CN100363259C - Method for preparing MCM-22 molecular sieve in high silicon - Google Patents
Method for preparing MCM-22 molecular sieve in high silicon Download PDFInfo
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- CN100363259C CN100363259C CNB2004101018032A CN200410101803A CN100363259C CN 100363259 C CN100363259 C CN 100363259C CN B2004101018032 A CNB2004101018032 A CN B2004101018032A CN 200410101803 A CN200410101803 A CN 200410101803A CN 100363259 C CN100363259 C CN 100363259C
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Abstract
The present invention relates to a method for preparing MCM-22 molecular sieves in high silicon, which comprises: the contact time of an MCM-22 molecular sieve with a low silica alumina ratio (Si/Al2<30) and ammonium fluorosilicate solution with the concentration of 0.01 to 0.8 mol/L is from 0.5h to 48h at the room temperature of 100 DEG C for generating an MCM-22 molecular sieve with a high silica alumina ratio. The silica alumina ratio of an obtained molecular sieve can change freely within the range of 50 to 180. The obtained molecular sieve has high crystallinity; simultaneously, other crystal phases are not generated in a treating process.
Description
Technical field
The present invention relates to a kind of preparation method of high silicon MCM-22 molecular sieve.Specifically, relate to a kind of method that the MCM-22 molecular sieve dealuminzation of low silica-alumina ratio is prepared high silicon MCM-22 molecular sieve with the mode of aftertreatment.
Background technology
The MCM-22 molecular sieve is a kind of novel molecular sieve of U.S. Mobil company in the nineteen ninety exploitation, and its structure is the MWW type, has two kinds of not connected pore canal system.One cover is for two-dimentional sinusoidal duct, and the effective pore radius is a ten-ring, another set ofly is made up of the supercage that contains twelve-ring, and its opening also is a ten-ring.Because but its unique pore passage structure, high specific surface, good thermostability and the acid performance of hydrothermal stability and modulation have obtained application widely in reactions such as alkylation, aromizing, toluene disproportionation, xylene isomerization.
Because the molecular sieve of high silica alumina ratio has high stability, high resistance to acid and high hydrothermal stability, so the investigator is attempting the MCM-22 molecular sieve of synthesizing high-silicon aluminum ratio always.But the raising of the silica alumina ratio that feeds intake can cause synthesize the decline of MCM-22 molecular sieve crystallinity and easily produce other stray crystal, as ZSM-5, ZSM-12 and Kenyaite etc.Document it is generally acknowledged the suitable silica alumina ratio scope of synthetic pure MCM-22 be 25-50 (Science Bulletin, 2004,49 (4), 325-330).The method for preparing the high MCM-22 molecular sieve of high silica alumina ratio and purity by the ammonium silicofluoride aftertreatment does not then have report.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of high silicon MCM-22 molecular sieve specifically, is the method for preparing high silica alumina ratio and highly purified MCM-22 molecular sieve by the method that the MCM-22 molecular sieve to low silica-alumina ratio carries out aftertreatment.
The present invention includes and make low silica-alumina ratio (Si/Al
2＜30) MCM-22 molecular sieve contacts certain hour at a certain temperature with certain density ammonium fluosilicate solution, to produce the MCM-22 molecular sieve of high silica alumina ratio, its silica alumina ratio can be in 50～180 scope modulation arbitrarily, the gained molecular sieve has high degree of crystallinity and do not have other crystalline phase in treating processes and produces.Contact conditions is ammonium silicofluoride concentration 0.01-0.8mol/L, and temperature is a room temperature to 100 ℃, and be 0.5h-48h duration of contact.
With low silica-alumina ratio (as Si/Al
2＜30) MCM-22 molecular screen primary powder is removed template in 400-600 ℃ of roasting, with ammonium ion exchange method it is become the intermediate ammonium form.Ammonium ion source can be NH
4Cl, NH
4NO
3Or (NH
4)
2SO
4, the ammonium ion exchange condition: ammonium concentration 0.2～2mol/l, liquid-solid ratio (volume) 5～20,20～100 ℃ of temperature exchange 1～3 time.With resulting ammonium type molecular sieve with certain density ammonium fluosilicate solution reflow treatment certain hour at a certain temperature, washing, drying makes the MCM-22 molecular sieve of high silica alumina ratio in 400-600 ℃ of roasting.
Press its step:
1) be Si/Al with silica alumina ratio
2＜30 MCM-22 molecular screen primary powder is removed template in 400-600 ℃ of roasting, with ammonium ion exchange method it is become the intermediate ammonium form; Ammonium ion source can be NH
4Cl, NH
4NO
3Or (NH
4)
2SO
4, ammonium ion exchange condition: ammonium concentration 0.2～2mol/l, volume liquid-solid ratio 5～20,20～100 ℃ of temperature.
2) molecular sieve that step 1 is obtained with resulting ammonium type molecular sieve with certain density ammonium fluosilicate solution (0.01-0.8mol/L) at certain temperature (room temperature to 100 ℃) reflow treatment certain hour (0.5-48h) down, use the deionized water repetitive scrubbing, 100-120 ℃ of drying, 400-600 ℃ of roasting makes the MCM-22 molecular sieve of high silica alumina ratio.
Description of drawings
Fig. 1 is the different Si/Al of the present invention
2The X-ray diffractogram of ratio.
Embodiment
Below be that non-limiting example of the present invention illustrates.
Embodiment 1
1) be Si/Al with silica alumina ratio
2=27 MCM-22 molecular screen primary powder is removed template in 500 ℃ of roastings, with ammonium ion exchange method it is become the intermediate ammonium form; Ammonium ion source NH
4NO
3, ammonium ion exchange condition: ammonium concentration 0.2mol/L, volume liquid- solid ratio 5,20 ℃ of temperature.
