CN104591214A - Small grain Y type molecular sieve and its preparation method - Google Patents
Small grain Y type molecular sieve and its preparation method Download PDFInfo
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- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/20—Faujasite type, e.g. type X or Y
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Abstract
The invention discloses a small grain Y type molecular sieve and its preparation method. The small grain Y type molecular sieve has following properties: a silica/alumina molar ratio of 40-120, a grain average diameter of 200-700nm, relative crystallinity of over 100%, a crystal lattice constant of 2.425-2.450nm, a specific surface area of 850-1000m2/g, a pore volume of 0.40-0.60mL/g, the pore volume of secondary pores with a pore volume of 1.7-10nm accounting for more than 50% of the total pore volume, and a sodium oxide content of not more than 0.15% by weight. The method includes adopting NaY type molecular sieve raw material with a high silica alumina ratio, high crystallinity and good stability, performing ammonium exchange, dealumination and silicon insertion, hydrothermal treatment and acid-ammonium salt mixed solution treatment, to obtain the small grain Y type molecular sieve. The inventive Y type molecular sieve is suitable as a cracking component, and a hydrocracking catalyst using the Y type molecular sieve as a key component has the advantages of good activity, stability, high target product selectivity and good product quality.
Description
Technical field
The present invention relates to a kind of Y zeolite and preparation method thereof, particularly a kind of small crystal grain Y-shaped molecular sieve and preparation method thereof.
Background technology
Y zeolite is cracking active component that at present can be the most general in heavy oil cracking field, crystal grain is generally about 1000nm, its crystal grain is larger, duct is relatively long, diffusional resistance is large, macromole is difficult to enter inside, duct and reacts, and after product is also more difficult diffuses out, so the selectivity of its cracking activity and object product receives restriction in reaction.Compared with conventional Y zeolite, small crystal grain Y-shaped molecular sieve has larger outer surface area and Geng Duo outside surface active centre, is conducive to improving macromole hydrocarbon cracking ability, thus has more superior catalytic perfomance.Meanwhile, reduce Y zeolite grain-size and can also improve internal surface active sites utilization ratio.In general, the diffusion of reactant molecule in molecular sieve endoporus duct is called micropore diffusion.Make molecular sieve internal surface all be used to carry out catalyzed conversion, micropore diffusion speed must be made to be greater than endoporus catalyzed conversion speed.Shortening the evolving path is the best way.The effective way overcoming micropore diffusion restriction reduces zeolite crystal size.This not only can increase the outer surface area of zeolite crystal, and shortens diffusion length simultaneously.EP0204236 compares small crystal grain NaY molecular sieve and large grain size NaY molecular sieve, and result shows, the former has higher activity and good selectivity to heavy oil fluid catalytic cracking.Therefore the technology of preparing of small crystal grain molecular sieve more and more causes the attention of people.
At present, NaY molecular sieve is adopt the directing agent method proposed in US 3639099 and US 3671191 substantially.First the method is that preparation mole consists of (15-17) Na
2o: Al
2o
3: (14-16) SiO
2: (285-357) H
2the directed agents of O, then by raw materials such as directed agents and water glass, sodium metaaluminate, Tai-Ace S 150 according to mol ratio (3-6) Na
2o: Al
2o
3: (8-12) SiO
2: (120-200) H
2the ratio of O is mixed with gel, then by gel about 100 DEG C crystallization.The NaY molecular sieve skeleton SiO of the method synthesis
2/ Al
2o
3usually about 5.0, generally lower than 5.2, grain size is generally 500-800nm.
The method preparing close grain Y zeolite 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 again after being chilled to room temperature, then crystallization is continued 5 ~ 25 hours at 80 DEG C ~ 100 DEG C, this processing step is more complicated and be difficult to control, and the hydrothermal stability of obtained close grain Y zeolite is poor.
By adding the crystal grain that the organic solvent dissolved each other with water reduces molecular sieve in synthetic system, adopt in such as USP3516786 and USP4372931 and add dispersion medium, the method of methyl alcohol, ethanol, dimethyl alum 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 lower, only can synthesize x type molecular sieve, and organic solvent easily volatilizees under hydrothermal crystallizing condition.
Adopt in USP4587115 and USP4778666 and improve synthesis technique, as the method for high-speed stirring, 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.
CN1789125A proposes the preparation method of NaY molecular sieve of a kind of high silica alumina ratio, little crystal grain, is the gel that ordinary method is synthesized after static crystallization 0 ~ 70h, is added silicon source, then continue crystallization 0.5 ~ 50h at 90 ~ 120 DEG C at 50 ~ 100 DEG C.Mend silicon after the method needs and improve silica alumina ratio, step is complicated.
