CN1500723A - Method for synthesizing MCM-22 molecular sieves - Google Patents

Method for synthesizing MCM-22 molecular sieves Download PDF

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CN1500723A
CN1500723A CNA021452342A CN02145234A CN1500723A CN 1500723 A CN1500723 A CN 1500723A CN A021452342 A CNA021452342 A CN A021452342A CN 02145234 A CN02145234 A CN 02145234A CN 1500723 A CN1500723 A CN 1500723A
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sio
molecular sieve
mcm
crystallization
synthetic method
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CN1207200C (en
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高焕新
周斌
方华
顾瑞芳
季树芳
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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Abstract

The present invention relates to the preparation process of MCM-22 molecular sieve and solves the problems in the preparation process, including long MCM-22 molecular sieve synthesizing period and low molecular sieve crystallization degree. The technological scheme of the present invention is that during the preparation of MCM-22 molecular sieve, the alkalinity of the molecular sieve precursor mixture is controlled and the mixture is aged at 0-100 deg.c for 0.5-720 hr before crystallization. The present invention may be used in industrial preparation.

Description

The synthetic method of MCM-22 molecular sieve
Technical field
The present invention relates to the synthetic method of MCM-22 molecular sieve.
Background technology
The MCM-22 molecular sieve is the novel catalytic material that plays report in nineteen ninety.It has two kinds of independently ten-ring pore canal system, and wherein a kind of inside of system comprises the large-scale supercage of 0.71 nanometer * 0.71 nanometer * 1.82 nanometers.These supercages are stacked on above another by overlapping one of six-ring, are applied in the window of approximate ellipsoidal ten-ring.Another kind of pore canal system forms two-dimentional sinusoidal waveform duct, on every side round the coincidence six-ring that links to each other with supercage.Because MCM-22 has the pore passage structure different with molecular sieve in the past, unusual thermostability and high-ratio surface, thereby crucial application is arranged in Industrial Catalysis.Such as in propylene and benzene preparing isopropylbenzene technology, can utilize the extraordinary selectivity of MCM-22 molecular sieve to replace solid phosphoric acid catalyst, improve the productive rate of isopropyl benzene in the catalytic process etc. greatly.
The method of at present synthetic MCM-22 mainly is a hydrothermal crystallization method.Document US 4954325 has been introduced a kind of composition and preparation and purposes of crystal formation material, and it is to make template R with hexamethylene imine, and the mol ratio of its silicon source, aluminium source, alkali, template and water is:
SiO 2/Al 2O 3＝10～60
OH -/SiO 2＝0.1～0.5
R/SiO 2＝0.1～0.5
M/SiO 2＝0.1～1.0
H 2O/SiO 2＝10～50
At crystallization temperature is 80～225 ℃, and crystallization time is a synthetic MCM-22 molecular sieve under 1～60 day condition.The silica alumina ratio of the synthetic MCM-22 of this piece patent institute is not high, and finds that from embodiment its crystallization time is longer, generally need 6～7 days, and do not relate to the degree of crystallinity of molecular sieve, confirm through test, US4954325 patented method synthetic MCM-22 molecular sieve crystallinity is about 80%, and is relatively low.
Summary of the invention
Technical problem to be solved by this invention is to exist MCM-22 molecular sieve generated time long in order to overcome in the past in the document, and the problem that the synthetic molecular sieve crystallinity is low provides a kind of synthetic method of new MCM-22 molecular sieve.It is short that this method has MCM-22 molecular sieve generated time, the MCM-22 molecular sieve silica alumina ratio height that obtains, and the high characteristics of molecular sieve crystallinity.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of synthetic method of MCM-22 molecular sieve, at first your ratio of silicon source, aluminium source, alkali, template and hydromassage is counted: SiO 2/ Al 2O 3Be 10～200, OH -/ SiO 2Be 0.1～1.0, H 2O/SiO 2Be 5～200, R/SiO 2It is 0.05～1.0 mixed, wherein R is a template, be selected from pentamethylene imines, hexamethylene imine, heptamethylene imines, 1, at least a in 4-phenodiazine suberane, suberane amine, hexamethylene alkanamine or the pentamethylene amine, with this mixture is under 120～180 ℃ of conditions at crystallization temperature under agitation, crystallization time is to take out after 5～100 hours, makes the MCM-22 molecular sieve through washing, drying, and wherein mixture is in ageing 0.5～720 hour under 0～100 ℃ of condition earlier before the crystallization.
