CN102030340A - Method for preparing mesoporous molecular sieve with Zeolite Socony Mobil-5 (ZSM-5) secondary structure unit - Google Patents
Method for preparing mesoporous molecular sieve with Zeolite Socony Mobil-5 (ZSM-5) secondary structure unit Download PDFInfo
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- CN102030340A CN102030340A CN 200910187764 CN200910187764A CN102030340A CN 102030340 A CN102030340 A CN 102030340A CN 200910187764 CN200910187764 CN 200910187764 CN 200910187764 A CN200910187764 A CN 200910187764A CN 102030340 A CN102030340 A CN 102030340A
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Abstract
The invention discloses a method for preparing a mesoporous molecular sieve with a Zeolite Socony Mobil-5 (ZSM-5) secondary structure unit. The method comprises the following steps of: mixing synthesized ZSM-5 zeolite and acid solution to prepare hydrogel; uniformly mixing the hydrogel and a template agent to prepare an MCM-41 molecular sieve synthesizing material; and crystallizing the MCM-41 molecular sieve synthesizing material under proper conditions to obtain the MCM-41 molecular sieve product with the ZSM-5 secondary structure unit. Compared with the prior art, the method provided by the invention makes the process simple, the synthesized molecular sieve has the MCM-41 molecular sieve structure as well as improved acidic and hydrothermal stability. The synthesized sieve product can be applied in the technical fields of catalytic cracking, hydrocracking, hydrotreating, hydromodification and the like.
Description
Technical field
The present invention relates to a kind of synthetic method of mesopore molecular sieve, it be a kind of with ZSM-5 zeolite raw material as silicon and aluminum source, the synthetic method that contains ZSM-5 secondary building units of zeolite mesopore molecular sieve.
Background technology
Micro porous molecular sieve has the microvoid structure and the strongly-acid of even prosperity, is shape-selective catalyst important in the modern petroleum industry, has bigger specific surface area (＞350m
2G
-1), adjustable aperture (0.2～1.2nm), characteristics such as wetting ability, higher thermostability (＞500 ℃) and chemical stability.Yet because the aperture is less, the major diameter molecule enters the duct difficulty, and the macromole that forms in the duct can not be overflowed fast, causes side reaction to take place, thereby makes its range of application be subjected to certain limitation.In general, micro porous molecular sieve is suitable for the reaction of the kinetic diameter of reactant molecule less than 1nm, therefore synthesizes to have the developing direction that more wide-aperture molecular sieve is this area always.And along with modern refining of petroleum industrial expansion, the wide aperture molecular sieve seems very important to handling heavy oil feedstock and synthetic macromolecule, particularly to complex reaction system.1992, U.S. Mobil company reported first has been synthesized M41S series mesoporous material, this kind material is with the one-dimensional tunnel structure of its long-range order, bigger characteristics such as aperture, pore volume and high-specific surface area, becomes in recent years one of primary study object in the Materials science.Up to now, people have carried out many researchs to the aspects such as synthesis condition, synthesis mechanism, structural characterization and catalytic applications of MCM-41, but more weak acidity and the relatively poor hydrothermal stability of MCM-41 mesopore molecular sieve is still two problems that need to be resolved hurrily.
U.S. Pat 5057296, its pore diameter range of US5108725 synthetic MCM-41 molecular sieve are 2～5nm, and specific surface area is 600～1100m
2/ g.Adopting palmityl trimethyl ammonium chloride in the above-mentioned patent working example is template, and the template dosage that it adopts is bigger, and synthetic cost is higher; The hydrothermal stability of institute's synthetic molecular sieve is poor.
The MCM-41 molecular sieve bore diameter that patent CN1110252A makes is 3.8nm, and silica alumina ratio is 40, and specific surface area is 1016m
2/ g.Adopting octadecyl trimethyl ammonium chloride in this patent example is template, and its template used dosage is bigger, and synthetic cost is higher, and the hydrothermal stability of institute's synthetic molecular sieve is still not enough.
Existing document has proposed some practicable methods with regard to the hydrothermal stability that improves mesopore material, but to improve how aspect the closely-related mesoporous molecular sieve of catalytic activity acid, and real effective means is still few.
U.S. Pat 5156829 control synthesis condition in the MCM-41 molecular sieve is synthetic is regulated experimental techniques such as silicate oligomerisation balance, to improve hydrothermal stability to thicken hole wall.This method has just been improved the hydrothermal stability of MCM-41 molecular sieve to a certain extent, and its shortcoming is the building-up process complexity, condition harshness (High Temperature High Pressure), raw material costliness.
