CN103803581B - A kind of nucleocapsid structure ZSM-5 composite molecular screen and its preparation method and application - Google Patents
A kind of nucleocapsid structure ZSM-5 composite molecular screen and its preparation method and application Download PDFInfo
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Abstract
The present invention's ZSM-5 composite molecular screen disclosing a kind of nucleocapsid structure and its preparation method and application, this molecular sieve has following character: nuclear phase is ZSM-5 molecular sieve, shell is the ZSM-5 molecular sieve containing meso-hole structure mutually, total mol ratio of silicon oxide and aluminum oxide is 30 ~ 80, and total specific surface is 460 ~ 550m
2/ g, total pore volume is 0.25 ~ 0.38ml/g; Its mesochite phase intermediary hole aperture is 2 ~ 2.5nm, and the mutually mesoporous specific surface of shell is 480 ~ 650m
2/ g, the mutually mesoporous pore volume of shell is 0.2 ~ 0.31ml/g.Preparation method is as follows: first the mixture containing sodium hydroxide, template, water, silicon source, aluminium source, tensio-active agent and ZSM-5 molecular sieve is carried out crystallization, then washs, dry, roasting crystallization product, obtains ZSM-5 composite molecular screen.The advantages such as this composite molecular screen is applied in aromatic conversion reaction, has high transformation efficiency and selectivity, and catalyst life is long.
Description
Technical field
The invention belongs to Zeolite synthesis field, ZSM-5 composite molecular screen specifically relating to a kind of nucleocapsid structure and its preparation method and application.
Background technology
Current composite molecular screen obtains the concern of increasing investigator, and various composite molecular screen is constantly synthesized out.2006 Younes Bouizi (Chem Mater 2006,18,4959 ~ 4966) report a kind of composite molecular screen Silicalite-1/MFI of nucleocapsid structure.ZSM-5 molecular sieve Silicalite-1 molecular sieve wraps up and formed with ZSM-5 by the method is core, and Silicalite-1 is the nucleocapsid composite molecular screen of shell, is 70% by single sintering process fraction of coverage.Concrete building-up process is: first by TPAOH, tetraethoxy, water solution system by nano level Silicalite-1 crystal seed at ZSM-5 molecular sieve surface deposition, and then the ZSM-5 molecular sieve of surface depositing nano level Silicalite-1 crystal seed is obtained the composite molecular screen of high coverage rate nucleocapsid structure by above-mentioned solution system second time Hydrothermal Synthesis.
The same year, (the Journal of Cataiysis 2006 such as D.Van Vu, 243,389 ~ 394) report one and prepare Silicalite-1/H-ZSM-5 compound molecule screen method: first synthesize ZSM-5 molecular sieve, then be HZSM-5 molecular sieve by ion-exchange by conversion molecular sieve, then HZSM-5 molecular sieve joined TEOS-TPAOH-EtOH-H
2in O system, (TEOS is tetraethoxy, TPAOH is TPAOH, EtOH is ethanol), the molecular sieve added and the mass ratio of system are 1:15, are obtained the Silicalite-1/H-ZSM-5 composite molecular screen of Silicalite-1 covering by intermediate water thermal synthesis.
Silicalite-1/ZSM-5 composite molecular screen is that one has nucleocapsid structure and belongs to MFI topological framework together, it is a kind of isomorphous composite molecular screen with nucleocapsid structure, ZSM-5 molecular sieve is wrapped up completely by Silicalite-1 molecular sieve, type of the selecting effect of Silicalite-1/ZSM-5 composite molecular screen is better than ZSM-5 molecular sieve, but because surface does not have acidity, reduce transformation efficiency.
The ZSM-5 molecular sieve composite molecular screen of the nucleocapsid structure with Different Silicon al proportion has been synthesized in CN101723401A, with the ZSM-5 zeolite molecular sieve of relatively low silica alumina ratio as crystal seed, the shell joining high silica alumina ratio coordinates in sizing material, the Hydrothermal Synthesis ZSM-5 molecular sieve composite molecular screen of nucleocapsid structure, but main existence is microvoid structure in such an embodiment, affect diffusion process, limit macromolecular diffusion, macromolecular reaction process cannot be applied to.
Summary of the invention
For the deficiencies in the prior art, ZSM-5 composite molecular screen that the invention provides a kind of nucleocapsid structure and its preparation method and application.ZSM-5 composite molecular screen in the present invention has obvious nucleocapsid structure, and core and shell have identical duct topological framework, wherein shell mutually in there is a large amount of meso-hole structure exist.The advantages such as this composite molecular screen is applied in aromatic conversion reaction, has high transformation efficiency and selectivity, and catalyst life is long.
