CN105314651A - Preparation method of small-crystal-particle NaY molecular sieve - Google Patents
Preparation method of small-crystal-particle NaY molecular sieve Download PDFInfo
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Abstract
The invention discloses a preparation method of a small-crystal-particle NaY molecular sieve. Hexamethylenetetramine is used as an additive, and the small-crystal-particle NaY molecular sieve is prepared in a segmental crystallization method. The method comprises the following steps: mixing a silicon source and an aluminum source, standing and aging for 2 to 72 hours at 5 to 60 DEG C to obtain a guide agent; then mixing the silicon source, the guide agent, the aluminum source and the hexamethylenetetramine to form cement, wherein in the reaction mixture gel, the molar ratio of Na2O, Al2O3, SiO2, H2O and C6H12N4 is (0.5-1):1:(5-40):(80-800):(0.5-10); static crystallizing in two segments under different temperatures, wherein the first-segment crystallization temperature is 60 to 85 DEG C, crystallizing for 12 to 48 hours, the second-segment crystallization temperature is 90 to 120 DEG C, and crystallizing for 12 to 72 hours; and finally filtering, washing and drying to obtain the small crystal-particle NaY molecular sieve. The relative crystallinity of the prepared composite molecular sieve is greater than 85 percent, and the size of a crystal size is 400nm to 600nm. The preparation method is easy for obtaining raw materials, low in preparation cost and good in industrial application prospect.
Description
Technical field
The invention belongs to molecular screen material and preparation field thereof, be specifically related to one and utilize vulkacit H as dispersion agent, prepared the method for small crystal grain NaY molecular sieve by segmentation crystallization.
Technical background
Y zeolite is the main active ingredient of multiple petrochemical catalyst, and its pore structure, acidity and stability are the important factors affecting catalytic performance and product slates.In recent years, petroleum refining industry generally faces a difficult problem for stock oil heaviness, therefore improves the accessibility in oil refining catalyst active centre, improves it and seems particularly important to macromole cracking capability.Along with continually developing of molecular screen material new synthetic process, little crystal grain or the molecular sieve with nanoscale become the emphasis of novel petroleum chemical catalytic material research and development.Small-grain Y molecular sieve, the active sites that surface can be made to expose due to granularity reduction significantly increases, and outside surface active centre number is many, and then improves catalytic activity, effectively reduces reaction depth and coking rate; On the other hand, granularity reduces to make it have the more duct identical with the external world, is easy to the diffusion of reactant and product, reduces diffusional resistance.Thus, for traditional Y zeolite, small-grain Y molecular sieve has more superior catalytic performance.
At present, with the particle diameter of Y zeolite of ordinary method synthesis at about 1 μm, can obtain by adding organic dispersing agent or modulation processing condition the small crystal grain NaY molecular sieve that particle diameter is less than 1 μm.US3755538 improves the basicity of plastic system by increasing directed agents consumption, synthesis obtains the NaY molecular sieve that crystal grain diameter is 60nm, but the framework si-al ratio of molecular sieve declines obviously.CN1046488C using the aluminum salt solution of acidifying as aluminium source, utilize the silicon of directed agents as the whole silicon sources in synthetic system, under conventional crystallization condition, synthesis obtains the Y zeolite of grain size within the scope of 100-500nm, and silica alumina ratio is greater than 5.0, and has heat and hydrothermal stability preferably.
(the CN100443407C such as Shen double-edged sword, CN100404418C) propose to prepare high silicon aluminium ratio small crystal NaY molecular sieve by the method for first dynamic crystallization, rear static crystallization, gained molecular sieve crystallinity is greater than 80%, and has good structural stability and catalytic activity.
At present, the preparation research for small crystal grain NaY molecular sieve is only limitted to from charge ratio and preparation technology's both direction, lacks systematic study to the material phase of molecular sieve plastic process and deployment conditions; Meanwhile, the dispersion agent complicated process of preparation of adding in synthesis, production cost are high, cause that small crystal grain molecular sieve combined coefficient is low, production cost is high.
Summary of the invention
Based on this, the object of the invention is to overcome the deficiencies in the prior art, a kind of preparation method of small crystal grain NaY molecular sieve is provided, the method is by adding the cheap and easy to get and free of contamination vulkacit H of low toxicity as organic additive, utilize it to the dissemination of sial species, by segmentation crystallization in differing temps section, obtain the small crystal grain NaY molecular sieve that grain-size is homogeneous, achieve the controlledly synthesis to Y molecular sieve different-grain diameter.
