CN104843737A - Y molecular sieve and preparation method therefor - Google Patents

Y molecular sieve and preparation method therefor Download PDF

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Publication number
CN104843737A
CN104843737A CN201510147789.8A CN201510147789A CN104843737A CN 104843737 A CN104843737 A CN 104843737A CN 201510147789 A CN201510147789 A CN 201510147789A CN 104843737 A CN104843737 A CN 104843737A
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molecular sieve
preparation
silica alumina
type zeolite
alumina ratio
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申宝剑
袁德林
高雄厚
王宝杰
赵红娟
孙建学
王闻年
李�浩
康春燕
郭巧霞
任申勇
郭成玉
米硕
赵妍
申波俊
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China University of Petroleum Beijing
China National Petroleum Corp
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China University of Petroleum Beijing
China National Petroleum Corp
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Abstract

The invention provides a Y molecular sieve and a preparation method therefor. The preparation method comprises the steps of: Y-type zeolite is subjected to pretreatment in an alkaline solution, the mass ratio of the alkaline solution to the Y zeolite is 1-(50:1), the pretreatment temperature is 0-120 DEG C, and the pretreatment time is 0.1-24h;the Y-type zeolite obtained through the pretreatment is subjected to gas phase desilicification silicon enhancement, as a result, the Y molecular sieve high in silica alumina ratio is prepared; under the condition of pH 2.0-5.0, the Y molecular sieve high in the silica alumina ratio is subjected to exchange of ammonium ion and burning so as to obtain the Y molecular sieve. The invention further provides a Y molecular sieve prepared by adopting the method, and the Y molecular sieve has the characteristic of large strong acid proportion, especially strong B acid proportion. The preparation method, provided by the present invention, is simple in operation, low in cost of the raw materials, and simple and easy to prepare the stable Y molecular sieve.

Description

A kind of Y molecular sieve and preparation method thereof
Technical field
The present invention relates to a kind of Y molecular sieve and preparation method thereof, belong to technical field of molecular sieve preparation.
Background technology
The nature and function of molecular sieve depend mainly on composition and the pore passage structure thereof of its skeleton principal element Si and Al, wherein, silica alumina ratio in framework of molecular sieve and the thermostability of molecular sieve, hydrothermal stability, chemical stability, the absorption property of molecular sieve, the acidity of molecular sieve and catalytic activity etc. are closely related.Silica alumina ratio (the SiO that dissimilar molecular sieve has it certain 2/ Al 2o 3) scope.For Y zeolite, silica alumina ratio height often has stronger heat-resisting, resistance to water vapour, capacity antacid.But, the silica alumina ratio that direct synthesis technique obtains Y zeolite reaches more than 6 very difficult, want to reach catalytic cracking catalyst condition, must on the basis of single sintering, product is adopted specific route and method, reprocess, namely secondary synthesis is to improve framework si-al ratio, thus changes its nature and function.
Wherein, dealuminzation is the main method improving framework of molecular sieve silica alumina ratio, and its route mainly contains two kinds: 1) molecular sieve thermal treatment at high temperature and hydrothermal treatment consists route, carries out dealuminzation super stabilizing; 2) the chemical dealuminization route of molecular sieve, comprises liquid-solid phase dealuminzation: mineral acid, organic acid, inner complex carry out framework dealumination method, also comprise gas-solid phase reaction, such as F 2, COCl 2deng, at a certain temperature, aluminium is become the method that volatile matter deviates from skeleton, wherein SiCl 4method dealumination complement silicon is the common method in this route.
Unexamined Patent 2-20, the 52 a kind of super stabilizing methods disclosing Y zeolite, under the method is included in the condition of exclusion of water, at the temperature of 150-450 DEG C, react NaY molecular sieve and gaseous silicon, the lattice constant of molecular sieve are contracted to silica alumina ratio is increased to 6.5-39.9, being equivalent to alumina content is 4.1-18.4wt%, the silica alumina ratio of described raw molecule sieve is 3-6, being equivalent to alumina content is 18.5-29.7wt%, when adopting in this way, halogenide can carry out dealuminzation to molecular sieve simultaneously and mend silicon, and products obtained therefrom skeleton room is few, that by product is easy washing and recycling, a small amount of NaCl and AlCl 3deng material, without obvious problem of environmental pollution.
