CN1207201C - Method for preparing MCM-56 molecular sieves - Google Patents
Method for preparing MCM-56 molecular sieves Download PDFInfo
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- CN1207201C CN1207201C CN 02145235 CN02145235A CN1207201C CN 1207201 C CN1207201 C CN 1207201C CN 02145235 CN02145235 CN 02145235 CN 02145235 A CN02145235 A CN 02145235A CN 1207201 C CN1207201 C CN 1207201C
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- mcm
- molecular sieve
- crystallization
- sio
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Abstract
The present invention relates to a preparation method of an MCM-56 molecular sieve, which mainly solves the problems that the MCM-56 molecular sieve has high synthesis cost and produces pollution to the environment in the prior art. The preparation method better solves the problems by adopting the technical scheme that one part or all parts of a template agent come from crystallisation mother liquid of the MCM-56 molecular sieve in the process for synthesizing the MCM-56 molecular sieve, and the preparation method can be used for industrial production.
Description
Technical field
The present invention relates to the preparation method of MCM-56 molecular sieve.
Background technology
Industrial, zeolite molecular sieve is the porous crystalline silico-aluminate, and it has regular orderly crystalline structure, therefore the X-ray diffraction with feature.The basic skeleton structure of molecular sieve is based on the three-dimensional TO of inflexible
4(SiO
4, AlO
4Deng) modular construction; TO in this structure
4Be to share Sauerstoffatom, skeleton tetrahedron such as AlO in the tetrahedron mode
4Charge balance be by surperficial positively charged ion such as Na
+, H
+Existence keep.This shows the skeleton character that can change zeolite molecular sieve by the cationic exchange mode.Simultaneously, in the structure of zeolite molecular sieve, exist pore canal system abundant, that the aperture is certain, the interlaced formation tridimensional network in these ducts.Therefore, molecular sieve not only has good catalytic activity, good shape selectivity and can realize good selectivity by modification various organic reactions.A large amount of nuances that studies show that the porous material microtexture can cause the great variety of its catalytic performance and characterization of adsorption.
Prepare in the industrial production of alkylbenzene in existing low-carbon alkene alkylation, extensively adopt molecular sieve,, improve the quality of products and reduce pollution environment to improve the throughput of device as catalyzer.The method of at present synthetic MCM-56 molecular sieve mainly is a hydrothermal crystallization method.Document US 5362697, US5557024 has all related to the synthetic method of MCM-56 molecular sieve in 5827491.They are to make template R with hexamethylene imine basically, and the mol ratio of its silicon source, aluminium source, alkali, template and water is:
SiO
2/Al
2O
3＝5～35
OH
-/SiO
2＝0.05～0.5
R/SiO
2＝0.1～0.5
H
2O/SiO
2＝10～70
At crystallization temperature is 120～160 ℃, and crystallization time is a synthetic MCM-56 molecular sieve under 73～130 hours conditions.Generally need to add in addition the element of IIA, IIIA, IVA, IB, IIB, IIIB, IVB, VIB or VIII in these several pieces of patents.Owing to all use expensive template hexamethylene imine in the building-up process of MCM-56 molecular sieve, cause molecular sieve preparation cost height in the above-mentioned document, itrogenous organic substance can pollute environment in the crystalline mother solution in addition.
Summary of the invention
Technical problem to be solved by this invention is to overcome in the past to have in the document that itrogenous organic substance causes big pollution problems to environment in preparation MCM-56 molecular sieve cost height and the crystalline mother solution, and a kind of preparation method of MCM-56 molecular sieve is provided.It is low that this method has a MCM-56 molecular sieve preparation cost, environment amenable characteristics in the preparation molecular sieve process.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of preparation method of MCM-56 molecular sieve, at first count your ratio of silicon source, aluminium source, alkali, template and hydromassage: SiO
2/ Al
2O
3Be 5～50, OH
-/ SiO
2Be 0.02～0.5, H
2O/SiO
2Be 5～100, R/SiO
2It is 0.05～1.0 mixed, wherein R is a template, be selected from least a in pentamethylene imines, hexamethylene imine, the heptamethylene imines, with said mixture is under 120～170 ℃ of conditions at crystallization temperature under agitation, crystallization time is 5～120 hours, fractional crystallization product and reclaim mother liquor then, crystallized product makes the MCM-56 molecular sieve through washing, drying, and wherein part or all of template is from MCM-56 crystallization of molecular sieves mother liquor.
