CN104591212B - A kind of preparation method of small crystal grain Y-shaped molecular sieve - Google Patents
A kind of preparation method of small crystal grain Y-shaped molecular sieve Download PDFInfo
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Abstract
The preparation method that the invention discloses a kind of small crystal grain Y-shaped molecular sieve.Silica alumina ratio is higher, degree of crystallinity is high, the NaY type Molecular sieve raw material of good stability in the method employing, and after sequentially passing through the mixed solution process of ammonium exchange, dealumination complement silicon, hydrothermal treatment consists and acid and ammonium salt, obtained small crystal grain Y-shaped molecular sieve is obtaining higher SiO2/A12O3While mol ratio, the ratio shared by secondary pore is higher, and maintains the stability of Y type molecular sieve, and molecular sieve has higher specific surface area and higher degree of crystallinity.The Y type molecular sieve of gained of the present invention is suitable to Cracking Component, and thus Y type molecular sieve has better activity, stability, higher purpose product selectivity and more excellent product quality as the hydrocracking catalyst of key component.
Description
Technical field
The preparation method that the present invention relates to a kind of Y type molecular sieve, the particularly preparation method of a kind of small crystal grain Y-shaped molecular sieve.
Background technology
Y type molecular sieve is cracking active component that at present can be the most general in residual oil cracking field, crystal grain is generally about 1000nm, its crystal grain is bigger, duct is relatively long, diffusional resistance is big, macromole is difficult to enter inside duct and reacts, and afterproduct is also more difficult diffuses out in reaction, so the selectivity of its cracking activity and purpose product receives restriction.Compared with conventional Y type molecular sieve, small crystal grain Y-shaped molecular sieve has bigger external surface area and more outer surface active center, is conducive to improving macromole hydrocarbon cracking capability, thus has more superior catalytic perfomance.Meanwhile, reduce Y type molecular sieve crystallite dimension and can also improve inner surface active sites utilization rate.In general, reactant molecule diffusion in molecular sieve endoporus duct is called micropore diffusion.Molecular sieve inner surface is made all to be used for catalyzed conversion, it is necessary to make micropore diffusion speed more than endoporus catalyzed conversion speed.Shortening the evolving path is the best way.Overcoming the effective way that micropore diffusion limits is reduce zeolite crystal size.This not only can increase the external surface area of zeolite crystal, and shorten diffusion length simultaneously.Small crystal grain NaY molecular sieve and big crystal NaY molecular sieve are compared by EP0204236, it is shown that RFCC is had higher activity and good selectivity by the former.Therefore the technology of preparing of small crystal grain molecular sieve increasingly causes the attention of people.
At present, NaY molecular sieve adopts directing agent method proposed in US3639099 and US3671191 substantially.First the method is prepare mole to consist of (15-17) Na2O∶Al2O3∶(14-16)SiO2∶(285-357)H2The directed agents of O, then it is directed to the raw materials such as agent and waterglass, sodium metaaluminate, aluminum sulfate according to mol ratio (3-6) Na2O∶Al2O3∶(8-12)SiO2∶(120-200)H2The ratio of O is mixed with gel, then by gel about 100 DEG C crystallization.The NaY molecular sieve skeleton SiO of the method synthesis2/Al2O3Generally about 5.0, being generally below 5.2, grain size is generally 500-800nm.
The method preparing fine grain Y type molecular sieve proposed in CN1081425A is first by crystallization l～10 hour pre-at the synthesis liquid 80 DEG C～180 DEG C of NaY, directed agents is added after being cooled to room temperature, then crystallization is continued 5～25 hours at 80 DEG C～100 DEG C, this processing step is more complicated and is difficult to control to, and the hydrothermal stability of the fine grain Y type molecular sieve prepared is poor.
The crystal grain of molecular sieve is reduced by adding the organic solvent dissolved each other with water in synthetic system, such as USP3516786 and USP4372931 adopts and adds disperse medium, the method of methanol, ethanol, dimethyl sulfoxide and left-right rotary sugar, the grain size of its synthetic product is 10～100nm.The sial of the molecular sieve synthesized by the method is relatively low, is only capable of synthesis x type molecular sieve, and organic solvent is readily volatilized when hydrothermal crystallizing.
Adopting in USP4587115 and USP4778666 and improve synthesis technique, such as the method for high-speed stirred, microwave heating, the grain size of its synthetic product is about 500nm.The method building-up process is complicated, and synthesis cost is high, and the silica alumina ratio of gained molecular sieve is low, and hydrothermal stability has much room for improvement.
The preparation method that CN1789125A proposes the NaY molecular sieve of a kind of high silica alumina ratio, little crystal grain, is that gel conventional method synthesized after static crystallization 0～70h, is added silicon source, then continued crystallization 0.5～50h at 90～120 DEG C at 50～100 DEG C.After the method needs, silicon reinsertion improves silica alumina ratio, and step is complicated.
The preparation method of a kind of high silicon aluminium ratio small crystal NaY molecular sieve that CN1785807A provides, 0.5～48 hour prepared crystallization director of ageing is stirred in advance at 15～60 DEG C, then be directed to agent, reactant mixture is made in water, silicon source, aluminum source, by reactant mixture crystallization in two steps after stirring, first step dynamic crystallization, second step static crystallization, eventually passes filter, washing, dries, prepare the relative crystallinity high silicon aluminium ratio small crystal NaY molecular sieve more than 80%.But hydrothermal stability is bad, HY molecular sieve crystallization reservation degree after 750 DEG C of hydrothermal treatment consists 2 hours is relatively low.
The preparation method of small crystal grain NaY molecular sieve disclosed in CN92105661.3, its preparation process is: first by the silica-alumina gel without directed agents in the input orientation agent again in 1 ~ 10 hour of 80 ~ 180 DEG C of crystallization, then crystallization is continued 5 ~ 25 hours at 90 ~ 100 DEG C, until crystallization is complete.The NaY molecular sieve that the small crystal grain NaY molecular sieve that the method prepares prepares with conventional method compares, and has identical silica alumina ratio and degree of crystallinity, and simply crystal grain less is 0.1 ~ 0.5 micron.Therefore, the silica alumina ratio of the small crystal grain NaY molecular sieve of the method gained is still relatively low, is generally less than 5, and its degree of crystallinity also awaits further raising.