Have research (Xu Hengyong, Zhang Yingzhen, Gu Shijian, Zheng Lubin. catalysis journal .1988 (9): 358-364) think, SiCl 4be not synchronously carry out to the dealumination complement silicon of framework of molecular sieve, first (SiCl 4-n) n+occupy molecular sieve cation position, such as formula (A), SiCl 4be chemisorbed on positively charged ion Na +position forms complex ion, and due to siloxane bond exceptional stability, complex ion decomposes immediately, replaces sodium ion thus form stable siloxane bond by silicon ion.Its exercising result is equivalent to (SiCl 3) +-Na +ion-exchange.Reaction (A) is rapid step, and reacts (B) and relate to removing of four-coordination framework aluminum, and needing higher temperature, is SiCl 4the rate-determining steps of isomorphous substitution dealuminzation.
Therefore, (the SiCl that (A) generates is reacted 3) +plug molecular sieve aperture, thus stop SiCl 4spread further to molecular sieve inner duct, only have when temperature is higher, sufficient energy just can make skeleton Al-O bond activation and then fracture, and simultaneous reactions (B) makes (SiCl 3) +ion decomposes further, and Siliciumatom replacement aluminium atom enters framework of molecular sieve on the one hand, removes the sterically hindered of molecular sieve aperture place, such SiCl on the other hand 4in succession could enter molecular sieve inner duct adsorption-decomposition function even dealuminzation.Therefore, it is contemplated that SiCl 4dealuminzation is mainly carried out to molecular sieve inside gradually by molecular sieve outer surface.Visible, SiCl 4gas molecule, in the diffusional limitation in molecular sieve aperture, result in the difference of dealumination complement silicon degree inside and outside molecular sieve crystal, must cause the serious uneven situation of Distribution of silicon and aluminium.
In addition, the research (H.K.Beyer and I.Belenykaja.In Catalysis by zeolites.Edited by B.Imelik et al.Elsevier, Amsterdam.1980.5,203.) of the people such as Beyer finds, at SiCl 4in dealumination complement silicon reaction, with gaseous state AlCl after only having part framework aluminum to remove 3form effusion, and another part AlCl 3because spreading not in time, be combined into not volatile Na (AlCl with NaCl 4) material remains in molecular sieve pore passage.Obvious Na (AlCl 4) existence of material can Severe blockage molecular sieve pore passage, and then have influence on the accessibility of acidic zeolite position.
There is above-mentioned defect owing to preparing molecular sieve by vapor phase process dealumination complement silicon, therefore, the effective ways providing a kind of vapor phase process dealumination complement silicon to prepare molecular sieve become a kind of needs.
Summary of the invention
In order to solve the problem, the object of the present invention is to provide a kind of Y molecular sieve and preparation method thereof, the Y molecular sieve that the preparation method of this Y molecular sieve obtains achieves dealuminzation super stabilizing, and strong B acid ratio is large.
To achieve these goals, the invention provides a kind of preparation method of Y molecular sieve, the method is before carrying out vapor phase process dealumination complement silicon, first carry out basic solution pre-treatment y-type zeolite, the Y molecular sieve of the high silicon content finally obtained, it is high that it has B acid acid amount, the feature that strong acid ratio is large, and this preparation method comprises the following steps:
In basic solution, carry out pre-treatment to y-type zeolite, wherein, the mass ratio of basic solution and y-type zeolite is 1-50:1, and pretreatment temperature is 0-120 DEG C, and pretreatment time is 0.1-24h; Pretreated temperature and time adjusts according to the concentration of basic solution and the degree for the treatment of of needs, and preferably, pretreatment temperature is 30-90 DEG C, and pretreatment time is 0.5-5h;
Vapor phase process dealumination complement silicon is carried out to the y-type zeolite that pre-treatment obtains, prepares high silica alumina ratio Y molecular sieve;
Under pH is 2.0-5.0, ammonium ion exchange, roasting are carried out to high silica alumina ratio Y molecular sieve, obtain described ultra-steady Y molecular sieve.
