CN106745045A - Nay molecular sieve and preparation method thereof - Google Patents
Nay molecular sieve and preparation method thereof Download PDFInfo
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Abstract
The invention provides a kind of NaY molecular sieve and preparation method thereof, first synthesize directed agents, the mixture of synthesis NaY molecular sieve is prepared again, surfactant is added in most backward mixture, it is the NaY molecular sieve of 100~1000nm to use hydrothermal crystallization method to synthesize average grain diameter, and the sieve particle has polymolecularity.
Description
Technical field
It is a kind of pore passage structure with large specific surface area, short and regular and the high dispersive NaY molecular sieve of micropore diffusion speed higher and preparation method thereof specifically the present invention relates to NaY molecular sieve and preparation method thereof.
Background technology
Between 1~100nm, its some physical properties and chemical property, such as wearability, intensity, heat endurance and catalysis activity are significantly higher than conventional molecular sieve to the particle diameter of nano molecular sieve.
One is with bigger external surface area.The channel surfaces product of molecular sieve is that the hole wall that is formed by micropore canals and cage wall are constituted, the particle diameter of conventional molecular sieve is general more than 1 μm, the shared ratio among total specific surface area of its external surface area is very low, therefore active sites on outer surface can be ignored for the contribution of catalytic cracking reaction.Compared to conventional molecular sieve, the particle diameter of nano molecular sieve is small, and the number of active center of outer surface is enough to be contended with the number of active center of body phase, even above the number of active center of body phase.With the increase of nano molecular sieve external surface area, exposure number of active center outside increases, and the acid amount of its outer surface is consequently increased, therefore the larger external surface area of nano molecular sieve has very big contribution to catalytic cracking.
The second is diffusion limitation can be effectively reduced.With the reduction of nano molecular sieve particle diameter, its duct shortens, exposure structure cell number outside becomes many, so that nano molecular sieve has more turnover apertures, greatly accelerate the micropore diffusion speed of reactant and product, this be for the reaction that is influenceed by micropore diffusion speed it is highly beneficial, it is largely effective especially for bulky molecular catalysis cracking reaction：Can not only be greatly improved the conversion ratio of catalytic cracking reaction, and the generation of carbon deposit can be effectively reduced, extend the life-span of molecular sieve.
The third is with larger pore volume and porosity.Because the particle diameter of nano molecular sieve is smaller, its surface can be larger, and easily aggregation forms intercrystalline voids, thus enhances adsorption capacity of the molecular sieve to macromolecular, and larger advantage is presented in bulky molecular catalysis cracking reaction.
Wang Bo thinks that influence of the ageing time of crystal seed glue to granularity is very big.The granularity of molecular sieve prepared by the general crystal seed glue by aging 8~22h is relatively small.When the ageing time of crystal seed glue continues to extend, the granularity of molecular sieve increases with the extension of time.
The research of horse allosaurus finds：Aging at 25 DEG C, in initial 4h, initial seed radius is larger, crystal seed amount and seed density are small, and with the extension of ageing time, crystal seed amount increases, gradually reduced again after seed density increase to a certain extent, but the radius of crystal seed is smaller, show at the nucleation stage initial stage, there is larger nucleus to be formed, but crystal seed amount is less, with the extension of ageing time, larger nucleus dissolving, while producing more small crystal nucleus.This process indicates the presence of self-catalysis nucleation process, i.e. with necessarily similar to crystal structure gel dissolving, produce new nucleus, when ageing time is more long, system comes into crystal growth phase, crystal seed radius and crystal seed amount all accordingly increase, and seed particles density is held essentially constant.It is aging at 40 DEG C, as ageing time increases to 12h from 2h, crystal seed radius is reduced to 0.028 μm from 0.072 μm, there is self-catalysis nucleation process, so the extension of ageing time is conducive to the generation of a large amount of nucleus, these nucleus presomas act as nuclearing centre in gel-sol system.
In order to allow crystal seed glue to form most crystal seeds, old English etc. of reading aloud is using the conventional opaque crystal seed glue of first synthesis, by its aging certain hour, then the method that a certain amount of water glass solution prepares transparent liquid phase crystal seed glue of the light transmittance more than 80% is added to, the small crystal grain NaY molecular sieve that particle diameter is 120nm is prepared.
Method disclosed in CN 1113814C is that organic dispersing agent is added in conventional directed agents with nucleus effective density in increasing directed agents, it is synthesized go out NaY molecular sieve crystal grain be 300~600nm.
Method disclosed in CN 1160676A is using the silicon in conventional directed agents as whole silicon sources, i.e., by increasing directed agents consumption, the NaY molecular sieve that particle diameter is 100~500nm to be synthesized with conventional crystallization method.
Method disclosed in CN 1074389C be in synthetic system addition can it is miscible with water and can with silicon source formed stable comple organic complexing agent, such as acetic acid, citric acid, ethylenediamine tetra-acetic acid, the NaY molecular sieve particle mean size for synthesizing is generally higher than 5.0, relative crystallinity and is generally higher than 80% less than 300nm, framework si-al ratio, and the wherein addition of organic complexing agent is 0.1~5 times of the aluminum oxide in raw material.
Method disclosed in US 3516786 be before synthetic system intensification crystallization, to added in synthetic system on a small quantity can be miscible with water organic reagent, such as methyl alcohol, ethanol, acetone, tetrahydrofuran, synthesis of molecular sieve crystallite dimension are 10~100nm.
US 4372931 and method disclosed in EP 0041338A are that on the premise of low temperature plastic, to monose or polysaccharide is added in reactant mixture, synthesized zeolite crystal size is 40~60nm.Molecular sieve majority framework si-al ratio synthesized by addition organic solvent or carbohydrate is relatively low, and generally below 2.5.
