 2.25TEABr: Al
2O
3: 144H
2O.
Embodiment 3
Take by weighing 0.65g NaOH and 10.2gTEABr and be dissolved in the 37.0ml deionized water, add 10.0gY type molecular sieve then while stirring, stir half an hour, add the 20.0ml Ludox again, move on in the closed stainless steel agitated reactor behind the stirring 2h.140 ℃ of following crystallization 4.5 days, obtain molecular sieve product, show that through analyzing molecular sieve product is the compound crystalline phase molecular sieve of Y/ZSM-12.
Synthetic material proportion: 1.18Na
2O: 10.5SiO
2: 2.21TEABr: Al
2O
3: 144H
2O.
Embodiment 4
Take by weighing 0.63g NaOH and 10.4gTEABr and be dissolved in the 37.0ml deionized water, add 10.0gY type molecular sieve then while stirring, stir half an hour, add the 20.0ml Ludox again, move on in the closed stainless steel agitated reactor behind the stirring 2h.139 ℃ of following crystallization 5.0 days, obtain molecular sieve product, show that through analyzing molecular sieve product is the compound crystalline phase molecular sieve of Y/ZSM-12.
Synthetic material proportion: 1.18Na
2O: 10.5SiO
2: 2.25TEABr: Al
2O
3: 144H
2O.
Take by weighing 0.65g NaOH and 10.4gTEABr and be dissolved in the 35.0ml deionized water, add 10.0gY type molecular sieve then while stirring, stir half an hour, add the 20.0ml Ludox again, move on in the closed stainless steel agitated reactor behind the stirring 2h.139 ℃ of following crystallization 5.0 days, obtain molecular sieve product, show that through analyzing molecular sieve product is the compound crystalline phase molecular sieve of Y/ZSM-12.
Synthetic material proportion: 1.18Na
2O: 10.5SiO
2: 2.25TEABr: Al
2O
3: 139H
2O.
Embodiment 6
Take by weighing 0.65g NaOH and 10.2gTEABr and be dissolved in the 35.0ml deionized water, add 10.0gY type molecular sieve then while stirring, stir half an hour, add the 20.0ml Ludox again, move on in the closed stainless steel agitated reactor behind the stirring 2h.145 ℃ of following crystallization 4.0 days, obtain molecular sieve product, show that through analyzing molecular sieve product is the compound crystalline phase molecular sieve of Y/ZSM-12.
Synthetic material proportion: 1.18Na
2O: 10.5SiO
2: 2.21TEABr: Al
2O
3: 139H
2O.
Embodiment 7
Take by weighing 0.67g NaOH and 10.2gTEABr and be dissolved in the 39.0ml deionized water, add 10.0gY type molecular sieve then while stirring, stir half an hour, add the 18.0ml Ludox again, move on in the closed stainless steel agitated reactor behind the stirring 2h.135 ℃ of following crystallization 6.0 days, obtain molecular sieve product, show that through analyzing molecular sieve product is the compound crystalline phase molecular sieve of Y/ZSM-12.
Synthetic material proportion: 1.19Na
2O: 9.9SiO
2: 2.21TEABr: Al
2O
3: 144H
2O.
The main character of the composite molecular screen of table 1 raw material Y zeolite and main embodiment preparation
Claims (6)
1. Y/ZSM-12 composite molecular screen, it is characterized in that: said composite molecular screen has Y molecular sieve crystalline phase and ZSM-12 molecular sieve crystalline phase.
2. the preparation method of the said composite molecular screen of claim 1; It is characterized in that the preparation process comprises: the Y zeolite powder is added contain in the solution of NaOH and template; Add the silicon source; Stirring obtains the reaction mixture gel system, and the mol ratio of reaction mixture gel system mixture is: (1.16-1.21) Na
2O: (9.0-11.0) SiO
2: (2.20-2.30) template: Al
2O
3: (135-150) H
2O, reactant mixture in confined conditions in 130 ℃-150 ℃ following crystallization 4-7 days, obtain the Y/ZSM-12 composite molecular screen.
3. according to the described method of claim 2, it is characterized in that: the silicon source is selected from Ludox.
4. according to the described method of claim 2, it is characterized in that: said Y zeolite powder is the synthetic sodium type Y molecular sieve of industry.
5. according to the described method of claim 2, it is characterized in that: template is tetraethylammonium bromide or tetraethyl ammonium hydroxide.
6. according to the described method of claim 4, it is characterized in that: the silica alumina ratio of said Y zeolite is 4.8-5.2.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104591218A (en) * | 2013-11-04 | 2015-05-06 | 中国石油化工股份有限公司 | Y and ZSM-35 composite molecular sieve and synthesizing method thereof |
| CN106669814A (en) * | 2015-11-11 | 2017-05-17 | 中国石油化工股份有限公司 | Preparation method of ZSM-48/Y composite molecular sieve |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1435374A (en) * | 2002-02-01 | 2003-08-13 | 中国石油天然气股份有限公司 | Composite molecular sieve and preparing process thereof |
| CN101596462A (en) * | 2008-06-03 | 2009-12-09 | 中国石油化工股份有限公司 | A kind of hydroisomerization catalyst and preparation method thereof |
| CN101723395A (en) * | 2008-10-29 | 2010-06-09 | 中国石油化工股份有限公司 | Method for preparing double-micropore composite molecular sieve |
-
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1435374A (en) * | 2002-02-01 | 2003-08-13 | 中国石油天然气股份有限公司 | Composite molecular sieve and preparing process thereof |
| CN101596462A (en) * | 2008-06-03 | 2009-12-09 | 中国石油化工股份有限公司 | A kind of hydroisomerization catalyst and preparation method thereof |
| CN101723395A (en) * | 2008-10-29 | 2010-06-09 | 中国石油化工股份有限公司 | Method for preparing double-micropore composite molecular sieve |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104591218A (en) * | 2013-11-04 | 2015-05-06 | 中国石油化工股份有限公司 | Y and ZSM-35 composite molecular sieve and synthesizing method thereof |
| CN104591218B (en) * | 2013-11-04 | 2017-01-11 | 中国石油化工股份有限公司 | Y and ZSM-35 composite molecular sieve and synthesizing method thereof |
| CN106669814A (en) * | 2015-11-11 | 2017-05-17 | 中国石油化工股份有限公司 | Preparation method of ZSM-48/Y composite molecular sieve |
| CN106669814B (en) * | 2015-11-11 | 2019-03-19 | 中国石油化工股份有限公司 | A kind of preparation method of ZSM-48/Y composite molecular screen |
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Application publication date: 20120509 |