The preparation method of a kind of high silicon aluminium ratio small crystal NaY molecular sieve that CN1785807A provides, ageing 0.5 ~ 48 hour obtained crystallization director is stirred in advance at 15 ~ 60 DEG C, then reaction mixture is made in directed agents, water, silicon source, aluminium source, by reaction mixture crystallization in two steps after stirring, the first step dynamic crystallization, second step static crystallization, finally by filtration, washing, drying, the high silicon aluminium ratio small crystal NaY molecular sieve that obtained relative crystallinity is greater than 80%.But hydrothermal stability is bad, HY molecular sieve is lower through 750 DEG C of hydrothermal treatment consists, 2 hours post crystallization reservation degree.
The preparation method of small crystal grain NaY molecular sieve disclosed in CN92105661.3, its preparation process is: first will not contain the silica-alumina gel of 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, until crystallization is complete at 90 ~ 100 DEG C.The NaY molecular sieve that the small crystal grain NaY molecular sieve that the method obtains obtains with conventional method compares, and has identical silica alumina ratio and degree of crystallinity, and just 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 lower, 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 sieve
2/ Al
2o
3mol ratio is 4.0 ~ 6.0, median size is at 100 ~ 700nm, prepared by the method adopting low temperature synthesis directed agents, low temperature synthesized gel rubber and two sections of alternating temperature dynamic crystallizations to combine, 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 lower, and its thermostability and hydrothermal stability await further raising.
At present, existing method fine grain NaY type molecular sieve is in preparation process, Silicified breccias easily runs off, silicon utilization ratio is low, and silicon, aluminium distributing inhomogeneity, easy appearance is reunited, and therefore still cannot to prepare silica alumina ratio high for existing method, and the fine grain NaY type molecular sieve that thermostability and hydrothermal stability are good again.
Small crystal grain NaY molecular sieve does not possess acidity, needs to carry out modification, to meet the performance requriements of cracking catalyst.CNl382632A discloses a kind of super stabilizing method of small-grain Y-type zeolite, the method uses dry gas and the fine grain NaY zeolitic contact of silicon tetrachloride, obtain after washing, due to the heat of its raw material self and hydrothermal stability just poor, this inventive method is the mode process molecular sieve adopting gas phase dealumination complement silicon simultaneously, this make the heat of product and hydrothermal stability poorer, active low.Especially to thermostability and the poor fine grain NaY zeolite of hydrothermal stability, the stability of itself sial skeleton structure is just poor, be easy to cause removing of framework aluminum in modifying process, simultaneously also some framework silicon also along with removing, be easy to cause part skeleton to occur the phenomenon of caving in, make the crystallization reservation degree of product lower, 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 for method disclosed in CN101722023A, i.e. SiO
2/ Al
2o
3mol ratio is 4.0 ~ 6.0, and median size, at 100 ~ 700nm, successively by the mixed aqueous solution process of successive modified i.e. ammonium exchange, ammonium hexafluorosilicate dealumination complement silicon, hydrothermal treatment consists, aluminium salt and acid, obtains small-grain Y molecular sieve.In the method, need first to raw material with after the process of ammonium hexafluorosilicate dealumination complement silicon, carry out the process such as hydrothermal treatment consists again, could reduce caving in of the skeleton structure of molecular sieve like this, improve the crystallization reservation degree of molecular sieve, but the method is due to after first using the process of ammonium hexafluorosilicate dealumination complement silicon, owing to there is sial isomorphous substitution, molecular sieve silica constructed of aluminium is more complete, then carries out hydrothermal treatment consists, and the secondary pore of formation is few.
At present, because the hydrothermal stability of small crystal grain NaY molecular sieve is poor, structural instability, through successive modified, can not obtain structural integrity, and degree of crystallinity is high and have 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 are many, the small crystal grain Y-shaped molecular sieve of bigger serface and preparation method thereof.The method preparation flow is simple, and preparation cost is low.
Small crystal grain Y-shaped molecular sieve of the present invention, character is as follows: SiO
2/ A1
2o
3mol ratio is 40 ~ 120, and average grain diameter is 200 ~ 700nm, preferably 300 ~ 500nm, and relative crystallinity is more than 100%, and be preferably 100% ~ 120%, lattice constant 2.425 ~ 2.450nm, specific surface area is 850 ~ 1000m
2/ g, pore volume is that the pore volume shared by secondary pore of 0.40 ~ 0.60mL/g, 1.7 ~ 10nm accounts for more than 50% of total pore volume, is preferably 50% ~ 75%, more preferably 60% ~ 70%, Na
2o content≤0.15wt%.
The preparation method of small crystal grain Y-shaped molecular sieve of the present invention, comprising:
(1) preparation of fine grain NaY type molecular sieve;
(2) fine grain NaY type molecular sieve is become Na
2the little crystal grain NH of O content≤2.5wt%
4naY;
(3) little crystal grain NH is obtained to step (2)
4naY 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 NH
4 +and H
+mixing solutions process, then washing and dry, obtains small crystal grain Y-shaped molecular sieve.