In above-mentioned document or patent, in the method for synthesizing small-grain molecular sieve, the size of an emphasis molecular sieve particle diameter, but molecular sieve decentralization do not investigated.The NaY molecular sieve of synthesis, because its particle diameter is smaller, easily reunites, it is difficult to filter in building-up process at present, and granularity is larger, bad dispersibility, makes its advantage be difficult to be played in industrial applications.
The content of the invention
Shortcoming of the present invention based on the sad filter of small particle NaY molecular sieve and easy reunion and bad dispersibility, by the synthetic technological condition of Improvement NaY molecular sieve, synthesize a series of NaY molecules of different grain sizes, the relation between the grain size and granularity of NaY molecular sieve is studied, synthesizes the NaY molecular sieve of high dispersive.
The present invention provides a kind of preparation method of NaY molecular sieve, comprises the following steps：
(1) preparation of directed agents
NaOH and silicon source are added to the water, or NaOH is added to the water after dissolving is added silicon source, form solution A, in solution A in terms of oxide, Al2O3Content be 2~11wt.%, Na2O content is 10~30wt.%；
By waterglass, a certain amount of water and add a certain amount of NaOH and be added in solution A under agitation, after stirring, 0.5~72h of static ageing, the directed agents needed for the present invention is obtained at 20~50 DEG C of temperature；
Each component mol ratio is Na in the directed agents2O:Al2O3:SiO2:H2O=13~25：1：6~34：150~550；
(2) preparation of reactant mixture
Water miscible silicon source is dissolved in water, in terms of oxide, Al is formed2O3Content is the solution B of 1~6wt.%；
NaOH is added to the water with silicon source, or NaOH is added to the water after dissolving and adds silicon source, after stirring, forms solution C, in solution C in terms of oxide, Al2O3Content be 4~10wt.%, Na2O content is 2~18wt.%；
Obtained directed agents, the solution B and the solution C in step (1) are added in water glass solution, a certain amount of surfactant is added, the reactant mixture of synthesis NaY molecular sieve is made；
Counted with the weight of reactant mixture as 100%, the addition of surfactant is 1~8wt.%；The addition of directed agents is 1~22wt.%, is synthesized in the reactant mixture of NaY molecular sieve, and in addition to surfactant, the mol ratio of remaining each component is Na2O:Al2O3:SiO2:H2O=2~14：1：6~28：160~450；
(3) hydrothermal crystallizing synthesis
The reactant mixture of the synthesis NaY molecular sieve that step (2) is obtained after 10~72h of crystallization at 80~150 DEG C, suction filtration, drying system required NaY molecular sieve.
The preparation method of NaY molecular sieve of the present invention, wherein：In terms of the weight of reactant mixture, the addition of surfactant is preferably 2~4wt.% described in step (2).
The preparation method of NaY molecular sieve of the present invention, wherein：The mol ratio of directed agents each component is preferably in step (1)：Na2O:Al2O3:SiO2:H2O=14~22：1：12~24：160~450.
The preparation method of NaY molecular sieve of the present invention, wherein：Step is counted in (2) with the weight of reactant mixture as 100%, and the addition of directed agents is preferably 2~16wt.%.
The preparation method of NaY molecular sieve of the present invention, wherein：In step (2) in the reactant mixture of synthesis NaY molecular sieve, in addition to surfactant, the mol ratio of remaining each component is preferably：Na2O:Al2O3:SiO2:H2O=3~12：1：8~22：220~360.
The preparation method of NaY molecular sieve of the present invention, wherein：The surfactant is preferably nonionic surfactant, more preferably Span-20.Nonionic surfactant, can be fatty acid glycerine esters, polyalcohols, polyoxyethylene, polymeric polyalcohols, alkylolamides class, fatty alcohol polyethenoxy ether class (such as AEO), polyoxyethylene carboxylate class, APES class (such as APE), sorbitan ester polyethenoxy ether class (such as Tween-20~Tween-85), sorbitan fatty acid ester class (such as Span-20~Span-85), or therein one or more.The present invention is not particularly limited the species of surfactant, and their performance characteristic is consistent.
The feed postition of surfactant can have an impact to the NaY molecular sieve relative crystallinity and framework si-al ratio that synthesize, because the associated methods of Al ions have difference in Si ions or sodium aluminate solution in surfactant and waterglass.In the present invention to make synthesized small crystal grain NaY molecular sieve that there is polymolecularity, therefore surfactant is added in the reactant mixture of synthesis NaY molecular sieve.Due to the addition of nonionic surface active agent, after the sieve synthesis of its inducing molecule, due to its have it is amphipathic, it is present in the hydrophobic group of surfactant of molecular sieve periphery outside, so that the sieve particle of generation virtually just produces certain mutually exclusive power, and then the agglomeration reduction of synthesized NaY molecular sieve, obtain the effect of high dispersive.Meanwhile, the addition of surfactant also has certain refining effect to the particle diameter of synthesized molecular sieve.
The present invention also provides a kind of NaY molecular sieve, and it is the NaY molecular sieve obtained by the preparation method of above-mentioned NaY molecular sieve.
NaY molecular sieve of the present invention, wherein：The average grain diameter of the NaY molecular sieve is preferably 100~1000nm, and framework si-al ratio is preferably 4.8~6.0, more preferably 4.9~5.4.
NaY molecular sieve of the present invention, wherein：In terms of meso-position radius D (v0.5), the granularity of the NaY molecular sieve is preferably smaller than 3 microns.
NaY molecular sieve of the present invention, wherein：The differential thermal fail temperature of the NaY molecular sieve is preferably 850 DEG C~950 DEG C, more preferably 880~920 DEG C.