2) molecular sieve that step 1 is obtained with resulting ammonium type molecular sieve with the ammonium fluosilicate solution of 0.01mol/L concentration reflow treatment 0.5h at room temperature, with deionized water repetitive scrubbing three times, 100-120 ℃ of drying, 550 ℃ of roastings, gained MCM-22 molecular sieve silica alumina ratio is 50, relative crystallinity＞99%, and do not have other crystalline phase generation, see accompanying drawing 1.
Embodiment 2
The preparation method of ammonium type molecular sieve is with embodiment 1, ammonium ion source NH
4Cl, ammonium ion exchange condition: ammonium concentration 1mol/L, volume liquid-solid ratio 10,80 ℃ of temperature.Is 70 ℃ following reflow treatment 10hs with the ammonium fluosilicate solution of 0.03mol/L concentration in temperature with the ammonium type molecular sieve that obtains, with deionized water repetitive scrubbing three times, 100-120 ℃ of drying, 600 ℃ of roastings, gained MCM-22 molecular sieve silica alumina ratio is 99, relative crystallinity＞99%, and do not have other crystalline phase generation, see accompanying drawing 1.
Embodiment 3
The preparation method of ammonium type molecular sieve is with embodiment 1, ammonium ion source (NH
4) SO
4, ammonium ion exchange condition: ammonium concentration 1.2mol/L, volume liquid-solid ratio 5,100 ℃ of temperature.Is 100 ℃ following reflow treatment 48hs with the ammonium fluosilicate solution of 0.8mol/L concentration in temperature with the ammonium type molecular sieve that obtains, with deionized water repetitive scrubbing three times, 100-120 ℃ of drying, 400 ℃ of roastings, gained MCM-22 molecular sieve silica alumina ratio is 180, relative crystallinity＞80%, and do not have other crystalline phase generation, see accompanying drawing 1.
Claims (2)
1. the preparation method of one kind high silicon MCM-22 molecular sieve the steps include:
A) with Si/Al
2The MCM-22 molecular screen primary powder of＜30 low silica-alumina ratio is removed template in 400-600 ℃ of roasting, with ammonium ion exchange method it is become the intermediate ammonium form; Ammonium ion source is NH
4Cl, NH
4NO
3Or (NH
4)
2SO
4, ammonium ion exchange condition: 20～100 ℃ of ammonium concentration 0.2～2mol/l, volume liquid-solid ratio 5～20, temperature;
B) the molecular sieve concentration that step a is obtained be the ammonium fluosilicate solution of 0.01-0.8mol/L under room temperature to 100 ℃, 0.5 hour-48 hours duration of contact, washing, drying makes the MCM-22 molecular sieve of high silica alumina ratio in 400-600 ℃ of roasting.
2. method according to claim 1 is characterized in that, prepared high its silica alumina ratio of silicon MCM-22 molecular sieve is any modulation in the scope of 50-180.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2004101018032A CN100363259C (en) | 2004-12-23 | 2004-12-23 | Method for preparing MCM-22 molecular sieve in high silicon |
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| CNB2004101018032A CN100363259C (en) | 2004-12-23 | 2004-12-23 | Method for preparing MCM-22 molecular sieve in high silicon |
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| CN1796279A CN1796279A (en) | 2006-07-05 |
| CN100363259C true CN100363259C (en) | 2008-01-23 |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101733146B (en) * | 2008-11-21 | 2012-09-05 | 中国石油化工股份有限公司 | Catalyst for synthesizing propylene by using ethylene and butylene |
| RU2638851C2 (en) * | 2012-10-18 | 2017-12-18 | Басф Се | Post-treatment of deborated zeolite mww |
| CN111250153B (en) * | 2018-11-30 | 2021-08-10 | 中国科学院大连化学物理研究所 | Al (aluminum)2O3Preparation method of Mo-loaded catalytic material of hierarchical pore molecular sieve and application of Mo-loaded catalytic material in preparation of propylene through disproportionation |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4954325A (en) * | 1986-07-29 | 1990-09-04 | Mobil Oil Corp. | Composition of synthetic porous crystalline material, its synthesis and use |
| WO2002060581A2 (en) * | 2001-01-29 | 2002-08-08 | Bp Corporation North America Inc. | Process for methylating naphthalenic compounds using a zeolite catalyst wherein a part of the al atom has been replaced by fe, the catalyst and a method for preparing the catalyst |
| CN1500722A (en) * | 2002-11-13 | 2004-06-02 | 中国石油化工股份有限公司 | Method for preparing MCM-22 molecular sieves |
-
2004
- 2004-12-23 CN CNB2004101018032A patent/CN100363259C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4954325A (en) * | 1986-07-29 | 1990-09-04 | Mobil Oil Corp. | Composition of synthetic porous crystalline material, its synthesis and use |
| WO2002060581A2 (en) * | 2001-01-29 | 2002-08-08 | Bp Corporation North America Inc. | Process for methylating naphthalenic compounds using a zeolite catalyst wherein a part of the al atom has been replaced by fe, the catalyst and a method for preparing the catalyst |
| CN1500722A (en) * | 2002-11-13 | 2004-06-02 | 中国石油化工股份有限公司 | Method for preparing MCM-22 molecular sieves |
Non-Patent Citations (1)
| Title |
|---|
| m-Xylene transformation over H-MCM-22......systems. S. Laforge et al.Microporous and Mesoporous Materials,Vol.67 No.2-3. 2004 * |
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