CN102910645A - Isomorphous phase compound molecular sieve and preparation method thereof - Google Patents
Isomorphous phase compound molecular sieve and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an isomorphous phase compound molecular sieve and a preparation method thereof. Two components in the isomorphous phase compound molecular sieve have the same ZSM-5 molecular sieve pore channel topological structure. The isomorphous phase compound molecular sieve is a core-shell structural molecular sieve which employs a ZSM-5 molecular sieve with a low silica-alumina ratio as a core and a ZSM-5 molecular sieve with a high silica-alumina ratio as a shell, wherein the molar ratio of silicon oxide to alumina in the ZSM-5 molecular sieve with the low silica-alumina ratio is 25-50; and the molar ratio of silicon oxide to alumina in the ZSM-5 molecular sieve with the high silica-alumina ratio is 80-300. The compound molecular sieve is obtained by adding the core molecular sieve with the low silica-alumina ratio to a mixed raw material for synthesizing the shell molecular sieve with the high silica-alumina ratio and then crystallizing. The compound molecular sieve product obtained by the method has different gradient silica-alumina ratios, has the characteristics of a micropore structure and a mesopore structure at the same time, and has wide application prospects in the field of isomerization, alkylation, catalytic cracking, etc.
Description
Technical field
The invention belongs to the Zeolite synthesis field, specifically relate to a kind ofly take the low silica-alumina ratio ZSM-5 molecular sieve as nuclear, the high silica alumina ratio ZSM-5 molecular sieve is composite molecular screen of shell and preparation method thereof.
Background technology
At present, composite molecular screen obtains increasing investigator's concern.Various composite molecular screens constantly are synthesized out.Such as the disclosed MCM-41/ZSM-5 composite molecular screen of CN98110934.9, the disclosed micro porous molecular sieve of CN200410012548.4 (ZSM-5, β zeolite, mordenite, zeolite L, MCM-22, ZSM-35) and mesopore molecular sieve (MCM-41) composite molecular screen, the disclosed ZSM-22/ZSM-23 composite molecular screen of CN200510066975.5, the disclosed ZSM-35/MCM-22 composite molecular screen of CN200610011231.8, the disclosed ZSM-5/ mordenite composite molecular sieve of CN200610027909.1, the disclosed ZSM-5/SAPO-5(of CN200810105646.0 or AlPO
4-5) composite molecular screen, (
Chem Mater 2006,18,4959-4966) the composite molecular screen Silicalite-1/MFI etc. of nucleocapsid structure of report.Different composite molecular screens has different character and use properties, and its synthetic method is not identical yet.
D.Van Vu etc. (
Journal of Cataiysis 243 (2006) 389-394) reported a kind of Silicalite-1/H-ZSM-5 of preparation compound molecule screen method: at first synthesize ZSM-5 molecular sieve, then by ion-exchange molecular sieve has been converted into the HZSM-5 molecular sieve.Then the HZSM-5 molecular sieve is joined TEOS-TPAOH-EtOH-H
2(TEOS is tetraethoxy in the O system, TPAOH is TPAOH, EtOH is ethanol), the molecular sieve that adds and the mass ratio of system are 1:15, obtained the Silicalite-1/H-ZSM-5 composite molecular screen that Silicalite-1 covers by the intermediate water thermal synthesis, this molecular sieve can improve Shape-selective.
Li Ruifeng in 2004 etc. have successfully prepared Y-β and β-Y composite zeolite molecular sieve catalytic material, successively disclose two pieces of patents, number of patent application: CN200410012333.2 and CN200410012336.6.CN200610048273.9 discloses a kind of composite zeolite molecular sieve that adopts high-Si Y-type molecular sieve to synthesize high silicon, this composite zeolite molecular sieve organically combines the characteristics of Y zeolite and β zeolite, prepared matrix material not only has the good hydrothermal stability of high-Si Y-type molecular sieve and acid acceptance, also have simultaneously the good heat of β zeolite and hydrothermal stability, acidity and acid acceptance and the hydrophobic properties of appropriateness.