Beneficial effects of the present invention：
Y type molecular sieve of the invention belongs to high-dispersity molecular sieve, and decentralization its granularity (in terms of meso-position radius Dv0.5) higher is smaller.When use Y type molecular sieve as catalyst active component when, the decentralization of molecular sieve is got over Gao Zeyue and is readily dispersed in matrix or effectively compound with other materials, Y type molecular sieve is exposed more outer surfaces simultaneously, reduce the diffusion path of reactant molecule, improve the activity of catalyst.
Specific embodiment
Embodiments of the invention are elaborated below：The present embodiment is implemented under premised on technical solution of the present invention; give detailed implementation method and process; but protection scope of the present invention is not limited to following embodiments, the experimental technique of unreceipted actual conditions in the following example, generally according to normal condition.
Analysis test method：
The structural parameters of NaY molecular sieve are determined：Using the D8Advance X-ray diffractometers of German Bruker companies production, condition determination is：CuK α are radiated, Ni is filtered, pipe presses 36kV, tube current 20mA, gather the diffraction spectrogram that 2 θ are 15 °~35 °, calculate the area of 15.7 °, 18.7 °, 20.4 °, 23.6 °, 27.1 °, 30.8 °, 31.5 ° and 34.2 ° this 8 characteristic diffraction peaks and, the NaY molecular sieve for taking high-purity makees standard sample, assuming that its crystallinity is 100%, the ratio between characteristic diffraction peak area summation of testing sample and NaY standard samples is the relative crystallinity of testing sample.The θ of sweep limits 2 of cell parameter is 28 °~32 °, with pure silicon (2 θ=28.443 °, (110) crystal face) used as internal standard, peak corresponding 2 θ of the accurate determination sample at 31.40 ° or so calculates the cell parameter a of NaY molecular sieve sample using bragg's formula to powder0, the framework si-al ratio of sieve sample is then calculated with Bu Laike curve methods.
The type SEM of Quanta 200 that sem analysis are produced using Dutch FEI Co., accelerating potential is 20kV, first by sample drying and ground when using, take on the conducting resinl during micro-example is applied to sample disc, after sample disc surface gold-plating, put it into SEM, be scanned test.
The grain size analysis of sample uses the type laser fineness gages of MASTER SIZER 2000 of Britain's Malvern (Malvern) Instrument Ltd., and using wet sample measurement, ethanol is dispersant.
Thermal stability analysis are carried out on German Nai Chi instrument companies STA 409PC type thermal analyzers.Experiment is carried out in an ar atmosphere, and heating rate is 15 DEG C/min, and temperature range is room temperature to 1200 DEG C.
Embodiment one：
A kind of synthesis of high dispersive NaY molecular sieve
(1) preparation of directed agents：Take 28.4g NaOH (Beijing Chemical Plant, technical grade) to be added in 66.9g water, stirring to NaOH is all dissolved, add 4.7g sodium metaaluminates (Beijing Chemical Plant, technical grade), continue to stir to sodium metaaluminate and all dissolve, obtain sodium aluminate solution A (Al2O3Content be 22wt.%, Na2O content is 3wt.%).Take the solution A of 38.2g and waterglass (the Red Star water glass plant of Beijing, SiO of 82g2Content 27.81wt.%, Na2O content 8.74wt.%) mixing and stirring, after stirring 2h, the aging 72h at 20 DEG C.Counted by 100wt.% of directed agents, the mol ratio of each component is：19Na2O:Al2O3:34SiO2:550H2O。
(2) preparation of NaY molecular sieve：75.5g aluminum sulfate is dissolved in 124.5g water, Al is formed2O3Content is the aluminum sulfate solution B of 6wt.%；19.4g NaOH is dissolved in 68.1g water, then adds 12.6g sodium metaaluminates (the same step of specification (1)), stirring forms sodium aluminate solution C (Al to being completely dissolved2O3Content be 15wt.%, Na2O content is 8wt.%).65g directed agents (accounting for the 11wt.% of raw material total amount), 163g solution Bs and 41g solution Cs are added sequentially in 450g waterglass (the same step of specification (1)) according to conventional NaY molecular sieve preparation process, add 600g water after stirring again, it is made the reactant mixture of synthesis NaY molecular sieve, it is eventually adding Span-20 (the Tianjin recovery fine chemistry industry research institutes of 105.5g, chemistry is pure, accounts for the 8wt.% of raw material total amount).The mol ratio of each component is 4.19Na in mixture2O:Al2O3:17SiO2:160H2O；During reactant mixture gone into autoclave, the crystallization 32h at 100 DEG C.Hydrothermal crystallizing is finished, and takes out molecular sieve and mother liquor, is filtered, washs, is dried, and obtains final product NaY type zeolite products.
The relative crystallinity of gained NaY molecular sieve is that 85%, framework si-al ratio is that 5.4, particle diameter is 200nm, and differential thermal fail temperature is 894.6 DEG C.
Particle size analysis the results are shown in Table one.
Embodiment two
Unless otherwise indicated, each raw material sources are same as embodiment one.
