CN102659133A - Preparation method for P type zeolite molecular sieve with core-shell structure - Google Patents
Preparation method for P type zeolite molecular sieve with core-shell structure Download PDFInfo
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- CN102659133A CN102659133A CN2012101166912A CN201210116691A CN102659133A CN 102659133 A CN102659133 A CN 102659133A CN 2012101166912 A CN2012101166912 A CN 2012101166912A CN 201210116691 A CN201210116691 A CN 201210116691A CN 102659133 A CN102659133 A CN 102659133A
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Abstract
The invention discloses a method for synthesizing a P type zeolite molecular sieve with a core-shell structure. The method includes following steps of dissolving an aluminum source in sodium hydroxide solution; adding a silicon source in the mixture, and stirring and dispersing the mixture for a period of time under high magnetic force at room temperature; mixing the solution with the uniformly dispersed silicon source and the uniformly dispersed aluminum source to form glue at the room temperature; adding kanemite or kenyaite phyllosillicate as seed crystal; stirring and mixing the mixture uniformly under high magnetic force at the room temperature; transferring the mixture into a reaction crystallization kettle; performing crystallization reaction for 0.5-3 days at the temperature ranging from 80 DEG C to 130 DEG C; and obtaining a solid product after conventional suction filtration, washing and drying. The synthesizing method has the advantages that the P type zeolite molecular sieve is not used as the seed crystal, an inorganic laminated precursor which is wide in source, cheap in price and easy to obtain is directly used as the seed crystal and is directly synthesized into the P type zeolite molecular sieve with the core-shell structure, crystallinity and purity of the prepared product are high, the size and the shape of primary crystalline grains are controllable, cost is low, environmental pollution is also low, and industrial large-scale production is facilitated.
Description
Technical field
The present invention relates to the synthetic of zeolite molecular sieve, specifically a kind of P type synthesis method of zeolite molecular sieve with nucleocapsid structure.
Background technology
Micro porous molecular sieve has uniform pore passage structure, proper acidic and good hydrothermal stability, has caused extensive studies interest in industries such as chemical industry, petrochemical complex, gas delivery, washing and printing and dyeing.Mainly washing industry for the applied research of P type zeolite molecular sieve at present, as washing auxiliary detergent, P type zeolite has the calcium ions and magnesium ions switching performance better than 4A type zeolite.In addition; Owing to have smaller particles size (usually less than 1.0 microns), the speed of IX is also faster, has avoided that active substance combines with the rapid of metals ion in the washing process; Make soil removability lasting, and in use need not to add any anti-sludging agent.Therefore, P type zeolite is considered to ideal 4A zeolite substitute products.
Zeolite P type series can be cube configuration, also can be the synthetic zeolite phase that cubic configuration exists, but be not limited to these forms, " zeolite molecular sieve " of the visible Donald W Breck of the structure of zeolite and characteristic.Zeolite P class has following typical oxide compound general formula: M
2/nAl
2O
3(1.8-5.00) SiO
25H
2O.Current P type zeolite synthetic mainly realized through the hydro-thermal synthesis strategy.As having reported direct use natural mineral kaolin among the Chinese patent CN102107884 A, just can directly synthesize P type zeolite through adding silicon or aluminium as the silicon source.But this synthesis strategy needs long crystallization time, in addition because impurity existence in the natural mineral causes synthetic the finished product purity not high.Recently, in order to shorten crystallization time, Chinese patent CN101428815A report utilizes the novel method of the synthetic P type zeolite of microwave method; Shortened crystallization time greatly; Synthesized high-quality P type zeolite, but microwave method is unfavorable for industriallization, has limited its scale operation.Use P type zeolite can greatly shorten crystallization time, and improve the percent crystallinity of product, be current synthesis strategy (European patent EP-A-565364 and Chinese patent CN1321891C) the most commonly used as the promotor of nucleation.But synthetic particulate size is unfavorable for the diffusion and the exchange of calcium magnesium particle usually greater than 1.0 microns.
Summary of the invention
The object of the present invention is to provide a kind of P type synthesis method of zeolite molecular sieve with nucleocapsid structure; As crystal seed, carry out the P type zeolite molecular sieve that crystallization obtains having nucleocapsid structure with inorganic laminated silicate cement silicon sodium stone (Kanemite) or fibrous morphology crystals (Kenyaite) at a certain temperature.This method has that synthesis material is cheap and easy to get, production cost is low, output is high, technological operation is simple, advantages of environment protection.The synthetic P of institute zeolite of the present invention has nucleocapsid structure, the elementary nanocrystalline grain size of homogeneous and pattern is controlled, crystallization time short and percent crystallinity and purity advantages of higher.