The ancestor protect Ning Dengye adopted in 2004 the homogeneous phase method successfully synthesize Mor/ β zeolite mixed crystal material (petrochemical complex, 2004,33(11), 1046-1050).The result shows: Mor zeolite and β zeolite are not to present pure physical mixed state, and total acid content, strong acid acid amount, weak acid acid amount are all greater than the acid amount of Mor molecular sieve, β zeolite and mechanical mixture.The alkylation of toluene Performance is the result show, dimethylbenzene yield in the Mor/ β zeolite mixed crystal material catalysis alkylation of toluene reaction product is that catalyzer is high by 27.2% respectively than β zeolite, mechanical mixture and Mor, 25.4% and 13.6%, and the content of benzene is minimum in the alkylation of toluene reaction product of Mor/ β zeolite mixed crystal material catalysis.
Because these matrix materials have the structure of two kinds of molecular sieves, the existence of double-pore structure, acidity simultaneously, hydrothermal stability and to water absorption can mediation, can improve catalytic performance, thereby polystep reaction is carried out at a catalyzer simultaneously, greatly reduce cost.The synthetic application of composite molecular screen has obtained everybody extensive approval, and composite molecular screen has embodied distinguished effect really.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of isomorphous ZSM-5 composite molecular screen with nucleocapsid structure and preparation method thereof.Wrap up the ZSM-5 of low silica-alumina ratio fully by the ZSM-5 molecular sieve of high silica alumina ratio, under the condition that does not affect Shape-selective, improved the activity of catalyzer, for the shape selective catalysis processes such as isomerization, alkylation provide a kind of good catalytic material.
The present invention has identical ZSM-5 molecular sieve duct topological framework with two kinds of components in the crystalline phase composite molecular screen, be a kind of ZSM-5 molecular sieve take low silica-alumina ratio as nuclear, the ZSM-5 molecular sieve of high silica alumina ratio is the core-shell structure compound molecular sieve of shell.For the silica/alumina molar ratio of ZSM-5 molecular sieve of the low silica-alumina ratio of nuclear is 25-50, for the silica/alumina molar ratio of the high silica alumina ratio ZSM-5 molecular sieve of shell is 80 to 300.The weight ratio of the ZSM-5 molecular sieve of low silica-alumina ratio and the ZSM-5 molecular sieve of high silica alumina ratio is 2:1 ~ 1:5.
The preparation method of isomorphous ZSM-5 composite molecular screen of the present invention is as follows: at first with dissolution of sodium hydroxide in deionized water, then the template 4-propyl bromide and/or the TPAOH that add aequum, the aluminium source that adds again aequum, add at last ZSM-5 molecular sieve, stir the silicon source that adds aequum, the reactor crystallization of packing into, last, the crystallization product that washing, drying, roasting obtain makes isomorphous ZSM-5 composite molecular screen.
Concrete preparation method of the present invention is as follows: at first with dissolution of sodium hydroxide in deionized water, then the template 4-propyl bromide and/or the TPAOH that add aequum, be preferably 4-propyl bromide or 4-propyl bromide weight and account for TPAOH more than 40% and the mixture of TPAOH, dissolve the aluminium source of rear adding aequum fully etc. template, dissolve rear adding ZSM-5 molecular sieve fully Deng it, stir the silicon source that adds aequum, the stainless steel cauldron crystallization of packing into, at last, washing, dry, the crystallization product that roasting obtains makes isomorphous ZSM-5 composite molecular screen.
In the inventive method, synthesis material adds suitable material according to the conventional knowledge in this area, and the mol ratio of described silicon source, aluminium source, template, sodium hydroxide and water (in oxide compound, not comprising the ZSM-5 molecular sieve of adding) is: (8.0-12.0) Na
2O:(40-160) SiO
2: Al
2O
3: (8.0-15.0) (TPA)
2O:(4000-6000) H
2O.Crystallization condition is at 100 ℃ ~ 180 ℃ crystallization 24h ~ 72h; The ZSM-5 molecular sieve that adds and the mass ratio of sodium hydroxide, template, water, aluminium source and silicon source compositional system are (1:10) ~ (1:50).(TPA)
2O is template.The concrete ratio of two kinds of molecular sieves can be regulated by regulating synthetic material as required.
In the inventive method, the ZSM-5 molecular sieve of employing can be NaZSM-5, also can be HZSM-5, can adopt the commercially available prod, also can prepare by this area ordinary method; The silica alumina ratio of used ZSM-5 molecular sieve (silica alumina ratio refers to the mol ratio of silicon oxide and aluminum oxide, lower with) can from 30 to 50.
