CN101941713B - Small-grain high-Si Y-type molecular sieve and preparation method thereof - Google Patents
Small-grain high-Si Y-type molecular sieve and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a small-grain high-Si Y-type molecular sieve and a preparation method thereof. The small-grain high-Si Y-type molecular sieve is a product prepared by using a small-grain NaY molecular sieve as a raw material and selecting proper modification processes, namely ammonia exchange, ammonium hexfluorosilicate for dealuminzation and silicon supplement, hydro-thermal treatment and aluminum salt aqueous solution treatment. The small-grain NaY molecular sieve used by the method can guarantee the skeleton continuity of the molecular sieve product, reduce the collapse possibility of skeleton structure and maximally retain the integrity of Si-Al-O structure of the product during the subsequent medication treatments due to the high thermal and hydrothermal stabilities, high Si-Al ratio, high stability and uniform skeleton Si-Al structure; therefore, the product still has a crystalline retention degree as high as above 95 percent while having the greatly improved Si-Al ratio. The Y-type molecular sieve can be used as the active component for the hydrocracking catalysts to improve the activities of the catalysts, selectivity of the target product and the quality of the product.
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
At present in the heavy oil cracking field, Y type, β type and ZSM etc. can be arranged as the molecular sieve of cracking activity component, wherein use the most generally with Y zeolite again.The method of industrial production Y zeolite all is the directed agents method that adopts U.S. GRACE company to propose in USP 3639099 and USP 4166099 basically at present, the crystal grain of the common Y zeolite that makes is generally about 1000nm, its crystal grain is larger, the duct is relatively long, diffusional resistance is large, macromole is difficult to enter inside, duct and reacts, the reaction after product also difficulty diffuse out, so the selectivity of its cracking activity and purpose product has been subject to restriction.
Thus, many investigators have synthesized small crystal grain Y-shaped molecular sieve, because it has larger external surface area, the duct is shorter, the intracrystalline diffusion is good, be conducive to macromolecular conversion, can reduce the characteristics such as generation of the side reactions such as secondary cracking, so small crystal grain Y-shaped molecular sieve has a good application prospect.But the silica alumina ratio of the small crystal grain NaY molecular sieve that prior art synthesizes is lower, and lattice constant is larger, and its thermostability and hydrothermal stability are relatively poor, and therefore, the stability that improves small crystal grain NaY molecular sieve is the emphasis of research.
Proposed a kind of method that silica alumina ratio is 2～3 X-type zeolite for preparing among the GB1223592, its system basicity is higher, can only obtain the X-type molecular sieve.USP4,66,099 and EP0435625A2 in also adopt the method for raising system basicity, the grain size of its synthetic product is below the 100nm, can obtain close grain although high alkalinity is synthetic, but can not get silica alumina ratio greater than 5 product, generally can only obtain X-type molecular sieve and silica alumina ratio less than 5 Y zeolite, and the thermostability of the molecular sieve that synthesizes and hydrothermal stability are not ideal.
By in synthetic system, adding the crystal grain that the organic solvent that dissolves each other with water reduces molecular sieve, such as USP3,516, adopt in 786 and USP4,372,931 and add dispersion medium, the method of methyl alcohol, ethanol, dimethyl alum and left-right rotary sugar, the grain size of its synthetic product are 10～100nm.The silica alumina ratio of the molecular sieve that the method is synthesized is lower, generally only can synthesize the X-type molecular sieve, and organic solvent easily volatilization under the hydrothermal crystallizing condition.
CN1081425A discloses a kind of preparation method of small crystal grain NaY molecular sieve, and the method is in order to reduce crystallite size, at first will not contain again input orientation agent after the silica-alumina gel crystallization of directed agents, continues crystallization again.Although the method crystal grain is little, degree of crystallinity is still hanged down below 90%.