Small crystal grain NaY molecular sieve described in step (1), its character is as follows: SiO
2/ Al
2o
3mol ratio is greater than 6.0 and not higher than 9.0, and preferably 6.5 ~ 9.0, more preferably 7.0 ~ 8.0, average grain diameter is 200 ~ 700nm, preferably 300 ~ 500nm; Specific surface area is 800 ~ 1000 m
2/ g, is preferably 850 ~ 950 m
2/ g, pore volume 0.30/ ~ 0.45mL/g, relative crystallinity is 90% ~ 130%, unit cell parameters is 2.460 ~ 2.470nm, through roasting in 650 DEG C of air after 3 hours relative crystallinity be more than 90%, be generally 90% ~ 110%, be preferably 90% ~ 105%, through 700 DEG C of water vapor hydrothermal treatment consists after 2 hours relative crystallinity be more than 90%, be generally 90% ~ 110%, be preferably 90% ~ 105%.
In the inventive method, in step (1), the preparation method of fine grain NaY type molecular sieve is as follows:
I, preparation directed agents: silicon source, aluminium source, alkali source and water are fed intake according to following proportioning: (6 ~ 30) Na
2o:Al
2o
3: (6 ~ 30) SiO
2: (100 ~ 460) H
2o, after stirring, stirs ageing 0.5 ~ 24 hour obtained directed agents at 0 ~ 20 DEG C by mixture;
II, employing preparing amorphous silicon alumnium using carbonization precursor, with the weight of the butt of amorphous aluminum silicide precursor for benchmark, silicon for 40wt% ~ 75wt%, is preferably 55 wt% ~ 70wt% in the content of silicon-dioxide; Its preparation process comprises:
A, respectively preparation sodium aluminate solution and sodium silicate solution;
B, to step a preparation sodium aluminate solution in add step a preparation part sodium silicate solution, then pass into CO
2gas, controlling temperature of reaction is 10 ~ 40 DEG C, is preferably 15 ~ 35 DEG C, and the pH value controlling cemented into bundles is 8 ~ 11; Wherein as the CO passed into
2gas volume accounts for 60% ~ 100% of total intake, when being preferably 80% ~ 100%, add remainder sodium silicate solution, wherein in step b, remainder sodium silicate solution accounts for step b in silicon-dioxide and adds sodium silicate solution total amount in the 5wt% ~ 85wt% of silicon-dioxide, is preferably 30wt% ~ 70wt%;
C, under the control temperature and pH value of step b, said mixture ventilate stablize 10 ~ 30 minutes;
III, prepare silica-alumina gel
By (0.5 ~ 6) Na
2o:Al
2o
3: (8 ~ 15) SiO
2: (100 ~ 460) H
2total molar ratio of O, under the condition of 0 ~ 40 DEG C of rapid stirring, add water, silicon source, directed agents and alkali source in the amorphous aluminum silicide precursor of Step II gained, and control ph is 9.5 ~ 12.0, uniform stirring, obtains silica-alumina gel; Wherein directed agents add-on accounts for 1% ~ 20% of silica-alumina gel weight,
The reaction mixture of IV, Step II I gained is through two step dynamic crystallizations, more after filtration, washing, drying, obtains small crystal grain NaY molecular sieve.
In the present invention, in step I and III, silicon source, alkali source are selected from water glass and sodium hydroxide respectively.In step I, aluminium source is selected from sodium metaaluminate.
In Step II, the concentration of the sodium aluminate solution that step a is used is for being preferably 15 ~ 55g Al
2o
3/ l, the concentration of sodium silicate solution is 50 ~ 150 gSiO
2/ l, step b CO used
2the concentration of gas is 30v% ~ 60v%.
In Step II I, control temperature of reaction 0 ~ 40 DEG C, preferably 10 ~ 30 DEG C, pH value 9.5 ~ 12.0, preferable ph 10 ~ 11.
In step IV, the reaction mixture of 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, more after filtration, washing, dry, obtained product.Two step dynamic crystallization condition optimizations are 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, crystallization time is 5 ~ 10 hours.
In step (3), the condition of described hydrothermal treatment consists is as follows: treatment temp controls at 500 ~ 750 DEG C, preferably controls at 600 ~ 700 DEG C, and pressure is 0.01 ~ 0.50MPa, and be preferably 0.05 ~ 0.30MPa, the treatment time is 1.0 ~ 4.0 hours.
In step (4), in water medium, add little crystal grain NH
4naY molecular sieve (solid-liquid weight ratio 1:4 ~ 1:8), stirs and is warmed up to 90 ~ 120 DEG C, being then added dropwise to hexafluorosilicic acid aqueous ammonium, and after dropwising, constant temperature stirs 1 ~ 2 hour, isolated molecule sieve and by product, and filter, dry.The concentration 10 wt ~ 40wt% of hexafluorosilicic acid aqueous ammonium, ammonium hexafluorosilicate add-on is NH
410 wt% ~ 50wt% of NaY molecular sieve.