In the technique scheme in the mixture with molar ratio computing preferable range: SiO 2/ Al 2O 3Be 20～80, OH -/ SiO 2Be 0.10～0.5, H 2O/SiO 2Be 10～50, R/SiO 2Be 0.1～0.6.The silicon source is selected from least a in soft silica, silicon sol, solid oxidation silicon, silica gel, diatomite or the water glass; The aluminium source is selected from least a in sodium aluminate, sodium metaaluminate, Tai-Ace S 150, aluminum nitrate, aluminum chloride, aluminium hydroxide, aluminum oxide, kaolin or the polynite; Alkali is mineral alkali, is selected from least a in lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide or the cesium hydroxide.The preferable range of crystallization temperature is 140～160 ℃, and the crystallization time preferable range is 20～60 hours.In ageing under 10～80 ℃ of conditions earlier before the crystallization, aged time preferable range is 5～240 hours before crystallization.Preferred version is to add MCM-22 molecular sieve crystal seed in mixture before crystallization or in the crystallization process, and the crystal seed add-on is 0.1～10% of synthetic MCM-22 molecular sieve amount by weight percentage.
Key of the present invention is that the concentration of alkaline solution in the raw mix and the ageing before crystallization are handled.If the excessive concentration of alkaline solution or low excessively all can not get MCM-22.
The present invention handles and adopts suitable alkali concn owing to carried out ageing earlier before the crystallization building-up process, make reaction mixture reach hypersaturated state rapidly from gel state, thereby help the quick formation of MCM-22 molecular sieve nucleus, thereby can shorten crystallization time greatly, enlarged the silica alumina ratio scope of molecular sieve simultaneously, the silica alumina ratio of MCM-22 molecular sieve can be reached more than 100.Make the degree of crystallinity of MCM-22 molecular sieve reach 100% simultaneously.The X diffracted ray collection of illustrative plates of the MCM-22 molecular sieve that makes is as follows:
D (A) relative intensity I/I 0
30.0 ±2.2 W-M
22.1 ±1.3 W
6.00 ±0.10 W-M
4.64 ±0.08 W
4.06 ±0.07 W-S
3.91 ±0.07 M-VS
Obtained better technical effect.
The present invention is further elaborated below by embodiment.
Embodiment
[embodiment 1]
With sodium aluminate (Al 2O 335.21 weight %, Na 2O31.12 weight %) 14.5 grams are dissolved in the 990 gram water, add sodium hydroxide 6.18 grams and make it dissolving, add organic amine template hexamethylene imine 49.5 grams then under condition of stirring, add silicon sol (SiO again 240 weight %) 150 grams are after waiting to stir, 40 ℃ of following ageings 72 hours.The material proportion of reactant (mol ratio) is:
SiO 2/Al 2O 3＝20
OH -/SiO 2＝0.3
R/SiO 2＝0.5
H 2O/SiO 2＝60
Stir after 30 minutes, in the stainless steel cauldron of packing into, under stirring state in 150 ℃ of crystallization 30 hours.After the taking-up after filtration, washing, drying.It is MCM-22 that X-ray diffractometer records the gained crystal.Get SiO through chemical analysis 2/ Al 2O 3Mol ratio is 18.7, and the degree of crystallinity of MCM-22 molecular sieve is 93%.
[embodiment 2]
With sodium metaaluminate (Al 2O 335.21 weight %, Na 2O31.12 weight %) 14.5 grams are dissolved in the 990 gram water, add sodium hydroxide 6.18 grams and make it dissolving, add organic amine template hexamethylene imine 49.5 grams then under condition of stirring, add silicon sol (SiO again 240 weight %) 150 grams are after waiting to stir, 80 ℃ of following ageings 120 hours.The material proportion of reactant (mol ratio) is:
SiO 2/Al 2O 3＝20
OH -/SiO 2＝0.3
R/SiO 2＝0.5
H 2O/SiO 2＝60
Stir after 30 minutes, in the stainless steel cauldron of packing into, under stirring state in 150 ℃ of crystallization 30 hours.After the taking-up after filtration, washing, drying.It is MCM-22 that X-ray diffractometer records the gained crystal.Get SiO through chemical analysis 2/ Al 2O 3Mol ratio is 19.3, and the degree of crystallinity of MCM-22 molecular sieve is 100%.
[embodiment 3]
With sodium metaaluminate (Al 2O 335.21 weight %, Na 2O31.12 weight %) 14.5 grams are dissolved in the 2970 gram water, add sodium hydroxide 18.18 grams and make it dissolving, add organic amine template hexamethylene imine 238 grams then under condition of stirring, add silicon sol (SiO again 240 weight %) 450.7 grams are after waiting to stir, 10 ℃ of following ageings 180 hours.The material proportion of reactant (mol ratio) is:
SiO 2/Al 2O 3＝60
OH -/SiO 2＝0.2
R/SiO 2＝0.8
H 2O/SiO 2＝60