CN101722023A discloses a kind of fine grain NaY type molecular sieve and preparation method thereof.The SiO of this fine grain NaY type molecular sieve2/Al2O3Mol ratio is 4.0～6.0, mean diameter is at 100～700nm, it is adopt the method that low temperature synthesis directed agents, low temperature synthesized gel rubber and two sections of alternating temperature dynamic crystallizations combine to prepare, the method is the fine grain NaY type molecular sieve adopting the method for optimum synthesis condition to prepare, its silica alumina ratio is still relatively low, and its heat stability and hydrothermal stability await further raising.
At present, existing method fine grain NaY type molecular sieve is in preparation process, and silicon and aluminum are easy to run off, silicon utilization rate is low, and silicon, aluminum distributing inhomogeneity, it is easy to occur reuniting, therefore existing method still cannot prepare silica alumina ratio height and the fine grain NaY type molecular sieve that heat stability and hydrothermal stability are good again.
Small crystal grain NaY molecular sieve is not possess acidity, it is necessary to be modified processing, to meet the performance requirement of Cracking catalyst.CNl382632A discloses a kind of super stabilizing method of small-grain Y-type zeolite, the method is with the dry gas of Silicon chloride. and fine grain NaY zeolitic contact, obtain after washing, owing to heat and the hydrothermal stability of its raw material self are just poor, this inventive method is that the mode adopting gas phase dealumination complement silicon processes molecular sieve simultaneously, this makes the heat of product and hydrothermal stability worse, and activity is low.Especially to the fine grain NaY zeolite that heat stability and hydrothermal stability are poor, the stability of itself sial framing structure is just poor, modifying process easily causes the elimination of framework aluminum, simultaneously also some framework silicon also with elimination, easily cause the phenomenon that caving in occurs in part skeleton, the crystallization reservation degree making product is relatively low, and the activity of molecular sieve and stability are not high.
CN200910165116.X discloses a kind of small crystal grain Y-shaped molecular sieve and preparation method thereof.Raw material small crystal grain NaY molecular sieve handled by the method is prepared by the method disclosed in CN101722023A, i.e. SiO2/Al2O3Mol ratio is 4.0～6.0, and mean diameter is at 100～700nm, and the mixed aqueous solution passing sequentially through successive modified i.e. ammonium exchange, ammonium hexafluorosilicate dealumination complement silicon, hydrothermal treatment consists, aluminium salt and acid processes, and obtains small-grain Y molecular sieve.In the method, need first to after raw material ammonium hexafluorosilicate dealumination complement silicon process, carry out hydrothermal treatment consists etc. again to process, so could reduce the caving in of framing structure of molecular sieve, the crystallization reservation degree of raising molecular sieve, but the method is due to after first processing with ammonium hexafluorosilicate dealumination complement silicon, owing to there is sial isomorphous substitution, molecular sieve silica constructed of aluminium ratio is more complete, then carries out hydrothermal treatment consists, the secondary pore formed is few, and secondary pore proportion is low.
At present, owing to the hydrothermal stability of small crystal grain NaY molecular sieve is poor, structural instability, through successive modified, it is impossible to obtains structural integrity, and degree of crystallinity is high and has the small crystal grain Y-shaped molecular sieve of more secondary pore.
Summary of the invention
In order to overcome weak point of the prior art, the invention provides that a kind of high silica alumina ratio, high-crystallinity, secondary pore be many, the preparation method of the small crystal grain Y-shaped molecular sieve of bigger serface.The method preparation flow is simple, and preparation cost is low.
The preparation method of the small crystal grain Y-shaped molecular sieve of the present invention, including:
(1) preparation of fine grain NaY type molecular sieve；
(2) fine grain NaY type molecular sieve is become Na2The little crystal grain NH of O content≤2.5wt%4NaY；
(3) step (2) is obtained little crystal grain NH4NaY molecular sieve carries out hydrothermal treatment consists；
(4) the molecular sieve hexafluorosilicic acid aqueous ammonium of step (3) gained carries out dealumination complement silicon, the molecular sieve obtained and separation of by-products；
(5) molecular sieve step (4) obtained is with containing NH4 +And H+Mixed solution process, be washed out and dry, obtain small crystal grain Y-shaped molecular sieve.
The preparation method of fine grain NaY type molecular sieve in step (1) in the inventive method, including:
A, preparation directed agents: silicon source, aluminum source, alkali source and water are fed intake according to following proportioning: (6～30) Na2O:Al2O3: (6～30) SiO2: (100～460) H2O, after stirring, stirs 0.5～24 hour prepared directed agents of ageing by mixture at 0～20 DEG C；
B, adopting acid-base precipitation method to prepare amorphous silica-alumina predecessor, with the weight of the butt of amorphous silica-alumina predecessor for benchmark, the content that silicon is counted with silicon dioxide is for 40wt%～75wt%, it is preferred to 55wt%～70wt%；Its preparation process includes acid-base neutralization plastic, aging, wherein silicon introduces the method for reaction system is in aluminiferous material and introducing portion is containing silicon materials before plastic and/or in plastic process, and remainder is in aluminiferous material containing silicon materials and after plastic and introduce before ageing；
C, prepare silica-alumina gel
By (0.5～6) Na2O:Al2O3: (7～11) SiO2: (100～460) H2Total molar ratio of O, adds water, silicon source, directed agents and alkali source when 0～40 DEG C of quick stirring in the amorphous silica-alumina predecessor of step (2) gained, and control ph is 9.5 ~ 12.0, uniform stirring, obtains silica-alumina gel；Wherein directed agents addition accounts for the 1%～20% of silica-alumina gel weight,
D, step C gained reactant mixture through two step dynamic crystallizations, then through filtration, washing, dry, obtain small crystal grain NaY molecular sieve.