In the inventive method, described silicon source can be silicon sol, also can be white carbon black; Described aluminium source can be Tai-Ace S 150, and aluminum nitrate also can be sodium aluminate.
In the inventive method, dry and roasting condition can be this area normal condition, as 80 ℃～200 dryings 2～20 hours, 400 ℃～600 roastings 1～6 hour.
Composite molecular screen of the present invention may be used for isomerization, alkylation, catalytic cracking, face the fields such as hydrogen dewaxing.
The inventive method is regulated the feed ratio in an amount of sodium hydroxide, template, water, aluminium source and silicon source, the isomorphous ZSM-5 composite molecular screen with nucleocapsid structure of preparation.This composite molecular screen nucleocapsid has identical crystalline structure, identical pore passage structure, and different silica alumina ratios is but arranged.The ZSM-5 molecular sieve of high silica alumina ratio wraps up the ZSM-5 of low silica-alumina ratio fully in this composite molecular screen, has formed the grade pore structure with micropore-mesopore-micropore.Show by experiment, the mixture that will contain the 4-propyl bromide template before adding the silicon source fully contacts with ZSM-5 molecular sieve, can make the ZSM-5 molecular sieve surface carry out suitable modification, be conducive to high silica alumina ratio ZSM-5 at the ZSM-5 molecular sieve Surface Creation, and cover evenly, be conducive to the industrial application of isomorphous ZSM-5 composite molecular screen.
Description of drawings
Fig. 1 is the XRD diffractogram of the embodiment of the invention 1 sintetics.
Fig. 2 is the scanning electron microscope picture of the embodiment of the invention 1 sintetics.
Embodiment
Further specify preparation process of the present invention below in conjunction with embodiment, dry 150 ℃ of dryings 8 hours, 450 ℃ of lower roastings 3 hours.
Embodiment 1
0.80 sodium hydroxide and 0.67g Tai-Ace S 150 are joined in the 75.0ml deionized water, taking by weighing 4-propyl bromide 5.4g joins in the solution, taking by weighing until completely dissolved 5.0gZSM-5 molecular sieve (silica alumina ratio is 40) joins in the solution, add the 10.0ml silicon sol after stirring half an hour, after stirring, in the stainless steel crystallizing kettle of packing into, 160 ℃ of thermostatic crystallizations 60 hours, then, washing, drying, roasting obtain the ZSM-5 composite molecular screen.As can be seen from Figure 1, the composite molecular screen that the present invention synthesizes is the ZSM-5 molecular sieve crystalline phase, and as can be seen from Figure 2, the composite molecular screen that the present invention synthesizes covers evenly fully, has formed nucleocapsid structure.
Proportioning (ZSM-5 that does not contain adding): 10.0Na
2O:60SiO
2: Al
2O
3: 10.2 (TPA)
2O:4722H
2O.
0.75 sodium hydroxide and 0.67g Tai-Ace S 150 are joined in the 65.0ml deionized water, taking by weighing 4-propyl bromide 5.4g joins in the solution, taking by weighing until completely dissolved 5.0gZSM-5 molecular sieve (silica alumina ratio is 43) joins in the solution, add the 10.0ml silicon sol after stirring half an hour, after stirring, in the stainless steel crystallizing kettle of packing into, 170 ℃ of thermostatic crystallizations 60 hours, then, washing, drying, roasting obtain the ZSM-5 composite molecular screen.
Proportioning (ZSM-5 that does not contain adding): 9.4Na
2O:60SiO
2: Al
2O
3: 10.2 (TPA)
2O:4166H
2O.
Embodiment 3
0.75 sodium hydroxide and 0.67g Tai-Ace S 150 are joined in the 55.0ml deionized water, taking by weighing 4-propyl bromide 5.4g joins in the sodium hydroxide solution, taking by weighing until completely dissolved 5.0gZSM-5 molecular sieve (silica alumina ratio is 40) joins in the solution, add the 20.0ml silicon sol after stirring half an hour, after stirring, in the stainless steel crystallizing kettle of packing into, 170 ℃ of thermostatic crystallizations 48 hours, then, washing, drying, roasting obtain the ZSM-5 composite molecular screen.
Proportioning (ZSM-5 that does not contain adding): 9.4Na
2O:120SiO
2: Al
2O
3: 10.2 (TPA)
2O:4166H
2O.