In recent years, the research of the mesoporous material of the zeolite precursor body of nano-scale and tensio-active agent assembling receives a lot of people's concern.Secondary building units of zeolite is incorporated in the hole wall of MCM-41, improve its acid and hydrothermal stability method enjoy people's attention in recent years.
Patent CN1349929A, CN1488577A and CN1488578A with the mesoporous material of the zeolite structured unit of nano-scale and tensio-active agent assembling improve its hydrothermal stability and acid aspect obtained certain progress.Though they have improved the acid and stable of MCM-41 molecular sieve to a certain extent, the building-up process more complicated all will experience the synthetic of presoma.
Summary of the invention
At the deficiencies in the prior art, the invention provides a kind of preparation method of MCM-41 of peracidity high stability of the ZSM-5 of containing secondary building units of zeolite, adopt a kind of new synthetic method, make the synthetic molecular sieve when having the MCM-41 molecular sieve structure, obviously improve acidity and hydrothermal stability.
The preparation method that the present invention contains ZSM-5 secondary structure unit mesopore molecular sieve comprises following process:
(1) industrial synthetic ZSM-5 zeolite is mixed with acid solution, make hydrogel;
(2) hydrogel that step (1) is prepared and mould agent mix and make MCM-41 molecular sieve compositions material, and template is cetyl trimethylammonium bromide or palmityl trimethyl ammonium chloride; According to the character requirement of preparing product, can in synthetic material, add silicon source or aluminium source adjusting silica alumina ratio;
(3) the synthetic material that obtains of step (2) crystallization 2～10d under optimum conditions promptly obtains containing the MCM-41 zeolite product of ZSM-5 secondary structure unit.
In the inventive method, the described acid solution of step (1) can be sulphuric acid soln, hydrochloric acid soln, salpeter solution etc. one or more, the concentration of acid is generally 0.2～5mol/L (following mol/L is designated as M) in the solution, acid solution and solid envelope-bulk to weight ratio are 10: 1～100: 1 (mL solution/g molecular sieve), the ZSM-5 zeolite adds the acid solution thorough mixing, reacts 1～15 hour down at 100 ℃～160 ℃ then.Industry synthetic ZSM-5 zeolite is according to the difference of synthetic method, can have different character, ZSM-5 zeolite as the Different Silicon aluminum ratio, can use the industrial ZSM-5 zeolite of any character in the inventive method, as direct synthetic NaZSM-5 zeolite, also can be the ZSM-5 zeolite through suitable treatment, as the ZSM-5 zeolite of hydrothermal treatment consists etc.
In the inventive method, in the step (2), the silicon source can be selected from silicon sol, water glass, silicoorganic compound etc.; The aluminium source can be selected from sodium metaaluminate, pseudo-boehmite, aluminum isopropylate etc.The composition of synthetic material can determine that (mol ratio) is as synthetic material proportion: SiO by the material proportion of the synthetic MCM-41 molecular sieve in this area
2: Al
2O
3: CTAB=(1～30): 0.1: (0.15～0.25), CTAB is template (cetyl trimethylammonium bromide or a palmityl trimethyl ammonium chloride).The pH value of synthetic material is generally 8～12, and is general earlier with alkali adjusting hydrogel pH value to 9～14, is adjusted to 8～12 with acid again after the adding template.
In the inventive method, the crystallization condition of step (3) is for carrying out under 90～150 ℃ and autogenous pressure, and crystallization can be carried out under static state, also can carry out under agitation condition.Behind the crystallization end of synthesis, separate, washing, drying and other steps obtain final zeolite product.
The mesopore molecular sieve of the inventive method preparation has MCM-41 framework of molecular sieve structure, contains the ZSM-5 secondary building units of zeolite in the hole wall, and this molecular sieve can be used for technical fields such as catalytic cracking, hydrocracking, hydrotreatment, hydro-upgrading.
The inventive method MCM-41 molecular sieve synthetic method and synthetic zeolite product have following characteristics:
(1) is silicon and aluminum source with the ZSM-5 zeolite, adds the silicon source or silica alumina ratio is regulated in the aluminium source; Silicon source such as silicon sol, water glass, silicoorganic compound etc., aluminium source such as sodium metaaluminate, pseudo-boehmite, aluminum isopropylate etc.