The objective of the invention is to realize like this:
A kind of preparation method with P type zeolite molecular sieve of nucleocapsid structure, this method comprises following concrete steps:
(1) with deionized water, sodium hydroxide and aluminium source uniform mixing, the room temperature lower magnetic force is stirred to clear liquid, then the silicon source is joined the strong magnetic agitation of this solution for continuous 1～3 hour; Used molar ratio of material: SiO
2: Al
2O
3=1～10, Na
2O: SiO
2=0.18～0.5, H
2O: SiO
2=10～80;
(2) join in the above-mentioned mixing solutions as crystal seed with inorganic laminated presoma, at room temperature continue to stir 0.5～3 hour, then 80～130
oC crystallization 0.5～3 day;
(3) crystallization finishes the direct suction filtration separation of back solid product, water washing to approaching neutral, and 80
oC was dried 24 hours down, obtained having the P type zeolite molecular sieve of nucleocapsid structure; Wherein:
Described inorganic laminated presoma is water silicon sodium stone (Kanemite) or fibrous morphology crystals (Kenyaite), and the add-on of crystal seed is 0.1～10 % of reactant feed mixture total weight amount;
Described silicon source is selected from a kind of in WHITE CARBON BLACK (silica gel of being fuming), silicon sol solution, Qingdao silica gel, column chromatography silica gel, pulverous silica gel G or the water glass;
Described aluminium source is selected from a kind of in aluminum nitrate, sodium metaaluminate, aluminum chloride, Tai-Ace S 150, aluminum isopropylate, white lake or the pseudo-boehmite;
Described the inorganic laminated presoma of interpolation is as crystal seed before crystallization, and the crystal seed add-on is 0.1～10 % of raw mix gross weight (silica-alumina gel mixture total weight amount), preferred 0.5～8.0 %;
According to method disclosed by the invention, can add the kind of crystal seed and the pattern of nucleocapsid structure, silica alumina ratio, particle diameter and the crystal grain of amount, basicity, the water yield, silicon source and aluminium source, crystallization temperature and time adjusting P zeolite through regulating synthetic system.
Utilize its phase structure of X-ray diffraction technical Analysis, grain size and percent crystallinity, with its pattern of SEM scanning electron microscope observation and grain size.The present invention directly adopts wide material sources, cheap inorganic laminated presoma as crystal seed, through the modulation synthesis condition, and synthetic P type zeolite molecular sieve with nucleocapsid structure.This compound method obtains the nucleocapsid structure that P type zeolite has homogeneous, novel crystal morphology; Different fully with the grain morphology that conventional hydrothermal method is synthetic regular; Sample has unequigranular cube of 50～200 nm or erose crystal grain and the structure and morphology of 1～5 μ m nucleocapsid that formed by its accumulation; And exist abundant secondary to pile up the hole, have bigger surface-area (57.9 m
2/ g) and pore volume (0.19 ml/g).
P type synthesis method of zeolite molecular sieve with nucleocapsid structure of the present invention compared with prior art has following characteristics: do not use P type molecular sieve as crystal seed, use wide material sources, inorganic laminated presoma cheap and easy to get as crystal seed.The introducing of layered silicate crystal seed plays a part to make " template ", " directed agents ", has promoted the formation of P type zeolite molecular sieve; On the other hand; The adding of inorganic laminated presoma crystal seed; Reaction mixture can be helped a large amount of P zeolite nucleus and form rapidly from the gel state state that reaches capacity rapidly, shortened crystallization time greatly; The a large amount of nucleus that produce are grown fast and are formed elementary crystal grain, and elementary crystal grain is grown recuperation to having a P type zeolite of nucleocapsid structure through reunion.Because special nucleus shell structure that it possessed and abundant intergranular are piled up the hole, current synthetic P type zeolite not only can be used as the auxiliary agent of clean-out system, also can be used as good support of the catalyst, plays a significant role in fields such as catalysis, absorption and separation.