(1) preparation of directed agents：Take 38.7g NaOH to be added in 33.2g water, stirring to NaOH is all dissolved, add 17.3g sodium metaaluminates, continue to stir to sodium metaaluminate and all dissolve, obtain sodium aluminate solution A (Al2O3Content be 11wt.%, Na2O content is 30wt.%).The solution A of 12g and the waterglass mixing and stirring of 56g are taken, 14.9g NaOH and 39g water is added, after stirring 2h, the aging 0.5h at 50 DEG C.Counted by 100wt.% of directed agents, the mol ratio of each component is：25Na2O:Al2O3:20SiO2:350H2O。
(2) preparation of NaY molecular sieve：37.7g aluminum sulfate is dissolved in 162.3g water, Al is formed2O3Content is the aluminum sulfate solution B of 3wt.%；46.5g NaOH is dissolved in 122.1g water, then adds 31.5g sodium metaaluminates, stirring forms sodium aluminate solution C (Al to being completely dissolved2O3Content be 18wt.%, Na2O content is 10wt.%).18g directed agents (accounting for the 1wt.% of raw material total amount), 516g solution Bs and 156g solution Cs are added sequentially in 390g waterglass according to conventional NaY molecular sieve preparation process, add 100g water after stirring again, the reactant mixture of synthesis NaY molecular sieve is made, the Span-20 (accounting for the 4.5wt.% of raw material total amount) of 53.72g is eventually adding.The mol ratio of each component is 2Na in mixture2O:Al2O3:6SiO2:160H2O；During reactant mixture gone into autoclave, the crystallization 10h at 150 DEG C.Hydrothermal crystallizing is finished, and takes out molecular sieve and mother liquor, is filtered, washs, is dried, and obtains final product NaY type zeolite products.
The relative crystallinity of gained NaY molecular sieve is that 87%, framework si-al ratio is that 5.2, particle diameter is 300nm, and differential thermal fail temperature is 908.9 DEG C.
Particle size analysis the results are shown in Table one.
Embodiment three
Unless otherwise indicated, each raw material sources are same as embodiment one.
(1) preparation of directed agents：Take 25.8g NaOH to be added in 64.8g water, stirring to NaOH is all dissolved, add 9.4g sodium metaaluminates, continue to stir to sodium metaaluminate and all dissolve, obtain sodium aluminate solution A (Al2O3Content be 6wt.%, Na2O content is 20wt.%).The solution A of 22g and the waterglass mixing and stirring of 45g are taken, 7g NaOH and 14g water is added, after stirring 2h, the aging 36h at 30 DEG C.Counted by 100wt.% of directed agents, the mol ratio of each component is：25Na2O:Al2O3:16SiO2:220H2O。
(2) preparation of NaY molecular sieve：37.7g aluminum sulfate is dissolved in 62.3g water, Al is formed2O3Content is the aluminum sulfate solution B of 6wt.%；19.4g NaOH is dissolved in 7.9g water, then adds 72.8g sodium metaaluminates, stirring forms sodium aluminate solution C (Al to being completely dissolved2O3Content be 15wt.%, Na2O content is 5wt.%).112g directed agents (accounting for the 22wt.% of raw material total amount), 44g solution Bs and 90.8g solution Cs are added sequentially in 460g waterglass according to conventional NaY molecular sieve preparation process, the reactant mixture of synthesis NaY molecular sieve is made, the Span-20 (accounting for the 1wt.% of raw material total amount) of 7.14g is eventually adding.The mol ratio of each component is 14Na in mixture2O:Al2O3:27SiO2:300H2O；During reactant mixture gone into autoclave, the crystallization 24h at 100 DEG C.Hydrothermal crystallizing is finished, and takes out molecular sieve and mother liquor, is filtered, washs, is dried, and obtains final product NaY type zeolite products.
The relative crystallinity of gained NaY molecular sieve is that 92%, framework si-al ratio is that 5.2, particle diameter is 500nm, and differential thermal fail temperature is 910.8 DEG C.
Particle size analysis the results are shown in Table one.
Example IV
Unless otherwise indicated, each raw material sources are same as embodiment one.
(1) preparation of directed agents：Take 25.8g NaOH to be added in 167.9g water, stirring to NaOH is all dissolved, add 6.3g sodium metaaluminates, continue to stir to sodium metaaluminate and all dissolve, obtain sodium aluminate solution A (Al2O3Content be 2wt.%, Na2O content is 10wt.%).The solution A of 134g and the waterglass mixing and stirring of 34g are taken, 6g NaOH is added, after stirring 2h, the aging 24h at 20 DEG C.Counted by 100wt.% of directed agents, the mol ratio of each component is：13Na2O:Al2O3:6SiO2:150H2O。
(2) preparation of NaY molecular sieve：25.2g aluminum sulfate is dissolved in 374.8g water, Al is formed2O3Content is the aluminum sulfate solution B of 1wt.%；10.3g NaOH is dissolved in 183.4g water, then adds 6.3g sodium metaaluminates, stirring forms sodium aluminate solution C (Al to being completely dissolved2O3Content be 2wt.%, Na2O content is 4wt.%).56g directed agents (accounting for the 5wt.% of raw material total amount), 368g solution Bs and 160g solution Cs are added sequentially in 440g waterglass according to conventional NaY molecular sieve preparation process, the reactant mixture of synthesis NaY molecular sieve is made, the Span-20 (accounting for the 5wt.% of raw material total amount) of 51.2g is eventually adding.The mol ratio of each component is 9.5Na in mixture2O:Al2O3:28SiO2:450H2O；During reactant mixture gone into autoclave, the crystallization 72h at 80 DEG C.Hydrothermal crystallizing is finished, and takes out molecular sieve and mother liquor, is filtered, washs, is dried, and obtains final product NaY type zeolite products.
The relative crystallinity of gained NaY molecular sieve is that 86%, framework si-al ratio is that 4.9, particle diameter is 1000nm, and differential thermal fail temperature is 903.0 DEG C.
Particle size analysis the results are shown in Table one.
Embodiment five
Unless otherwise indicated, each raw material sources are same as embodiment one.