ZSM-5 composite molecular screen in the present invention has following character: nuclear phase is ZSM-5 molecular sieve, and shell is the ZSM-5 molecular sieve containing meso-hole structure mutually, and total mol ratio of silicon oxide and aluminum oxide is 30 ~ 80, and total specific surface is at 460 ~ 550m
2between/g, total pore volume is between 0.25 ~ 0.38ml/g; Its mesochite phase intermediary hole aperture is between 2 ~ 2.5nm, and the mutually mesoporous specific surface of shell is at 480 ~ 650m
2between/g, the mutually mesoporous pore volume of shell is between 0.2 ~ 0.31ml/g.
Concrete preparation method of the present invention is as follows: first will mix containing sodium hydroxide, template, aluminium source, water and ZSM-5 molecular sieve, under whipped state, slowly add the tensio-active agent of aequum, then the silicon source adding aequum is stirred, load reactor crystallization 24 ~ 72h at 100 ~ 180 DEG C, washing, dry, roasting crystallization product, obtained ZSM-5 composite molecular screen.
In the inventive method, the template of employing is 4-propyl bromide or TPAOH.
In the inventive method, the tensio-active agent of employing is cetyl trimethylammonium bromide (CTAB).
In the inventive method, the ZSM-5 molecular sieve of employing can be NaZSM-5, also can be HZSM-5, can adopt commercially available prod, also can prepare by this area ordinary method; The silica/alumina molar ratio of ZSM-5 molecular sieve used is 20 ~ 110.
In the inventive method, described silicon source is silicon sol or white carbon black; Described aluminium source is one or more in Tai-Ace S 150, aluminum nitrate or sodium aluminate.
In the inventive method, synthesis material adds suitable component according to this area Conventional wisdom, described silicon source, aluminium source, template, sodium hydroxide, tensio-active agent and water compositional system in the mol ratio of following substances be: 8 ~ 15Na
2o:25 ~ 60SiO
2: Al
2o
3: 10 ~ 20 (TPA)
2o:0.5 ~ 3CTAB:4000 ~ 6000H
2o, the mass ratio of the ZSM-5 molecular sieve added and above-mentioned system is 1:20 ~ 1:40, wherein (TPA)
2o represents template 4-propyl bromide or TPAOH, CTAB presentation surface lammonium bromide.
Catalyzer prepared by the ZSM-5 composite molecular screen provided in the present invention is applicable to methyl alcohol and alkylation of toluene is reacted, the mol ratio that reaction conditions is generally methyl alcohol and toluene is 1:1 ~ 1:10, reaction pressure is normal pressure ~ 5.0 MPa, temperature of reaction is 350 ~ 500 DEG C, hydrogen oil (hydrogen and toluene and methyl alcohol, under standard state) volume ratio is 300:1 ~ 3000:1, the cumulative volume air speed of toluene and methyl alcohol is 0.5 ~ 6h
-1.
The customary preparation methods of catalyzer described in the present invention, comprises one of the following two kinds method:
(1) by after the kneading and compactings such as Hydrogen ZSM-5 composite molecular screen and inorganic refractory oxide, peptization acid and extrusion aid, drying and roasting obtain carrier; Then the loaded modified elementary composition of pickling process is adopted.
(2) by after the kneading and compactings such as Hydrogen ZSM-5 composite molecular screen and inorganic refractory oxide, peptization acid, extrusion aid and modifying element compound, drying and roasting obtain final catalyzer.
Inorganic refractory oxide can be selected from one or more in aluminum oxide, titanium oxide, silicon oxide and clay, be preferably aluminum oxide and/or silicon oxide, be more preferably aluminum oxide, its precursor can be selected from boehmite, pseudo-boehmite, diaspore, gibbsite and visit in aluminium stone one or more, be preferably pseudo-boehmite; Peptization is sour as nitric acid, hydrochloric acid, acetic acid, citric acid etc., preferred nitric acid; Extrusion aid is the material being conducive to extruded moulding, as graphite, starch, Mierocrystalline cellulose, sesbania powder etc., and preferred sesbania powder.
In catalyzer, loaded modified element is generally the alkaline-earth metal such as Ca, Mg, the non-metallic elements such as thulium and B, P, Si such as La, Ce, Pr.
