CN105314651B - A kind of preparation method of small crystal grain NaY molecular sieve - Google Patents
A kind of preparation method of small crystal grain NaY molecular sieve Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of small crystal grain Y-shaped molecular sieve.This method, as additive, prepares small crystal grain NaY molecular sieve, specific step is using hexa using crystallization method is segmented：Silicon source is mixed with silicon source, directed agents are made when static aging 2~72 is small at 5~60 DEG C；Then silicon source, directed agents, silicon source, hexa are mixed into plastic, the molar ratio of each component is 0.5~10Na in reaction mixture gel2O∶1Al2O3: 5~40SiO2: 80~800H2O: 0.5~10C6H12N4；Then it is divided to two sections of static crystallizations at different temperatures, first segment crystallization temperature is 60~85 DEG C, and when crystallization 12~48 is small, second segment crystallization temperature is 90~120 DEG C, when crystallization 12~72 is small；Last filtered, washing, dry, obtained small crystal grain NaY molecular sieve.Gained composite molecular screen relative crystallinity is more than 85%, and crystallite dimension is in 400~600nm.The preparation method raw material is easy to get, manufacturing cost is low, has good prospects for commercial application.
Description
Technical field
The invention belongs to molecular screen material and its preparation field, and in particular to one kind using hexa as disperse
Agent, the method for preparing small crystal grain NaY molecular sieve by being segmented crystallization.
Technical background
Y type molecular sieve is the main active component of a variety of petrochemical catalysts, its pore structure, acidity and stability are to influence
An important factor for catalytic performance and product are distributed.In recent years, petroleum refining industry generally faces the problem of feedstock oil heaviness, therefore
Improve the accessibility in oil refining catalyst activated centre, improve it and macromolecular cracking capability is particularly important.With molecule
Sieve materials synthesis new process is continually developed, and little crystal grain or the molecular sieve with nanoscale become novel petroleum chemical catalysis material
Expect the emphasis of research and development.Small-grain Y molecular sieve, is significantly increased since granularity reduces the active sites that can expose surface,
Outer surface activated centre number is more, and then improves catalytic activity, effectively reduces reaction depth and coking rate；On the other hand,
Granularity, which reduces, makes it have more ducts identical with the external world, is easy to the diffusion of reactant and product, reduces diffusional resistance.
Thus, for traditional Y type molecular sieve, small-grain Y molecular sieve has more superior catalytic performance.
At present, the particle diameter of the Y type molecular sieve synthesized with conventional method is at 1 μm or so, by adding organic dispersing agent or tune
The small crystal grain NaY molecular sieve that particle diameter is less than 1 μm can be made by becoming process conditions.US3755538 is improved by increasing directed agents dosage
The basicity of plastic system, synthesis has obtained the NaY molecular sieve that crystal grain diameter is 60nm, but the framework si-al ratio decline of molecular sieve is bright
It is aobvious.CN1046488C is using the aluminum salt solution of acidifying as silicon source, by the use of the silicon of directed agents as whole silicon sources in synthetic system,
Synthesis obtains Y type molecular sieve of the grain size in the range of 100-500nm under conventional crystallization condition, and silica alumina ratio is more than 5.0,
And with preferable heat and hydrothermal stability.
Shen double-edged sword etc. (CN100443407C, CN100404418C) is proposed by first dynamic crystallization, the side of rear static crystallization
Method prepares high silicon aluminium ratio small crystal NaY molecular sieve, and gained molecular sieve crystallinity is more than 80%, and has good stable structure
Property and catalytic activity.
At present, the preparation research for small crystal grain NaY molecular sieve is only limitted to from charge ratio and preparation process both direction,
System research is lacked to the material phase and deployment conditions of molecular sieve plastic process；Meanwhile the dispersant system added in synthesis
Standby complex process, production cost are high, cause that small crystal grain molecular sieve combined coefficient is low, production cost is high.
The content of the invention
Based on this, the purpose of the present invention is overcome the deficiencies of the prior art and provide a kind of preparation of small crystal grain NaY molecular sieve
Method, this method is used as organic additive by adding cheap and easy to get and less toxic free of contamination hexa, using it to silicon
The peptizaiton of aluminium species, by being segmented crystallization in different temperatures section, has obtained the homogeneous fine grain NaY molecule of crystallite dimension
Sieve, realizes the controlledly synthesis to Y molecular sieve different-grain diameter.
