CN102452659B - Preparation method of MCM-22 zeolite - Google Patents
Preparation method of MCM-22 zeolite Download PDFInfo
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- CN102452659B CN102452659B CN 201010514409 CN201010514409A CN102452659B CN 102452659 B CN102452659 B CN 102452659B CN 201010514409 CN201010514409 CN 201010514409 CN 201010514409 A CN201010514409 A CN 201010514409A CN 102452659 B CN102452659 B CN 102452659B
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Abstract
The invention discloses a preparation method of MCM-22 zeolite. The method which treats pretreated attapulgite as a silicon source concretely comprises the following steps: 1, carrying out high speed shear stirring on an attapulgite suspension, filtering, and crushing; 2, quenching the substance obtained in step 1 with a liquid inert gas; 3, carrying out high temperature roasting on the product obtained in step 2 to form an active silicon source; and 4, synthesizing the MCM-22 zeolite under routine hydrothermal conditions. The method allows the utilization range of an MCM-22 zeolite raw material to be enlarged, and the MCM-22 zeolite raw material has the advantages of wide source and low price, so the preparation cost of the MCM-22 zeolite is reduced.
Description
Technical field
The present invention relates to a kind of preparation method of MCM-22 zeolite, belong to the zeolite synthesis technical field, particularly synthesize the method for MCM-22 zeolite take attapulgite as the silicon source.
Background technology
Micro-pore zeolite MCM-22 has ten-ring and twelve-ring two overlaps independently pore canal system, and the MCM-22 zeolite also has higher thermostability, hydrothermal stability and suitable acidity simultaneously.Therefore, the MCM-22 zeolite demonstrates higher using value at aspects such as alkylation, aromizing and toluene disproportionations.
The MCM-22 zeolite has higher using value, but present synthesis condition is comparatively harsh, and cost is higher.For reducing synthetic cost, natural mineral resource with wide material sources, relative low price replaces traditional industrial chemicals synthetic zeolite, not only can efficiently utilize mineral wealth, improve the added value of natural mineral, but also be the important channel of widening zeolite Application Areas and its potential value of exploitation.
Attapulgite is the sticking stone ore thing of a kind of natural reserves crystalline hydrate zeopan large, that have distinct layer chain-like structure feature.Have higher silica content in the attapulgite, therefore, under certain conditions can be with the silicon source of attapulgite as zeolite synthesis through suitable treatment.
CN101618880A discloses take the method for attapulgite synthetic 4A zeolite, P type zeolite and square natrolite as the silicon source.Synthetic method comprises: high-temperature calcination attapulgite at first, then the attapulgite with the dipping by lye calcining must contain Na
2SiO
3Leach liquor, it is synthetic that hydrothermal crystallizing is carried out in the aluminium source of adding different ratios in the most backward alkaline leaching liquid, after filtration, washing and drying obtain respectively 4A zeolite, P type zeolite, sodalite.Yet, the activity of soaking gained silicon source by alkali is lower, compares with sodalite with 4A zeolite, P type zeolite, and the synthesis condition of MCM-22 zeolite is comparatively harsh, activity to the silicon source is had relatively high expectations, can not be for the synthesis of the MCM-22 zeolite with the described treatment process to attapulgite of the method.
CN101337681A disclose a kind of take attapulgite as raw material the method for synthetic X-type zeolite, this synthetic method comprises: high-temperature calcination attapulgite at first, the attapulgite after the acidification high temperature calcining then, the attapulgite after the alkali pickling must contain Na again
2SiO
3Leach liquor, add a certain proportion of aluminium source in the most backward leach liquor and carry out Hydrothermal Synthesis, after filtration, washing and dry X-type zeolite.The method has increased acidification step to the processing of attapulgite, is conducive to improve the purity of attapulgite, but treatment process is also more loaded down with trivial details, after acid treatment again alkali to soak the activity in the silicon source that obtains not high equally.With X-type zeolite facies ratio, the synthesis condition of MCM-22 zeolite is comparatively harsh, and the activity in silicon source is had relatively high expectations, can not be for the synthesis of the MCM-22 zeolite with the described treatment process to attapulgite of this patent.