The preparation method of the small crystal grain NaY molecular sieve that CN1785807A provides is as follows: made crystallization director in 0.5～48 hour 15～60 ℃ of lower stirring ageings in advance, then at 15～80 ℃ reaction mixture is made in directed agents, water, silicon source, aluminium source, after stirring with reaction mixture crystallization in two steps, the first step was 20～80 ℃ of dynamic crystallizations 0.5～48 hour, second step was 90～140 ℃ of static crystallizations 5～100 hours, finally by filtration, washing, drying, make small crystal grain NaY molecular sieve.This HY molecular sieve is 28% (specifically seeing embodiment 1 table 3 data) through 750 ℃ of hydrothermal treatment consists post crystallization reservation in 2 hours degree, and hydrothermal stability is bad.Because its second segment crystallization adopts the method for static crystallization, in the situation that do not stir, intermediates can be deposited at the bottom of the still, and form the interfacial layer of a class solid-liquid with synthesis mother liquid, Siliciumatom in the supernatant liquid and aluminium atom are just more difficult to get access in the skeleton of molecular sieve so, cause thermostability and the hydrothermal stability of product relatively poor, increased simultaneously preparation cost.
Synthetic small crystal grain NaY molecular sieve is not possess acidity, need to carry out modification, to satisfy the performance requriements of cracking catalyst.CN1382632A discloses a kind of super stabilizing method of small-grain Y-type zeolite, the method is to use the dry gas of silicon tetrachloride to contact with the fine grain NaY zeolite, obtain after the washing, because heat and the hydrothermal stability of its raw material self are just relatively poor, this inventive method is to adopt the mode of gas phase dealumination complement silicon to process molecular sieve simultaneously, this is active low so that the heat of product and hydrothermal stability are poorer; This gas phase treatment method exists in batches littlely in industrial production in addition, and the shortcoming such as consume energy higher.During especially to the relatively poor fine grain NaY zeolite of thermostability and hydrothermal stability (as adopting the synthetic NaY zeolite of CN1081425A among the embodiment) modification, its crystallization reservation degree is below 95%, because the poor-performing of raw material, sial skeleton structure less stable in the molecular sieve, in modifying process, be easy to cause removing of framework aluminum, simultaneously also some framework silicon also along with removing, be easy to the phenomenon that causes the part skeleton to occur caving in, so that the crystallization reservation degree of product is lower, the activity of molecular sieve is not high.The method of modifying of Comparative Examples 3 is to carry out the ammonium exchange with ammonium sulfate first, then add ammonium silicofluoride, the little crystal grain BM-3 that obtains, its crystallization reservation degree is lower, only is 70%, method preparations of adopting non-directed agents at Comparative Examples 3 Raws, so the framework silicon-aluminum of its raw material is lower, in the process of carrying out aftertreatment, be easy to cause the big area of framework silicon-aluminum to cave in, cause the poor activity of product, crystallization reservation degree is lower.
Summary of the invention
In order to overcome weak point of the prior art, the invention provides the good high silica alumina ratio of a kind of thermostability and hydrothermal stability, high-crystallinity small crystal grain Y-shaped molecular sieve and preparation method thereof.The method preparation flow is simple, and preparation cost is low.
The SiO of high silica alumina ratio of the present invention, high-crystallinity small crystal grain Y-shaped molecular sieve
2/ Al
2O
3Mol ratio 10.0～120.0, preferred 15.0～80.0, average grain diameter is 100～700nm, preferred 300～500nm; Unit cell parameters is 2.420～2.445nm, and crystallization reservation degree is greater than 95%, and is preferred 98%～110% generally below 120%, sodium oxide weight content≤0.1wt%.
The character of the little crystal grain high silica alumina ratio of the present invention high-crystallinity Y zeolite is as follows: specific surface 750m
2/ g～980m
2/ g is preferably 850～950m
2/ g, pore volume 0.30ml/g～0.50ml/g, relative crystallinity is 90%～130%, is preferably 100%～130%.