A kind of preparation method of small crystal grain NaY molecular sieve, concrete technology step include：
(1) preparation of directed agents
At 5~60 DEG C, silicon source, silicon source are mixed, each material mole adding proportion is 3~45Na2O：Al2O3∶ 5
~80SiO2: 100~800H2O, is made when static aging 2~72 is small at 5 DEG C~60 DEG C after stirring completely；
(2) plastic
Directed agents are mixed at 20~60 DEG C and are mixed with silicon source, then silicon source is added and hexa is prepared
Gel, each material mole adding proportion are：0.5~10Na2O：Al2O3: 5~40SiO2: 80~800H2O：0.5~
10C6H12N4, it is sufficiently stirred, when mixing time is 0.5~6 small；
(3) crystallization
Above-mentioned colloidal sol is transferred in reaction kettle, is warming up to 60~85 DEG C of progress first segment crystallization, static crystallization, during crystallization
Between 6~36 it is small when；Then it is rapidly heated small for 12~72 to 90~120 DEG C of progress second segment crystallization, static crystallization, crystallization time
When；Product filtering, washing, drying after above-mentioned crystallization are obtained into small crystal grain NaY molecular sieve；
Wherein, the silicon source is the one or more in silica gel, Ludox, sodium metasilicate, white carbon and waterglass；The aluminium
Source is the one or more in aluminium oxide, aluminium hydroxide, aluminum sulfate and Aluminum sol；The alkali is sodium hydroxide.
According to preparation method of the present invention, its preferred solution is characterized in that：
Processing step includes：
(1) preparation of directed agents
At 15~50 DEG C, silicon source, silicon source are mixed, each material mole adding proportion is 5~20Na2O： Al2O3∶
10~50SiO2: 200~500H2O, is made when static aging 12~48 is small at 15 DEG C~50 DEG C after stirring completely；
(2) plastic
Directed agents are mixed at 20~50 DEG C and are mixed with silicon source, then silicon source is added and hexa is prepared
Gel, each material mole adding proportion are：2~8Na2O：Al2O3: 10~35SiO2: 150~500H2O：2~8C6H12N4, fill
Divide stirring, when mixing time is 2~4 small；
(3) crystallization
Above-mentioned colloidal sol is transferred in reaction kettle, is warming up to 65~80 DEG C of progress first segment crystallization, static crystallization, during crystallization
Between 10~24 it is small when；It is 16~36 to be then rapidly heated to 95~110 DEG C of progress second segment crystallization, static crystallization, crystallization time
Hour；Product filtering, washing, drying after above-mentioned crystallization are obtained into small crystal grain NaY molecular sieve.
Compared with prior art, the present invention its innovative point and advantage are：
1. the hexa that synthetic method provided by the invention is added, cheap and easy to get, non-volatility, to environment and
Body harm is small, reduces the discharge of production cost and organic pollution.
2. segmentation crystallization method used by synthetic method provided by the invention, improves the utilization rate and product of reactant
Yield, reduces production cost.
3. the small crystal grain NaY molecular sieve crystallinity of synthetic method provided by the invention synthesis is high, crystallite dimension 400~
600nm, particle size are homogeneous.
Brief description of the drawings
Fig. 1 is X-ray diffraction (XRD) spectrogram of gained molecular sieve in the embodiment of the present invention 1.
Fig. 2 is the surface sweeping electromicroscopic photograph (SEM) of gained molecular sieve in the embodiment of the present invention 1.
Fig. 3 is X-ray diffraction (XRD) spectrogram of gained molecular sieve in the embodiment of the present invention 2.
Fig. 4 is the surface sweeping electromicroscopic photograph (SEM) of gained molecular sieve in the embodiment of the present invention 2.
Fig. 5 is the surface sweeping electromicroscopic photograph (SEM) of gained molecular sieve in comparative example of the present invention.
Embodiment
The present invention is further described with comparative example by the following examples, but it is not thereby limiting the invention
Can practical range.