In the present invention, in step A and C, silicon source, alkali source can adopt routine to prepare silicon source and the alkali source of molecular sieve, and in the present invention, preferred silicon source adopts sodium silicate, and alkali source adopts sodium hydroxide.In step A, aluminum source can adopt routine to prepare the aluminum source of molecular sieve, preferably employs sodium metaaluminate in the present invention.
In the present invention, step B preferably in aluminiferous material and after plastic and the silicon that introduces before ageing account for the 5wt% ~ 85wt% in silicon dioxide of the silicon in amorphous silica-alumina predecessor in silicon dioxide, it is preferred to 30wt% ~ 70wt%.
In the present invention, the preparation method of the amorphous silica-alumina predecessor of step B adopts conventional acid-base precipitation method, including acid-base neutralization plastic, aging, and wherein acid-base neutralization plastic process is usually the neutralization course of reaction of acid material and alkaline material.Neutralize plastic process and can adopt the mode of acid material or the continuous acid-base titration of alkaline material, it would however also be possible to employ acid material and alkaline material also flow the mode of neutralization.The method that wherein silicon introduces in reaction system is as follows: introducing portion is containing silicon materials in aluminiferous material and before plastic and/or in plastic process, and remainder is in aluminiferous material containing silicon materials and after plastic and introduce before ageing.Silicon can be neutralized plastic after mixing with acid material or alkaline material according to the different character containing silicon materials again (time such as containing silicon materials employing sodium metasilicate, sodium metasilicate can mix with alkaline material in aluminiferous material and before plastic and/or in plastic process；When adopting Ludox containing silicon materials, add acid aluminiferous material), it is also possible to and plastic process will be individually added in reaction system in aluminiferous material containing silicon materials, it is also possible to be the combination of said method.Plastic material generally comprises aluminiferous material (Al2(SO4)3、AlCl3、Al(NO3)3And NaAlO2Deng in one or more), containing silicon materials (one or more in waterglass, Ludox and organic silicon-containing compound etc., wherein organic silicon-containing compound is one or more in silanol, silicon ether and siloxanes, precipitant is divided into acidic precipitation agent and alkaline precipitating agent, wherein alkaline precipitating agent is one or more in sodium hydroxide, ammonia, sodium carbonate, sodium bicarbonate, and acidic precipitation agent is CO2Or nitric acid, using according to the different choice of plastic process, conventional mode of operation mainly has: (1) acid aluminium salt (Al2(SO4)3、AlCl3、Al(NO3)3) and basic aluminium salt (NaAlO2) or alkaline precipitating agent (NaOH, NH4OH) plastic, (2) basic aluminium salt (NaAlO are neutralized2) and acidic precipitation agent (CO2) neutralize plastic.Described plastic process is typically at room temperature ~ 85 DEG C to carry out, be relatively suitably for 40 ~ 80 DEG C, it is preferred to 50 ~ 70 DEG C.The pH value of described plastic process control system is 7.0 ~ 10.0, it is preferred to 7.5 ~ 9.0.When adopting continuous acid-base titration, the pH value controlling final plastic system is 7.0 ~ 10.0, it is preferred to 7.5 ~ 9.0, neutralizes plastic time control and makes the pH value of colloid system when adopting and flowing and remain 7.0 ~ 10.0, it is preferred to 7.5 ~ 9.0.Carrying out aging after plastic, aging condition is as follows: pH is 7.0 ~ 10.0, it is preferred to 7.0 ~ 9.5, and ageing time 0.2 ~ 8.0 hour is relatively adapted at 0.5 ~ 5 hour, it is preferred to 1 ~ 3 hour, and aging temperature is room temperature ~ 85 DEG C, it is preferred to 40 ~ 80 DEG C.Temperature and pH when temperature time aging and pH and neutralization are preferably identical.
In step C, control reaction temperature 0～40 DEG C, it is preferable that 10 ~ 30 DEG C, pH value 9.5～12.0, it is preferable that pH value 10～11.
The reactant mixture of step D gained carries out crystallization and adopts two step dynamic crystallizations, and wherein to carry out the condition of dynamic crystallization as follows for the first step: temperature controls at 50～90 DEG C, and crystallization time is 0.5～18 hour；The condition that second step carries out dynamic crystallization is as follows: temperature controls at 80～140 DEG C, and crystallization time is 3～10 hours, after crystallization completes, then through filtering, wash, drying, prepares product.Two step dynamic crystallization conditions are preferably as follows: the first step: temperature controls at 60～80 DEG C, and crystallization time is 1～10 hour；Second step: temperature controls at 80～120 DEG C, and crystallization time is 5～10 hours.
Small crystal grain NaY molecular sieve described in step (1), its character is as follows: SiO2/Al2O3Mol ratio is 5.0 ~ 9.0, it is preferable that 6.0～9.0, more preferably 7.0～8.0, and average grain diameter is 200～700nm, it is preferable that 300～500nm；Specific surface area is 800～1000m2/ g, it is preferred to 850～950m2/ g, pore volume is 0.30/～0.45mL/g, relative crystallinity is 90%～130%, cell parameter is 2.460～2.470nm, after roasting in 650 DEG C of air 3 hours, relative crystallinity is generally more than 85%, being preferably 90%～110%, after 700 DEG C of water vapour hydrothermal treatment consists 2 hours, relative crystallinity is generally more than 85%, it is preferred to 90%～110%.
In step (3), the condition of described hydrothermal treatment consists is as follows: treatment temperature controls at 500～750 DEG C, it is preferable that controlling at 600～700 DEG C, pressure is 0.01～0.50MPa, it is preferred to 0.05～0.30MPa, and the process time is 1.0～4.0 hours.