(1) preparation of directed agents：Take 241.5g NaOH to be added in 450g water, stirring to NaOH is all dissolved, add 65.3g sodium metaaluminates, continue to stir to sodium metaaluminate and all dissolve, obtain sodium aluminate solution A.The solution A of 280g and the waterglass mixing and stirring of 400g are taken, 2g NaOH and 240g water is added, after stirring 2h, the aging 24h at 20 DEG C.Counted by 100wt.% of directed agents, the mol ratio of each component is：16Na2O:Al2O3:16SiO2:315H2O。
(2) preparation of NaY molecular sieve：144.8g aluminum sulfate is dissolved in 506g water, Al is formed2O3Content is the aluminum sulfate solution B of 3.4wt.%；44.7g NaOH is dissolved in 502.6g water, then adds 100g sodium metaaluminates, stirring forms sodium aluminate solution C to being completely dissolved.104g directed agents, 160g solution Bs and 120g solution Cs are added sequentially in 400g waterglass according to conventional NaY molecular sieve preparation process, add 75g water after stirring again, be made the reactant mixture of synthesis NaY molecular sieve, be eventually adding the Span-20 of 30.06g.The mol ratio of each component is 6.5Na in mixture2O:Al2O3:14SiO2:230H2O；During reactant mixture gone into autoclave, the crystallization 24h at 100 DEG C.Hydrothermal crystallizing is finished, and takes out molecular sieve and mother liquor, is filtered, washs, is dried, and obtains final product NaY type zeolite products.
The relative crystallinity of gained NaY molecular sieve is that 88%, framework si-al ratio is that 5.2, particle diameter is 100nm, and differential thermal fail temperature is 881.5 DEG C.
Particle size analysis the results are shown in Table one.
Embodiment six
Unless otherwise indicated, each raw material sources are same as embodiment one.
(1) preparation of directed agents：Take 241.5g NaOH to be added in 450g water, stirring to NaOH is all dissolved, add 65.3g sodium metaaluminates, continue to stir to sodium metaaluminate and all dissolve, obtain sodium aluminate solution A.The solution A of 70g and the waterglass mixing and stirring of 100g are taken, 0.5g NaOH and 83.5g water is added, after stirring 2h, the aging 24h at 20 DEG C.Counted by 100wt.% of directed agents, the mol ratio of each component is：16Na2O:Al2O3:16SiO2:360H2O。
(2) preparation of NaY molecular sieve：144.8g aluminum sulfate is dissolved in 506g water, Al is formed2O3Content is the aluminum sulfate solution B of 3.4wt.%；44.7g NaOH is dissolved in 502.6g water, then adds 100g sodium metaaluminates, stirring forms sodium aluminate solution C to being completely dissolved.104g directed agents, 160g solution Bs and 120g solution Cs are added sequentially in 400g waterglass according to conventional NaY molecular sieve preparation process, add 76g water after stirring again, be made the reactant mixture of synthesis NaY molecular sieve, be eventually adding the Span-20 of 4.63g.The mol ratio of each component is 6.4Na in mixture2O:Al2O3:13.4SiO2:230H2O；During reactant mixture gone into autoclave, the crystallization 24h at 100 DEG C.Hydrothermal crystallizing is finished, and takes out molecular sieve and mother liquor, is filtered, washs, is dried, and obtains final product NaY type zeolite products.
The relative crystallinity of gained NaY molecular sieve is that 97%, framework si-al ratio is that 5.2, particle diameter is 700nm, and differential thermal fail temperature is 917.4 DEG C.
Particle size analysis the results are shown in Table one.
Embodiment seven
Unless otherwise indicated, each raw material sources are same as embodiment one.
(1) preparation of directed agents：Take 241.5g NaOH to be added in 450g water, stirring to NaOH is all dissolved, add 65.3g sodium metaaluminates, continue to stir to sodium metaaluminate and all dissolve, obtain sodium aluminate solution A.The solution A of 176g and the waterglass mixing and stirring of 180g are taken, 116g water is added, after stirring 2h, the aging 24h at 20 DEG C.Counted by 100wt.% of directed agents, the mol ratio of each component is：16Na2O:Al2O3:16SiO2:380H2O。
(2) preparation of NaY molecular sieve：144.8g aluminum sulfate is dissolved in 506g water, Al is formed2O3Content is the aluminum sulfate solution B of 3.4wt.%；44.7g NaOH is dissolved in 502.6g water, then adds 100g sodium metaaluminates, stirring forms sodium aluminate solution C to being completely dissolved.104g directed agents, 160g solution Bs and 120g solution Cs are added sequentially in 405g waterglass according to conventional NaY molecular sieve preparation process, add 84g water after stirring again, be made the reactant mixture of synthesis NaY molecular sieve, be eventually adding the Span-20 of 3.46g.The mol ratio of each component is 6.5Na in mixture2O:Al2O3:13.5SiO2:230H2O；During reactant mixture gone into autoclave, the crystallization 24h at 100 DEG C.Hydrothermal crystallizing is finished, and takes out molecular sieve and mother liquor, is filtered, washs, is dried, and obtains final product NaY type zeolite products.
The relative crystallinity of gained NaY molecular sieve is that 97%, framework si-al ratio is that 5.2, particle diameter is 600nm, and differential thermal fail temperature is 907.2 DEG C.
Particle size analysis the results are shown in Table one.
Embodiment eight
Unless otherwise indicated, each raw material sources are same as embodiment one.