A preparation method for small crystal grain NaY molecular sieve, concrete technology step comprises:
(1) preparation of directed agents
At 5 ~ 60 DEG C, mixed in silicon source, aluminium source, each material mole adding proportion is 3 ~ 45Na
2o:Al
2o
3: 5 ~ 80SiO
2: 100 ~ 800H
2o, to stir completely at 5 DEG C ~ 60 DEG C static aging 2 ~ 72 hours and obtains;
(2) plastic
Directed agents mixing mixed with silicon source at 20 ~ 60 DEG C, then add aluminium source and vulkacit H prepares gel, each material mole adding proportion is: 0.5 ~ 10Na
2o:Al
2o
3: 5 ~ 40SiO
2: 80 ~ 800H
2o:0.5 ~ 10C
6h
12n
4, fully stir, churning time is 0.5 ~ 6 hour;
(3) crystallization
Above-mentioned colloidal sol is transferred in reactor, is warming up to 60 ~ 85 DEG C and carries out first paragraph crystallization, static crystallization, crystallization time 6 ~ 36 hours; Then be rapidly heated to 90 ~ 120 DEG C and carry out second segment crystallization, static crystallization, crystallization time is 12 ~ 72 hours; Above-mentioned crystallization after product filtration, washing, oven dry are obtained small crystal grain NaY molecular sieve;
Wherein, described silicon source is one or more in silica gel, silicon sol, water glass, white carbon black and water glass; Described aluminium source is one or more in aluminum oxide, aluminium hydroxide, Tai-Ace S 150 and Alumina gel; Described alkali is sodium hydroxide.
According to preparation method of the present invention, its preferred version is characterised in that:
Processing step comprises:
(1) preparation of directed agents
At 15 ~ 50 DEG C, mixed in silicon source, aluminium source, each material mole adding proportion is 5 ~ 20Na
2o:Al
2o
3: 10 ~ 50SiO
2: 200 ~ 500H
2o, to stir completely at 15 DEG C ~ 50 DEG C static aging 12 ~ 48 hours and obtains;
(2) plastic
Directed agents mixing mixed with silicon source at 20 ~ 50 DEG C, then add aluminium source and vulkacit H prepares gel, each material mole adding proportion is: 2 ~ 8Na
2o:Al
2o
3: 10 ~ 35SiO
2: 150 ~ 500H
2o:2 ~ 8C
6h
12n
4, fully stir, churning time is 2 ~ 4 hours;
(3) crystallization
Above-mentioned colloidal sol is transferred in reactor, is warming up to 65 ~ 80 DEG C and carries out first paragraph crystallization, static crystallization, crystallization time 10 ~ 24 hours; Then be rapidly heated to 95 ~ 110 DEG C and carry out second segment crystallization, static crystallization, crystallization time is 16 ~ 36 hours; Above-mentioned crystallization after product filtration, washing, oven dry are obtained small crystal grain NaY molecular sieve.
Compared with prior art, its innovative point and advantage are in the present invention:
1. the vulkacit H that adds of synthetic method provided by the invention, cheap and easy to get, non-volatility, to environment and body harm little, reduce the discharge of production cost and organic pollutant.
2. the segmentation crystallization method that adopts of synthetic method provided by the invention, improves utilization ratio and the product yield of reactant, reduces production cost.
3. the small crystal grain NaY molecular sieve degree of crystallinity of synthetic method synthesis provided by the invention is high, and grain-size is at 400 ~ 600nm, and particle size is homogeneous.
Accompanying drawing explanation
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
With comparative example, the present invention is further described by the following examples, but not thereby limiting the invention can practical range.
In embodiments, all XRD is carried out to synthetic product and characterize the framework si-al ratio and relative crystallinity that calculate each sample, wherein, framework si-al ratio (SiO
2/ Al
2o
3) be the brilliant bag parameter a determining molecular sieve according to RIPP145-90 standard method
0afterwards according to formula S iO
2/ Al
2o
3mol ratio=(2.5935-a
0)/(a
0-2.4212) × 2 calculate; Relative crystallinity is for standard specimen calculates with the NaY molecular sieve of Nankai University.
Embodiment 1:
At 80 DEG C, by 8.8g sodium metaaluminate (Al
2o
3content is 41wt%, Na
2o content is 28.7%) be dissolved in 60g deionized water, add 42g sodium hydroxide (purity 96%) under mechanical stirring, continue to stir, make it dissolve completely, obtain high alkalinity sodium aluminate solution.Under whipped state, above-mentioned high alkalinity sodium aluminate solution is joined 204g water glass (SiO
2content is 26.2wt%, Na
2o content is 8.3%) in, mix rear continuation stirring 2 hours, then at 15 DEG C, leave standstill aging 24 hours, obtained directed agents.