In step (4), aqueous medium adds little crystal grain NH4NaY molecular sieve (solid-liquid weight ratio 1:4 ~ 1:8), stirs and is warmed up to 90～120 DEG C, be then added dropwise to hexafluorosilicic acid aqueous ammonium, and after dropwising, constant temperature stirs 1～2 hour, separates molecular sieve and by-product, and filters, dries.The concentration 10wt% of hexafluorosilicic acid aqueous ammonium ~ 40wt%, ammonium hexafluorosilicate addition is little crystal grain NH410wt% ~ the 50wt% of NaY molecular sieve
In step (5), by the molecular sieve after hydrothermal treatment consists with acid and containing NH4 +Salt composition mixed solution contact, exchange molecular sieve in Na+With the part non-framework aluminum in elimination molecular sieve, acid therein can be one or more in hydrochloric acid, carbonic acid, nitric acid, sulphuric acid, containing NH4 +Salt be one or more in the ammonium salt containing above acid group；H in mixed solution+Concentration be 0.05～0.6mol/L, NH4 +Concentration be 0.5～3.0mol/L, exchange temperature is 70～120 DEG C, exchange serosity Middle molecule sieve concentration be 0.1～0.5g/mL, swap time is 0.5～3.0 hour, and exchange step may be repeated 1～4 time.Then remove mother solution, wash with water, dry.
Other operating procedure in the modified Y molecular sieve preparation method of the present invention, as ammonium salt exchange can adopt operational approach and the condition of this area routine, specific as follows: with NaY molecular sieve for raw material, with the aqueous solution of solubility ammonium salt such as ammonium chloride, ammonium carbonate, ammonium nitrate, ammonium sulfate, ammonium acetate, ammonium oxalate, ammonium citrate etc., the concentration of ammonium salt solution is 0.5～5.0mol/L.At 70～120 DEG C, it is preferred to exchange 0.5～3.0 hour at 80～100 DEG C, Y molecular sieve concentration in exchange serosity is 0.05～0.50g/mL, repeated exchanged l～5 time, elimination mother solution, and washing is dry.
The small-grain Y molecular sieve of the present invention, character is as follows: SiO2/ A12O3Mol ratio is 30～120, and average grain diameter is 200～700nm, it is preferable that 300～500nm, and relative crystallinity is more than 100%, it is preferred to 100% ~ 120%, lattice constant 2.425～2.450nm, and specific surface area is 850～1000m2/ g, pore volume is that the pore volume shared by the secondary pore of 0.40～0.60mL/g, 1.7～10nm accounts for more than the 50% of total pore volume, it is preferred to 50% ~ 70%, more preferably 55% ~ 65%, Na2O content≤0.15wt%.
Preparation method provided by the invention has the advantage that the silica alumina ratio of the NaY type Molecular sieve raw material due to present invention process is higher, degree of crystallinity is high, good stability, so in follow-up modification process, particularly in just carrying out hydrothermal treatment consists before dealumination complement silicon, so be conducive to improving the ratio shared by secondary pore of molecular sieve, and owing to the particularity of raw material makes molecular sieve remain in that good stability through hydrothermal treatment consists, it is also beneficial to the carrying out of follow-up dealumination complement silicon, acid treatment, and does not affect the stability of final molecular sieve.The small crystal grain Y-shaped molecular sieve prepared by method provided by the invention is obtaining higher SiO2/A12O3While mol ratio, the ratio shared by secondary pore is higher, and maintain Y type molecular sieve stability, molecular sieve has higher specific surface area and higher degree of crystallinity.The Y type molecular sieve of gained of the present invention is as Cracking Component, be conducive to the diffusion rate in the catalyst of the macromole in raising raw material, the molecular sieve performance as acid cracking center can be played better, avoid second pyrolysis, reduce carbon deposit, thus Y type molecular sieve can be made to have better activity, stability, higher purpose product selectivity and more excellent product quality as the hydrocracking catalyst of key component.
Accompanying drawing explanation
Fig. 1 is the SEM electromicroscopic photograph of embodiment l gained NY-1；
Fig. 2 is the XRD diffraction pattern of embodiment l gained NY-1.
Detailed description of the invention
In order to the present invention is better described, further illustrate the present invention below in conjunction with embodiment and comparative example.But the scope of the present invention is not limited solely to the scope of these embodiments.The present invention analyzes method: specific surface area, pore volume adopt low temperature liquid nitrogen physisorphtion, relative crystallinity and cell parameter adopt x-ray diffraction method, silica alumina ratio adopts chemical method, the grain size of molecular sieve adopts the mode of SEM (scanning electron microscope) to measure, and sodium content adopts plasma emission spectrometry.
Embodiment 1
The present embodiment is to prepare raw material small crystal grain NaY molecular sieve
The preparation of NY-1
(1) preparation of directed agents: take 8g sodium hydrate solid and be dissolved in 80g water, adds sodium metaaluminate 2.5g (Al2O3Content is 45wt%, Na2O content is 41wt%), then add 40g waterglass (SiO2Content is 28wt%, Na2O content is 8wt%), stir 4 hours prepared directed agents of ageing at 18 DEG C after mix homogeneously.
(2) preparation of amorphous silica-alumina predecessor
It is 100gA1 that solid sodium aluminate is configured to 0.3L concentration2O3/ L sodium aluminate working solution (a).Strong aqua ammonia is added appropriate distilled water diluting into about 10wt% weak ammonia (b).Take containing SiO2The sodium silicate solution of 28wt%, then to be diluted to 0.5L concentration be 140gSiO2/ L sodium silicate working solution (c).Take the steel retort of one 5 liters, after tank adding 0.5 liter of distilled water and being heated with stirring to 70 DEG C, open the valve having (a) and (b) and (c) Sulfur capacity device respectively simultaneously, control the flow of (a) and (c) so that neutralizing the response time at 40 minutes, and the flow adjusting rapidly (b) makes the pH value of system be maintained at 7～8, and control the temperature of system at about 60 DEG C.After reacting aluminum sulfate completes, stopping adding (b), the addition of (c) is 0.17L, after the silicon-aluminum sol of generation stablizes 20 minutes, continuously add (c) 0.33L, add in 10 minutes, start the ageing process of system, keep pH value 8.0, temperature 60 C, aging 30 minutes.