In step (5), by the Y molecular sieve after hydrothermal treatment consists with acid with containing NH
4 +the mixing solutions contact of salt composition, exchange the Na in molecular sieve
+with the part non-framework aluminum removed in molecular sieve, acid wherein can be hydrochloric acid, carbonic acid, nitric acid, sulfuric acid, containing NH
4 +salt be containing above acid group ammonium salt in one or more; H in mixing solutions
+concentration be 0.05 ~ 0.6mol/L, NH
4 +concentration be 0.5 ~ 3.0mol/L, exchange temperature is 70 ~ 120 DEG C, and the concentration exchanging slurries Middle molecule sieve is 0.1 ~ 0.5g/mL, and swap time is 0.5 ~ 3.0 hour, and exchange step can repeat 1 ~ 4 time.Then remove mother liquor, wash with water, dry.
Other operation steps in modified Y molecular sieve preparation method of the present invention, as ammonium salt exchanges working method and the condition that can adopt this area routine, specific as follows: to take NaY molecular sieve as raw material, with the aqueous solution of solubility ammonium salt as ammonium chloride, volatile salt, 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, preferably exchange 0.5 ~ 3.0 hour at 80 ~ 100 DEG C, Y molecular sieve is 0.05 ~ 0.50g/mL exchanging the concentration in slurries, repeated exchanged l ~ 5 time, elimination mother liquor, and washing is dry.
Preparation method's tool provided by the invention has the following advantages: because the silica alumina ratio of the NaY type Molecular sieve raw material of process of the present invention is higher, degree of crystallinity is high, good stability, so in follow-up modification process, especially before dealumination complement silicon, just hydrothermal treatment consists is carried out, be conducive to the ratio shared by secondary pore improving molecular sieve like this, and make molecular sieve still keep satisfactory stability through hydrothermal treatment consists due to the singularity of raw material, also be conducive to follow-up dealumination complement silicon, acid-treatedly carry out, and do 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 SiO
2/ A1
2o
3while mol ratio, the ratio shared by secondary pore is higher, and maintain Y zeolite stability, molecular sieve has higher specific surface area and higher degree of crystallinity.The Y zeolite of gained of the present invention is as Cracking Component, be conducive to improving the macromole rate of diffusion in the catalyst in raw material, the performance of molecular sieve as acid cracking center can be played better, avoid second pyrolysis, reduce carbon deposit, Y zeolite thus can be made to have better activity, stability, higher object product selectivity and more excellent quality product as the hydrocracking catalyst of key ingredient.
Accompanying drawing explanation
Figure l is the SEM electromicroscopic photograph of EXAMPLE l gained NY-1;
Fig. 2 is the XRD diffractogram of EXAMPLE l gained NY-1.
Embodiment
In order to better the present invention is described, further illustrate the present invention below in conjunction with embodiment and comparative example.But scope of the present invention is not only limited to the scope of these embodiments.Analytical procedure of the present invention: specific surface area, pore volume adopt low temperature liquid nitrogen physisorphtion, relative crystallinity and unit cell parameters adopt x-ray diffraction method, silica alumina ratio adopts chemical method, the grain size of molecular sieve adopts the mode of SEM (scanning electronic microscope) to measure, and sodium content adopts plasma emission spectrometry.
Embodiment 1
The present embodiment is raw materials small crystal grain NaY molecular sieve
The preparation of NY-1
(1) preparation of directed agents: get 10 g sodium hydrate solids and be dissolved in 80g water, add sodium metaaluminate 2g (Al
2o
3content is 45wt%, Na
2o content is 41wt%), and then add 36g water glass (SiO
2content is 28wt%, Na
2o content is 8 wt%), stir ageing 4 hours obtained directed agents at 15 DEG C after mixing.
(2) preparation of amorphous aluminum silicide precursor
Solid sodium aluminate being mixed with concentration is 40gAl
2o
3/ L sodium aluminate working solution, gets containing SiO
2the sodium silicate solution of 28wt%, redilution becomes concentration to be 100g SiO
2/ L water glass working solution.Get 1L sodium aluminate working solution and be placed in plastic cans, then add 0.2L water glass working solution, control temperature of reaction 20 DEG C, pass into the CO that concentration is 50v%
2gas, stops logical CO when pH value reaches 10.0
2, then add 0.4L water glass working solution, then ventilate and stablize 20 minutes.
(3) preparation of gel
100g SiO is added in the slurries that step (2) obtains
2directed agents 120g prepared by/L water glass working solution 1.5L and step (1), the pH value of gel is 12, and control temperature of reaction 20 DEG C, uniform stirring 30 minutes, staticizes 2 hours.
(4) crystallization
The gel that step (2) obtains is poured in stainless steel cauldron, stirs crystallization 4 hours at 70 DEG C, be then warming up to 100 DEG C, stir crystallization 8 hours, then filter, wash, dry NaY molecular sieve product NY-1, product property is in table 1.
The preparation of NY-2
(1) preparation of directed agents: get 8 g sodium hydrate solids and be dissolved in 80g water, adds sodium metaaluminate 2.5 g (Al
2o
3content is 45wt%, Na
2o content is 41wt%).And then add 40g water glass (SiO
2content is 28wt%, Na
2o content is 8 wt%), stir ageing 4 hours obtained directed agents at 18 DEG C after mixing.