The preparation method of the little crystal grain high silica alumina ratio of the present invention, high-crystallinity Y zeolite comprises the steps:
(1) preparation of fine grain NaY type molecular sieve;
(2) the fine grain NaY type molecular sieve with step (1) gained becomes little crystal grain NH
4NaY;
(3) with (NH
4)
2SiF
6In the aqueous solution to the little crystal grain NH of step (2) gained
4NaY carries out dealumination complement silicon to be processed;
(4) step (3) gained Y zeolite is carried out hydrothermal treatment consists;
(5) with the molecular sieve of aluminum saline solution treatment step (4) gained, drying and obtain the small crystal grain Y-shaped molecular sieve of high silica alumina ratio, high-crystallinity then.
The preparation method of fine grain NaY type molecular sieve is as follows in the step in the inventive method (1):
A, preparation directed agents: more than 0 ℃ and under less than 15 ℃ temperature, be preferably under 4～10 ℃ the temperature, high alkali deflection aluminium acid sodium solution and water glass are mixed, then more than 0 ℃ and under less than 15 ℃ temperature, be preferably under 4～10 ℃ the temperature static aging 10～14 hours, make directed agents;
B, preparation gel: under 0 ℃～10 ℃ temperature, the prepared directed agents of water glass, alum liquor, low alkali aluminium acid sodium solution and steps A is mixed, the synthetic liquid that then will obtain is static wearing out 5～10 hours under said temperature, obtains gel; The Al in the directed agents wherein
2O
3Weight accounts for the middle Al that always feeds intake
2O
33wt%～the 10wt% of weight;
C, crystallization: the gel that step B is obtained was 50 ℃～90 ℃ and the Water Under thermal crystallisation that stirs 5～10 hours, then heat up, hydrothermal crystallizing 5～10 hours again under 80 ℃～120 ℃ and the condition that stirs, crystallization obtains fine grain NaY type molecular sieve by filtration, washing, drying.
Steps A and step B can feed intake according to the proportioning raw materials that routine prepares NaY type molecular sieve in the inventive method, and the inventive method is recommended as follows: the described high alkali deflection aluminium acid sodium solution of steps A and water glass are pressed Na
2O: Al
2O
3: SiO
2: H
2The mol ratio of O=10～20: 1: 10～20: 300～400 feeds intake; The described water glass of step B, alum liquor, low alkali aluminium acid sodium solution and the prepared directed agents of steps A are pressed Na
2O: Al
2O
3: SiO
2: H
2The mol ratio of O=2～4: 1: 6～12: 150～300 feeds intake; Wherein water can add separately, also can together add with solution.
Little crystal grain high-crystallinity of the present invention, high silica alumina ratio Y zeolite, as raw material take the good small crystal grain NaY molecular sieve of thermostability and hydrothermal stability, and the suitable modifying process of selection, it is the product that obtains after ammonium exchange, ammonium hexafluorosilicate dealumination complement silicon, hydrothermal treatment consists and aluminum saline solution are processed, the crystallization reservation degree of this product is high, reaches more than 95%.Be hot and the higher small crystal grain Y-shaped molecular sieve of hydrothermal stability because the method is raw materials used, its silica alumina ratio is higher, good stability, uniform framework silicon-aluminum structure, in the process of carrying out the post-modification processing, can guarantee the skeleton continuity of zeolite product, reduced the possibility that skeleton structure is caved in, the integrity that has kept to greatest extent product sial oxide structure, so product has very high crystallization reservation degree.
The present invention adopts the small crystal grain Y-shaped molecular sieve after aluminum saline solution is processed hydrothermal treatment consists, because the pH value of aluminum saline solution is moderate, can avoid the infringement to framework of molecular sieve, and can also make the molecular sieve after the hydrothermal treatment consists in the situation that keep high-crystallinity, remove to greatest extent non-framework aluminum, make the duct unimpeded, make macromole more easily enter crystals and can touch more active centre, product is more easily diffused out, reduce second pyrolysis.