At 80 DEG C, 10.8g sodium metaaluminate is dissolved in 72g deionized water, under mechanical stirring, adds 36g sodium hydroxide, continue to stir, make it dissolve completely, obtain low alkalinity sodium aluminate solution.Under whipped state, gelling temperature 20 DEG C, is poured into the directed agents prepared in 486g water glass, mixes, and then adds 235g alum liquor (Al
2o
3content 90g/L), above-mentioned gained low alkalinity sodium aluminate solution and 6.5g vulkacit H, stir after 1 hour, gained silica-alumina gel loaded and has in the stainless steel crystallizing kettle of polytetrafluoro liner, be warming up to 70 DEG C of crystallization, crystallization 24 hours; Then be warming up to 100 DEG C, crystallization 48 hours, after filtration, wash, in 110 DEG C of oven dry, obtain solid sample S1.Products therefrom is carried out XRD phenetic analysis, and show that product is Y zeolite, its framework si-al ratio is 5.57, and relative crystallinity is 96%
Embodiment 2:
Each raw material sources are with embodiment 1.
At 80 DEG C, 15g sodium metaaluminate is dissolved in 35g deionized water, under mechanical stirring, adds 52g sodium hydroxide, continue to stir, make it dissolve completely, obtain high alkalinity sodium aluminate solution.Under whipped state, above-mentioned high alkalinity sodium aluminate solution is joined in 52g water glass, mix rear continuation stirring 2 hours, then at 20 DEG C, leave standstill aging 36 hours, obtained directed agents.
At 80 DEG C, 9.3g sodium metaaluminate is dissolved in 60g deionized water, under mechanical stirring, adds 18g sodium hydroxide, continue to stir, make it dissolve completely, obtain low alkalinity sodium aluminate solution.Under whipped state, gelling temperature 30 DEG C, the directed agents prepared is poured in 412g water glass, mix, then add 216g alum liquor, above-mentioned gained low alkalinity sodium aluminate solution and 7.2g vulkacit H, stir after 1 hour, gained silica-alumina gel is loaded and has in the stainless steel crystallizing kettle of polytetrafluoro liner, be warming up to 80 DEG C of crystallization, crystallization 12 hours; Then be warming up to 95 DEG C, crystallization 48 hours, after filtration, wash, in 110 DEG C of oven dry, obtain solid sample S2.Products therefrom is carried out XRD phenetic analysis, and show that product is Y zeolite, its framework si-al ratio is 5.73, and relative crystallinity is 92%.
Embodiment 3:
Each raw material sources are with embodiment 1.
At 80 DEG C, 21g sodium metaaluminate is dissolved in 25g deionized water, under mechanical stirring, adds 26g sodium hydroxide, continue to stir, make it dissolve completely, obtain high alkalinity sodium aluminate solution.Under whipped state, above-mentioned high alkalinity sodium aluminate solution is joined in 188g water glass, mix rear continuation stirring 2 hours, then at 5 DEG C, leave standstill aging 60 hours, obtained directed agents.
At 80 DEG C, 5.8g sodium metaaluminate is dissolved in 56g deionized water, under mechanical stirring, adds 40g sodium hydroxide, continue to stir, make it dissolve completely, obtain low alkalinity sodium aluminate solution.Under whipped state, gelling temperature 40 DEG C, the directed agents prepared is poured in 404g water glass, mix, then add 195g alum liquor, above-mentioned gained low alkalinity sodium aluminate solution and 8.8g vulkacit H, stir after 1 hour, gained silica-alumina gel is loaded and has in the stainless steel crystallizing kettle of polytetrafluoro liner, be warming up to 60 DEG C of crystallization, crystallization 48 hours; Then be warming up to 120 DEG C, crystallization 12 hours, after filtration, wash, in 110 DEG C of oven dry, obtain solid sample S3.Products therefrom is carried out XRD phenetic analysis, and show that product is Y zeolite, its framework si-al ratio is 5.67, and relative crystallinity is 91%.
Embodiment 4:
Each raw material sources are with embodiment 1.
At 80 DEG C, 7.5g sodium metaaluminate is dissolved in 88g deionized water, under mechanical stirring, adds 74g sodium hydroxide, continue to stir, make it dissolve completely, obtain high alkalinity sodium aluminate solution.Under whipped state, above-mentioned high alkalinity sodium aluminate solution is joined in 268g water glass, mix rear continuation stirring 2 hours, then at 45 DEG C, leave standstill aging 24 hours, obtained directed agents.