(2) mesoporous wall contains the secondary structure unit of ZSM-5 zeolite, and pore wall thickness exceeds 25%～50% than traditional mesoporous molecular sieve such as MCM-41, and when silica alumina ratio was close, acid amount and acidity all were significantly improved;
(3) be silicon and aluminum source with the ZSM-5 zeolite, the mesopore molecular sieve structure that contains the ZSM-5 secondary building units of zeolite is the hexagonal phase structure of similar MCM-41;
(4) hydrothermal stability is good, does not destroy in 800～1000 ℃ of roastings or 750 ℃ of 100% steam treatment 2h back skeleton structure;
(5) show as unique tight pattern on the mesopore molecular sieve microscopic pattern, be different from the pattern of ordinary method synthetic MCM-41 surface porosity;
(6) mesopore molecular sieve that contains the ZSM-5 secondary building units of zeolite has good arylhydrocarbon in diesel oil hydrogenation sulfur resistance and open-loop performance.
In the inventive method, with the ZSM-5 zeolite is silicon source and aluminium source, through suitable preprocessing process and crystallization building-up process, the ZSM-5 secondary building units of zeolite has been incorporated in the hole wall of MCM-41, improved the acidity and the hydrothermal stability of molecular sieve, the building-up process of having saved presoma, preparation process is simple, the handiness height, the silica alumina ratio variable range is bigger.
Description of drawings
Fig. 1 is X-ray diffraction (XRD) figure of the embodiment of the invention 1 synthetic MCM-41 molecular sieve;
Fig. 2-1 is high-resolution electron microscopy (HRTEM) figure of the embodiment of the invention 1 synthetic MCM-41;
Fig. 2-2 is another one angle high-resolution electron microscopy (HRTEM) figure of the embodiment of the invention 1 synthetic MCM-41.
Embodiment
Embodiment 1
With industrial synthetic NaZSM-5 (SiO
2/ Al
2O
3The molecule mol ratio is 38, below is SiO
2/ Al
2O
3Be the molecule mol ratio) zeolite 6.2g is dispersed in the 200mL 4M HCl solution, forms hydrogel, stir 1h at normal temperatures after, in the synthesis reactor of packing into, place 6h for 120 ℃, the cooling back with 6M NaOH adjusting pH value to 13 about; Then 12.5g 16wt% palmityl trimethyl ammonium chloride drips of solution is gone in the hydrogel, 50 ℃ are stirred 40min, and hydrochloric acid is regulated about pH=10; Stir with pack into the crystallizing kettle of inner liner polytetrafluoroethylene of material, in 110 ℃ of crystallization 4d; Filter then, wash, dry 24h under 100 ℃; In air atmosphere following 550 ℃ again, roasting 8h obtains the purpose product.Obtain the sieve sample that crystalline phase is MCM-41 through XRD analysis.Analyze through IR (infrared spectra), contain the ZSM-5 secondary building units of zeolite in the skeleton.
Embodiment 2
With industrial synthetic Na ZSM-5 (SiO
2/ Al
2O
3The molecule mol ratio is 38, below is SiO
2/ Al
2O
3Being the molecule mol ratio) zeolite 7.2g is dispersed in 240mL 4M H
2SO
4In the solution, form hydrogel, stir 1h at normal temperatures after, in the synthesis reactor of packing into, 110 ℃ of static placements 12h, the cooling back with 6M NaOH adjusting pH value to 13 about; Then 17.5g 16wt% palmityl trimethyl ammonium chloride drips of solution is gone in the hydrogel, 50 ℃ are stirred 40min, add the 8g tetraethoxy again, and hydrochloric acid is regulated about pH=10; Stir with pack into the crystallizing kettle of inner liner polytetrafluoroethylene of material, in 100 ℃ of crystallization 8d; Filter then, wash, dry 24h under 100 ℃; In air atmosphere following 550 ℃ again, roasting 8h obtains the purpose product.Obtain the sieve sample that crystalline phase is MCM-41 through XRD analysis.Analyze through IR, contain the ZSM-5 secondary building units of zeolite in the skeleton.
Embodiment 3
With industrial synthetic Na ZSM-5 zeolite, SiO
2/ Al
2O
3=50,4.8g is dispersed in the 200mL 3M HCl solution, forms hydrogel, stirs 2h at normal temperatures, in the synthesis reactor of packing into, places 5h for 120 ℃, regulates pH value to 13 with 6MNaOH; Then 14.5g 20wt% palmityl trimethyl ammonium chloride drips of solution is gone in the hydrogel, 50 ℃ are stirred 40min, and sulfuric acid is regulated about pH=9.6; Pack into after the stirring crystallizing kettle of inner liner polytetrafluoroethylene is in 110 ℃ of crystallization 4d; Filter then, wash, dry 24h under 100 ℃; In air atmosphere following 550 ℃ again, roasting 8h obtains the purpose product.Obtain the sieve sample that crystalline phase is MCM-41 through XRD analysis.Analyze through IR, contain the ZSM-5 secondary building units of zeolite in the skeleton.