The quality of the y-type zeolite described in the present invention and high silica alumina ratio Y molecular sieve refers to the butt quality of y-type zeolite and high silica alumina ratio Y molecular sieve.
According to the specific embodiment of the present invention, after y-type zeolite is carried out pre-treatment in basic solution, after carrying out drying to pH close to neutrality through washing, suction filtration, then next step can be carried out.
In the preparation method of Y molecular sieve provided by the invention, preferably, the y-type zeolite of employing comprises synthesis NaY zeolite, NH 4y zeolite or HY zeolite.
In the preparation method of Y molecular sieve provided by the invention, preferably, with SiO 2and Al 2o 3meter, the silica alumina ratio of described y-type zeolite is preferably 3-6:1, most preferably is 5-6:1.
In the preparation method of Y molecular sieve provided by the invention, preferably, the concentration of the basic solution of employing is 0.01-5mol/L, and more preferably concentration is 0.2-2mol/L; Wherein, basic solution comprises NaOH solution, KOH solution and Na 2cO 3the combination of one or more in solution.
In the preparation method of Y molecular sieve provided by the invention, preferably, the dealumination complement silicon agent that described vapor phase process dealumination complement silicon adopts comprises SiCl 4, SiHCl 3or SiH 2cl 2.
In the preparation method of Y molecular sieve provided by the invention, the step of described vapor phase process dealumination complement silicon vapor phase process dealumination complement silicon is conveniently carried out, and preferably, generally comprises following steps:
Y-type zeolite pre-treatment obtained processes 1-10h at 300-600 DEG C, obtains treated y-type zeolite, and the water-content of the y-type zeolite that pre-treatment obtains is lower than 10wt%, and more preferably, the water-content of the Y zeolite that pre-treatment obtains is lower than 5wt%;
Cool the temperature to 100-600 DEG C;
In anhydrous dry environment, passing into by the saturated dry gas of dealumination complement silicon agent in treated y-type zeolite, reaction 0.5-24h (more preferably 0.5-10h), wherein, is 50mL/min by the speed that passes into of the saturated dry gas of dealumination complement silicon agent; Or under anhydrous dry environment, temperature is at the uniform velocity warming up to while 250 DEG C-700 DEG C, pass in treated y-type zeolite by the saturated dry gas of dealumination complement silicon agent, reaction 0.5-24h (more preferably 0.5-10h), wherein, temperature rise rate is 0.5 DEG C/min-10 DEG C/min is 50mL/min by the speed that passes into of the saturated dry gas of dealumination complement silicon agent;
Reaction terminates rear stopping and passing into by the saturated dry gas of dealumination complement silicon agent, maintains temperature of reaction, and dry gas continues to purge 1-5h, completes vapor phase process dealumination complement silicon.
In the preparation method of Y molecular sieve provided by the invention, preferably, the dry gas of employing comprises dry air, high pure nitrogen, high-purity argon gas or high-purity helium.
In the preparation method of Y molecular sieve provided by the invention, the step that high silica alumina ratio Y molecular sieve carries out ammonium ion exchange ammonium ion exchange is conveniently carried out, and preferably, generally comprises following steps:
Carry out ammonium ion exchange to high silica alumina ratio Y molecular sieve, the mass ratio of high silica alumina ratio Y molecular sieve, ammonium salt and water is 1:0.5-2:5-30, stirs 0.5-2h, complete the ammonium ion exchange of high silica alumina ratio Y molecular sieve at 60-95 DEG C.
According to the specific embodiment of the present invention, when carrying out ammonium ion exchange, high silica alumina ratio Y molecular sieve carries out filtering, wash to pH and carry out ammonium ion exchange close to after neutrality, or directly carries out ammonium ion exchange without washing; The step of ammonium ion exchange can repeatedly one or many.
In the preparation method of Y molecular sieve provided by the invention, preferably, the concentration of ammonium salt used in ammonium ion exchange process is 0.1-3mol/L, and wherein, the ammonium salt of employing comprises the combination of one or more in ammonium sulfate, ammonium chloride, ammonium nitrate and ammonium phosphate.