In the technique scheme in the mixture with molar ratio computing: SiO
2/ Al
2O
3Preferable range is 5～30, OH
-/ SiO
2Preferable range is 0.02～0.1, H
2O/SiO
2Preferable range is 10～20, R/SiO
2Preferable range is 0.1～0.5.Silicon source preferred version is selected from least a in soft silica, silicon sol, solid oxidation silicon, silica gel, diatomite or the water glass; Aluminium source preferred version is selected from least a in sodium aluminate, sodium metaaluminate, Tai-Ace S 150, aluminum nitrate, aluminum chloride, aluminium hydroxide or the pseudo-boehmite; Alkali is mineral alkali, and preferred version is selected from alkali metal hydroxide.The crystallization temperature preferable range is 125～140 ℃, and the crystallization time preferable range is 30～60 hours.Preferred version is a MCM-56 crystallization of molecular sieves mother liquor of recycling recovery in the synthetic MCM-56 molecular sieve process, the mol ratio of template is 0.1～0.8 in template in the MCM-56 crystallization of molecular sieves mother liquor that reclaims and the MCM-56 molecular sieve precursor mixture, and preferable range is 0.1～0.5.
The present invention owing to recycle the crystallization of molecular sieves mother liquor, can constantly recycle the template in the crystalline mother solution, thereby has reduced the consumption of template in synthetic MCM-56 molecular sieve process, has reduced the synthetic cost of MCM-56 molecular sieve.In addition since the crystallization of molecular sieves mother liquor recycled, thereby eliminated in the crystallization mother liquor nitrogenous organic liquid waste to the pollution of environment.The X diffracted ray collection of illustrative plates of the MCM-56 molecular sieve that makes is as follows:
D (A) relative intensity I/I
0
12.4 ±0.2 VS
9.9 ±0.3 M-S
6.9 ±0.1 W
6.2 ±0.1 S
3.55 ±0.07 M-S
3.42 ±0.07 VS
Obtained better technical effect.
The present invention is further elaborated below by embodiment.
Embodiment
[embodiment 1]
Get the silicon sol of 600 grams 40% (weight), add 500 gram water, 38.9 gram sodium metaaluminate [Al
2O
3, 42% (weight)] and 2 gram sodium hydroxide, afterwards, add the crystalline mother solution that 112 gram hexamethylene imines (HMI) and 213 grams contain hexamethylene imine 13 grams again.Said mixture, elevated temperature to 138 ℃ crystallization, crystallization 48 hours.Distilled water cleans to neutral, oven dry.The X-ray powder diffraction shows that (XRD) institute synthetic product is MCM-56.In the wherein above-mentioned reaction mixture with molar ratio computing: SiO
2/ Al
2O
3Be 25, OH
-/ SiO
2Be 0.093, H
2O/SiO
2Be 14.72, HMI/SiO
2Be 0.32, the MCM-56 molecular sieve silica alumina ratio SiO that is obtained
2/ Al
2O
3Be 24.3.
[embodiment 2]
Press each condition and the step of embodiment 1, just change the source amount of template hexamethylene imine, wherein template (HMI) all derives from MCM-56 crystallization of molecular sieves mother liquor, its result is: the X-ray powder diffraction shows that (XRD) institute synthetic product is MCM-56, according to another measuring the MCM-56 molecular sieve silica alumina ratio SiO that is obtained
2/ Al
2O
3Be 23.5.
[embodiment 3]
Press each condition and the step of embodiment 1, just change the source amount of template hexamethylene imine, wherein the amount of the hexamethylene imine (HMI) that directly adds is 25 grams, amount from template in the crystalline mother solution is 100 grams, its result is: the X-ray powder diffraction shows that (XRD) institute synthetic product is MCM-56, according to another measuring the MCM-56 molecular sieve silica alumina ratio SiO that is obtained
2/ Al
2O
3Be 23.8.
[embodiment 4]
Press each condition and the step of embodiment 1, just change the source amount of template hexamethylene imine, wherein the amount of the hexamethylene imine (HMI) that directly adds is 62.5 grams, amount from template in the crystalline mother solution is 62.5 grams, its result is: the X-ray powder diffraction shows that (XRD) institute synthetic product is MCM-56, according to another measuring the MCM-56 molecular sieve silica alumina ratio SiO that is obtained
2/ Al
2O
3Be 24.2.