(3) preparation of gel
The serosity that step (2) is obtained adds 1LH2O、140gSiO2Directed agents 100g prepared by/L sodium silicate working solution 0.6L and step (1), the pH value of gel is 11.5, controls reaction temperature 15 DEG C, uniform stirring 30 minutes, staticizes 2.5 hours.
(4) crystallization
Gel obtained for step (2) is poured in stainless steel cauldron, stirs crystallization 5 hours at 75 DEG C, then heat to 110 DEG C, stirring crystallization 7 hours, then filter, washing, dry to obtain NaY molecular sieve product NY-1, character is listed in table l.
The preparation of NY-2
(1) preparation of directed agents: take 10g sodium hydrate solid and be dissolved in 90g water, adds sodium metaaluminate 3g (Al2O3Content is 45wt%, Na2O content is 41wt%), then add 50g waterglass (SiO2Content is 28wt%, Na2O content is 8wt%), stir 4 hours prepared directed agents of ageing at 20 DEG C after mix homogeneously.
(2) preparation of amorphous silica-alumina predecessor
It is 80gA1 that Solid aluminum sulfate is configured to 0.5L concentration2O3/ L aluminum sulfate working solution (a).Strong aqua ammonia is added appropriate distilled water diluting into about 10wt% weak ammonia (b).Take containing SiO2The sodium silicate solution of 28wt%, then to be diluted to 0.4L concentration be 150gSiO2/ L sodium silicate working solution (c).Take the steel retort of one 5 liters, after tank adding 0.5 liter of distilled water and being heated with stirring to 70 DEG C, open the valve having (a) and (b) and (c) container respectively simultaneously, control the flow of (a) and (c) so that neutralizing the response time at 40 minutes, and the flow adjusting rapidly (b) makes the pH value of system be maintained at 7～8, and control the temperature of system at about 60 DEG C.After reacting aluminum sulfate completes, stopping adding (b), the addition of (c) is 0.2L, after the silicon-aluminum sol of generation stablizes 20 minutes, continuously add (c) 0.2L, add in 10 minutes, start the ageing process of system, keep pH value 8.0, temperature 60 C, aging 30 minutes.
(3) preparation of gel
The serosity that step (2) is obtained adds 1.2LH2O、150gSiO2Directed agents 120g prepared by/L sodium silicate working solution 0.8L and step (1), the pH value of gel is 12, controls reaction temperature 30 DEG C, uniform stirring 30 minutes, staticizes 3 hours.
(4) crystallization
Gel obtained for step (2) is poured in stainless steel cauldron, stirs crystallization 6 hours at 80 DEG C, then heat to 120 DEG C, stirring crystallization 5 hours, then filter, washing, dry to obtain NaY molecular sieve product NY-2, character is listed in table l.
Embodiment 2
First raw material small crystal grain NaY molecular sieve NY-1 is carried out ammonium exchange.Compound concentration is 0.5mol/L aqueous ammonium nitrate solution 10 liters.Weighing small crystal grain NaY molecular sieve 1000 grams, join in 10 liters of aqueous ammonium nitrate solutions prepared, speed of agitator is 300rpm, and at 90 DEG C, constant temperature stirs l hour, then filtering molecular sieve, and stays sample, analyzes Na2O content；Repeat aforesaid operations, until Na in molecular sieve2O content reach 2.5wt%, obtaining dried sample number into spectrum is NNY-1.
Embodiment 3
First raw material small crystal grain NaY molecular sieve NY-2 is carried out ammonium exchange.Compound concentration is 0.8mol/L aqueous ammonium nitrate solution 10 liters.Weighing small crystal grain NaY molecular sieve 1000 grams, join in 10 liters of aqueous ammonium nitrate solutions prepared, speed of agitator is 300rpm, and at 95 DEG C, constant temperature stirs l hour, then filtering molecular sieve, and stays sample, analyzes Na2O content；Repeat aforesaid operations, until Na in molecular sieve2The content of O reaches 2.5wt%, and obtaining dried sample number into spectrum is NNY-2.
Embodiment 4
Taking 100 grams of NNY-1 and be placed in heat-treatment furnace, control the heating rate of 500 DEG C/h, temperature rises to 600 DEG C, the water vapor pressure simultaneously maintaining system is 0.15MPa, processes 2 hours, and sample is taken out in cooling；Sample deionized water is pulled an oar, and it is brought rapidly up 95 DEG C when stirring, then in 2 hours, the aqueous solution configured by 25 grams of ammonium hexafluorosilicate and 150m1 deionized water is dripped with uniform speed, add rear slurry constant temperature 2 hours under 95 DEG C of stirring conditions, stand 10 minutes, through 3 washings, filter；By filter cake 500mL containing NH4 +And H+Concentration respectively 0.6mol/L and 0.1mol/L mixed solution (ammonium chloride and hydrochloric acid) process, non-framework aluminum in elimination sample, dealuminzation condition is process 2 hours at 80 DEG C, and use hot deionized water washing leaching cake, after 7, washing, filter cake 120 DEG C dry 5 hours in an oven are stopped with the pH value of cleaning mixture, obtaining the small crystal grain Y-shaped molecular sieve product A of the present invention, the physico-chemical property of product A is in Table 2.
Embodiment 5
Take 100 grams of NNY-1 molecular sieves and be placed in heat-treatment furnace, control the heating rate of 400 DEG C/h, temperature is risen to 650 DEG C, maintain the steam partial pressure 0.08MPa of system simultaneously, process 2 hours, cooling, take out sample；Sample deionized water is pulled an oar, and it is brought rapidly up 90 DEG C when stirring, then in 2 hours, the aqueous solution configured by 30 grams of ammonium hexafluorosilicate and 150m1 deionized water is dripped with uniform speed, add rear slurry constant temperature 2 hours under 90 DEG C of stirring conditions, stand 10 minutes, through 3 washings, filter；By filter cake 400mL containing NH4 +And H+Concentration respectively 0.8mol/L and 0.2mol/L mixed solution (ammonium nitrate and nitric acid) process, non-framework aluminum in elimination sample, dealuminzation condition is process 3 hours at 70 DEG C, filter, and use hot deionized water washing leaching cake, stopping washing, filter cake 120 DEG C dry 5 hours in an oven with the pH value of cleaning mixture after 7, obtain the small crystal grain Y-shaped molecular sieve product B of the present invention, the physico-chemical property of product B is in Table 2.