In the preparation method of Y molecular sieve provided by the invention, preferably, when in ammonium ion exchange process, adjust ph is 2.0-5.0, be that the acidic solution being 0.05-1mol/L by concentration regulates, more preferably, the concentration of acidic solution is 0.1-1mol/L; Wherein, the acidic solution of employing comprises the combination of one or more in hydrochloric acid, sulfuric acid, nitric acid, acetic acid, oxalic acid and phosphoric acid solution.
Present invention also offers a kind of Y molecular sieve, it is that above-mentioned preparation method prepares.
Alkaline purification combines with vapor phase process dealumination complement silicon technology by the present invention, weakens the diffusional limitation of dealumination complement silicon agent in isomorphous substitution process, thus improves the Acidity of Y molecular sieve.
The operation steps of the preparation method of Y molecular sieve provided by the invention is simple, and reagent cost is low, low to the requirement of processing unit, has very strong applicability.
Preparation method provided by the invention carries out pre-treatment to y-type zeolite first before gas phase dealumination complement silicon in basic solution, compared with carrying out separately the method for existing gas phase dealumination complement silicon, the rich silicon molecular sieve by crystal skeleton that preparation method of the present invention obtains has following features: suitably destroy the skeleton structure of zeolite by first implementing alkaline purification to y-type zeolite raw material, play the object of reaming, and then carry out dealumination complement silicon process and ammonium ion exchange, final Y molecular sieve modified product not only achieves dealuminzation super stabilizing, silica alumina ratio is high, but also it is large to have strong acid ratio, especially the feature that strong B acid ratio is large.
Embodiment
In order to there be understanding clearly to technical characteristic of the present invention, object and beneficial effect, existing following detailed description is carried out to technical scheme of the present invention, but can not be interpreted as to of the present invention can the restriction of practical range.
In each embodiment and comparative example:
The pore volume low temperature nitrogen determination of adsorption method of molecular sieve, then with reference to method described in USP5601798, to choose in framework of molecular sieve diameter in the hole of 2-60nm scope to calculate the volume of secondary pore;
Lattice constant and the relative crystallinity x-ray powder diffraction of molecular sieve measure, adopt RIPP145-90 standard method (see " Petrochemical Engineering Analysis method " (R work and test method), the Yang Cui volume such as surely, Science Press, nineteen ninety version);
Framework si-al ratio calculates according to following formula: SiO 2/ Al 2o 3(SiO 2and Al 2o 3mol ratio)=2 × (25.8575-ɑ 0)/(ɑ 0-24.191);
The acid amount of molecular sieve adopts pyridine infrared analysis.
The thermostability of molecular sieve for bioassay standard, adopts dsc (DSC) analytical technology to measure with lattice collapse temperature.
Embodiment 1
Present embodiments provide a kind of Y molecular sieve, it is prepared by following steps:
The NaOH solid of 10g and 700g deionized water are hybridly prepared into sodium hydroxide solution, warming-in-water to 40 DEG C, takes NaY zeolite (butt quality, the degree of crystallinity 90% of 100g, silica alumina ratio is 5.6) put in above-mentioned basic solution, maintain stir and in 40 DEG C of alkaline purification 1h; Alkaline purification terminates, and is filtered by slurries, is washed till pH=8,120 DEG C of oven drying 10h;
After weighing 20.0g alkaline purification, NaY zeolite sample is placed in crystal reaction tube, pass into nitrogen, carry out leak detection work, after ready, setting nitrogen purging speed 55-60mL/min (glass rotameter), setting Reaktionsofen heating schedule: keep 120min by starting temperature 30 DEG C after 100min is warming up to 500 DEG C, now stop heating, when temperature Temperature fall is to 250 DEG C, pass into by SiCl 4saturated N 2, after being warmed up to 550 DEG C with the temperature rise rate 60min of 5 DEG C/min, stop passing into by SiCl simultaneously 4saturated N 2, N 2continuing to purge 120min, stop heating Temperature fall afterwards, taking out sample obtains high silica alumina ratio NaY molecular sieve through washing drying;
The NaY molecular sieve sample of high silica alumina ratio and ammonium chloride, deionized water are mixed according to the mass ratio of 1:1:10 and pulls an oar evenly, at 90 DEG C, stir 1h, filter obtained NH 4y sample, baking oven 120 DEG C of dry 10h, retort furnace 550 DEG C of roasting 4h, obtain described Y molecular sieve.