(1) preparation of directed agents：Take 241.5g NaOH to be added in 450g water, stirring to NaOH is all dissolved, add 65.3g sodium metaaluminates, continue to stir to sodium metaaluminate and all dissolve, obtain sodium aluminate solution A.The solution A of 70g and the waterglass mixing and stirring of 106g are taken, 22.7g water is added, after stirring 2h, the aging 24h at 20 DEG C.Counted by 100wt.% of directed agents, the mol ratio of each component is：18Na2O:Al2O3:24SiO2:375H2O。
(2) preparation of NaY molecular sieve：144.8g aluminum sulfate is dissolved in 506g water, Al is formed2O3Content is the aluminum sulfate solution B of 3.4wt.%；44.7g NaOH is dissolved in 502.6g water, then adds 100g sodium metaaluminates, stirring forms sodium aluminate solution C to being completely dissolved.65g directed agents, 160g solution Bs and 120g solution Cs are added sequentially in 400g waterglass according to conventional NaY molecular sieve preparation process, the NaOH and 90g water of 6g are added after stirring, the reactant mixture of synthesis NaY molecular sieve is made, the Span-20 of 7.76g is eventually adding.The mol ratio of each component is 6.5Na in mixture2O:Al2O3:13.5SiO2:230H2O；During reactant mixture gone into autoclave, the crystallization 24h at 100 DEG C.Hydrothermal crystallizing is finished, and takes out molecular sieve and mother liquor, is filtered, washs, is dried, and obtains final product NaY type zeolite products.
The relative crystallinity of gained NaY molecular sieve is that 88%, framework si-al ratio is that 5.1, particle diameter is 130nm, and differential thermal fail temperature is 887.5 DEG C.
Particle size analysis the results are shown in Table one.
Embodiment nine
Unless otherwise indicated, each raw material sources are same as embodiment one.
(1) preparation of directed agents：Take 241.5g NaOH to be added in 450g water, stirring to NaOH is all dissolved, add 65.3g sodium metaaluminates, continue to stir to sodium metaaluminate and all dissolve, obtain sodium aluminate solution A.The solution A of 490g and the waterglass mixing and stirring of 700g are taken, 3.5g NaOH and 218.4g water is added, after stirring 2h, the aging 24h at 20 DEG C.Counted by 100wt.% of directed agents, the mol ratio of each component is：16Na2O:Al2O3:16SiO2:260H2O。
(2) preparation of NaY molecular sieve：144.8g aluminum sulfate is dissolved in 506g water, Al is formed2O3Content is the aluminum sulfate solution B of 3.4wt.%；44.7g NaOH is dissolved in 502.6g water, then adds 100g sodium metaaluminates, stirring forms sodium aluminate solution C to being completely dissolved.104g directed agents, 185.6g solution Bs and 139.2g solution Cs are added sequentially in 464g waterglass according to conventional NaY molecular sieve preparation process, add 110.2g water after stirring again, the reactant mixture of synthesis NaY molecular sieve is made, the Span-20 of 10.78g is eventually adding.The mol ratio of each component is 6.6Na in mixture2O:Al2O3:13.5SiO2:230H2O；During reactant mixture gone into autoclave, the crystallization 24h at 100 DEG C.Hydrothermal crystallizing is finished, and takes out molecular sieve and mother liquor, is filtered, washs, is dried, and obtains final product NaY type zeolite products.
The relative crystallinity of gained NaY molecular sieve is that 89%, framework si-al ratio is that 5.4, particle diameter is 150nm, and differential thermal fail temperature is 892.6 DEG C.
Particle size analysis the results are shown in Table one.
Embodiment ten
Unless otherwise indicated, each raw material sources are same as embodiment one.
(1) preparation of directed agents：Take 241.5g NaOH to be added in 450g water, stirring to NaOH is all dissolved, add 65.3g sodium metaaluminates, continue to stir to sodium metaaluminate and all dissolve, obtain sodium aluminate solution A.The solution A of 143g and the waterglass mixing and stirring of 145g are taken, 1.2g NaOH and 49.5g water is added, after stirring 2h, the aging 24h at 20 DEG C.Counted by 100wt.% of directed agents, the mol ratio of each component is：16Na2O:Al2O3:16SiO2:320H2O。
(2) preparation of NaY molecular sieve：144.8g aluminum sulfate is dissolved in 506g water, Al is formed2O3Content is the aluminum sulfate solution B of 3.4wt.%；44.7g NaOH is dissolved in 502.6g water, then adds 100g sodium metaaluminates, stirring forms sodium aluminate solution C to being completely dissolved.90g directed agents, 160g solution Bs and 120g solution Cs are added sequentially in 400g waterglass according to conventional NaY molecular sieve preparation process, add 82g water after stirring again, be made the reactant mixture of synthesis NaY molecular sieve, be eventually adding the Span-20 of 9.44g.The mol ratio of each component is 6.5Na in mixture2O:Al2O3:13.5SiO2:230H2O；During reactant mixture gone into autoclave, the crystallization 24h at 100 DEG C.Hydrothermal crystallizing is finished, and takes out molecular sieve and mother liquor, is filtered, washs, is dried, and obtains final product NaY type zeolite products.
The relative crystallinity of gained NaY molecular sieve is that 85%, framework si-al ratio is that 5.1, particle diameter is 400nm, and differential thermal fail temperature is 909.5 DEG C.
Particle size analysis the results are shown in Table one.
Embodiment 11
Unless otherwise indicated, each raw material sources are same as embodiment one.
