CN102442682A - Preparation method of mesoporous molecular sieve containing L zeolite secondary structural unit - Google Patents
Preparation method of mesoporous molecular sieve containing L zeolite secondary structural unit Download PDFInfo
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- CN102442682A CN102442682A CN2010105092726A CN201010509272A CN102442682A CN 102442682 A CN102442682 A CN 102442682A CN 2010105092726 A CN2010105092726 A CN 2010105092726A CN 201010509272 A CN201010509272 A CN 201010509272A CN 102442682 A CN102442682 A CN 102442682A
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Abstract
The invention discloses a preparation method of a mesoporous molecular sieve containing an L zeolite secondary structural unit. The method comprises the following steps of: mixing industrial L zeolite with an acid solution to obtain aqua gel; uniformly mixing the aqua gel with a template to obtain an MCM-41 molecular sieve synthetic material; and crystalizing under appropriate conditions to obtain an MCM-41 molecular sieve product containing the L zeolite secondary structural unit. Compared with the prior art, the method has the advantages that: the process is simple, the synthetic molecular sieve has an MCM-41 molecular sieve structure, and the acidity and hydrothermal stability are enhanced remarkably. The synthetic molecular sieve product can be applied in the technical fields of catalytic cracking, hydrocracking, hydrotreatment, hydrogenation modification and the like.
Description
Technical field
The present invention relates to a kind of compound method of mesopore molecular sieve, it be a kind of with L zeolite raw material as silicon and aluminum source, the synthetic method that contains L 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 chemicalstability.Yet because the aperture is less, the major diameter molecule gets into the duct difficulty, and the macromole that in the duct, forms can not be overflowed fast, causes side reaction to take place, thereby makes its range of application receive 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.
US5057296, 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 CN1110252A makes is 3.8nm, and silica alumina ratio is 40, and specific surface area is 1016m
2/ g.Adopting OTAC in this patent instance 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.
US5156829 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 that building-up process is complicated, condition harsh (HTHP), expensive raw materials.
In recent years, the research of the mesoporous material of the zeolite precursor body of nano-scale and tensio-active agent assembling receives the concern of much human.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.
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
Deficiency to prior art; The present invention provides a kind of preparation method of MCM-41 of peracidity high stability of the L of containing secondary building units of zeolite; Adopt a kind of new compound 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 L secondary building units of zeolite mesopore molecular sieve comprises following process:
(1) the L zeolite is mixed with acid solution, process hydrogel;
(2) hydrogel of step (1) preparation and template are mixed process MCM-41 molecular sieve compositions material, 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 L secondary building units of zeolite.
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; The envelope-bulk to weight ratio of acid solution and solid L zeolite is 10: 1～100: 1 (a mL solution/g molecular sieve), thorough mixing behind the L zeolite adding acid solution, and under 100 ℃～160 ℃, reacted 1～15 hour.Industry L zeolite can have different character according to the difference of compound method, like the L zeolite of Different Silicon aluminum ratio, can use the industrial L zeolite of any character in the inventive method, as directly synthesizing the NH after exchanging
4The L zeolite also can be the L zeolite through suitable treatment, like the L zeolite of hydrothermal treatment consists etc.
In the inventive method, the silicon source in the step (2) 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 be confirmed by the material proportion of the synthetic MCM-41 molecular sieve in this area, be generally (mol ratio): SiO like synthetic material proportion
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) for 90～150 ℃ with autogenous pressure under carry out, crystallization can be carried out under static state, also can under agitation condition, carry out.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; Contain the L secondary building units of zeolite in the hole wall; This molecular sieve can be used for technical fields such as catalytic cracking, hydrogen cracking, hydrotreatment, hydro-upgrading; Experiment shows that catalytic process such as fields such as catalytic cracking, hydrogen cracking that this molecular sieve is used for the bigger hydrocarbon raw material of molecular weight have a significant effect.
The inventive method MCM-41 molecular sieve compound method and synthetic zeolite product have following characteristics:
(1) is silicon and aluminum source with the L 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 L zeolite, and pore wall thickness exceeds 25%～50% than traditional mesoporous molecular sieve such as MCM-41, and when the sintetics sial was close, acid amount and acidity all were significantly improved simultaneously;
(3) be silicon and aluminum source with the L zeolite, the mesopore molecular sieve structure that contains the L 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, and then hydrothermal stability is relatively poor to adopt the mesopore molecular sieve that has method (as pressing the CN1597516A method) preparation now;
(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 L secondary building units of zeolite has good arylhydrocarbon in diesel oil hydrogenation sulfur resistance and open-loop performance.
In the inventive method; With the L zeolite is silicon source and aluminium source; Preprocessing process and crystallization building-up process through suitable have been incorporated into the L secondary building units of zeolite in the hole wall of MCM-41, have improved the acidity and the hydrothermal stability of molecular sieve; Saved the building-up process of presoma, and 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 is ESEM (SEM) figure of the embodiment of the invention 1 synthetic MCM-41;
Fig. 3 is ESEM (SEM) figure of ordinary method synthetic MCM-41.