The test that the Y molecular sieve obtained the present embodiment is correlated with characterizes, and it the results are shown in table 1 and table 2.
Comparative example 1
Prepare contrast molecular sieve by the preparation method of embodiment 1, difference is that NaY molecular sieve does not carry out pre-treatment before dealumination complement silicon in basic solution.
The test that the Y molecular sieve obtained this comparative example is correlated with characterizes, and it the results are shown in table 1 and table 2.
Embodiment 2
Present embodiments provide a kind of Y molecular sieve, it is prepared by following steps:
The NaOH solid of 10g and 500g deionized water are hybridly prepared into sodium hydroxide solution, warming-in-water to 60 DEG C, take the NH of 100g 4y zeolite (silica alumina ratio is 5.6 for butt quality, degree of crystallinity 90%) is put in above-mentioned basic solution, maintain stir and in 60 DEG C of alkaline purification 2h; Alkaline purification terminates, and is filtered by slurries, is washed till pH=8,120 DEG C of oven drying 10h;
NH after weighing 20.0g alkaline purification 4y zeolite sample is placed in crystal reaction tube, pass into nitrogen, carry out leak detection work, after ready, setting nitrogen purging speed 55-60mL/min (glass rotameter), setting Reaktionsofen heating schedule: keep 120min by starting temperature 30 DEG C after 100min is warming up to 500 DEG C, now stop heating, when temperature Temperature fall is to 250 DEG C, pass into by SiCl 4saturated N 2, after being warmed up to 550 DEG C with the temperature rise rate 60min of 5 DEG C/min, stop passing into by SiCl simultaneously 4saturated N 2, N 2continuing to purge 120min, stop heating Temperature fall afterwards, taking out sample obtains high silica alumina ratio NaY molecular sieve through washing drying;
By the NH of high silica alumina ratio 4y molecular sieve sample and ammonium chloride, deionized water mix according to the mass ratio of 1:1:10 pulls an oar evenly, stirs 1h, filter obtained NH at 90 DEG C 4y sample, baking oven 120 DEG C of dry 10h, retort furnace 550 DEG C of roasting 4h, obtain described Y molecular sieve.
The test that the Y molecular sieve obtained the present embodiment is correlated with characterizes, and it the results are shown in table 1 and table 2.
Embodiment 3
Present embodiments provide a kind of Y molecular sieve, it is prepared by following steps:
The NaOH solid of 20g and 700g deionized water are hybridly prepared into sodium hydroxide solution, warming-in-water to 95 DEG C, takes NaY zeolite (butt quality, the degree of crystallinity 90% of 50g, silica alumina ratio is 5.6) put in above-mentioned basic solution, maintain stir and in 95 DEG C of alkaline purification 2h; Alkaline purification terminates, and is filtered by slurries, is washed till pH=8,120 DEG C of oven drying 10h;
After weighing 20.0g alkaline purification, NaY zeolite sample is placed in crystal reaction tube, pass into nitrogen, carry out leak detection work, after ready, setting nitrogen purging speed 55-60mL/min (glass rotameter), setting Reaktionsofen heating schedule: keep 120min by starting temperature 30 DEG C after 100min is warming up to 500 DEG C, now stop heating, when temperature Temperature fall is to 250 DEG C, pass into by SiCl 4saturated N 2, after being warmed up to 550 DEG C with the temperature rise rate 60min of 5 DEG C/min, stop passing into by SiCl simultaneously 4saturated N 2, N 2continuing to purge 120min, stop heating Temperature fall afterwards, taking out sample obtains high silica alumina ratio NaY molecular sieve through washing drying;
The NaY molecular sieve sample of high silica alumina ratio and ammonium chloride, deionized water are mixed according to the mass ratio of 1:1:10 and pulls an oar evenly, at 90 DEG C, stir 1h, filter obtained NH 4y sample, baking oven 120 DEG C of dry 10h, retort furnace 550 DEG C of roasting 4h, obtain described Y molecular sieve.
The test that the Y molecular sieve obtained the present embodiment is correlated with characterizes, and it the results are shown in table 1 and table 2.