(1) preparation of directed agents：Take 241.5g NaOH to be added in 450g water, stirring to NaOH is all dissolved, add 65.3g sodium metaaluminates, continue to stir to sodium metaaluminate and all dissolve, obtain sodium aluminate solution A.The solution A of 143g and the waterglass mixing and stirring of 145g are taken, 1.2g NaOH and 106.5g water is added, after stirring 2h, the aging 24h at 20 DEG C.Counted by 100wt.% of directed agents, the mol ratio of each component is：16Na2O:Al2O3:16SiO2:395H2O。
(2) preparation of NaY molecular sieve：144.8g aluminum sulfate is dissolved in 506g water, Al is formed2O3Content is the aluminum sulfate solution B of 3.4wt.%；44.7g NaOH is dissolved in 502.6g water, then adds 100g sodium metaaluminates, stirring forms sodium aluminate solution C to being completely dissolved.90g directed agents, 160g solution Bs and 120g solution Cs are added sequentially in 400g waterglass according to conventional NaY molecular sieve preparation process, add 64g water after stirring again, be made the reactant mixture of synthesis NaY molecular sieve, be eventually adding the Span-20 of 17.11g.The mol ratio of each component is 6.5Na in mixture2O:Al2O3:13.5SiO2:230H2O；During reactant mixture gone into autoclave, the crystallization 24h at 100 DEG C.Hydrothermal crystallizing is finished, and takes out molecular sieve and mother liquor, is filtered, washs, is dried, and obtains final product NaY type zeolite products.
The relative crystallinity of gained NaY molecular sieve is that 89%, framework si-al ratio is that 5.2, particle diameter is 900nm, and differential thermal fail temperature is 921.4 DEG C.
Particle size analysis the results are shown in Table one.
Comparative example one：
Using the condition of embodiment one, but surfactant is added without when the mixture of NaY molecular sieve is prepared.
(1) preparation of directed agents：241.5g NaOH (specification is with embodiment one) is taken to be added in 450g water, stirring to NaOH all dissolves, 65.3g sodium metaaluminates (specification is with embodiment one) are added, is continued to stir to sodium metaaluminate and is all dissolved, obtain sodium aluminate solution A.The solution A of 420g and waterglass (specification is with embodiment one) mixing and stirring of 600g are taken, 3g NaOH and 219g water is added, after stirring 2h, the aging 24h at 20 DEG C.Counted by 100wt.% of directed agents, the mol ratio of each component is：16Na2O:Al2O3:16SiO2:270H2O。
(2) preparation of NaY molecular sieve：144.8g aluminum sulfate is dissolved in 506g water, Al is formed2O3Content is the aluminum sulfate solution B of 3.4wt.%；44.7g NaOH is dissolved in 502.6g water, then adds 100g sodium metaaluminates, stirring forms sodium aluminate solution C to being completely dissolved.104g directed agents, 160g solution Bs and 120g solution Cs are added sequentially in 400g waterglass according to conventional NaY molecular sieve preparation process, add 93g water after stirring again, be made the reactant mixture of synthesis NaY molecular sieve.The mol ratio of each component is 6.5Na in mixture2O:Al2O3:13.5SiO2:230H2O；During reactant mixture gone into autoclave, the crystallization 24h at 100 DEG C.After hydrothermal crystallizing, molecular sieve and mother liquor are taken out, filter, wash, dry, obtain final product NaY type zeolite products.
The relative crystallinity of gained NaY molecular sieve is that 80%, framework si-al ratio is that 5.2, particle diameter is 600nm, and differential thermal fail temperature is 800.6 DEG C.
Particle size analysis the results are shown in Table one.
Comparative example two
Small crystal grain NaY molecular sieve is prepared by the method for the embodiment one of CN 1033503C.
(1) preparation of directed agents：Take 29.5g NaOH to be added in 75g water, stirring to NaOH is all dissolved, add 4.78g sodium metaaluminates, stirring to sodium metaaluminate is all dissolved, and obtains sodium aluminate solution.200g waterglass is added to the sodium aluminate solution of above-mentioned preparation and 12g deionized waters mix 1h at 35 DEG C, it is 16Na aging 6h then to be stood at 35 DEG C mol ratio is obtained2O:Al2O3:15SiO2:320H2The directed agents of O.
By in 189g specifications waterglass addition directed agents same as described above, after placing 1.5h at 30 DEG C, it is 20.6Na to obtain a mole composition2O:Al2O3:30SiO2:495H2The directing agent solution of O, uses after room temperature is placed 24 hours.
(2) preparation of NaY types molecular sieve：According to mol ratio 3.84Na2O:Al2O3:12SiO2:220H2The synthesizing formula of O, by 250g specifications waterglass same as described above, the improvement directed agents of the above-mentioned preparations of 510g, 160g Al2O3Content is the aluminum sulfate solution and 9.7g sodium aluminate solutions (Al of 6.8wt.%2O3Content 7.5wt.%, Na2O content is 15wt.%) 1h is mixed, 97 DEG C are then heated to, crystallization 26h is filtered, dried.
The relative crystallinity of gained NaY molecular sieve is that 86%, framework si-al ratio is that 5.0, particle diameter is 500nm, and differential thermal fail temperature is 880.6 DEG C.
Particle size analysis the results are shown in Table one.
Comparative example three：
The synthesis of industrial NaY
(1) preparation of directed agents：Take 241.5g NaOH to be added in 450g water, stirring to NaOH is all dissolved, add 65.3g sodium metaaluminates, continue to stir to sodium metaaluminate and all dissolve, obtain sodium aluminate solution A.The solution A of 120g and the waterglass mixing and stirring of 80g are taken, 6g NaOH and 4g water is added, after stirring 2h, the aging 24h at 20 DEG C.Counted by 100wt.% of directed agents, the mol ratio of each component is：16.27Na2O:Al2O3:10.65SiO2:220.46H2O。
(2) preparation of NaY molecular sieve：144.8g aluminum sulfate is dissolved in 506g water, Al is formed2O3Content is the aluminum sulfate solution B of 3.4wt.%；44.7g NaOH is dissolved in 502.6g water, then adds 100g sodium metaaluminates, stirring forms sodium aluminate solution C to being completely dissolved.7.82g directed agents, 160g solution Bs and 170g solution Cs are added sequentially in 390g waterglass according to conventional NaY molecular sieve preparation process, add 62g water after stirring again, be made the reactant mixture of synthesis NaY molecular sieve.The mol ratio of each component is 4.93Na in mixture2O:Al2O3:10.21SiO2:180.38H2O；During reactant mixture gone into autoclave, the crystallization 24h at 100 DEG C.Hydrothermal crystallizing is finished, and takes out molecular sieve and mother liquor, is filtered, washs, is dried, and obtains final product NaY type zeolite products.