Embodiment
Embodiment 1
With the synthetic NH of industry
4NH after the exchange
4L (SiO
2/ Al
2O
3The molecule mol ratio is 10, below is SiO
2/ Al
2O
3Be the molecule mol ratio) zeolite 7.2g 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 16.5g 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 spectra (IR), contain the L secondary building units of zeolite in the MCM-41 product skeleton.
With the synthetic NH of industry
4NH after the exchange
4L (SiO
2/ Al
2O
3The molecule mol ratio is 10, below is SiO
2/ Al
2O
3Being the molecule mol ratio) zeolite 5.2g is dispersed in 200mL 4M H
2SO
4In the solution, form hydrogel, stir 1h at normal temperatures after, in the synthesis reactor of packing into, place 12h for 100 ℃, the cooling back with 6M NaOH adjusting pH value to 13 about; Then 14.5g 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 130 ℃ of crystallization 3d; 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 spectra (IR), contain the L secondary building units of zeolite in the MCM-41 product skeleton.
Embodiment 3
With the synthetic pretreated L zeolite of industry, SiO
2/ Al
2O
3=30,12.2g is dispersed in 300mL 0.5MHNO
3In the solution, form hydrogel, stir 1h at normal temperatures, in the synthesis reactor of packing into, place 3h for 150 ℃, regulate pH value to 13 with 6M NaOH; Then 12.0g 16wt% cetyl trimethylammonium bromide drips of solution is gone in the hydrogel, 50 ℃ are stirred 40min, and hydrochloric acid is regulated about pH=10; Pack into after the stirring crystallizing kettle of inner liner polytetrafluoroethylene is in 110 ℃ of crystallization 3d; 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 spectra (IR), contain the L secondary building units of zeolite in the MCM-41 product skeleton.
Embodiment 4
With the synthetic pretreated L zeolite of industry, SiO
2/ Al
2O
3=30,10.8g is dispersed in the 240mL 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 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 spectra (IR), contain the L secondary building units of zeolite in the MCM-41 product skeleton.
With the synthetic pretreated L zeolite of industry, SiO
2/ Al
2O
3=30,10.8g is dispersed in the 340mL 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 24.5g 20wt% cetyl trimethylammonium bromide drips of solution is gone in the hydrogel, 50 ℃ are stirred 40min, add the 5.2g 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 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 spectra (IR), contain the L secondary building units of zeolite in the MCM-41 product skeleton.
Embodiment 6
With the synthetic pretreated L zeolite of industry, SiO
2/ Al
2O
3=20,8.8g is dispersed in the 240mL 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 10.5g 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 120 ℃ of crystallization 3d; 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 spectra (IR), contain the L secondary building units of zeolite in the MCM-41 product skeleton.
Embodiment 7
With the synthetic pretreated L zeolite of industry, SiO
2/ Al
2O
3=20,6.8g is dispersed in the 240mL 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 17.5g 20wt% cetyl trimethylammonium bromide drips of solution is gone in the hydrogel, 50 ℃ are stirred 40min, add the 8.2g 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 120 ℃ of crystallization 3d; 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 spectra (IR), contain the L secondary building units of zeolite in the MCM-41 product skeleton.
Table 1 exemplary embodiments synthetic zeolite product main character
Claims (10)
1. preparation method who contains L secondary building units of zeolite mesopore molecular sieve comprises following process:
(1) the L zeolite is mixed with acid solution, process hydrogel;
(2) hydrogel of step (1) preparation and template are mixed process MCM-41 molecular sieve compositions material, 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 L secondary building units of zeolite.
2. according to the described method of claim 1, it is characterized in that: add silicon source or aluminium source adjusting silica alumina ratio in the synthetic material of step (2).
3. according to the described method of claim 1, it is characterized in that: the described acid solution of step (1) be in sulphuric acid soln, hydrochloric acid soln or the salpeter solution one or more, in the solution acid concentration be 0.2～5mol/L.
4. according to claim 1 or 3 described methods, it is characterized in that: the envelope-bulk to weight ratio of the acid solution of step (1) and solid L zeolite is 10: 1～100: 1, and unit is: mL solution/g molecular sieve.
5. according to claim 1 or 3 described methods, it is characterized in that: thorough mixing behind the L zeolite adding acid solution, and under 100 ℃～160 ℃, reacted 1～15 hour.
6. according to the described method of claim 2, it is characterized in that: 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. according to the described method of claim 1, it is characterized in that: 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. according to the described method of 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. according to the described method of claim 1, it is characterized in that: the crystallization condition of step (3) for 90～150 ℃ with autogenous pressure under carry out, crystallization time is 2～10 days.
10. according to the described method of claim 1, it is characterized in that: behind the crystallization end of synthesis, separate, washing, drying step obtain final zeolite product.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1597516A (en) * | 2004-09-21 | 2005-03-23 | 太原理工大学 | Micropore mesopore composite molecular sieve and its preparation method |
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2010
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1597516A (en) * | 2004-09-21 | 2005-03-23 | 太原理工大学 | Micropore mesopore composite molecular sieve and its preparation method |
Non-Patent Citations (1)
| Title |
|---|
| 王珊等: "强酸性和水热稳定的MCM-41分子筛的合成", 《太原理工大学学报》 * |
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Application publication date: 20120509 |