(2) preparation of amorphous aluminum silicide precursor
Solid sodium aluminate being mixed with concentration is 30gAl
2o
3/ L sodium aluminate working solution, gets containing SiO
2the sodium silicate solution of 28wt%, redilution becomes concentration to be 70g SiO
2/ L water glass working solution.Get 1L sodium aluminate working solution and be placed in plastic cans, then add 0.4L water glass working solution, control temperature of reaction 18 DEG C, pass into the CO that concentration is 50v%
2gas, stops logical CO when pH value reaches 10.2
2, then add 0.6L water glass working solution, then ventilate and stablize 20 minutes.
(3) preparation of gel
70g SiO is added in the slurries that step (2) obtains
2directed agents 100g prepared by/L water glass working solution 1.5L and step (1), the pH value of gel is 11.5, and control temperature of reaction 15 DEG C, uniform stirring 30 minutes, staticizes 2.5 hours.
(4) crystallization
The gel that step (2) obtains is poured in stainless steel cauldron, stirs crystallization 5 hours at 75 DEG C, be then warming up to 110 DEG C, stir crystallization 7 hours, then filter, wash, dry NaY molecular sieve product NY-2, product property is in table 1.
Embodiment 2
First ammonium exchange is carried out to raw material small crystal grain NaY molecular sieve NY-1.Compound concentration is 0.5mol/L aqueous ammonium nitrate solution 10 liters.Take small crystal grain NaY molecular sieve 1000 grams, join in 10 liters of aqueous ammonium nitrate solutions prepared, mixing speed is 300rpm, and at 90 DEG C, constant temperature stirs l hour, then filtering molecular sieve, and stays sample, analyzes Na
2o content; Repeat aforesaid operations, until Na in molecular sieve
20 content reach 2.5wt%, obtaining dried sample number into spectrum is NNY-1.
Embodiment 3
First ammonium exchange is carried out to raw material small crystal grain NaY molecular sieve NY-2.Compound concentration is 0.8mol/L aqueous ammonium nitrate solution 10 liters.Take small crystal grain NaY molecular sieve 1000 grams, join in 10 liters of aqueous ammonium nitrate solutions prepared, mixing speed is 300rpm, and at 95 DEG C, constant temperature stirs l hour, then filtering molecular sieve, and stays sample, analyzes Na
2o content; Repeat aforesaid operations, until Na in molecular sieve
2o content reach 2.5wt%, obtaining dried sample number into spectrum is NNY-2.
Embodiment 4
Get 100 grams of NNY-1 and be placed in heat treatment furnace, control the temperature rise rate of 500 DEG C/h, temperature is risen 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 stir condition under rapid temperature increases to 95 DEG C, then in 2 hours, the aqueous solution configured by 25 grams of ammonium hexafluorosilicate and 150mL deionized water is dripped with uniform speed, add rear slurry constant temperature 2 hours under 95 DEG C of agitation conditions, leave standstill 10 minutes, through 3 washings, filter; Filter cake 500mL is contained NH
4 +and H
+the concentration mixing solutions (ammonium chloride and hydrochloric acid) that is respectively 0.6mol/L and 0.1mol/L process, remove the non-framework aluminum in sample, dealuminzation condition is 80 DEG C of process 2 hours, and use hot deionized water washing leaching cake, with the pH value of washings close to stopping the 120 DEG C of dryings 5 hours in an oven of washing, filter cake after 7, obtain 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
Get 100 grams of NNY-1 molecular sieves and be placed in heat treatment furnace, control the temperature rise 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 stir condition under rapid temperature increases to 90 DEG C, then in 2 hours, the aqueous solution configured by 30 grams of ammonium hexafluorosilicate and 150mL deionized water is dripped with uniform speed, add rear slurry constant temperature 2 hours under 90 DEG C of agitation conditions, leave standstill 10 minutes, through 3 washings, filter; Filter cake 400mL is contained NH
4 +and H
+the concentration mixing solutions (ammonium nitrate and nitric acid) that is respectively 0.8mol/L and 0.2mol/L process, remove the non-framework aluminum in sample, dealuminzation condition is process 3 hours at 70 DEG C, filter, and use hot deionized water washing leaching cake, with the pH value of washings close to stopping the 120 DEG C of dryings 5 hours in an oven of washing, filter cake after 7, obtain 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
Get 100 grams of NNY-2 molecular sieves and be placed in heat treatment furnace, control the temperature rise 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 stir condition under rapid temperature increases to 100 DEG C, then in 2 hours, the aqueous solution configured by 20 grams of ammonium hexafluorosilicate and 150mL deionized water is dripped with uniform speed, add rear slurry constant temperature 2 hours under 100 DEG C of agitation conditions, leave standstill 10 minutes, through 3 washings, filter; Filter cake 400mL is contained NH
4 +and H
+the concentration mixing solutions (ammonium chloride and hydrochloric acid) that is respectively 1.0mol/L and 0.2mol/L process, remove the non-framework aluminum in sample, dealuminzation condition is at 75 DEG C, process 3 hours filter, and use hot deionized water washing leaching cake, with the pH value of washings close to stopping the 120 DEG C of dryings 6 hours in an oven of washing, filter cake after 7, obtain 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 with reference to CN101722023A preparation
Feedstock property used in this comparative example is as follows: low alkali sodium metaaluminate: Na
2o content 120g/L, Al
2o
3content 40g/L; Water glass: SiO
2content 250g/L; Tai-Ace S 150: Al
2o
3content 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 agitation condition, 59.4mL Tai-Ace S 150, the low sodium metaaluminate of 62.7mL and 42.2mL directed agents is added successively in the water glass 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, and constant temperature stirs crystallization 7 hours; After low temperature crystallized end, in 20 minutes, the temperature in synthesis reactor is brought up to 120 DEG C, then constant temperature stirs 6 hours.After filtration, wash and drying, obtain the little crystal grain CNY-l of product, product property is in table 1.