Embodiment 4
0.75 sodium hydroxide and 0.67g Tai-Ace S 150 are joined in the 65.0ml deionized water, the mixture that takes by weighing 4-propyl bromide 4.0g and TPAOH 1.0g joins in the sodium hydroxide solution, taking by weighing until completely dissolved 5.0gZSM-5 molecular sieve (silica alumina ratio is 45) joins in the solution, add the 20.0ml silicon sol after stirring half an hour, after stirring, in the stainless steel crystallizing kettle of packing into, 160 ℃ of thermostatic crystallizations 60 hours, then, washing, drying, roasting obtain the ZSM-5 composite molecular screen.
Proportioning (ZSM-5 that does not contain adding): 9.4Na
2O:120SiO
2: Al
2O
3: 9.4 (TPA)
2O:4722H
2O.
0.90 sodium hydroxide and 0.67g Tai-Ace S 150 are joined in the 75.0ml deionized water, taking by weighing 4-propyl bromide 6.0g joins in the sodium hydroxide solution, taking by weighing until completely dissolved 5.0gZSM-5 molecular sieve (silica alumina ratio is 40) joins in the solution, add the 20.0ml silicon sol after stirring half an hour, after stirring, in the stainless steel crystallizing kettle of packing into, 160 ℃ of thermostatic crystallizations 60 hours, then, washing, drying, roasting obtain the ZSM-5 composite molecular screen.
Proportioning (ZSM-5 that does not contain adding): 11.3Na
2O:120SiO
2: Al
2O
3: 11.3 (TPA)
2O:5277H
2O.
The sign of composite molecular screen:
The XPS technology can characterize the elementary composition of plane of crystal 10.0nm thickness, is used for measuring the shell molecular sieve silica alumina ratio of the composite molecular screen that is synthesized.
The XRF technology can characterize the elementary composition of crystal, is used for measuring total molecular sieve silica alumina ratio of the composite molecular screen that is synthesized.
N
2Adsorption-desorption be used for to characterize the pore passage structure of molecular sieve.
SEM is used for observing the pattern on molecular sieve surface.
The main character of table 1 exemplary complex molecular sieve.
| Sample | Specific surface (m 2/g) | Pore volume (ml/g) | Total silica alumina ratio (XRF mensuration) | Shell silica alumina ratio (XPS mensuration) | Shell content, wt% |
| HZSM-5 | 375 | 0.17 | 28.2 | 10.2 | - |
| NaZSM-5 | 360 | 0.17 | 25.8 | 9.3 | - |
| Embodiment 1 | 400 | 0.22 | 40.1 | 110.5 | 46 |
| |
351 | 0.20 | 42.5 | 140.5 | 42 |
| Embodiment 3 | 410 | 0.21 | 40.6 | 122.8 | 61 |
| Embodiment 4 | 405 | 0.21 | 45.1 | 204..0 | 65 |
| |
360 | 0.20 | 40.7 | 125.4 | 52 |
After embodiment 1 composite molecular screen was converted into Hydrogen, when being used for catalytic dewaxing catalyst with common Hydrogen ZSM-5 molecular sieve, when the product condensation point was identical, the purpose product yield improved about 5 percentage points.When being used for catalytic dewaxing catalyst with Silicalite-1/H-ZSM-5, when the product condensation point was identical, temperature of reaction can reduce about 12 ℃.
Claims (10)
1. one kind with the crystalline phase composite molecular screen, it is characterized in that: have identical ZSM-5 molecular sieve duct topological framework with two kinds of components in the crystalline phase composite molecular screen, be a kind of ZSM-5 molecular sieve take low silica-alumina ratio as nuclear, the ZSM-5 molecular sieve of high silica alumina ratio is the core-shell structure compound molecular sieve of shell; For the silica/alumina molar ratio of ZSM-5 molecular sieve of the low silica-alumina ratio of nuclear is 25-50, for the silica/alumina molar ratio of the high silica alumina ratio ZSM-5 molecular sieve of shell is 80 to 300.
2. according to composite molecular screen claimed in claim 1, it is characterized in that: the weight ratio of the ZSM-5 molecular sieve of low silica-alumina ratio and the ZSM-5 molecular sieve of high silica alumina ratio is 2:1 ~ 1:5.