Embodiment 4
With industrial synthetic Na ZSM-5 zeolite, SiO
2/ Al
2O
3=50,4.8g is dispersed in 400mL 0.5MHNO
3In the solution, form hydrogel, stir 2h at normal temperatures, in the synthesis reactor of packing into, place 2h for 150 ℃, regulate pH value to 13 with 6M NaOH; Then 14.5g 20wt% cetyl trimethylammonium bromide drips of solution is gone in the hydrogel, 50 ℃ are stirred 40min, add the 2.2g sodium metaaluminate again, and acetic acid is regulated about pH=9.6; Pack into after continuing the to stir crystallizing kettle of inner liner polytetrafluoroethylene is in 140 ℃ of crystallization 2d; Filter then, wash, dry 24h under 100 ℃; In air atmosphere following 550 ℃ again, roasting 8h obtains the purpose product.Obtain the sieve sample that crystalline phase is MCM-41 through XRD analysis.Analyze through IR, contain the ZSM-5 secondary building units of zeolite in the skeleton.
Embodiment 5
With industrial synthetic Na ZSM-5 zeolite, SiO
2/ Al
2O
3=50,4.8g is dispersed in the 150mL 3M HCl solution, forms hydrogel, stirs 2h at normal temperatures, in the synthesis reactor of packing into, places 5h for 120 ℃, regulates pH value to 13 with 6MNaOH; Then 16.5g 20wt% cetyl trimethylammonium bromide drips of solution is gone in the hydrogel, 50 ℃ are stirred 40min, add the 10.2g silicon sol again, and acetic acid is regulated about pH=9.6; Pack into after continuing the to stir crystallizing kettle of inner liner polytetrafluoroethylene is in 110 ℃ of crystallization 4d; Filter then, wash, dry 24h under 100 ℃; In air atmosphere following 550 ℃ again, roasting 8h obtains the purpose product.Obtain the sieve sample that crystalline phase is MCM-41 through XRD analysis.Analyze through IR, contain the ZSM-5 secondary building units of zeolite in the skeleton.
Embodiment 6
With industrial synthetic Na ZSM-5 zeolite, SiO
2/ Al
2O
3=100,6.4g is dispersed in the 220mL 3MHCl solution, forms hydrogel, stirs 2h at normal temperatures, in the synthesis reactor of packing into, places 5h for 120 ℃, regulates pH value to 13 with 6M NaOH; Then 16.5g 20wt% cetyl trimethylammonium bromide drips of solution is gone in the hydrogel, 50 ℃ are stirred 40min, and acetic acid is regulated about pH=9.6; Pack into after continuing the to stir crystallizing kettle of inner liner polytetrafluoroethylene is in 110 ℃ of crystallization 4d; Filter then, wash, dry 24h under 100 ℃; In air atmosphere following 550 ℃ again, roasting 8h obtains the purpose product.Obtain the sieve sample that crystalline phase is MCM-41 through XRD analysis.Analyze through IR, contain the ZSM-5 secondary building units of zeolite in the skeleton.
Embodiment 7
With industrial synthetic NaZSM-5 zeolite, SiO
2/ Al
2O
3=120,5.8g is dispersed in the 260mL 3.5MHCl solution, forms hydrogel, stirs 2h at normal temperatures, in the synthesis reactor of packing into, places 5h for 120 ℃, regulates pH value to 13 with 6M NaOH; Then 17.5g 25wt% cetyl trimethylammonium bromide drips of solution is gone in the hydrogel, 50 ℃ are stirred 40min, and acetic acid is regulated about pH=9.6; Pack into after continuing the to stir crystallizing kettle of inner liner polytetrafluoroethylene is in 110 ℃ of crystallization 4d; Filter then, wash, dry 24h under 100 ℃; In air atmosphere following 550 ℃ again, roasting 8h obtains the purpose product.Obtain the sieve sample that crystalline phase is MCM-41 through XRD analysis.Analyze through IR, contain the ZSM-5 secondary building units of zeolite in the skeleton.