2, carry out ammonium exchange to raw material small crystal grain NaY molecular sieve CNY-1, treatment condition are with embodiment 2, and obtaining dried sample number into spectrum is CNNY-1.
3, carry out subsequent disposal to CNNY-1, 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 with reference to CN1785807A preparation
The preparation of directed agents: the preparation of directed agents is with NY-1 in embodiment 1.
Be positioned in beaker by 14.21g water, controlling fluid temperature in beaker is 60 DEG C, adds the A1 of 12.79g50wt% under rapid stirring simultaneously
2(SO
4)
3) solution and 31.91g water glass.After stirring, add above-mentioned directed agents 1.90g, the pH value of gel is 12.5, after stirring, loaded in stainless steel cauldron, stir crystallization 6 hours at 60 DEG C, be then warming up to 100 DEG C of static crystallizations 60 hours, then filter, wash, dry CNY-2 zeolite product, product property is in table 1.
2, carry out ammonium exchange to raw material small crystal grain NaY molecular sieve CNY-1, treatment condition are with embodiment 2, and obtaining dried sample number into spectrum is CNNY-2.
3, carry out subsequent disposal to CNNY-2, 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 with reference to CN92105661.3 preparation
The feedstock property that in this comparative example, NaY is used is as follows: low alkali sodium metaaluminate: Na
2o content 120g/L, Al
2o
3content 40g/L; Water glass: SiO
2content 250g/L; Tai-Ace S 150: Al
2o
3content 90g/L.
(1) preparation of directed agents: the preparation of directed agents is with NY-1 in embodiment 1.
(2) preparation of gel: the low sodium metaaluminate adding 60mL Tai-Ace S 150,60mL in the water glass of 220mL successively, then constant temperature constant speed stirs 0.5 hour, obtained silica-alumina gel.
(3) crystallization: under agitation, was raised to 140 DEG C by the gel in synthesis reactor in 30 minutes, and constant temperature stirs crystallization 2 hours; Add 35mL directed agents, mixing and stirring, then continue crystallization 15 hours at 100 DEG C, after filtration, wash and drying, obtain products C NY-3, product property is in table 1.
2, carry out ammonium exchange to raw material small crystal grain NaY molecular sieve CNY-3, treatment condition are with embodiment 2, and obtaining dried sample number into spectrum is CNNY-3.
3, carry out subsequent disposal to CNNY-3, 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, fine grain NaY preparation
(1) preparation of directed agents: the preparation of directed agents is with NY-1 in embodiment 1.
(2) preparation of amorphous aluminum silicide precursor.
Solid sodium aluminate being mixed with concentration is 40gAl
2o
3/ L sodium aluminate working solution, gets containing SiO
2the sodium silicate solution of 28wt%, redilution becomes concentration to be 100g SiO
2/ L water glass working solution.Get 1L sodium aluminate working solution and be placed in plastic cans, then add 0.6L water glass working solution, control temperature of reaction 20 DEG C, pass into the CO that concentration is 50v%
2gas, stops logical CO when pH value reaches 10.0
2, then ventilate and stablize 20 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, carry out ammonium exchange to raw material small crystal grain NaY molecular sieve CNY-4, treatment condition are with embodiment 2, and obtaining dried sample number into spectrum is CNNY-4.
3, carry out subsequent disposal to CNNY-4, 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 modification of CN200910165116.X is adopted, specific as follows: to get 100 grams of CNNY-5 100mL deionized water making beating, and stir condition under rapid temperature increases to 95 DEG C, 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 agitation conditions, leave standstill 10 minutes, through 3 washings, filtration, drying; Sample after above-mentioned drying is placed in heat treatment furnace, and control the temperature rise rate of 500 DEG C/h, temperature is risen 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 contains Al
3+and H
+the concentration mixing solutions (aluminum nitrate and nitric acid) that is respectively 1.0mol/L and 0.5mol/L remove non-framework aluminum in sample, dealuminzation condition is 80 DEG C of process 2 hours, and use hot deionized water washing leaching cake, with the pH value of washings close to stopping the 120 DEG C of dryings 5 hours in an oven of washing, filter cake after 7, obtain Reference Product CE.The physico-chemical property of CE is in table 2.