Embodiment 6
Take 100 grams of NNY-2 molecular sieves and be placed in heat-treatment furnace, control the heating rate of 400 DEG C/h, temperature is risen to 700 DEG C, maintain the steam partial pressure 0.1MPa of system simultaneously, process 2 hours, cooling, take out sample；Sample deionized water is pulled an oar, and it is brought rapidly up 100 DEG C when stirring, then in 2 hours, the aqueous solution configured by 20 grams of ammonium hexafluorosilicate and 150m1 deionized water is dripped with uniform speed, add rear slurry constant temperature 2 hours under 100 DEG C of stirring conditions, stand 10 minutes, through 3 washings, filter；By filter cake 400mL containing NH4 +And H+Concentration respectively 1.0mol/L and 0.2mol/L mixed solution (ammonium chloride and hydrochloric acid) process, non-framework aluminum in elimination sample, dealuminzation condition is process 3 hours to filter at 75 DEG C, and use hot deionized water washing leaching cake, after 7, washing, filter cake 120 DEG C dry 6 hours in an oven are stopped with the pH value of cleaning mixture, obtaining the small crystal grain Y-shaped molecular sieve products C of the present invention, the physico-chemical property of products C is in Table 2.
Comparative example 1
1, fine grain NaY is prepared with reference to CN101722023A
Feedstock property used in this comparative example is as follows: low alkali sodium metaaluminate: Na2O content 120g/L, Al2O3Content 40g/L；Waterglass: SiO2Content 250g/L；Aluminum sulfate: Al2O3Content 90g/L.
(1) preparation of directed agents: the preparation of directed agents is with NY-1 in embodiment 1.
(2) preparation of gel: temperature is 8 DEG C, under stirring condition, 59.4mL aluminum sulfate, the low sodium metaaluminate of 62.7mL and 42.2mL directed agents it is sequentially added in the waterglass of 208mL, then constant temperature constant speed stirs 1.5 hours, then by the synthesis liquid that obtains static aging 8 hours at the temperature disclosed above, gel is obtained.
(3) crystallization: under agitation, was raised to 50 DEG C by the gel in synthesis reactor in 20 minutes, constant temperature stirring crystallization 7 hours；After low temperature crystallized end, in 20 minutes, the temperature in synthesis reactor being brought up to 120 DEG C, then constant temperature stirs 6 hours.Through filtering, wash and being dry, obtaining the little crystal grain CNY-l of product, product property is in Table 1.
2, raw material small crystal grain NaY molecular sieve CNY-1 being carried out ammonium exchange, treatment conditions are with embodiment 2, and obtaining dried sample number into spectrum is CNNY-1.
3, CNNY-1 is carried out subsequent treatment, processing mode and condition with embodiment 4, obtain Reference Product CA.The physico-chemical property of CA is in Table 2.
Comparative example 2
1, fine grain NaY is prepared with reference to CN1785807A
The preparation of directed agents: the preparation of directed agents is with NY-1 in embodiment 1.
Being positioned in beaker by 14.21g water, controlling temperature of liquid in beaker is 60 DEG C, is quickly simultaneously introduced the A1 of 12.79g50wt% under stirring2(SO4)3) solution and 31.91g waterglass.After stirring, add above-mentioned directed agents 1.90g, the pH value of gel is 12.5, after stirring, it is loaded in stainless steel cauldron, stirs crystallization 6 hours at 60 DEG C, then heat to 100 DEG C of static crystallizations 60 hours, then filtering, washing, dry to obtain CNY-2 zeolite product, product property is in Table 1.
2, raw material small crystal grain NaY molecular sieve CNY-1 being carried out ammonium exchange, treatment conditions are with embodiment 2, and obtaining dried sample number into spectrum is CNNY-2.
3, CNNY-2 is carried out subsequent treatment, processing mode and condition with embodiment 4, obtain Reference Product CB.The physico-chemical property of CB is in Table 2.
Comparative example 3
1, fine grain NaY is prepared with reference to CN92105661.3
In this comparative example, the feedstock property used by NaY is as follows: low alkali sodium metaaluminate: Na2O content 120g/L, Al2O3Content 40g/L；Waterglass: SiO2Content 250g/L；Aluminum sulfate: Al2O3Content 90g/L.
(1) preparation of directed agents: the preparation of directed agents is with NY-1 in embodiment 1.
(2) preparation of gel: be sequentially added into the low sodium metaaluminate of 60mL aluminum sulfate, 60mL in the waterglass of 220mL, then constant temperature constant speed stirs 0.5 hour, prepares silica-alumina gel.
(3) crystallization: under agitation, was raised to 140 DEG C by the gel in synthesis reactor in 30 minutes, constant temperature stirring crystallization 2 hours；Adding 35mL directed agents, mixing and stirring, then continue crystallization 15 hours at 100 DEG C, through filtering, wash and being dry, obtain products C NY-3, product property is in Table 1.
2, raw material small crystal grain NaY molecular sieve CNY-3 being carried out ammonium exchange, treatment conditions are with embodiment 2, and obtaining dried sample number into spectrum is CNNY-3.
3, CNNY-3 is carried out subsequent treatment, processing mode and condition with embodiment 4, obtain Reference Product CC.The physico-chemical property of CC is in Table 2.
Comparative example 4
1, prepared by fine grain NaY
(1) preparation of directed agents: the preparation of directed agents is with NY-1 in embodiment 1.
(2) preparation of amorphous silica-alumina predecessor.