Summary of the invention
In order to overcome the deficiencies in the prior art, the invention provides a kind of preparation method of cheaply MCM-22 zeolite.The inventive method is translated into the synthetic available high reactivity silicon of MCM-22 zeolite source by the pre-treatment to attapulgite, can be for the synthesis of the MCM-22 zeolite under conventional hydrothermal condition.
The preparation method of MCM-22 zeolite of the present invention comprises the steps:
(1) attapulgite is pulverized as small-particle, be mixed into suspension liquid with water, then use the high speed shear agitator to stir this suspension liquid, with the attapulgite suspension liquid filtering separation after the shear agitation, it is the following particles of 200 orders that the gained filter cake is pulverized;
(2) the filter cake particle of step (1) gained was dipped in the liquid inert gas chilling 1～60 minute, takes out also in 60～120 ℃ of lower oven dry 10～24 hours;
(3) product of step (2) gained was 450～700 ℃ of lower roastings 1～10 hour.
(4) with the product of step (3) gained as the silicon source, after aluminium source, alkali source, template and water mix, after 24～168 hours, after washing drying, obtain the MCM-22 zeolite 150～190 ℃ of lower hydro-thermal reactions.
Silica content is at least 90wt% in the attapulgite described in the step (1), and used water is preferably distilled water or deionized water.The solid content of described attapulgite suspension liquid is 5～60wt%.The stirring velocity that described high speed shear stirs is 1000～2000rpm, and shear time is 30～120 minutes.
Liquid inert gas described in the step (2) is liquid nitrogen, liquid argon or liquid helium, is preferably liquid nitrogen.The volumetric usage of described liquid inert gas at least can fully submergence step (1) gained the filter cake particle.
In the step of the present invention (4), raw material adds by following mole proportioning: SiO
2/ Al
2O
3Be 15～60, OH
-/ SiO
2Be 0.12～0.40, H
2O/SiO
2Be 20～45, R/SiO
2Be 0.3～0.8, wherein R is the template hexamethylene imine.
In the step of the present invention (4), the silicon source is the attapulgite of step (3) gained, the raw material of commonly using when aluminium source, template and alkali all adopt hydrothermal synthesis method to prepare the MCM-22 zeolite.The aluminium source is selected from one or more in sodium aluminate, aluminum nitrate, aluminum chloride, Tai-Ace S 150, aluminum oxide and aluminium hydroxide, boehmite and the pseudo-boehmite, preferred sodium aluminate.Alkali source is selected from alkali metal hydroxide, is preferably sodium hydroxide.
The present invention is by being dispersed in water the attapulgite small-particle, make moisture enter into as much as possible the various holes of attapulgite by wicking action, then by the high speed shear effect make the attapulgite particle tear as far as possible dispersion, particle size reduces as much as possible, pass through again very low temperature quenching means, make the expansion of condensing of water in the attapulgite hole, thereby attapulgite coacervate and brilliant Shu Fasheng are dissociated, then after the relatively lower temp roasting, attapulgite can be converted into the less high reactivity silicon source of particle, thereby for the synthesis of the MCM-22 zeolite.
Description of drawings
Fig. 1 is the X-ray diffraction figure line of the MCM-22 zeolite of embodiment 1 preparation, sees curve (1); The X-ray diffraction figure line of Comparative Examples 1 products therefrom is seen curve (2).
Fig. 2 is the scanning electron microscope image of the MCM-22 zeolite of embodiment 1 preparation.
Embodiment
Below by embodiment the inventive method is illustrated, embodiment is not the restriction to content of the present invention.
Silica content is that attapulgite small-particle and the distilled water of 95wt% is mixed into the suspension liquid that solid content is 10wt%, then use the high speed shear agitator of 2000rpm to stir this suspension liquid 30 minutes, with the attapulgite suspension liquid filtering separation after the shear agitation, it is the following particles of 200 orders that the gained filter cake is pulverized.