Description of drawings
Fig. 1 is the X-ray powder diffraction collection of illustrative plates of the synthetic P type zeolite molecular sieve with nucleocapsid structure that obtains of the present invention;
Fig. 2 is ESEM (SEM) figure of the synthetic P type zeolite molecular sieve with nucleocapsid structure that obtains of the present invention;
Fig. 3 is transmission electron microscope (TEM) figure of the synthetic P type zeolite molecular sieve with nucleocapsid structure that obtains of the present invention;
Fig. 4 is the N of the synthetic P type zeolite molecular sieve with nucleocapsid structure that obtains of the present invention
2The adsorption/desorption graphic representation.
Embodiment
Through embodiment the present invention is described further below, its purpose only is better to understand research contents of the present invention and unrestricted protection scope of the present invention.
Embodiment 1
6.3g NaOH joined contain 80 ml deionized waters, stir to clarify solution, 4.6 g sodium metaaluminates are joined in the above-mentioned solution, room temperature continues to be stirred to solid and all dissolves.The 13.8 g silica gel of being fuming is joined in the above-mentioned mixing solutions; Continued strong magnetic agitation 1 hour; Then 1.8 g stratum water silicon sodium stone layered silicates are joined in the reaction system as crystal seed, add continued and stirred 0.5 hour, at last mixture is put into the stainless steel crystallizing kettle of teflon lined; Airtight back crystallization 24 hours in 130 ℃ of baking ovens must solid product after conventional suction filtration, washing, drying.The mole of the initial colloidal sol of this mixture consists of: SiO
2: Al
2O
3=10, Na
2O: SiO
2=0.46, H
2O: SiO
2=18.
Solid product is a P type zeolite through x-ray analysis, and what finally obtain is the P type zeolite that 500 nm have nucleocapsid structure, and shell structure is that the elementary nanocrystal reunion growth of 50～100 nm forms X-ray diffraction, SEM, TEM and N
2Absorption representation result such as Fig. 1, Fig. 2, Fig. 3 and Fig. 4.
Except that replace the silica gel of being fuming among the embodiment 1 as the silicon source with column chromatography silica gel, other preparation condition is all identical with embodiment 1.
Solid product is the P type zeolite molecular sieve with nucleocapsid structure through X-ray and sem analysis.
Embodiment 3
Except that replace the silica gel of being fuming among the embodiment 1 as the silicon source with Qingdao silica gel, other preparation condition is all identical with embodiment 1.
Solid product is the P type zeolite molecular sieve with nucleocapsid structure through X-ray and sem analysis.
Claims (2)
1. preparation method with P type zeolite molecular sieve of nucleocapsid structure is characterized in that this method comprises following concrete steps:
(1) with deionized water, sodium hydroxide and aluminium source uniform mixing, the room temperature lower magnetic force is stirred to clear liquid, then the silicon source is joined the strong magnetic agitation of this solution for continuous 1～3 hour; The mole of its material consists of SiO
2: Al
2O
3=1～10; Na
2O: SiO
2=0.18～0.5, H
2O: SiO
2=10～80;
(2) join in the above-mentioned solution as crystal seed with inorganic laminated presoma, at room temperature continue to stir 0.5～3 hour, and then placed in the static still 80～130 ℃ of crystallizations 0.5～3 day;
(3) crystallization finishes the direct suction filtration separation after overcooling of back solid product, water washing is extremely neutral, dries 24 hours down, obtains having the P type zeolite molecular sieve of nucleocapsid structure for 80 ℃; Wherein:
Described inorganic laminated presoma is a layered silicate, and the add-on of crystal seed is 0.1～10 % of reactant feed mixture total weight amount;
Described silicon source is a kind of in WHITE CARBON BLACK, silicon sol solution, Qingdao silica gel, column chromatography silica gel, pulverous silica gel G or the water glass;
Described aluminium source is a kind of in aluminum nitrate, sodium metaaluminate, aluminum chloride, Tai-Ace S 150, aluminum isopropylate, white lake or the pseudo-boehmite.