The present invention, by adding tensio-active agent in building-up process, prepares the ZSM-5 composite molecular screen that surperficial shell has micropore-mesopore distribution nucleocapsid structure mutually.Mesoporous generation by between micropore, micropore and mesoporous between be together in series better, more active centre is made to participate in catalytic process, considerably increase the rate of diffusion of reactant and product simultaneously, improve the transformation efficiency of reactant, prevent the generation of more side reactions, improve the selectivity of object product.When reacting for alkylation of toluene methanol, through the catalyzed reaction of 300 hours, its average toluene conversion is 27%, and Selectivity for paraxylene is 92%, shows satisfactory stability, reactive behavior and object selectivity of product.
Accompanying drawing explanation
Fig. 1 is the XRD spectra of the embodiment of the present invention 1 sintetics.
Fig. 2 is the mesoporous pore size distribution plan of the embodiment of the present invention 1 sintetics.
Embodiment
Preparation process of the present invention is further illustrated below in conjunction with embodiment.
Embodiment 1
Sodium hydroxide and Tai-Ace S 150 are joined in deionized water, taking 4-propyl bromide joins in solution, until completely dissolved ZSM-5 molecular sieve (silicon oxide and alumina molar ratio are 25) is joined in solution, add CTAB after stirring, after continuing to stir half an hour, add silicon sol, after stirring, load in stainless steel crystallizing kettle, 160 DEG C of thermostatic crystallizations 60 hours, then, washing, dry, roasting obtain ZSM-5 composite molecular screen.The character of molecular sieve is in table 1.
The mol ratio of sodium hydroxide, template, water, aluminium source, tensio-active agent and silicon source compositional system: 10.0Na
2o:45SiO
2: Al
2o
3: 10.2 (TPA)
2o:CTAB:4722H
2o, the mass ratio of the ZSM-5 molecular sieve added and above-mentioned system is 1:23.
Embodiment 2
Sodium hydroxide and Tai-Ace S 150 are joined in deionized water, taking 4-propyl bromide joins in solution, until completely dissolved ZSM-5 molecular sieve (silicon oxide and alumina molar ratio are 38) is joined in solution, add CTAB after stirring, after continuing to stir half an hour, add silicon sol, after stirring, load in stainless steel crystallizing kettle, 170 DEG C of thermostatic crystallizations 60 hours, then, washing, dry, roasting obtain ZSM-5 composite molecular screen.The character of molecular sieve is in table 1.
The mol ratio of sodium hydroxide, template, water, aluminium source, tensio-active agent and silicon source compositional system: 9.4Na
2o:45SiO
2: Al
2o
3: 10.2 (TPA)
2o:1.5CTAB:4166H
2o, the mass ratio of the ZSM-5 molecular sieve added and above-mentioned system is 1:27.
Embodiment 3
Sodium hydroxide and sodium aluminate are joined in deionized water, taking 4-propyl bromide joins in sodium hydroxide solution, until completely dissolved ZSM-5 molecular sieve (silicon oxide and alumina molar ratio are 73) is joined in solution, add CTAB after stirring, after continuing to stir half an hour, add silicon sol, after stirring, load in stainless steel crystallizing kettle, 170 DEG C of thermostatic crystallizations 48 hours, then, washing, dry, roasting obtain ZSM-5 composite molecular screen.The character of molecular sieve is in table 1.
The mol ratio of sodium hydroxide, template, water, aluminium source, tensio-active agent and silicon source compositional system: 9.4Na
2o:30SiO
2: Al
2o
3: 10.2 (TPA)
2o:0.5CTAB:4166H
2o, the mass ratio of the ZSM-5 molecular sieve added and above-mentioned system is 1:23.
Embodiment 4
Sodium hydroxide and Tai-Ace S 150 are joined in deionized water, taking 4-propyl bromide joins in sodium hydroxide solution, until completely dissolved ZSM-5 molecular sieve (silicon oxide and alumina molar ratio are 102) is joined in solution, add CTAB after stirring, after continuing to stir half an hour, add white carbon black, after stirring, load in stainless steel crystallizing kettle, 160 DEG C of thermostatic crystallizations 60 hours, then, washing, dry, roasting obtain ZSM-5 composite molecular screen.The character of molecular sieve is in table 1.
The mol ratio of sodium hydroxide, template, water, aluminium source, tensio-active agent and silicon source compositional system: 9.4Na
2o:30SiO
2: Al
2o
3: 9.4 (TPA)
2o:CTAB:4722H
2o.The mass ratio of the ZSM-5 molecular sieve added and above-mentioned system is 1:39.