The mass ratio of above-mentioned wet granular according to 1: 4 is soaked in the liquid nitrogen, kept 5 minutes.Attapulgite after the taking-up quenching is in 60 ℃ of lower oven dry 24 hours, then 500 ℃ of lower roastings 10 hours.
Attapulgite after the above-mentioned processing is prepared initial colloidal sol: SiO as the silicon source by following molar ratio
2/ Al
2O
3=25, OH
-/ SiO
2=0.13, hexamethylene imine HMI/SiO
2=0.3, H
2O/SiO
2=28 proportioning mixes silicon source, sodium aluminate, sodium hydroxide, hexamethylene imine, water under the condition that constantly stirs.Afterwards said mixture is packed in the 100ml reactor in 155 ℃ of crystallizations 85 hours.
Above-mentioned product separation, washing, drying by XRD analysis, are turned out to be the MCM-22 zeolite, and the degree of crystallinity of MCM-22 is 95%.
Embodiment 2
Silica content is that attapulgite small-particle and the distilled water of 99wt% is mixed into the suspension liquid that solid content is 40wt%, then use the high speed shear agitator of 2000rpm to stir this suspension liquid 60 minutes, with the attapulgite suspension liquid filtering separation after the shear agitation, it is the following particles of 200 orders that the gained filter cake is pulverized.
Then the mass ratio of wet granular according to 1: 4 is soaked in the liquid argon, kept 5 minutes.Attapulgite after the taking-up quenching was in 60 ℃ of lower oven dry 24 hours.Then 600 ℃ of lower roastings 10 hours.
Attapulgite after the above-mentioned processing is as the silicon source, according to SiO
2/ Al
2O
3=30, OH
-/ SiO
2=0.16, HMI/SiO
2=0.25, H
2O/SiO
2=28 mole proportioning just silicon source, sodium aluminate, sodium hydroxide, hexamethylene imine, water mixes under the condition that constantly stirs.Afterwards said mixture is packed in the 100ml reactor in 170 ℃ of crystallizations 72 hours.
Product separation, washing, drying by XRD analysis, are turned out to be the MCM-22 zeolite, and the degree of crystallinity of MCM-22 is 98%.
Embodiment 3
Silica content is that attapulgite small-particle and the distilled water of 99wt% is mixed into the suspension liquid that solid content is 60wt%, then use the high speed shear agitator of 1000rpm to stir this suspension liquid 120 minutes, with the attapulgite suspension liquid filtering separation after the shear agitation, it is the following particles of 200 orders that the gained filter cake is pulverized.
Then with wet granular according to being soaked in the liquid nitrogen of 1: 4 mass ratio, kept 60 minutes.Attapulgite after the taking-up quenching is in 120 ℃ of lower oven dry 10 hours, then 700 ℃ of lower roastings 5 hours.
Attapulgite after the above-mentioned processing is as the silicon source, according to Al
2O
3/ SiO
2=35, OH
-/ SiO
2=0.20, mould silicon is than (HMI/SiO
2)=0.35, H
2O/SiO
2=28 molar ratio mixes silicon source, sodium aluminate, sodium hydroxide, hexamethylene imine, water under the condition that constantly stirs, be mixed with initial colloidal sol.Initial colloidal sol is packed in the reactor into airtight 185 ℃ of crystallization 65 hours that are heated to.
Above-mentioned product through XRD analysis, turns out to be the MCM-22 zeolite, degree of crystallinity 96% after separation, washing, drying.