Stir after 30 minutes, in the stainless steel cauldron of packing into, under stirring state in 150 ℃ of crystallization 50 hours.After the taking-up after filtration, washing, drying.It is MCM-22 that X-ray diffractometer records the gained crystal.Get SiO through chemical analysis 2/ Al 2O 3Mol ratio is 52, the degree of crystallinity 99.5% of MCM-22 molecular sieve.
[embodiment 4]
With sodium metaaluminate (Al 2O 335.21 weight %, Na 2O31.12 weight %) 14.5 grams are dissolved in the 3780 gram water, add sodium hydroxide 18.18 grams and make it dissolving, add organic amine template hexamethylene imine 297 grams then under condition of stirring, and MCM-22 molecular sieve crystal seed 2 grams add silicon sol (SiO again 240 weight %) 901 grams are after waiting to stir, 50 ℃ of following ageings 20 hours.The material proportion of reactant (mol ratio) is:
SiO 2/Al 2O 3＝120
OH -/SiO 2＝0.1
R/SiO 2＝0.5
H 2O/SiO 2＝60
Stir after 30 minutes, in the stainless steel cauldron of packing into, under stirring state in 150 ℃ of crystallization 30 hours.After the taking-up after filtration, washing, drying.It is MCM-22 that X-ray diffractometer records the gained crystal.Get SiO through chemical analysis 2/ Al 2O 3Mol ratio is 114.3, the degree of crystallinity 98.9% of MCM-22 molecular sieve.
[embodiment 5]
With sodium aluminate (Al 2O 335.21 weight %, Na 2O31.12 weight %) 14.5 grams are dissolved in the 4050 gram water, add sodium hydroxide 74.2 grams and make it dissolving, add organic amine template hexamethylene imine 99 grams then under condition of stirring, and MCM-22 molecular sieve crystal seed 1 gram adds silicon sol (SiO again 240 weight %) 750 grams are after waiting to stir, 60 ℃ of following ageings 60 hours.The material proportion of reactant (mol ratio) is:
SiO 2/Al 2O 3＝100
OH -/SiO 2＝0.4
R/SiO 2＝0.2
H 2O/SiO 2＝50
Stir after 30 minutes, in the stainless steel cauldron of packing into, under stirring state in 160 ℃ of crystallization 40 hours.After the taking-up after filtration, washing, drying.It is MCM-22 that X-ray diffractometer records the gained crystal.Get SiO through chemical analysis 2/ Al 2O 3Mol ratio is 89.7, the degree of crystallinity 99.3% of MCM-22 molecular sieve.
[embodiment 6]
With sodium metaaluminate (Al 2O 335.21 weight %, Na 2O31.12 weight %) 14.5 grams are dissolved in the 13700 gram water, add potassium hydroxide 43.38 grams and make it dissolving, add organic amine template hexamethylene imine 297 grams then under condition of stirring, and MCM-22 molecular sieve crystal seed 0.5 gram adds silicon sol (SiO again 240 weight %) 1127 grams are after waiting to stir, 70 ℃ of following ageings 100 hours.The material proportion of reactant (mol ratio) is:
SiO 2/Al 2O 3＝150
OH -/SiO 2＝0.35
R/SiO 2＝0.4
H 2O/SiO 2＝40
Stir after 30 minutes, in the stainless steel cauldron of packing into, under stirring state in 160 ℃ of crystallization 30 hours.After the taking-up after filtration, washing, drying.It is MCM-22 that X-ray diffractometer records the gained crystal.Get SiO through chemical analysis 2/ Al 2O 3Mol ratio is 138.7, the degree of crystallinity 100% of MCM-22 molecular sieve.
[embodiment 7～11]
The organic formwork agent that uses is respectively 1,4-phenodiazine suberane (A), Azacyclooctane (heptamethylene imines) (B), suberane amine (C), hexamethylene alkanamine (D), pentamethylene amine (E).The order of adding raw material and ageing treatment condition are with reference to the scheme of embodiment 1, and crystallization temperature and crystallization time and material proportion (mol ratio) are:
Embodiment 789 10 11
Template A B C D E
Crystallization temperature (℃) 143 150 160 150 160
Crystallization time (hour) 30 50 50 60 40
SiO 2/Al 2O 3 30 25 60 80 95
OH -/SiO 2 0.18 0.2 0.3 0.25 0.4
H 2O/SiO 2 20 30 50 60 45
R/SiO 2 0.35 0.35 0.35 0.40 0.45
MCM-22?SiO 2/Al 2O 3 28.6 21.7 48.6 53.7 72.8
MCM-22 molecular sieve crystallinity (%) 99.3 99.1 98.9 98.8 98.4
It is MCM-22 that products therefrom is carried out XRD determining.
[comparative example]
Sodium aluminate (Al 2O 343.5 weight %, Na 2O32.2 weight %) 12.86 grams are dissolved in the aqueous sodium hydroxide solution of 12.8 grams 50%, add 57.6 gram hexamethylene imines, add 109.4 gram precipitated silica (SiO in gained solution 290 weight %), the mol ratio of reaction mixture is:
SiO 2/Al 2O 3＝30
OH -/SiO 2＝0.18
R/SiO 2＝0.35
Na/SiO 2＝0.18
H 2O/SiO 2＝45
R is a hexamethylene imine.Mixture in 150 ℃ of following crystallization 30 hours, takes out part with product in the stainless steel crystallizing kettle, washing, and 110 ℃ of dryings, the XRD determining product is amorphous.Continue crystallization to 7 day, product is taken out, washing, 110 ℃ of dryings are MCM-22 through the XRD determining product, the MCM-22 molecular sieve crystallinity is 80.1%.