Embodiment 5
Sodium hydroxide and aluminum nitrate are joined in deionized water, taking 4-propyl bromide joins in sodium hydroxide solution, until completely dissolved ZSM-5 molecular sieve (silicon oxide and alumina molar ratio are 38) is joined in solution, add CTAB after stirring, after continuing to stir half an hour, add silicon sol, after stirring, load in stainless steel crystallizing kettle, 160 DEG C of thermostatic crystallizations 60 hours, then, washing, dry, roasting obtain ZSM-5 composite molecular screen.The character of molecular sieve is in table 1.
The mol ratio of sodium hydroxide, template, water, aluminium source, tensio-active agent and silicon source compositional system: 11.3Na
2o:30SiO
2: Al
2o
3: 11.3 (TPA)
2o:CTAB:5277H
2o, the mass ratio of the ZSM-5 molecular sieve added and above-mentioned system is 1:36.
The character of table 1 ZSM-5 composite molecular screen.
| Sequence number | Silica alumina ratio (mol/mol) | Specific surface (m 2/g) | Pore volume, (ml/g) | Aperture (nm) | Mesoporous specific surface (m 2/g) | Mesopore volume (ml/g) | Mesoporous content (%) |
| Embodiment 1 | 35 | 533 | 0.37 | 2.4 | 630 | 0.29 | 54 |
| Embodiment 2 | 42 | 521 | 0.36 | 2.4 | 618 | 0.28 | 54 |
| Embodiment 3 | 52 | 488 | 0.35 | 2.2 | 557 | 0.25 | 53 |
| Embodiment 4 | 78 | 479 | 0.32 | 2.2 | 520 | 0.25 | 52 |
| Embodiment 5 | 33 | 462 | 0.28 | 2.1 | 490 | 0.22 | 51 |
Embodiment 6
The preparation of alkylation of toluene methanol catalyzer:
(1) molecular sieve process.Preparing ZSM-5 composite molecular screen 100g according to embodiment 1, is that the ammonium nitrate solution of 50% exchanges 3 times at 80 DEG C by 200g mass concentration, each 2 hours, 110 DEG C of dryings 6 hours, 550 DEG C of roastings 4 hours, obtained Hydrogen ZSM-5 composite molecular screen.
(2) preparation of catalyzer.Get above-mentioned Hydrogen ZSM-5 composite molecular screen 80g, SB powder 28g, sesbania powder 2.5g, mixes, then 60g deionized water, 2.5ml concentrated nitric acid (66.5wt%) and 2.5ml citric acid is added, on rolling machine, abundant kneading, makes it to become paste plastic, banded extruder is extruded the cylindrical bars of diameter 1.5mm, 110 DEG C of dryings 8 hours, then in air atmosphere, 550 DEG C of roastings obtain support of the catalyst in 4 hours, get appropriate carrier, form loaded modified elements La and magnesium by table 1.First lanthanum nitrate hexahydrate is used to flood, then 110 DEG C of dryings 6 hours, 540 DEG C of roastings 4 hours.Again with magnesium acetate solution dipping, then 110 DEG C of dryings 6 hours, 540 DEG C of roastings obtain catalyzer C1 in 4 hours.
Comparative example 1
(1) Silicalite-1/ZSM-5 core-shell molecular sieve preparation.
The 10g 25wt%TPAOH aqueous solution, 4g tetraethoxy and 200g water are mixed, stirs 4 hours, then add 20g(SiO
2/ A1
2o
3mol ratio is 25) ZSM-5 nuclear phase molecular sieve, put into stainless steel crystallizing kettle, airtight, be warming up to 180 DEG C, thermostatic crystallization 24 hours.Solid product filtration, washing, oven dry, roasting are obtained Silicalite-1/ZSM-5 core-shell molecular sieve.Its mesochite phase SiO
2/ A1
2o
3mol ratio is 458 by analysis.
(2) molecular sieve process (with embodiment 6).
(3) catalyst preparing (with embodiment 6), obtains catalyst B C1.
Comparative example 2
(1) ZSM-5/ZSM-5 core-shell molecular sieve preparation.
0.8 sodium hydroxide and 0.67g Tai-Ace S 150 are joined in 75g deionized water, taking 4-propyl bromide 5.4g joins in solution, taking 5g ZSM-5 molecular sieve until completely dissolved joins in solution, 12g silicon sol is added after stirring half an hour, after stirring, load in stainless steel crystallizing kettle, 160 DEG C of thermostatic crystallizations 60 hours.Solid product filtration, washing, oven dry, roasting are obtained ZSM-5/ZSM-5 core-shell molecular sieve.Its mesochite phase SiO
2/ A1
2o
3mol ratio is 58 by analysis.