The relative crystallinity of gained NaY molecular sieve is that 98%, framework si-al ratio is that 5.0, particle diameter is 1000nm, and differential thermal fail temperature is 895.1 DEG C.
Particle size analysis the results are shown in Table one.
The analysis result of the different crystal NaY molecular sieve granularities of table one
| Sample | D(v 0.5)/μm | D(v 0.9)/μm |
| Embodiment one | 0.8 | 6.2 |
| Embodiment two | 0.4 | 5.8 |
| Embodiment three | 0.7 | 5.0 |
| Example IV | 2.8 | 6.0 |
| Embodiment five | 2.3 | 9.6 |
| Embodiment six | 0.9 | 4.1 |
| Embodiment seven | 0.7 | 4.7 |
| Embodiment eight | 1.2 | 8.7 |
| Embodiment nine | 1.8 | 7.4 |
| Embodiment ten | 0.6 | 5.3 |
| Embodiment 11 | 1.6 | 5.1 |
| Comparative example one | 3.2 | 10.4 |
| Comparative example two | 4.6 | 6.9 |
| Comparative example three | 4.1 | 8.0 |
By table one, it can be seen that：The D (v0.5) (meso-position radius) of Y type molecular sieve of the invention is less than 3.0 μm, respectively less than 3.2 μm of the D (v0.5) of comparative example, the characteristics of with high degree of dispersion, it is set to be more prone to be scattered in use in matrix or effectively compound with other materials, Y type molecular sieve exposes more outer surfaces and plays its catalytic performance simultaneously, and then improves the activity of catalyst.
Claims (11)
1. a kind of preparation method of NaY molecular sieve, comprises the following steps：
(1) preparation of directed agents
NaOH and silicon source are added to the water, or by NaOH be added to the water dissolving after add
Silicon source, forms solution A, in solution A in terms of oxide, Al2O3Content be 2~11wt.%, Na2O
Content is 10~30wt.%；
By waterglass, a certain amount of water and add a certain amount of NaOH and be added to solution A under agitation
In, after stirring, 0.5~72h of static ageing at 20~50 DEG C of temperature is obtained leading needed for the present invention
To agent；
Each component mol ratio is Na in the directed agents2O:Al2O3:SiO2:H2O=13~25：1：6~34：
150~550；
(2) preparation of reactant mixture
Water miscible silicon source is dissolved in water, in terms of oxide, Al is formed2O3Content is 1~6wt.%'s
Solution B；
NaOH is added to the water with silicon source, or NaOH is added to the water after dissolving and adds aluminium
Source, after stirring, forms solution C, in solution C in terms of oxide, Al2O3Content be 4~10wt.%,
Na2O content is 2~18wt.%；
Obtained directed agents, the solution B and the solution C in step (1) are added to waterglass molten
In liquid, a certain amount of surfactant is added, be made the reactant mixture of synthesis NaY molecular sieve；
Counted with the weight of reactant mixture as 100%, the addition of surfactant is 1~8wt.%；It is oriented to
The addition of agent is 1~22wt.%, in the reactant mixture of synthesis NaY molecular sieve, in addition to surfactant,
The mol ratio of remaining each component is Na2O:Al2O3:SiO2:H2O=2~14：1：6~28：160~450；
(3) hydrothermal crystallizing synthesis
The reactant mixture of the synthesis NaY molecular sieve that step (2) is obtained crystallization at 80~150 DEG C
After 10~72h, suction filtration, the required NaY molecular sieve of drying system.
2. the preparation method of NaY molecular sieve according to claim 1, it is characterised in that：To react
The weight meter of mixture, the addition of surfactant described in step (2) is 2~4wt.%.
3. the preparation method of NaY molecular sieve according to claim 1, it is characterised in that：Step (1)
The mol ratio of middle directed agents each component is：Na2O:Al2O3:SiO2:H2O=14~22：1：12~24：
160~450.
4. the preparation method of NaY molecular sieve according to claim 1, it is characterised in that：Step (2)
In counted with the weight of reactant mixture as 100%, the addition of directed agents is 2~16wt.%.
5. the preparation method of NaY molecular sieve according to claim 1, it is characterised in that：Step (2)
In the reactant mixture of middle synthesis NaY molecular sieve, in addition to surfactant, the mol ratio of remaining each component
For：Na2O:Al2O3:SiO2:H2O=3~12：1：8~22：220~360.
6. the preparation method of NaY molecular sieve according to claim 1, it is characterised in that：The table
Face activating agent is nonionic surfactant.
7. the preparation method of NaY molecular sieve according to claim 6, it is characterised in that：It is described non-
Ionic surface active agent is Span-20.
8. a kind of NaY molecular sieve, it is the system of the NaY molecular sieve described in any one of claim 1~7
NaY molecular sieve obtained by Preparation Method.
9. NaY molecular sieve according to claim 8, it is characterised in that：The NaY molecular sieve
Average grain diameter be 100~1000nm, framework si-al ratio be 4.9~5.4.
10. NaY molecular sieve according to claim 8, it is characterised in that：With meso-position radius D (v0.5)
Meter, the granularity of the NaY molecular sieve is less than 3 microns.
11. NaY molecular sieves according to claim 8, it is characterised in that：The NaY molecular sieve
Differential thermal fail temperature be 880~920 DEG C.
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