It is 100gA1 that solid sodium aluminate is configured to 0.3L concentration2O3/ L sodium aluminate working solution (a).Strong aqua ammonia is added appropriate distilled water diluting into about 10wt% weak ammonia (b).Take containing SiO2The sodium silicate solution of 28wt%, then to be diluted to 0.5L concentration be 140gSiO2/ L sodium silicate working solution (c).Take the steel retort of one 5 liters, after tank adding 0.5 liter of distilled water and being heated with stirring to 70 DEG C, open the valve having (a) and (b) and (c) container respectively simultaneously, control the flow of (a) so that neutralizing the response time at 40 minutes, and the flow adjusting rapidly (b) makes the pH value of system be maintained at 7～8, and control the temperature of system at about 60 DEG C.After reacting aluminum sulfate completes, stopping adding (b), the silicon-aluminum sol of generation stablizes 40 minutes.
(3) preparation of gel is with embodiment 1.
(4) crystallization is with embodiment 1, obtains products C NY-4, and product property is in Table 1.
2, raw material small crystal grain NaY molecular sieve CNY-4 being carried out ammonium exchange, treatment conditions are with embodiment 2, and obtaining dried sample number into spectrum is CNNY-4.
3, CNNY-4 is carried out subsequent treatment, processing mode and condition with embodiment 4, obtain Reference Product CD.The physico-chemical property of CD is in Table 2.
Comparative example 5
The preparation of CNNY-5 is with comparative example 1.Then the method adopting CN200910165116.X modifiies, specific as follows: to take 100 grams of CNNY-5 100mL deionized water making beating, and it is brought rapidly up 95 DEG C when stirring, then in 2 hours, the aqueous solution configured by 25 grams of ammonium hexafluorosilicate and 150m1 deionized water is dripped with uniform speed, add rear slurry constant temperature 2 hours under 95 DEG C of stirring conditions, stand 10 minutes, through 3 washings, filtration, dry；Being placed in heat-treatment furnace by above-mentioned dried sample, control the heating rate of 500 DEG C/h, temperature rises to 600 DEG C, the water vapor pressure simultaneously maintaining system is 0.15MPa, processes 2 hours, and sample is taken out in cooling；Final sample 400mL is containing Al3+And H+The mixed solution (aluminum nitrate and nitric acid) of concentration respectively 1.0mol/L and 0.5mol/L remove the non-framework aluminum in sample, dealuminzation condition is process 2 hours at 80 DEG C, and use hot deionized water washing leaching cake, after 7, stop washing, filter cake 120 DEG C dry 5 hours in an oven with the pH value of cleaning mixture, obtain Reference Product CE.The physico-chemical property of CE is in Table 2.
Comparative example 6
Taking 100gNNY-1, adopt the method for CN200910165116.X to modifiy the NNY-1 of the present invention, concrete method of modifying, with comparative example 5, obtains Reference Product CF.The physico-chemical property of CF is in Table 2.
The character of table 1 small crystal grain NaY molecular sieve
In table 1, * roasting condition: roasting 3 hours in 650 DEG C of air；The condition of * hydrothermal treatment consists: 700 DEG C of steam treatment 2 hours.
The character of table 2 finished product small crystal grain Y-shaped molecular sieve
Claims (17)
1. a preparation method for small crystal grain Y-shaped molecular sieve, including:
(1) preparation of fine grain NaY type molecular sieve；
(2) fine grain NaY type molecular sieve is become Na2The little crystal grain NH of O content≤2.5wt%4NaY；
(3) step (2) is obtained little crystal grain NH4NaY molecular sieve carries out hydrothermal treatment consists；
(4) the molecular sieve hexafluorosilicic acid aqueous ammonium of step (3) gained carries out dealumination complement silicon, the molecular sieve obtained and separation of by-products；
(5) molecular sieve step (4) obtained is with containing NH4 +And H+Mixed solution process, be washed out and dry, obtain small crystal grain Y-shaped molecular sieve,
The wherein preparation method of fine grain NaY type molecular sieve in step (1), including:
A, preparation directed agents: silicon source, aluminum source, alkali source and water are fed intake according to following proportioning: (6～30) Na2O:Al2O3: (6～30) SiO2: (100～460) H2O, after stirring, stirs 0.5～24 hour prepared directed agents of ageing by mixture at 0～20 DEG C；
B, adopting acid-base precipitation method to prepare amorphous silica-alumina predecessor, with the weight of the butt of amorphous silica-alumina predecessor for benchmark, the content that silicon is counted with silicon dioxide is for 40wt%～75wt%；Its preparation process includes acid-base neutralization plastic, aging, wherein silicon introduces the method for reaction system is in aluminiferous material and introducing portion is containing silicon materials before plastic and/or in plastic process, and remainder is in aluminiferous material containing silicon materials and after plastic and introduce before ageing；
C, prepare silica-alumina gel: by (0.5～6) Na2O:Al2O3: (7～11) SiO2: (100～460) H2Total molar ratio of O, adds water, silicon source, directed agents and alkali source when 0～40 DEG C of quick stirring in the amorphous silica-alumina predecessor of step B gained, and control ph is 9.5 ~ 12.0, uniform stirring, obtains silica-alumina gel；Wherein directed agents addition accounts for the 1%～20% of silica-alumina gel weight,
D, step C gained reactant mixture through two step dynamic crystallizations, then through filtration, washing, dry, obtain small crystal grain NaY molecular sieve.
2. in accordance with the method for claim 1, it is characterised in that in step B, amorphous silica-alumina predecessor, with the weight of the butt of amorphous silica-alumina predecessor for benchmark, the content that silicon is counted with silicon dioxide is for 55wt%～70wt%.
3. in accordance with the method for claim 1, it is characterized in that in step B, in the preparation process of amorphous silica-alumina predecessor, in aluminiferous material and after plastic and the silicon that introduces before ageing account for the 5wt% ~ 85wt% in silicon dioxide of the silicon in amorphous silica-alumina predecessor in silicon dioxide.
4. in accordance with the method for claim 1, it is characterized in that in step B, in the preparation process of amorphous silica-alumina predecessor, in aluminiferous material and after plastic and the silicon that introduces before ageing account for the 30wt% ~ 70wt% in silicon dioxide of the silicon in amorphous silica-alumina predecessor in silicon dioxide.
5. in accordance with the method for claim 1, it is characterised in that in step A and C, silicon source, alkali source respectively sodium silicate and sodium hydroxide；In step A, aluminum source is selected from sodium metaaluminate.