Comparative example 6
Get 100gNNY-1, NNY-1 of the present invention is adopted to the method modification of CN200910165116.X, concrete preparation method, 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-treated 2 hours.
The character of table 2 finished product small crystal grain Y-shaped molecular sieve
Claims (24)
1. a small crystal grain Y-shaped molecular sieve, character is as follows: SiO
2/ A1
2o
3mol ratio is 40 ~ 120, and average grain diameter is 200 ~ 700nm, and relative crystallinity is more than 100%, and lattice constant 2.425 ~ 2.450nm, specific surface area is 850 ~ 1000m
2/ g, pore volume is that the pore volume shared by secondary pore of 0.40 ~ 0.60mL/g, 1.7 ~ 10nm accounts for more than 50%, Na of total pore volume
2o content≤0.15wt%.
2., according to molecular sieve according to claim 1, it is characterized in that the average grain diameter of described small crystal grain Y-shaped molecular sieve is 300 ~ 500nm.
3., according to molecular sieve according to claim 1, it is characterized in that the relative crystallinity of described small crystal grain Y-shaped molecular sieve is 100% ~ 120%.
4., according to molecular sieve according to claim 1, it is characterized in that in described small crystal grain Y-shaped molecular sieve, the pore volume shared by secondary pore of 1.7 ~ 10nm account for 50% ~ 75% of total pore volume.
5., according to molecular sieve according to claim 1, it is characterized in that in described small crystal grain Y-shaped molecular sieve, the pore volume shared by secondary pore of 1.7 ~ 10nm account for 60% ~ 70% of total pore volume.
6. the preparation method of molecular sieve according to claim 1, comprising:
(1) preparation of fine grain NaY type molecular sieve;
(2) fine grain NaY type molecular sieve is become Na
2the little crystal grain NH of O content≤2.5wt%
4naY;
(3) little crystal grain NH is obtained to step (2)
4naY 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 NH
4 +and H
+mixing solutions process, then washing and dry, obtains small crystal grain Y-shaped molecular sieve,
The small crystal grain NaY molecular sieve that wherein step (1) is used, its character is as follows: SiO
2/ Al
2o
3mol ratio is greater than 6.0 and not higher than 9.0, average grain diameter is 200 ~ 700nm, specific surface 800 ~ 1000 m
2/ g, pore volume 0.30/ ~ 0.45mL/g, relative crystallinity is 90% ~ 130%, and unit cell parameters is 2.460 ~ 2.470nm, through roasting in 650 DEG C of air after 3 hours relative crystallinity be more than 90%, through 700 DEG C of water vapor hydrothermal treatment consists after 2 hours relative crystallinity be more than 90%.
7. in accordance with the method for claim 6, it is characterized in that: the SiO of small crystal grain NaY molecular sieve used
2/ Al
2o
3mol ratio is 6.5 ~ 9.0.
8. in accordance with the method for claim 6, it is characterized in that: the SiO of small crystal grain NaY molecular sieve used
2/ Al
2o
3mol ratio is 7.0 ~ 8.0.
9. in accordance with the method for claim 6, it is characterized in that: the average grain diameter of small crystal grain NaY molecular sieve used is 300 ~ 500nm.
10. in accordance with the method for claim 6, it is characterized in that: small crystal grain NaY molecular sieve used through roasting in 650 DEG C of air after 3 hours relative crystallinity be 90% ~ 110%, through 700 DEG C of water vapor hydrothermal treatment consists after 2 hours relative crystallinity be 90% ~ 110%.
11. in accordance with the method for claim 6, it is characterized in that: the preparation method of small crystal grain NaY molecular sieve used, comprising:
I, preparation directed agents: silicon source, aluminium source, alkali source and water are fed intake according to following proportioning: (6 ~ 30) Na
2o:Al
2o
3: (6 ~ 30) SiO
2: (100 ~ 460) H
2o, after stirring, stirs ageing 0.5 ~ 24 hour obtained directed agents at 0 ~ 20 DEG C by mixture;
II, adopt preparing amorphous silicon alumnium using carbonization precursor, with the weight of the butt of amorphous aluminum silicide precursor for benchmark, silicon in the content of silicon-dioxide for 40wt% ~ 75wt%; Its preparation process comprises:
A, respectively preparation sodium aluminate solution and sodium silicate solution;
B, to step a preparation sodium aluminate solution in add step a preparation part sodium silicate solution, then pass into CO
2gas, controlling temperature of reaction is 10 ~ 40 DEG C, and the pH value controlling cemented into bundles is 8 ~ 11; Wherein as the CO passed into
2when gas volume accounts for 60% ~ 100% of total intake, add remainder sodium silicate solution, wherein in step b, remainder sodium silicate solution accounts for step b in silicon-dioxide and adds sodium silicate solution total amount in the 5wt% ~ 85wt% of silicon-dioxide;
C, under the control temperature and pH value of step b, said mixture ventilate stablize 10 ~ 30 minutes;
III, prepare silica-alumina gel: by (0.5 ~ 6) Na
2o:Al
2o
3: (8 ~ 15) SiO
2: (100 ~ 460) H
2total molar ratio of O, under the condition of 0 ~ 40 DEG C of rapid stirring, add water, silicon source, directed agents and alkali source in the amorphous aluminum silicide precursor of Step II gained, and control ph is 9.5 ~ 12.0, uniform stirring, obtains silica-alumina gel; Wherein directed agents add-on accounts for 1% ~ 20% of silica-alumina gel weight,
The reaction mixture of IV, Step II I gained is through two step dynamic crystallizations, more after filtration, washing, drying, obtains small crystal grain NaY molecular sieve.