3. the preparation method of the described composite molecular screen of claim 1, it is characterized in that comprising following process: at first with dissolution of sodium hydroxide in deionized water, then the template 4-propyl bromide and/or the TPAOH that add aequum, add again the aluminium source of aequum, add at last ZSM-5 molecular sieve, stir the silicon source that adds aequum, the reactor crystallization of packing into, at last, the crystallization product that washing, drying, roasting obtain makes isomorphous ZSM-5 composite molecular screen.
4. in accordance with the method for claim 3, it is characterized in that: template is 4-propyl bromide, or 4-propyl bromide weight accounts for TPAOH more than 40% and the mixture of TPAOH.
5. it is characterized in that in accordance with the method for claim 3: the described silicon of synthesis material source, aluminium source, template, sodium hydroxide and water take the oxide compound mol ratio as (8.0-12.0) Na
2O:(40-160) SiO
2: Al
2O
3: (8.0-15.0) (TPA)
2O:(4000-6000) H
2O, (TPA)
2O is template.
6. it is characterized in that in accordance with the method for claim 3: the mass ratio of the ZSM-5 molecular sieve of adding and sodium hydroxide, template, water, aluminium source and silicon source compositional system is (1:10) ~ (1:50).
7. according to claim 3 or 5 described methods, it is characterized in that: crystallization condition is at 100 ℃ ~ 180 ℃ crystallization 24h ~ 72h.
8. in accordance with the method for claim 3, it is characterized in that: the ZSM-5 molecular sieve of use is NaZSM-5, or HZSM-5.
9. according to claim 3 or 8 described methods, it is characterized in that: the silicon oxide of used ZSM-5 molecular sieve and the mol ratio of aluminum oxide are 30～50.
10. it is characterized in that in accordance with the method for claim 3: the silicon source is silicon sol or white carbon black; The aluminium source is Tai-Ace S 150, aluminum nitrate or sodium aluminate.
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| CN104556125A (en) * | 2013-10-23 | 2015-04-29 | 中国石油化工股份有限公司 | Isomorphous composite molecular sieve and preparation method and application thereof |
| CN104549452A (en) * | 2013-10-22 | 2015-04-29 | 中国石油化工股份有限公司 | Toluene and methanol alkylation catalyst and preparation method and application thereof |
| CN104211085B (en) * | 2013-06-05 | 2017-01-25 | 中国石油天然气股份有限公司 | Core-shell type ZSM-5 molecular sieve and preparation and application thereof |
| CN106698464A (en) * | 2016-12-31 | 2017-05-24 | 武汉理工大学 | ZSM-5 microsphere and preparation method thereof |
| CN109996765A (en) * | 2016-10-03 | 2019-07-09 | 巴斯夫公司 | Aluminium gradient aluminosilicate zeolite composition |
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| CN104549452A (en) * | 2013-10-22 | 2015-04-29 | 中国石油化工股份有限公司 | Toluene and methanol alkylation catalyst and preparation method and application thereof |
| CN104549452B (en) * | 2013-10-22 | 2017-01-18 | 中国石油化工股份有限公司 | Toluene and methanol alkylation catalyst and preparation method and application thereof |
| CN104556125A (en) * | 2013-10-23 | 2015-04-29 | 中国石油化工股份有限公司 | Isomorphous composite molecular sieve and preparation method and application thereof |
| CN109996765A (en) * | 2016-10-03 | 2019-07-09 | 巴斯夫公司 | Aluminium gradient aluminosilicate zeolite composition |
| CN106698464A (en) * | 2016-12-31 | 2017-05-24 | 武汉理工大学 | ZSM-5 microsphere and preparation method thereof |
| CN106698464B (en) * | 2016-12-31 | 2019-07-23 | 武汉理工大学 | A kind of ZSM-5 microballoon and preparation method thereof |
| CN111233000A (en) * | 2018-11-28 | 2020-06-05 | 中国科学院大连化学物理研究所 | Synthesis method of MTT type molecular sieve with low silicon-aluminum ratio |
| CN112619698A (en) * | 2019-09-24 | 2021-04-09 | 中国石油化工股份有限公司 | ZSM-5/ZSM-35 composite molecular sieve and preparation method thereof |
| CN112619698B (en) * | 2019-09-24 | 2023-03-10 | 中国石油化工股份有限公司 | ZSM-5/ZSM-35 composite molecular sieve and preparation method thereof |
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Application publication date: 20130206 |