In embodiments, XRD characterization is carried out to synthetic product and calculates the framework si-al ratio of each sample and opposite crystallization
Degree, wherein, framework si-al ratio (SiO2/Al2O3) it is the brilliant bag parameter a that molecular sieve is determined according to RIPP145-90 standard methods0
Afterwards according to formula S iO2/Al2O3Molar ratio=(2.5935-a0)/(a0- 2.4212) × 2 it is calculated；On the south relative crystallinity is
The NaY molecular sieve for opening university is calculated for standard specimen.
Embodiment 1：
At 80 DEG C, by 8.8g sodium metaaluminates (Al2O3Content is 41wt%, Na2O content is 28.7%) to be dissolved in 60g to go
In ionized water, 42g sodium hydroxides (purity 96%) are added under mechanical agitation, continues to stir, is completely dissolved it, obtain high alkalinity
Sodium aluminate solution.Under stirring, above-mentioned high alkalinity sodium aluminate solution is added to 204g waterglass (SiO2Content is
26.2wt%, Na2O content be 8.3%) in, continue after mixing stirring 2 it is small when, then at 15 DEG C stand aging 24 it is small
When, directed agents are made.
At 80 DEG C, 10.8g sodium metaaluminates are dissolved in 72g deionized waters, 36g hydroxides are added under mechanical agitation
Sodium, continues to stir, is completely dissolved it, obtains low alkalinity sodium aluminate solution.Under stirring, 20 DEG C of gelling temperature will
The directed agents being prepared are poured into 486g waterglass, are uniformly mixed, and then add 235g aluminum sulfate solutions (Al2O3Content
90g/L), above-mentioned gained low alkalinity sodium aluminate solution and 6.5g hexas, stirring 1 it is small when after, gained sial is coagulated
Mucilage binding enters in the stainless steel crystallizing kettle with polytetrafluoro liner, 70 DEG C of crystallization is warming up to, when crystallization 24 is small；Then it is warming up to 100
DEG C, when crystallization 48 is small, filtered, washing, in 110 DEG C of drying, obtains solid sample S1.Products therefrom is subjected to XRD characterization analysis,
It is Y type molecular sieve to show product, its framework si-al ratio is 5.57, relative crystallinity 96%.
Embodiment 2：
Each raw material sources are the same as embodiment 1.
At 80 DEG C, 15g sodium metaaluminates are dissolved in 35g deionized waters, 52g sodium hydroxides are added under mechanical agitation,
Continue to stir, be completely dissolved it, obtain high alkalinity sodium aluminate solution.Under stirring, by above-mentioned high alkalinity meta-aluminic acid
Sodium solution is added in 52g waterglass, continue after mixing stirring 2 it is small when, then at 20 DEG C stand aging 36 it is small when, system
Obtain directed agents.
At 80 DEG C, 9.3g sodium metaaluminates are dissolved in 60g deionized waters, 18g sodium hydroxides are added under mechanical agitation,
Continue to stir, be completely dissolved it, obtain low alkalinity sodium aluminate solution.Under stirring, 30 DEG C of gelling temperature, will prepare
Obtained directed agents are poured into 412g waterglass, are uniformly mixed, and then add 216g aluminum sulfate solutions, above-mentioned gained low alkalinity
Sodium aluminate solution and 7.2g hexas, when stirring 1 is small after, gained silica-alumina gel is loaded with polytetrafluoro liner
In stainless steel crystallizing kettle, 80 DEG C of crystallization are warming up to, when crystallization 12 is small；Then it is warming up to 95 DEG C, when crystallization 48 is small, it is filtered, wash
Wash, in 110 DEG C of drying, obtain solid sample S2.Products therefrom is subjected to XRD characterization analysis, it is Y type molecular sieve to show product, its
Framework si-al ratio is 5.73, relative crystallinity 92%.
Embodiment 3：
Each raw material sources are the same as embodiment 1.
At 80 DEG C, 21g sodium metaaluminates are dissolved in 25g deionized waters, 26g sodium hydroxides are added under mechanical agitation,
Continue to stir, be completely dissolved it, obtain high alkalinity sodium aluminate solution.Under stirring, by above-mentioned high alkalinity meta-aluminic acid
Sodium solution is added in 188g waterglass, continue after mixing stirring 2 it is small when, then at 5 DEG C stand aging 60 it is small when, system
Obtain directed agents.