Comparative Examples 1
The method that provides according to CN101337681A prepares the MCM-22 zeolite.Specific as follows: 600 ℃ of roasting attapulgites 2 hours, then used after the roasting of 10wt% salt acid soak attapulgite 1 hour, refilter afterwards washing until washings for neutral.Product after the washing is constantly stirred in the 5mol/L sodium hydroxide solution that is dissolved in 80 ℃, after 2 hours, filter the Na that obtains
2SiO
3Leach liquor.Take this leach liquor as the silicon source, for the synthesis of the MCM-22 zeolite.According to following condition SiO
2/ Al
2O
3=25, OH
-/ SiO
2=0.13, hexamethylene imine HMI/SiO
2=0.3, H
2O/SiO
2=28, add in right amount water, sodium hydroxide, sodium aluminate and hexamethylene imine and make whole system satisfy the aforementioned proportion relation.Reacting used crystallization time and temperature is respectively 155 ℃, 85 hours.
The XRD of products therefrom spectrum by analysis as can be known, is the mixture of multiple crystallisate by analysis, can not synthesize pure MCM-22 zeolite.
Claims (9)
1. the preparation method of a MCM-22 zeolite comprises the steps:
(1) attapulgite is pulverized as small-particle, be mixed into suspension liquid with water, then use the high speed shear agitator to stir this suspension liquid, with the attapulgite suspension liquid filtering separation after the shear agitation, it is the following particles of 200 orders that the gained filter cake is pulverized;
(2) the filter cake particle of step (1) gained was dipped in the liquid inert gas chilling 1～60 minute, takes out also in 60～120 ℃ of lower oven dry 10～24 hours;
(3) product of step (2) gained was 450～700 ℃ of lower roastings 1～10 hour;
(4) with the product of step (3) gained as the silicon source, after aluminium source, alkali source, template and water mix, after 24～168 hours, after washing drying, obtain the MCM-22 zeolite 150～190 ℃ of lower hydro-thermal reactions; In the step (4), raw material adds by following mole proportioning: SiO
2/ Al
2O
3Be 15～60, OH-/SiO
2Be 0.12～0.40, H
2O/SiO
2Be 20～45, R/SiO
2Be 0.3～0.8, wherein R is the template hexamethylene imine.
2. in accordance with the method for claim 1, it is characterized in that silica content is at least 90wt% in the described attapulgite of step (1).
3. in accordance with the method for claim 1, it is characterized in that the used water of step (1) is distilled water or deionized water.
4. the solid content that in accordance with the method for claim 1, it is characterized in that the described suspension liquid of step (1) is 5wt%～60wt%.
5. in accordance with the method for claim 1, it is characterized in that the stirring velocity that described high speed shear stirs is 1000～2000rpm, shear time is 30～120 minutes.
6. in accordance with the method for claim 1, it is characterized in that the liquid inert gas described in the step (2) is liquid nitrogen, liquid argon or liquid helium.
7. in accordance with the method for claim 1, it is characterized in that the volumetric usage of the liquid inert gas described in the step (2) can flood the filter cake particle of step (1) gained at least fully.
8. in accordance with the method for claim 1, it is characterized in that the aluminium source is selected from one or more in sodium aluminate, aluminum nitrate, aluminum chloride, Tai-Ace S 150, aluminum oxide and aluminium hydroxide, boehmite and the pseudo-boehmite in the step (4); Alkali source is selected from one or more in the alkali metal hydroxide.
9. in accordance with the method for claim 1, it is characterized in that in the step (4), the aluminium source is sodium aluminate, alkali source is sodium hydroxide.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1296913A (en) * | 1999-11-17 | 2001-05-30 | 中国石油化工集团公司 | Process for preparing molecular sieve (MCM-22) with special crystal structure |
| CN101337681A (en) * | 2008-08-15 | 2009-01-07 | 淮阴工学院 | Method for synthesizing X-shaped zeolite using attapulgite clay as raw material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1296913A (en) * | 1999-11-17 | 2001-05-30 | 中国石油化工集团公司 | Process for preparing molecular sieve (MCM-22) with special crystal structure |
| CN101337681A (en) * | 2008-08-15 | 2009-01-07 | 淮阴工学院 | Method for synthesizing X-shaped zeolite using attapulgite clay as raw material |
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