2. the P type prepare zeolite method with nucleocapsid structure according to claim 1 is characterized in that layered silicate is water silicon sodium stone or fibrous morphology crystals.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103072990A (en) * | 2012-12-20 | 2013-05-01 | 华南理工大学 | Preparation method of two-dimensional layered-structure material kenyaite |
| CN103183358A (en) * | 2013-01-21 | 2013-07-03 | 华东师范大学 | Preparation method of ZSM-5 molecular sieve |
| CN103274427A (en) * | 2013-06-18 | 2013-09-04 | 北京北大先锋科技有限公司 | Preparation method for P-shaped molecular sieve |
| CN103787356A (en) * | 2014-01-24 | 2014-05-14 | 东南大学 | Preparation method for hierarchical pore P-type molecular sieve |
| CN104445263A (en) * | 2013-09-24 | 2015-03-25 | 中国石油化工股份有限公司 | SCM-3 molecular sieve and preparation method thereof |
| CN104591202A (en) * | 2013-11-04 | 2015-05-06 | 中国石油化工股份有限公司 | Hollow P type zeolite and preparation method thereof |
| CN105460954A (en) * | 2014-09-09 | 2016-04-06 | 中国石油化工股份有限公司 | Sn-SCM-3 zeolite molecular sieve and a preparation method therefor |
| CN106745058A (en) * | 2016-12-28 | 2017-05-31 | 河南大学 | A kind of microwave preparation of p-type molecular sieve |
| CN110485170A (en) * | 2019-08-28 | 2019-11-22 | 中国第一汽车股份有限公司 | A kind of leather surface layer slurry of anion polyurethane resin |
| CN111054433A (en) * | 2019-12-27 | 2020-04-24 | 辽宁师范大学 | Preparation method of beta zeolite molecular sieve catalyst for cyclohexanol dehydration |
| CN112812092A (en) * | 2021-01-08 | 2021-05-18 | 北华大学 | Secondary molecular sieve and application thereof |
| CN112850737A (en) * | 2021-02-07 | 2021-05-28 | 北京工业大学 | Synthesis method of clinoptilolite with disordered accumulation and flaky morphology |
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Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103072990A (en) * | 2012-12-20 | 2013-05-01 | 华南理工大学 | Preparation method of two-dimensional layered-structure material kenyaite |
| CN103183358A (en) * | 2013-01-21 | 2013-07-03 | 华东师范大学 | Preparation method of ZSM-5 molecular sieve |
| CN103274427A (en) * | 2013-06-18 | 2013-09-04 | 北京北大先锋科技有限公司 | Preparation method for P-shaped molecular sieve |
| CN104445263A (en) * | 2013-09-24 | 2015-03-25 | 中国石油化工股份有限公司 | SCM-3 molecular sieve and preparation method thereof |
| CN104445263B (en) * | 2013-09-24 | 2016-02-10 | 中国石油化工股份有限公司 | SCM-3 molecular sieve and preparation method thereof |
| CN104591202A (en) * | 2013-11-04 | 2015-05-06 | 中国石油化工股份有限公司 | Hollow P type zeolite and preparation method thereof |
| CN104591202B (en) * | 2013-11-04 | 2016-03-30 | 中国石油化工股份有限公司 | A kind of hollow P type zeolite and preparation method thereof |
| CN103787356A (en) * | 2014-01-24 | 2014-05-14 | 东南大学 | Preparation method for hierarchical pore P-type molecular sieve |
| CN105460954A (en) * | 2014-09-09 | 2016-04-06 | 中国石油化工股份有限公司 | Sn-SCM-3 zeolite molecular sieve and a preparation method therefor |
| CN106745058A (en) * | 2016-12-28 | 2017-05-31 | 河南大学 | A kind of microwave preparation of p-type molecular sieve |
| CN106745058B (en) * | 2016-12-28 | 2019-09-10 | 河南大学 | A kind of microwave preparation of p-zeolite |
| CN110485170A (en) * | 2019-08-28 | 2019-11-22 | 中国第一汽车股份有限公司 | A kind of leather surface layer slurry of anion polyurethane resin |
| CN111054433A (en) * | 2019-12-27 | 2020-04-24 | 辽宁师范大学 | Preparation method of beta zeolite molecular sieve catalyst for cyclohexanol dehydration |
| CN111054433B (en) * | 2019-12-27 | 2022-11-29 | 辽宁师范大学 | Preparation method of beta zeolite molecular sieve catalyst for cyclohexanol dehydration |
| CN112812092A (en) * | 2021-01-08 | 2021-05-18 | 北华大学 | Secondary molecular sieve and application thereof |
| CN112850737A (en) * | 2021-02-07 | 2021-05-28 | 北京工业大学 | Synthesis method of clinoptilolite with disordered accumulation and flaky morphology |
| CN112850737B (en) * | 2021-02-07 | 2022-09-09 | 北京工业大学 | Synthesis method of clinoptilolite with disordered accumulation and flaky morphology |
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Application publication date: 20120912 |