6. in accordance with the method for claim 1, it is characterised in that in step B, aluminiferous material is Al2(SO4)3、AlCl3、Al(NO3)3And NaAlO2In one or more, it is one or more in waterglass, Ludox and organic silicon-containing compound containing silicon materials, wherein organic silicon-containing compound is one or more in silanol, silicon ether and siloxanes, precipitant is acidic precipitation agent or alkaline precipitating agent, wherein alkaline precipitating agent is one or more in sodium hydroxide, ammonia, sodium carbonate, sodium bicarbonate, acidic precipitation agent carbon dioxide or nitric acid.
7. in accordance with the method for claim 1, it is characterized in that in the step B acid-base precipitation method adopted, acid-base neutralization plastic process is the neutralization course of reaction of acid material and alkaline material, neutralize plastic process and adopt the mode of acid material or the continuous acid-base titration of alkaline material, or adopt acid material and alkaline material and flow the mode of neutralization.
8. in accordance with the method for claim 7, it is characterized in that in step B, introduce in aluminiferous material and before plastic and/or in plastic process containing silicon materials, it is be neutralized plastic again after mixing with acid material or alkaline material according to the different character containing silicon materials, or and will be individually added in reaction system in plastic process in aluminiferous material containing silicon materials, or the combination of said method.
9. in accordance with the method for claim 1, it is characterised in that in step B, described plastic process carries out at room temperature ~ 85 DEG C, and the pH value controlling system is 7.0 ~ 10.0；Carrying out aging after plastic, aging condition is as follows: aging pH is 7.0 ~ 10.0, ageing time 0.2 ~ 8.0 hour, and aging temperature is room temperature ~ 85 DEG C.
10. in accordance with the method for claim 1, it is characterised in that in step C, control reaction temperature 10 ~ 30 DEG C, pH value 10～11.
11. in accordance with the method for claim 1, it is characterised in that step D adopts two step dynamic crystallizations, wherein the first step to carry out the condition of dynamic crystallization as follows: temperature controls at 50～90 DEG C, and crystallization time is 0.5～18 hour；The condition that second step carries out dynamic crystallization is as follows: temperature controls at 80～140 DEG C, and crystallization time is 3～10 hours.
12. in accordance with the method for claim 1, it is characterised in that step D adopts two step dynamic crystallizations, wherein the first step to carry out the condition of dynamic crystallization as follows: temperature controls at 60～80 DEG C, and crystallization time is 1～10 hour；The condition that second step carries out dynamic crystallization is as follows: temperature controls at 80～120 DEG C, and crystallization time is 5～10 hours.
13. in accordance with the method for claim 1, it is characterised in that in step (3), the condition of described hydrothermal treatment consists is as follows: treatment temperature controls at 500～750 DEG C, and pressure is 0.01～0.50MPa, and the process time is 1.0～4.0 hours.
14. in accordance with the method for claim 1, it is characterised in that in step (3), the condition of described hydrothermal treatment consists is as follows: treatment temperature controls at 600～700 DEG C, and pressure is 0.05～0.30MPa, and the process time is 1.0～4.0 hours.
15. in accordance with the method for claim 1, it is characterised in that in step (4), press solid-liquid weight ratio 1:4 ~ 1:8 in aqueous medium to add little crystal grain NH4NaY molecular sieve, stirs and is warmed up to 90～120 DEG C, is then added dropwise to hexafluorosilicic acid aqueous ammonium, constant temperature stirring after dropwising, separates molecular sieve and by-product, and filters, dries, the wherein concentration 10wt% of hexafluorosilicic acid aqueous ammonium ~ 40wt%, ammonium hexafluorosilicate addition is little crystal grain NH410wt% ~ the 50wt% of NaY molecular sieve.
16. in accordance with the method for claim 1, it is characterised in that in step (5), by the molecular sieve after hydrothermal treatment consists with acid and containing NH4 +Salt composition mixed solution contact, exchange molecular sieve in Na+With the part non-framework aluminum in elimination molecular sieve, acid therein is one or more in hydrochloric acid, carbonic acid, nitric acid, sulphuric acid, containing NH4 +Salt be one or more in the ammonium salt containing above acid group；H in mixed solution+Concentration be 0.05～0.6mol/L, NH4 +Concentration be 0.5～3.0mol/L, exchange temperature is 70～120 DEG C, exchange serosity mesolite concentration be 0.1～0.5g/mL, swap time is 0.5～3.0 hour, and exchange step repeats 1～4 time.
17. in accordance with the method for claim 1, it is characterized in that: step (2) adopts the method for ammonium salt exchange, process is as follows: with NaY molecular sieve for raw material, exchange 0.5～3.0 hour at 70～120 DEG C with the aqueous solution of solubility ammonium salt, molecular sieve concentration in exchange serosity is 0.05～0.50g/mL, repeated exchanged l～5 time, elimination mother solution, washing, dry；Ammonium salt is one or more in ammonium chloride, ammonium carbonate, ammonium nitrate, ammonium sulfate, ammonium acetate, ammonium oxalate, ammonium citrate, and the concentration of ammonium salt solution is 0.5～5.0mol/L.
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| CN114684831B (en) * | 2020-12-31 | 2024-02-09 | 中海油天津化工研究设计院有限公司 | High silicon-aluminum ratio Y molecular sieve with high relative crystallinity and preparation method thereof |
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| CN101759198A (en) * | 2008-12-24 | 2010-06-30 | 中国石油化工股份有限公司 | Small crystal particle Y-shaped molecular sieve and preparation method thereof |
| CN101941713A (en) * | 2009-07-09 | 2011-01-12 | 中国石油化工股份有限公司抚顺石油化工研究院 | Small-grain high-Si Y-type molecular sieve and preparation method thereof |
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| GB2546614A (en) * | 2014-12-01 | 2017-07-26 | China Petroleum & Chem Corp | H-Y Molecular sieve, and preparation methods thereof, hydrocracking catalyst, and hydrocracking method |
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