At 80 DEG C, 5.8g sodium metaaluminates are dissolved in 56g deionized waters, 40g sodium hydroxides are added under mechanical agitation,
Continue to stir, be completely dissolved it, obtain low alkalinity sodium aluminate solution.Under stirring, 40 DEG C of gelling temperature, will prepare
Obtained directed agents are poured into 404g waterglass, are uniformly mixed, and then add 195g aluminum sulfate solutions, above-mentioned gained low alkalinity
Sodium aluminate solution and 8.8g hexas, when stirring 1 is small after, gained silica-alumina gel is loaded with polytetrafluoro liner
In stainless steel crystallizing kettle, 60 DEG C of crystallization are warming up to, when crystallization 48 is small；Then it is warming up to 120 DEG C, when crystallization 12 is small, it is filtered, wash
Wash, in 110 DEG C of drying, obtain solid sample S3.Products therefrom is subjected to XRD characterization analysis, it is Y type molecular sieve to show product, its
Framework si-al ratio is 5.67, relative crystallinity 91%.
Embodiment 4：
Each raw material sources are the same as embodiment 1.
At 80 DEG C, 7.5g sodium metaaluminates are dissolved in 88g deionized waters, 74g sodium hydroxides are added under mechanical agitation,
Continue to stir, be completely dissolved it, obtain high alkalinity sodium aluminate solution.Under stirring, by above-mentioned high alkalinity meta-aluminic acid
Sodium solution is added in 268g waterglass, continue after mixing stirring 2 it is small when, then at 45 DEG C stand aging 24 it is small when,
Directed agents are made.
At 80 DEG C, 7.3g sodium metaaluminates are dissolved in 78g deionized waters, 48g sodium hydroxides are added under mechanical agitation,
Continue to stir, be completely dissolved it, obtain low alkalinity sodium aluminate solution.Under stirring, 50 DEG C of gelling temperature, will prepare
Obtained directed agents are poured into 452g waterglass, are uniformly mixed, and then add 235g aluminum sulfate solutions, above-mentioned gained low alkalinity
Sodium aluminate solution and 6.6g hexas, when stirring 1 is small after, gained silica-alumina gel is loaded with polytetrafluoro liner
In stainless steel crystallizing kettle, 85 DEG C of crystallization are warming up to, when crystallization 36 is small；Then it is warming up to 110 DEG C, when crystallization 12 is small, it is filtered, wash
Wash, in 110 DEG C of drying, obtain solid sample 4.Products therefrom is subjected to XRD characterization analysis, shows that product is Y type molecular sieve, its bone
Frame silica alumina ratio is 5.81, relative crystallinity 93%.
Embodiment 5：
Each raw material sources are the same as embodiment 1.
At 80 DEG C, 15g sodium metaaluminates are dissolved in 83g deionized waters, 47g sodium hydroxides are added under mechanical agitation,
Continue to stir, be completely dissolved it, obtain high alkalinity sodium aluminate solution.Under stirring, by above-mentioned high alkalinity meta-aluminic acid
Sodium solution is added in 211g waterglass, continue after mixing stirring 2 it is small when, then at 60 DEG C stand aging 12 it is small when,
Directed agents are made.
At 80 DEG C, 6.8g sodium metaaluminates are dissolved in 55g deionized waters, 38g sodium hydroxides are added under mechanical agitation,
Continue to stir, be completely dissolved it, obtain low alkalinity sodium aluminate solution.Under stirring, 25 DEG C of gelling temperature, will prepare
Obtained directed agents are poured into 425g waterglass, are uniformly mixed, and then add 188g aluminum sulfate solutions, above-mentioned gained low alkalinity
Sodium aluminate solution and 8.2g hexas, when stirring 1 is small after, gained silica-alumina gel is loaded with polytetrafluoro liner
In stainless steel crystallizing kettle, 80 DEG C of crystallization are warming up to, when crystallization 12 is small；Then it is warming up to 90 DEG C, when crystallization 72 is small, it is filtered, wash
Wash, in 110 DEG C of drying, obtain solid sample S5.Products therefrom is subjected to XRD characterization analysis, it is Y type molecular sieve to show product, its
Framework si-al ratio is 5.62, relative crystallinity 95%.