Little crystal grain high-crystallinity high silica alumina ratio Y zeolite of the present invention can be applicable in the cracking reaction.In this reaction, can relatively increase the active centre, and can make the heavy oil macromole more easily near the active centre, the conversion capability of heavy oil is improved, crackate is easier simultaneously diffuses out from chain carrier, has reduced the repeatedly probability of cracking of product, and gas yield is descended, coke yield reduces, so cracking catalyst can show good cracking activity and product selectivity.
The inventive method preparation process is simple, and production cost is low, and the pollution to environment in the production process is little.
Description of drawings
Fig. 1 is the SEM photo of small crystal grain Y-shaped molecular sieve LY-1.
Fig. 2 is the XRD figure of small crystal grain Y-shaped molecular sieve LY-1.
Embodiment
In the inventive method step (1), Na in the described high alkali deflection aluminium acid sodium solution
2O content is 260～320g/L, Al
2O
3Content is 30～50g/L, and solution does not contain floss or precipitation for the clarification shape, can adopt the ordinary method preparation.Na in the described low alkali aluminium acid sodium solution
2O content is 100～130g/L, Al
2O
3Content is 60～90g/L, and solution does not contain floss or precipitation for the clarification shape, can adopt the ordinary method preparation.Al in the described alum liquor
2O
3Content be 80～100g/L.SiO in the described water glass
2Content be 200～300g/L, modulus is 2.8～3.5.
The preparation method of fine grain NaY type molecular sieve of the present invention specifically comprises the steps:
A, low temperature prepare directed agents.
According to Na
2O: Al
2O
3: SiO
2: H
2The molar ratio of O=10～20: 1: 10～20: 300～400, more than 0 ℃ and under less than 15 ℃ of temperature, be preferably under 0～10 ℃ of temperature, under the condition that stirs, water glass slowly joined in the high alkali deflection aluminium acid sodium solution and mix, afterwards, the constant temperature constant speed stirred 0.5～2 hour under said temperature; Then mixed solution is enclosed in the synthesis reactor, aging 10～14 hours of static constant temperature makes directed agents; This directed agents preferably adds the water purification that accounts for directed agents weight 20%～40% before use.
B, low temperature prepare gel.
Under 0 ℃～10 ℃ and agitation condition, the directed agents of water glass, alum liquor, low alkali sodium metaaluminate and steps A gained is evenly mixed, then the constant temperature constant speed stirred 0.5～2 hour under said temperature; To synthesize liquid after stirring finishes and wear out 5～10 hours under 0 ℃～10 ℃ conditions of temperature, the synthetic liquid that then will obtain is static wearing out 5～10 hours under said temperature, gets gel; Wherein the molar ratio of gel is Na
2O: Al
2O
3: SiO
2: H
2O=2～4: 1: 6～12: 150～300, the wherein Al in the directed agents
2O
3Weight accounts for the middle Al that always feeds intake
2O
33wt%～the 10wt% of weight; The feeding sequence of the water glass described in the step B, alum liquor, low alkali aluminium acid sodium solution and steps A gained directed agents can adopt conventional feeding sequence, and preferably the order according to water glass, alum liquor, low alkali aluminium acid sodium solution and steps A gained directed agents adds.
The method Hydrothermal Synthesis fine grain NaY type molecular sieve of C, employing variable temperature crystallization.