Embodiment 8
With industrial synthetic Na ZSM-5 zeolite, SiO
2/ Al
2O
3=120,5.8g is dispersed in the 260mL 3.5MHCl solution, forms hydrogel, stirs 2h at normal temperatures, in the synthesis reactor of packing into, places 5h for 120 ℃, regulates pH value to 13 with 6M NaOH; Then 17.5g 25wt% cetyl trimethylammonium bromide drips of solution is gone in the hydrogel, add the 8.5g aluminum isopropylate again, sulfuric acid is regulated about pH=9.6; Pack into after continuing the to stir crystallizing kettle of inner liner polytetrafluoroethylene is in 120 ℃ of crystallization 4d; Filter then, wash, dry 24h under 100 ℃; In air atmosphere following 550 ℃ again, roasting 8h obtains the purpose product.Obtain the sieve sample that crystalline phase is MCM-41 through XRD analysis.Analyze through IR, contain the ZSM-5 secondary building units of zeolite in the skeleton.
Table 1 exemplary embodiments synthetic zeolite product main character
Claims (10)
1. preparation method who contains ZSM-5 secondary structure unit mesopore molecular sieve comprises following process:
(1) industrial synthetic ZSM-5 zeolite is mixed with acid solution, make hydrogel;
(2) hydrogel that step (1) is prepared and mould agent mix and make MCM-41 molecular sieve compositions material, and template is cetyl trimethylammonium bromide or palmityl trimethyl ammonium chloride;
(3) the synthetic material that obtains of step (2) crystallization under optimum conditions promptly obtains containing the MCM-41 zeolite product of ZSM-5 secondary structure unit.
2. in accordance with the method for claim 1, it is characterized in that: the described acid solution of step (1) is one or more of sulphuric acid soln, hydrochloric acid soln or salpeter solution, and the concentration of acid is 0.2～5mol/L in the solution.
3. in accordance with the method for claim 1, it is characterized in that: described acid solution of step (1) and solid envelope-bulk to weight ratio are 10: 1～100: 1, unit: mL solution/g molecular sieve.
4. it is characterized in that in accordance with the method for claim 1: reacted 1～15 hour down at 100 ℃～160 ℃ behind ZSM-5 zeolite and the acid solution thorough mixing in the step (1).
5. it is characterized in that in accordance with the method for claim 1: add silicon source or aluminium source adjusting silica alumina ratio in the synthetic material of step (2).
6. it is characterized in that in accordance with the method for claim 5: the silicon source is selected from silicon sol, water glass or silicoorganic compound; The aluminium source is selected from sodium metaaluminate, pseudo-boehmite or aluminum isopropylate.
7. it is characterized in that in accordance with the method for claim 1: the mole proportioning of synthetic material is: SiO
2: Al
2O
3: CTAB=(1～30): 0.1: (0.15～0.25), CTAB is a template.
8. in accordance with the method for claim 1, it is characterized in that: the pH value of synthetic material is 8～12, regulates hydrogel pH value to 9～14 with alkali earlier, is adjusted to 8～12 with acid again after the adding template.
9. in accordance with the method for claim 1, it is characterized in that: the crystallization condition of step (3) is for carrying out under 90～150 ℃ and autogenous pressure, and crystallization time is 2～10d.
10. in accordance with the method for claim 1, it is characterized in that: behind the crystallization end of synthesis, separate, washing, drying and other steps obtain final zeolite product.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103723741A (en) * | 2013-12-19 | 2014-04-16 | 大同煤矿集团有限责任公司 | Method for synthesizing ZSM-5/MCM-41 composite molecular sieve |
| CN104058421A (en) * | 2014-06-09 | 2014-09-24 | 罗小林 | Preparation method of microporous-mesoporous ZSM-5/MCM-41 composite molecular sieve with core-shell structure |
-
2009
- 2009-09-28 CN CN 200910187764 patent/CN102030340A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103723741A (en) * | 2013-12-19 | 2014-04-16 | 大同煤矿集团有限责任公司 | Method for synthesizing ZSM-5/MCM-41 composite molecular sieve |
| CN103723741B (en) * | 2013-12-19 | 2015-09-30 | 大同煤矿集团有限责任公司 | A kind of method of synthesizing ZSM-5/MCM-41 composite molecular screen |
| CN104058421A (en) * | 2014-06-09 | 2014-09-24 | 罗小林 | Preparation method of microporous-mesoporous ZSM-5/MCM-41 composite molecular sieve with core-shell structure |
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Application publication date: 20110427 |