Before and after the alkaline purification of table 1 zeolite and final modified sample degree of crystallinity, silica alumina ratio data
Table 2 modified sample meleic acid character data
Embodiment 4
Present embodiments provide a kind of Y molecular sieve, it is prepared by following steps:
The NaOH solid of 20g and 700g deionized water are hybridly prepared into sodium hydroxide solution, warming-in-water to 95 DEG C, takes NaY zeolite (butt quality, the degree of crystallinity 95% of 50g, silica alumina ratio is 4.8) put in above-mentioned basic solution, maintain stir and in 95 DEG C of alkaline purification 2h; Alkaline purification terminates, and is filtered by slurries, is washed till pH=8,120 DEG C of oven drying 10h;
After weighing 20.0g alkaline purification, NaY zeolite sample is placed in crystal reaction tube, pass into nitrogen, carry out leak detection work, after ready, setting nitrogen purging speed 55-60mL/min (glass rotameter), setting Reaktionsofen heating schedule: keep 120min by starting temperature 30 DEG C after 100min is warming up to 500 DEG C, now stop heating, when temperature Temperature fall is to 250 DEG C, pass into by SiCl 4saturated N 2, after being warmed up to 550 DEG C with the temperature rise rate 60min of 5 DEG C/min, stop passing into by SiCl simultaneously 4saturated N 2, N 2continuing to purge 120min, stop heating Temperature fall afterwards, taking out sample obtains high silica alumina ratio NaY molecular sieve through washing drying;
The NaY molecular sieve sample of high silica alumina ratio and ammonium chloride, deionized water are mixed according to the mass ratio of 1:1:10 and pulls an oar evenly, at 90 DEG C, stir 1h, filter obtained NH 4y sample, baking oven 120 DEG C of dry 10h, retort furnace 550 DEG C of roasting 4h, obtain described Y molecular sieve.
The test that the Y molecular sieve obtained the present embodiment is correlated with characterizes, and it the results are shown in table 1 and table 2.
Comparative example 2
Prepare contrast molecular sieve by the preparation method of embodiment 4, difference is that NaY molecular sieve does not carry out pre-treatment before dealumination complement silicon in basic solution.
The test that the Y molecular sieve obtained this comparative example is correlated with characterizes, and it the results are shown in table 1 and table 2.
Embodiment 5
Present embodiments provide a kind of Y molecular sieve, it is prepared by following steps:
The NaOH solid of 20g and 500g deionized water are hybridly prepared into sodium hydroxide solution, warming-in-water to 70 DEG C, takes NaY zeolite (butt quality, the degree of crystallinity 95% of 50g, silica alumina ratio is 4.8) put in above-mentioned basic solution, maintain stir and in 70 DEG C of alkaline purification 7h; Alkaline purification terminates, and is filtered by slurries, is washed till pH=8,120 DEG C of oven drying 10h;
After weighing 20.0g alkaline purification, NaY zeolite sample is placed in crystal reaction tube, pass into nitrogen, carry out leak detection work, after ready, setting nitrogen purging speed 55-60mL/min (glass rotameter), setting Reaktionsofen heating schedule: keep 120min by starting temperature 30 DEG C after 100min is warming up to 500 DEG C, now stop heating, when temperature Temperature fall is to 250 DEG C, pass into by SiCl 4saturated N 2, after being warmed up to 550 DEG C with the temperature rise rate 60min of 5 DEG C/min, stop passing into by SiCl simultaneously 4saturated N 2, N 2continuing to purge 120min, stop heating Temperature fall afterwards, taking out sample obtains high silica alumina ratio NaY molecular sieve through washing drying;
The NaY molecular sieve sample of high silica alumina ratio and ammonium chloride, deionized water are mixed according to the mass ratio of 1:1:10 and pulls an oar evenly, at 90 DEG C, stir 1h, filter obtained NH 4y sample, baking oven 120 DEG C of dry 10h, retort furnace 550 DEG C of roasting 4h, obtain described Y molecular sieve.
The test that the Y molecular sieve obtained the present embodiment is correlated with characterizes, and it the results are shown in table 1 and table 2.