At 80 DEG C, 7.3g sodium metaaluminate is dissolved in 78g deionized water, under mechanical stirring, adds 48g sodium hydroxide, continue to stir, make it dissolve completely, obtain low alkalinity sodium aluminate solution.Under whipped state, gelling temperature 50 DEG C, the directed agents prepared is poured in 452g water glass, mix, then add 235g alum liquor, above-mentioned gained low alkalinity sodium aluminate solution and 6.6g vulkacit H, stir after 1 hour, gained silica-alumina gel is loaded and has in the stainless steel crystallizing kettle of polytetrafluoro liner, be warming up to 85 DEG C of crystallization, crystallization 36 hours; Then be warming up to 110 DEG C, crystallization 12 hours, after filtration, wash, in 110 DEG C of oven dry, obtain solid sample 4.Products therefrom is carried out XRD phenetic analysis, and show that product is Y zeolite, its framework si-al ratio is 5.81, and relative crystallinity is 93%.
Embodiment 5:
Each raw material sources are with embodiment 1.
At 80 DEG C, 15g sodium metaaluminate is dissolved in 83g deionized water, under mechanical stirring, adds 47g sodium hydroxide, continue to stir, make it dissolve completely, obtain high alkalinity sodium aluminate solution.Under whipped state, above-mentioned high alkalinity sodium aluminate solution is joined in 211g water glass, mix rear continuation stirring 2 hours, then at 60 DEG C, leave standstill aging 12 hours, obtained directed agents.
At 80 DEG C, 6.8g sodium metaaluminate is dissolved in 55g deionized water, under mechanical stirring, adds 38g sodium hydroxide, continue to stir, make it dissolve completely, obtain low alkalinity sodium aluminate solution.Under whipped state, gelling temperature 25 DEG C, the directed agents prepared is poured in 425g water glass, mix, then add 188g alum liquor, above-mentioned gained low alkalinity sodium aluminate solution and 8.2g vulkacit H, stir after 1 hour, gained silica-alumina gel is loaded and has in the stainless steel crystallizing kettle of polytetrafluoro liner, be warming up to 80 DEG C of crystallization, crystallization 12 hours; Then be warming up to 90 DEG C, crystallization 72 hours, after filtration, wash, in 110 DEG C of oven dry, obtain solid sample S5.Products therefrom is carried out XRD phenetic analysis, and show that product is Y zeolite, its framework si-al ratio is 5.62, and relative crystallinity is 95%.
Embodiment 6:
Each raw material sources are with embodiment 1.
At 80 DEG C, 8.2g sodium metaaluminate is dissolved in 77g deionized water, under mechanical stirring, adds 65g sodium hydroxide, continue to stir, make it dissolve completely, obtain high alkalinity sodium aluminate solution.Under whipped state, above-mentioned high alkalinity sodium aluminate solution is joined in 240g water glass, mix rear continuation stirring 2 hours, then at 25 DEG C, leave standstill aging 72 hours, obtained directed agents.
At 80 DEG C, 7.9g sodium metaaluminate is dissolved in 78g deionized water, under mechanical stirring, adds 51g sodium hydroxide, continue to stir, make it dissolve completely, obtain low alkalinity sodium aluminate solution.Under whipped state, gelling temperature 35 DEG C, the directed agents prepared is poured in 436g water glass, mix, then add 205g alum liquor, above-mentioned gained low alkalinity sodium aluminate solution and 6.4g vulkacit H, stir after 1 hour, gained silica-alumina gel is loaded and has in the stainless steel crystallizing kettle of polytetrafluoro liner, be warming up to 70 DEG C of crystallization, crystallization 30 hours; Then be warming up to 100 DEG C, crystallization 36 hours, after filtration, wash, in 110 DEG C of oven dry, obtain solid sample S6.Products therefrom is carried out XRD phenetic analysis, and show that product is Y zeolite, its framework si-al ratio is 5.77, and relative crystallinity is 90%.
Comparative example:
Adopt ordinary method to prepare NaY molecular sieve, each raw material sources are with embodiment 1.
At 80 DEG C, 6.8g sodium metaaluminate is dissolved in 55g deionized water, under mechanical stirring, adds 45g sodium hydroxide, continue to stir, make it dissolve completely, obtain high alkalinity sodium aluminate solution.Under whipped state, above-mentioned high alkalinity sodium aluminate solution is joined in 232g water glass, mix rear continuation stirring 2 hours, then at 25 DEG C, leave standstill aging 20 hours, obtained directed agents.