(2) molecular sieve process (with embodiment 6).
(3) catalyst preparing (with embodiment 6), obtains catalyst B C2.
The evaluation of reactivity worth.
Catalyzer of the present invention adopts 10ml fixed-bed micro-reactor to evaluate, with toluene, methyl alcohol for raw material, toluene and methanol molar ratio are 2:1, loaded catalyst is 5g (40 ~ 60 order), before charging, activation is carried out two hours to catalyzer, activation condition is: temperature 440 DEG C, pressure 0.2MPa.Reaction product carries out quantitative analysis on gas chromatograph.Evaluating catalyst processing condition are: pressure 0.2MPa, temperature 440 DEG C, and hydrogen to oil volume ratio is under 900:1(standard conditions), the cumulative volume air speed of toluene and methyl alcohol is 2.0h
-1.
Toluene conversion (%)=(in 1-product toluene mole number/product in aromatic hydrocarbons total mole number) × 100%.
Dimethylbenzene total mole number × 100% in p-Xylol mole number/product in Selectivity for paraxylene (%)=product.
Catalyzer composition and evaluation result are in table 2.
Table 2 catalyzer composition and evaluation result.
| Catalyzer | La 2O 3(wt%) | MgO (wt%) | Initial reaction stage toluene conversion % | Initial reaction stage Selectivity for paraxylene % | Reaction later stage toluene conversion % | Reaction later stage Selectivity for paraxylene % | Evaluation time (hour) |
| C1 | 20 | 10 | 35.74 | 91.32 | 18.50 | 93.20 | 300 |
| BC1 | 20 | 10 | 18.45 | 95.48 | 7.90 | 97.18 | 300 |
| BC2 | 20 | 10 | 32.91 | 86.45 | 12.55 | 89.98 | 300 |
As can be seen from Table 2, the catalyzer that prepared by composite molecular screen of the present invention has higher activity (showing as toluene conversion) and higher object selectivity of product (showing as the selectivity of p-Xylol) in alkylation of toluene methanol reaction process.
Claims (5)
1. a ZSM-5 composite molecular screen for nucleocapsid structure, is characterized in that: nuclear phase is ZSM-5 molecular sieve, and shell is the ZSM-5 molecular sieve containing meso-hole structure mutually, and total mol ratio of silicon oxide and aluminum oxide is 30 ~ 80, and total specific surface is at 460 ~ 550m
2between/g, total pore volume is between 0.25 ~ 0.38ml/g; Its mesochite phase intermediary hole aperture is between 2 ~ 2.5nm, and the mutually mesoporous specific surface of shell is at 480 ~ 650m
2between/g, the mutually mesoporous pore volume of shell is between 0.2 ~ 0.31ml/g.
2. the preparation method of the ZSM-5 composite molecular screen of nucleocapsid structure according to claim 1, it is characterized in that comprising: first will mix containing sodium hydroxide, template, aluminium source, water and ZSM-5 molecular sieve, under whipped state, add the tensio-active agent of aequum, then the silicon source adding aequum is stirred, load reactor crystallization 24 ~ 72h at 100 ~ 180 DEG C, washing, dry, roasting crystallization product, obtained ZSM-5 composite molecular screen; Described template is 4-propyl bromide or TPAOH; Described tensio-active agent is cetyl trimethylammonium bromide; Described raw material ZSM-5 molecular sieve is NaZSM-5 or HZSM-5, and silica/alumina molar ratio is 20 ~ 110; Described silicon source, aluminium source, template, sodium hydroxide, tensio-active agent and water compositional system in the mol ratio of following substances are: 8 ~ 15Na
2o:25 ~ 60SiO
2: Al
2o
3: 10 ~ 20 (TPA)
2o:0.5 ~ 3CTAB:4000 ~ 6000H
2o, wherein (TPA)
2o represents template 4-propyl bromide or TPAOH, CTAB presentation surface lammonium bromide; The mass ratio of ZSM-5 molecular sieve and sodium hydroxide, template, water, aluminium source, tensio-active agent and silicon source component material system is 1:20 ~ 1:40.
3. in accordance with the method for claim 2, it is characterized in that: described silicon source is silicon sol or white carbon black.
4. in accordance with the method for claim 2, it is characterized in that: described aluminium source is one or more in Tai-Ace S 150, aluminum nitrate or sodium aluminate.
5. the application of ZSM-5 composite molecular screen in alkylation of toluene methanol reaction of nucleocapsid structure according to claim 1.
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