Embodiment 6
Present embodiments provide a kind of Y molecular sieve, it is prepared by following steps:
The NaOH solid of 50g and 1000g deionized water are hybridly prepared into sodium hydroxide solution, warming-in-water to 75 DEG C, takes NaY zeolite (butt quality, the degree of crystallinity 95% of 50g, silica alumina ratio is 4.8) put in above-mentioned basic solution, maintain stir and in 70 DEG C of alkaline purification 7h; Alkaline purification terminates, and is filtered by slurries, is washed till pH=8,120 DEG C of oven drying 10h;
After weighing 20.0g alkaline purification, NaY zeolite sample is placed in crystal reaction tube, pass into nitrogen, carry out leak detection work, after ready, setting nitrogen purging speed 55-60mL/min (glass rotameter), setting Reaktionsofen heating schedule: keep 120min by starting temperature 30 DEG C after 100min is warming up to 500 DEG C, now stop heating, when temperature Temperature fall is to 250 DEG C, pass into by SiCl 4saturated N 2, after being warmed up to 550 DEG C with the temperature rise rate 60min of 5 DEG C/min, stop passing into by SiCl simultaneously 4saturated N 2, N 2continuing to purge 120min, stop heating Temperature fall afterwards, taking out sample obtains high silica alumina ratio NaY molecular sieve through washing drying;
The NaY molecular sieve sample of high silica alumina ratio and ammonium chloride, deionized water are mixed according to the mass ratio of 1:1:10 and pulls an oar evenly, at 90 DEG C, stir 1h, filter obtained NH 4y sample, baking oven 120 DEG C of dry 10h, retort furnace 550 DEG C of roasting 4h, obtain described Y molecular sieve.
The test that the Y molecular sieve obtained the present embodiment is correlated with characterizes, and it the results are shown in table 1 and table 2.
Embodiment 7
Present embodiments provide a kind of Y molecular sieve, it is prepared by following steps:
The NaOH solid of 10g and 700g deionized water are hybridly prepared into sodium hydroxide solution, warming-in-water to 90 DEG C, takes NaY zeolite (butt quality, the degree of crystallinity 90% of 100g, silica alumina ratio is 5.6) put in above-mentioned basic solution, maintain stir and in 90 DEG C of alkaline purification 2h; Alkaline purification terminates, and is filtered by slurries, is washed till pH=8,120 DEG C of oven drying 10h;
After weighing 20.0g alkaline purification, NaY zeolite sample is placed in crystal reaction tube, pass into nitrogen, carry out leak detection work, after ready, setting nitrogen purging speed 55-60mL/min (glass rotameter), setting Reaktionsofen heating schedule: keep 120min by starting temperature 30 DEG C after 100min is warming up to 500 DEG C, now stop heating, when temperature Temperature fall is to 250 DEG C, pass into by SiCl 4saturated N 2, after being warmed up to 600 DEG C with the temperature rise rate 100min of 3.5 DEG C/min, stop passing into by SiCl simultaneously 4saturated N 2, N 2continuing to purge 120min, stop heating Temperature fall afterwards, taking out sample obtains high silica alumina ratio NaY molecular sieve through washing drying;
The NaY molecular sieve sample of high silica alumina ratio and ammonium chloride, deionized water are mixed according to the mass ratio of 1:1:10 and pulls an oar evenly, at 90 DEG C, stir 1h, filter obtained NH 4y sample, baking oven 120 DEG C of dry 10h, retort furnace 550 DEG C of roasting 4h, obtain described Y molecular sieve.
The test that the Y molecular sieve obtained the present embodiment is correlated with characterizes, and it the results are shown in table 1 and table 2.
Comparative example 3
Prepare contrast molecular sieve by the preparation method of embodiment 7, difference is that NaY molecular sieve does not carry out pre-treatment before dealumination complement silicon in basic solution.
The test that the Y molecular sieve obtained this comparative example is correlated with characterizes, and it the results are shown in table 1 and table 2.
Above embodiment shows, the molecular sieve that the preparation method of Y molecular sieve provided by the invention prepares achieves dealuminzation super stabilizing, but also has the large feature of strong B acid ratio.