At 80 DEG C, 11.8g sodium metaaluminate is dissolved in 80g deionized water, under mechanical stirring, adds 52g sodium hydroxide, continue to stir, make it dissolve completely, obtain low alkalinity sodium aluminate solution.Under whipped state, gelling temperature 20 DEG C, is poured into the directed agents prepared in 419g water glass, mixes, then add 201g alum liquor and above-mentioned gained low alkalinity sodium aluminate solution, stir after 1 hour, gained silica-alumina gel is loaded and has in the stainless steel crystallizing kettle of polytetrafluoro liner, be warming up to 100 DEG C of crystallization, crystallization 24 hours, after filtration, wash, in 110 DEG C of oven dry, obtain solid sample D.Products therefrom is carried out XRD phenetic analysis, and show that product is Y zeolite, its framework si-al ratio is 5.52, and relative crystallinity is 87%.
Table 1 is the specific surface area of embodiment 1 ~ 6 and comparative example gained sample, pore volume and average diameter of particles result.
Table 1
| Sample number into spectrum | Specific surface area (m 2/g) | Pore volume (m 3/g) | Mean particle size (nm) |
| Embodiment 1 gained sample S1 | 697 | 0.367 | 559 |
| Embodiment 2 gained sample S2 | 721 | 0.369 | 488 |
| Embodiment 3 gained sample S3 | 734 | 0.371 | 463 |
| Embodiment 4 gained sample S4 | 689 | 0.364 | 573 |
| Embodiment 5 gained sample S5 | 711 | 0.374 | 505 |
| Embodiment 6 gained sample S6 | 706 | 0.372 | 528 |
| Comparative example gained sample D | 659 | 0.358 | 867 |
Claims (2)
1. a preparation method for small crystal grain Y-shaped molecular sieve, is characterized in that, utilizes vulkacit H as auxiliary agent, and adopt the preparation technology of differing temps segmentation crystallization, described method comprises following processing step:
(1) directed agents preparation: by silicon source, aluminium source, alkali and water according to 3 ~ 45Na
2o:1Al
2o
3: 5 ~ 80SiO
2: 100 ~ 800H
2mol ratio mixing at 5 ~ 60 DEG C of O, to stir completely at 5 ~ 60 DEG C static aging 2 ~ 72 hours and obtains;
(2) at 20 ~ 60 DEG C, directed agents mixing is mixed with silicon source, then add aluminium source and vulkacit H prepares gel, make each component in described gel by the mol ratio of its oxide compound be: 0.5 ~ 10Na
2o:1Al
2o
3: 5 ~ 40SiO
2: 80 ~ 800H
2o:0.5 ~ 10C
6h
12n
4, fully stir, churning time is 0.5 ~ 6 hour;
(3) then two sections of crystallization are divided at different temperatures by described gel, first paragraph crystallization hydrogel warms to 60 ~ 85 DEG C, crystallization 12 ~ 48 hours, then carry out second segment crystallization, by hydrogel warms to 90 ~ 120 DEG C, crystallization 12 ~ 72 hours, finally by filtration, washing, dry obtained small crystal grain NaY molecular sieve;
Wherein, described silicon source is one or more in silica gel, silicon sol, water glass, white carbon black and water glass; Described aluminium source is one or more in aluminum oxide, aluminium hydroxide, Tai-Ace S 150 and Alumina gel; Described alkali is sodium hydroxide.
2., according to the preparation method described in claims 1, it is characterized in that, comprising:
(1) directed agents preparation: by silicon source, aluminium source, alkali and water according to 5 ~ 20Na
2o:1Al
2o
3: 10 ~ 50SiO
2: 200 ~ 500H
2the mol ratio of O mixes at 15 ~ 50 DEG C, to stir completely at 15 ~ 50 DEG C static aging 12 ~ 48 hours and obtains;
(2) at 20 ~ 50 DEG C, directed agents mixing is mixed with silicon source, then add aluminium source and vulkacit H prepares gel, make each component in this gel by the mol ratio of its oxide compound be: 2 ~ 8Na
2o:1Al
2o
3: 10 ~ 35SiO
2: 150 ~ 500H
2o:2 ~ 8C
6h
12n
4, fully stir, churning time is 2 ~ 4 hours;
(3) then two sections of crystallization are divided at different temperatures by this gel, first paragraph crystallization hydrogel warms to 65 ~ 80 DEG C, crystallization 10 ~ 24 hours, then carry out second segment crystallization, by hydrogel warms to 95 ~ 110 DEG C, crystallization 16 ~ 36 hours, finally by filtration, washing, dry obtained small crystal grain NaY molecular sieve.
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| CN114684831A (en) * | 2020-12-31 | 2022-07-01 | 中海油天津化工研究设计院有限公司 | High-silica-alumina-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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