12. in accordance with the method for claim 11, it is characterized in that in Step II, amorphous aluminum silicide precursor, and with the weight of the butt of amorphous aluminum silicide precursor for benchmark, silicon is 55 wt% ~ 70wt% in the content of silicon-dioxide.
13. in accordance with the method for claim 11, it is characterized in that: it is 15 ~ 35 DEG C that step b controls temperature of reaction.
14. in accordance with the method for claim 11, it is characterized in that: in step b, as the CO passed into
2when gas volume accounts for 80% ~ 100% of total intake, add remainder sodium silicate solution.
15. in accordance with the method for claim 11, it is characterized in that: in step b, remainder sodium silicate solution accounts for step b in silicon-dioxide and adds sodium silicate solution total amount in the 30wt% ~ 70wt% of silicon-dioxide.
16. in accordance with the method for claim 11, and it is characterized in that, in step I and III, silicon source, alkali source are selected from water glass and sodium hydroxide respectively, in step I, aluminium source is selected from sodium metaaluminate.
17. in accordance with the method for claim 11, it is characterized in that in Step II I, controls temperature of reaction 10 ~ 30 DEG C, pH value 10 ~ 11.
18. in accordance with the method for claim 11, it is characterized in that step IV 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.
19. in accordance with the method for claim 11, it is characterized in that step IV adopts two step dynamic crystallizations, and wherein to carry out the condition of dynamic crystallization as follows for the first step: 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.
20. in accordance with the method for claim 6, and it is characterized in that in step (3), the condition of described hydrothermal treatment consists is as follows: treatment temp controls at 500 ~ 750 DEG C, pressure is 0.01 ~ 0.50MPa, and the treatment time is 1.0 ~ 4.0 hours.
21. in accordance with the method for claim 6, and it is characterized in that in step (3), the condition of described hydrothermal treatment consists is as follows: treatment temp controls at 600 ~ 700 DEG C, pressure is 0.05 ~ 0.30MPa, and the treatment time is 1.0 ~ 4.0 hours.
22. in accordance with the method for claim 6, it is characterized in that, in step (4), in water medium, adding little crystal grain NH by solid-liquid weight ratio 1:4 ~ 1:8
4naY molecular sieve, stirs and is warmed up to 90 ~ 120 DEG C, being then added dropwise to hexafluorosilicic acid aqueous ammonium, after dropwising, constant temperature stirs, isolated molecule sieve and by product, and filter, dry, the wherein concentration 10wt% ~ 40wt% of hexafluorosilicic acid aqueous ammonium, ammonium hexafluorosilicate add-on is little crystal grain NH
410wt% ~ the 50wt% of NaY molecular sieve.
23. in accordance with the method for claim 6, it is characterized in that in step (5), by the molecular sieve after hydrothermal treatment consists with acid with containing NH
4 +the mixing solutions contact of salt composition, exchange the Na in molecular sieve
+with the part non-framework aluminum removed in molecular sieve, acid is wherein one or more in hydrochloric acid, carbonic acid, nitric acid, sulfuric acid, containing NH
4 +salt be containing above acid group ammonium salt in one or more; H in mixing solutions
+concentration be 0.05 ~ 0.6mol/L, NH
4 +concentration be 0.5 ~ 3.0mol/L, exchange temperature is 70 ~ 120 DEG C, and the concentration exchanging slurries Middle molecule sieve is 0.1 ~ 0.5g/mL, and swap time is 0.5 ~ 3.0 hour, and exchange step repeats 1 ~ 4 time.
24. in accordance with the method for claim 1, it is characterized in that: the method that step (2) adopts ammonium salt to exchange, process is as follows: take NaY molecular sieve as raw material, at 70 ~ 120 DEG C, 0.5 ~ 3.0 hour is exchanged with the aqueous solution of solubility ammonium salt, molecular sieve is 0.05 ~ 0.50g/mL exchanging the concentration in slurries, repeated exchanged l ~ 5 time, elimination mother liquor, washing, dry; Ammonium salt is one or more in ammonium chloride, volatile salt, 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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