Claims (10)

1. a preparation method for Y molecular sieve, this preparation method comprises the following steps:
In basic solution, carry out pre-treatment to y-type zeolite, wherein, the mass ratio of basic solution and y-type zeolite is 1-50:1, and pretreatment temperature is 0-120 DEG C, and pretreatment time is 0.1-24h; Preferably, pretreatment temperature is 30-90 DEG C, and pretreatment time is 0.5-5h;
Vapor phase process dealumination complement silicon is carried out to the y-type zeolite that pre-treatment obtains, prepares high silica alumina ratio Y molecular sieve;
Be under the condition of 2.0-5.0 at pH, ammonium ion exchange, roasting carried out to high silica alumina ratio Y molecular sieve, obtains described Y molecular sieve.
2. preparation method according to claim 1, wherein, described y-type zeolite comprises synthesis NaY zeolite, NH 4y zeolite or HY zeolite, with SiO 2and Al 2o 3meter, the silica alumina ratio of described y-type zeolite is 3-6:1, is preferably 5-6:1.
3. preparation method according to claim 1, wherein, the concentration of described basic solution is 0.01-5mol/L; Preferred concentration is 0.2-2mol/L; Described basic solution comprises NaOH solution, KOH solution and Na 2cO 3the combination of one or more in solution.
4. preparation method according to claim 1, wherein, the dealumination complement silicon agent that described vapor phase process dealumination complement silicon adopts comprises SiCl 4, SiHCl 3or SiH 2cl 2.
5. the preparation method according to claim 1 or 4, wherein, described vapor phase process dealumination complement silicon comprises the following steps:
Y-type zeolite pre-treatment obtained processes 1-10h at 300-600 DEG C, obtains treated y-type zeolite, the water-content of the y-type zeolite that pre-treatment obtains lower than 10wt%, preferably lower than 5wt%;
Cool the temperature to 100-600 DEG C;
In anhydrous dry environment, pass in treated y-type zeolite by the saturated dry gas of dealumination complement silicon agent, reaction 0.5-24h; Or under anhydrous dry environment, temperature is at the uniform velocity warming up to while 250 DEG C-700 DEG C, pass into by the saturated dry gas of dealumination complement silicon agent in treated y-type zeolite, reaction 0.5-24h, temperature rise rate is 0.5 DEG C/min-10 DEG C/min;
Reaction terminates rear stopping and passing into by the saturated dry gas of dealumination complement silicon agent, maintains temperature of reaction, and dry gas continues to purge 1-5h, completes vapor phase process dealumination complement silicon.
6. preparation method according to claim 5, wherein, described dry gas comprises dry air, high pure nitrogen, high-purity argon gas or high-purity helium.
7. preparation method according to claim 1, wherein, described high silica alumina ratio Y molecular sieve carries out ammonium ion exchange and comprises the following steps:
Carry out ammonium ion exchange to high silica alumina ratio Y molecular sieve, the mass ratio of high silica alumina ratio Y molecular sieve, ammonium salt and water is 1:0.5-2:5-30, stirs 0.5-2h, complete the ammonium ion exchange of high silica alumina ratio Y molecular sieve at 60-95 DEG C.
8. the preparation method according to claim 1 or 7, wherein, the concentration of ammonium salt used in described ammonium ion exchange process is 0.1-3mol/L, and described ammonium salt comprises the combination of one or more in ammonium sulfate, ammonium chloride, ammonium nitrate and ammonium phosphate.
9. preparation method according to claim 1, wherein, the adjustment of pH value is undertaken by the acidic solution that concentration is 0.05-1mol/L, and the concentration of preferred acidic solution is 0.1-1mol/L; Described acidic solution comprises the combination of one or more in hydrochloric acid, sulfuric acid, nitric acid, acetic acid, oxalic acid and phosphoric acid solution.
10. a Y molecular sieve, it is prepared by the preparation method described in any one of claim 1-9.
CN201510147789.8A 2015-03-31 2015-03-31 Y molecular sieve and preparation method therefor Pending CN104843737A (en)

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CN107758684A (en) * 2016-08-23 2018-03-06 中国石油天然气集团公司 A kind of high mesoporous amount y-type zeolite and preparation method thereof
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CN114618430A (en) * 2020-12-10 2022-06-14 中国科学院大连化学物理研究所 Y-type molecular sieve and preparation method and application thereof
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
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

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