Embodiment 6：
Each raw material sources are the same as embodiment 1.
At 80 DEG C, 8.2g sodium metaaluminates are dissolved in 77g deionized waters, 65g sodium hydroxides are added under mechanical agitation,
Continue to stir, be completely dissolved it, obtain high alkalinity sodium aluminate solution.Under stirring, by above-mentioned high alkalinity meta-aluminic acid
Sodium solution is added in 240g waterglass, continue after mixing stirring 2 it is small when, then at 25 DEG C stand aging 72 it is small when,
Directed agents are made.
At 80 DEG C, 7.9g sodium metaaluminates are dissolved in 78g deionized waters, 51g sodium hydroxides are added under mechanical agitation,
Continue to stir, be completely dissolved it, obtain low alkalinity sodium aluminate solution.Under stirring, 35 DEG C of gelling temperature, will prepare
Obtained directed agents are poured into 436g waterglass, are uniformly mixed, and then add 205g aluminum sulfate solutions, above-mentioned gained low alkalinity
Sodium aluminate solution and 6.4g hexas, when stirring 1 is small after, gained silica-alumina gel is loaded with polytetrafluoro liner
In stainless steel crystallizing kettle, 70 DEG C of crystallization are warming up to, when crystallization 30 is small；Then it is warming up to 100 DEG C, when crystallization 36 is small, it is filtered, wash
Wash, in 110 DEG C of drying, obtain solid sample S6.Products therefrom is subjected to XRD characterization analysis, it is Y type molecular sieve to show product, its
Framework si-al ratio is 5.77, relative crystallinity 90%.
Comparative example：
NaY molecular sieve is prepared using conventional method, each raw material sources are the same as embodiment 1.
At 80 DEG C, 6.8g sodium metaaluminates are dissolved in 55g deionized waters, 45g sodium hydroxides are added under mechanical agitation,
Continue to stir, be completely dissolved it, obtain high alkalinity sodium aluminate solution.Under stirring, by above-mentioned high alkalinity meta-aluminic acid
Sodium solution is added in 232g waterglass, continue after mixing stirring 2 it is small when, then at 25 DEG C stand aging 20 it is small when,
Directed agents are made.
At 80 DEG C, 11.8g sodium metaaluminates are dissolved in 80g deionized waters, 52g hydroxides are added under mechanical agitation
Sodium, continues to stir, is completely dissolved it, obtains low alkalinity sodium aluminate solution.Under stirring, 20 DEG C of gelling temperature will
The directed agents being prepared are poured into 419g waterglass, are uniformly mixed, and then add 201g aluminum sulfate solutions and above-mentioned gained
Low alkalinity sodium aluminate solution, stirring 1 it is small when after, by gained silica-alumina gel load with polytetrafluoro liner stainless steel crystallizing kettle
In, 100 DEG C of crystallization are warming up to, when crystallization 24 is small, filtered, washing, in 110 DEG C of drying, obtains solid sample D.By products therefrom
XRD characterization analysis is carried out, it is Y type molecular sieve to show product, its framework si-al ratio is 5.52, relative crystallinity 87%.
Table 1 is embodiment 1~6 and specific surface area, pore volume and the average diameter of particles result of comparative example gained sample.