Claims (8)
1, a kind of preparation method of MCM-56 molecular sieve at first counts your ratio of silicon source, aluminium source, alkali, template and hydromassage: SiO
2/ Al
2O
3Be 5～50, OH
-/ SiO
2Be 0.02～0.5, H
2O/SiO
2Be 5～100, R/SiO
2It is 0.05～1.0 mixed, wherein R is a template, be selected from least a in pentamethylene imines, hexamethylene imine, the heptamethylene imines, with said mixture is under 120～170 ℃ of conditions at crystallization temperature under agitation, crystallization time is 5～120 hours, fractional crystallization product and reclaim mother liquor then, crystallized product makes the MCM-56 molecular sieve through washing, drying, and part or all that it is characterized in that template is from MCM-56 crystallization of molecular sieves mother liquor.
2,, it is characterized in that in the mixture with molar ratio computing: SiO according to the preparation method of the described MCM-56 molecular sieve of claim 1
2/ Al
2O
3Be 5～30, OH
-/ SiO
2Be 0.02～0.1, H
2O/SiO
2Be 10～20, R/SiO
2Be 0.1～0.5.
3,, it is characterized in that the silicon source is selected from least a in soft silica, silicon sol, solid oxidation silicon, silica gel, diatomite or the water glass according to the preparation method of the described MCM-56 molecular sieve of claim 1; The aluminium source is selected from least a in sodium aluminate, sodium metaaluminate, Tai-Ace S 150, aluminum nitrate, aluminum chloride, aluminium hydroxide or the pseudo-boehmite; Alkali is mineral alkali, is selected from alkali metal hydroxide.
4, according to the preparation method of the described MCM-56 molecular sieve of claim 1, it is characterized in that crystallization temperature is 125～140 ℃, crystallization time is 40～60 hours.
5, according to the preparation method of the described MCM-56 molecular sieve of claim 1, it is characterized in that before crystallization or in mixture, add MCM-56 molecular sieve crystal seed in the crystallization process that the crystal seed add-on is 0.1～5% of synthetic MCM-56 molecular sieve amount by weight percentage.
6,, it is characterized in that recycling the synthetic MCM-56 molecular sieve of MCM-56 crystallization of molecular sieves mother liquor of recovery according to the preparation method of the described MCM-56 molecular sieve of claim 1.
7, according to the preparation method of the described MCM-56 molecular sieve of claim 1, the mol ratio of template is 0.1～0.8 in template in the MCM-56 crystallization of molecular sieves mother liquor that it is characterized in that reclaiming and the MCM-56 molecular sieve precursor mixture.
8, according to the preparation method of the described MCM-56 molecular sieve of claim 7, the mol ratio of template is 0.1～0.5 in template in the MCM-56 crystallization of molecular sieves mother liquor that it is characterized in that reclaiming and the MCM-56 molecular sieve precursor mixture.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02145235 CN1207201C (en) | 2002-11-13 | 2002-11-13 | Method for preparing MCM-56 molecular sieves |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02145235 CN1207201C (en) | 2002-11-13 | 2002-11-13 | Method for preparing MCM-56 molecular sieves |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1500724A CN1500724A (en) | 2004-06-02 |
| CN1207201C true CN1207201C (en) | 2005-06-22 |
Family
ID=34232330
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 02145235 Expired - Lifetime CN1207201C (en) | 2002-11-13 | 2002-11-13 | Method for preparing MCM-56 molecular sieves |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8816145B2 (en) | 2007-06-21 | 2014-08-26 | Exxonmobil Chemical Patents Inc. | Liquid phase alkylation process |
| TWI483775B (en) * | 2011-09-16 | 2015-05-11 | Exxonmobil Chem Patents Inc | Improved mcm-56 manufacture |
| KR101942128B1 (en) * | 2011-09-16 | 2019-01-24 | 엑손모빌 케미칼 패턴츠 인코포레이티드 | Improved mcm-56 manufacture |
| CN107459439B (en) * | 2011-09-16 | 2023-06-13 | 埃克森美孚化学专利公司 | Improved liquid phase alkylation process |
| CN104743570B (en) * | 2013-12-26 | 2017-03-01 | 中国石油化工股份有限公司 | A kind of synthetic method of MCM 56 molecular sieve |
| CN105217651B (en) * | 2014-07-03 | 2017-07-14 | 中国石油化工股份有限公司 | Si-Al molecular sieve SCM 6, its preparation method and use |
-
2002
- 2002-11-13 CN CN 02145235 patent/CN1207201C/en not_active Expired - Lifetime
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