Claims (7)

1, a kind of synthetic method of MCM-22 molecular sieve is at first counted your ratio of silicon source, aluminium source, alkali, template and hydromassage: SiO 2/ Al 2O 3Be 10～200, OH -/ SiO 2Be 0.1～1.0, H 2O/SiO 2Be 5～200, R/SiO 2It is 0.05～1.0 mixed, wherein R is a template, be selected from pentamethylene imines, hexamethylene imine, heptamethylene imines, 1, at least a in 4-phenodiazine suberane, suberane amine, hexamethylene alkanamine or the pentamethylene amine, with this mixture is under 120～180 ℃ of conditions at crystallization temperature under agitation, crystallization time is to take out after 5～100 hours, through washing, drying makes the MCM-22 molecular sieve, it is characterized in that mixture is in ageing 0.5～720 hour under 0～100 ℃ of condition earlier before the crystallization.
2,, it is characterized in that in the mixture with molar ratio computing: SiO according to the synthetic method of the described MCM-22 molecular sieve of claim 1 2/ Al 2O 3Be 20～80, OH -/ SiO 2Be 0.10～0.5, H 2O/SiO 2Be 10～50, R/SiO 2Be 0.1～0.6.
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 synthetic method of the described MCM-22 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, aluminum oxide, kaolin or the polynite; Alkali is that mineral alkali is selected from least a in lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide or the cesium hydroxide.
4, according to the synthetic method of the described MCM-22 molecular sieve of claim 1, it is characterized in that crystallization temperature is 140～160 ℃, crystallization time is 20～60 hours.
5,, it is characterized in that in ageing under 10～80 ℃ of conditions earlier before the crystallization according to the synthetic method of the described MCM-22 molecular sieve of claim 1.
6,, it is characterized in that the aged time is 5～240 hours before crystallization according to the synthetic method of the described MCM-22 molecular sieve of claim 1.
7, according to the synthetic method of the described MCM-22 molecular sieve of claim 1, it is characterized in that before crystallization or in mixture, add MCM-22 molecular sieve crystal seed in the crystallization process that the crystal seed add-on is 0.1～10% of synthetic MCM-22 molecular sieve amount by weight percentage.
CN 02145234 2002-11-13 2002-11-13 Method for synthesizing MCM-22 molecular sieves Expired - Lifetime CN1207200C (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102311127A (en) * 2010-07-07 2012-01-11 中国石油化工股份有限公司 Method for preparing small-grain MCM-22 molecular sieve
CN105217646A (en) * 2014-07-03 2016-01-06 中国石油化工股份有限公司 The method of synthesizing Si-Al zeolite molecular sieve
CN105439166A (en) * 2014-08-27 2016-03-30 中国石油化工股份有限公司 A method of synthesizing a MWW-structure molecular sieve
CN106115728A (en) * 2016-06-24 2016-11-16 中国科学院上海高等研究院 A kind of method synthesizing MCM 22 molecular sieve

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102311127A (en) * 2010-07-07 2012-01-11 中国石油化工股份有限公司 Method for preparing small-grain MCM-22 molecular sieve
CN102311127B (en) * 2010-07-07 2013-06-19 中国石油化工股份有限公司 Method for preparing small-grain MCM-22 molecular sieve
CN105217646A (en) * 2014-07-03 2016-01-06 中国石油化工股份有限公司 The method of synthesizing Si-Al zeolite molecular sieve
CN105217646B (en) * 2014-07-03 2017-06-20 中国石油化工股份有限公司 The method of synthesizing Si-Al zeolite molecular sieve
CN105439166A (en) * 2014-08-27 2016-03-30 中国石油化工股份有限公司 A method of synthesizing a MWW-structure molecular sieve
CN105439166B (en) * 2014-08-27 2018-06-08 中国石油化工股份有限公司 The method for synthesizing MWW structure molecular screens
CN106115728A (en) * 2016-06-24 2016-11-16 中国科学院上海高等研究院 A kind of method synthesizing MCM 22 molecular sieve

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