Table 1
| Sample number into spectrum | Specific surface area (m2/g) | Pore volume (m3/g) | Mean particle size (nm) |
| 1 gained sample S1 of embodiment | 697 | 0.367 | 559 |
| 2 gained sample S2 of embodiment | 721 | 0.369 | 488 |
| 3 gained sample S3 of embodiment | 734 | 0.371 | 463 |
| 4 gained sample S4 of embodiment | 689 | 0.364 | 573 |
| 5 gained sample S5 of embodiment | 711 | 0.374 | 505 |
| 6 gained sample S6 of embodiment | 706 | 0.372 | 528 |
| Sample D obtained by comparative example | 659 | 0.358 | 867 |
Claims (2)
1. a kind of preparation method of small crystal grain Y-shaped molecular sieve, it is characterised in that by the use of hexa as auxiliary agent, use
Different temperatures is segmented the preparation process of crystallization, and the described method includes following processing step：
(1) prepared by directed agents：By silicon source, silicon source, alkali and water according to 3~45Na2O：1Al2O3：5~80SiO2：100~800H2O
Molar ratio mix mixing at 5~60 DEG C, be made when static aging 2~72 is small at 5~60 DEG C after stirring completely；
(2) directed agents are mixed at 20~60 DEG C and is mixed with silicon source, then added silicon source and hexa is prepared
Gel, makes each component in the gel be by the molar ratio of its oxide：0.5~10Na2O：1Al2O3：5~40SiO2：80
~800H2O：0.5~10C6H12N4, it is sufficiently stirred, when mixing time is 0.5~6 small；
(3) and then by the gel it is divided to two sections of crystallization at different temperatures, first segment crystallization hydrogel warms are brilliant to 60~85 DEG C
When change 12~48 is small, second segment crystallization is then carried out, by hydrogel warms to 90~120 DEG C, when crystallization 12~72 is small, is finally passed through
Filter, washing, dry obtained small crystal grain NaY molecular sieve；
Wherein, the silicon source is the one or more in silica gel, Ludox, sodium metasilicate, white carbon and waterglass；Source of aluminium is
One or more in aluminium oxide, aluminium hydroxide, aluminum sulfate and Aluminum sol；The alkali is sodium hydroxide.
2. preparation method described in accordance with the claim 1, it is characterised in that including：
(1) prepared by directed agents：By silicon source, silicon source, alkali and water according to 5~20Na2O：1Al2O3：10~50SiO2：200~500H2O
Molar ratio mixed at 15~50 DEG C, be made when static aging 12~48 is small at 15~50 DEG C after stirring completely；
(2) directed agents are mixed at 20~50 DEG C and is mixed with silicon source, then added silicon source and hexa is prepared
Gel, makes each component in the gel be by the molar ratio of its oxide：2~8Na2O：1Al2O3：10~35SiO2：150~
500H2O：2~8C6H12N4, it is sufficiently stirred, when mixing time is 2~4 small；
(3) and then by the gel it is divided to two sections of crystallization at different temperatures, first segment crystallization hydrogel warms are to 65~80 DEG C, crystallization 10
~24 it is small when, then carry out second segment crystallization, by hydrogel warms to 95~110 DEG C, when crystallization 16~36 is small, it is last it is filtered,
Washing, dry obtained small crystal grain NaY molecular sieve.
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| CN114684831B (en) * | 2020-12-31 | 2024-02-09 | 中海油天津化工研究设计院有限公司 | High silicon-aluminum ratio Y molecular sieve with high relative crystallinity and preparation method thereof |
| CN116062765A (en) * | 2021-10-29 | 2023-05-05 | 中国石油化工股份有限公司 | Preparation method of nano Y-type molecular sieve |
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| CN1785808A (en) * | 2004-12-09 | 2006-06-14 | 中国石油天然气股份有限公司 | Preparation method of high silicon aluminium ratio small crystal NaY molecular sieve |
| CN101767799A (en) * | 2008-12-31 | 2010-07-07 | 中国石油化工股份有限公司 | Method for synthesizing high-silicon small grain NaY molecular sieve |
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| CN102616807A (en) * | 2012-03-29 | 2012-08-01 | 北京化工大学 | Method for synthesizing Y type molecular sieve |
| CN104229822A (en) * | 2013-06-13 | 2014-12-24 | 天津神能科技有限公司 | Preparation method for small-crystal-grain Y molecular sieve with high specific surface area and high silicon-aluminium ratio |
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| CN1785808A (en) * | 2004-12-09 | 2006-06-14 | 中国石油天然气股份有限公司 | Preparation method of high silicon aluminium ratio small crystal NaY molecular sieve |
| CN101767799A (en) * | 2008-12-31 | 2010-07-07 | 中国石油化工股份有限公司 | Method for synthesizing high-silicon small grain NaY molecular sieve |
| CN102424399A (en) * | 2011-09-05 | 2012-04-25 | 中国科学院过程工程研究所 | Preparation process for aluminosilicophosphate molecular sieve |
| CN102616807A (en) * | 2012-03-29 | 2012-08-01 | 北京化工大学 | Method for synthesizing Y type molecular sieve |
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