The gel that step B is obtained adopts two sections alternating temperature dynamic crystallization methods in confined conditions.Describedly dynamically refer to crystallization under agitation condition.Under agitation condition, at first gel quick (generally at 3～8 ℃/minutes) is warmed up under 50 ℃～90 ℃ conditions, and under this temperature thermostatic crystallization 5～10 hours, the low temperature crystallized method of this elder generation can make the quantity of small crystal nucleus in the synthetic system increase, and guarantee that the crystal growth is unlikely to too fast, excessive, and can fully consume raw material in the synthetic system, and improve the output of molecular sieve, reduce synthetic cost.Improve crystallization temperature after the low temperature crystallized end, fast (generally at 3～8 ℃/minutes) are warmed up under 80 ℃～120 ℃ conditions incubation water heating crystallization 5～10 hours again, make molecular sieve Fast Growth in the synthetic system to the globule size that is fit to.Simultaneously the variable temperature crystallization method can make molecular sieve crystal framework silicon, Distribution of Al more even, is conducive to improve the hydrothermal stability of molecular sieve.Two sections crystallization cool synthesis reactor after finishing fast, after filtration, washing and dry, obtain fine grain NaY type molecular sieve.
The used raw material small crystal grain NaY molecular sieve character of the present invention is as follows: SiO
2/ Al
2O
3Mol ratio 4.0～6.0, average grain diameter are 100～700nm, specific surface 800m
2/ g～950m
2/ g, pore volume 0.30ml/g～0.40ml/g, relative crystallinity are 90%～130%, unit cell parameters is 2.462～2.470nm, Na
2O content is 8～10wt%.
The inventive method step (2), (3), (4) and (5) all can adopt the method for conventional Modified Zeolite Y to carry out.
Step in the inventive method (2) can be take ammonium concentration as 0.1mol/L～1.0mol/L ammonium salt solution, described ammonium salt is selected from one or more in ammonium nitrate, ammonium sulfate, ammonium chloride and the ammonium acetate, it is 50～100 ℃ in temperature, solvent and solute weight ratio is under 8: 1～15: 1 the condition, constant temperature is processed fine grain NaY, and the time is 0.5～1.5 hour, after filtration, then repeat under these conditions ammonium exchange, the product that obtains after filtration, stand-by after dry.Wherein requiring the weight content of sodium oxide in the small crystal grain molecular sieve after the control ammonium exchanges is 2.5%～5.0%.
Step in the inventive method (3) is the product (NH that will obtain in the step (2)
4)
2SiF
6The aqueous solution process, in the molecular sieve dealumination complement silicon, remove to greatest extent the sodium ion of equilibrium electronegativities in the molecular sieve.At first the molecular sieve that obtains in the step (2) is pulled an oar in the aqueous solution, solvent and solute weight ratio is 3: 1～10: 1, and temperature is 80～120 ℃, and mixing speed is 200～400rpm; Secondly, after temperature reaches to fixed temperature, in slurry, add (NH with certain speed
4)
2SiF
6The aqueous solution adds 10～60 gram (NH according to per 100 gram Y molecular sieves
4)
2SiF
6Amount add (NH
4)
2SiF
6The aqueous solution, the speed that adds simultaneously is too not fast, and requires at the uniform velocity to add, and general warranty per hour every 100gY type molecular sieve can add 3～30 gram (NH
4)
2SiF
6, add (NH
4)
2SiF
6The aqueous solution take disposed slurry temperature as 80～120 ℃ under, the constant temperature constant speed stirred 0.5～5 hour, then filtration drying obtains product.
Step of the present invention (4) is the product water thermal treatment that will obtain in the step (3) and obtaining.With the molecular sieve that obtains in the saturated steam treatment step (3), in the pipe type water heat treatment furnace, add the molecular sieve that obtains in the step (3), treatment condition: gauge pressure 0.05～0.4MPa, be preferably 0.1～0.2MPa, 450～750 ℃ of temperature, be preferably 450～700 ℃, 0.5～5 hour treatment time, preferred 1～3 hour;
Step of the present invention (5) molecular sieve of gained in the aluminum saline solution treatment step (4).Add aluminum saline solution in return-flow system and airtight container, wherein the aluminium salt concn is (with Al
3+Meter) 0.2～4.0mol/L, preferred 1.0～2.0mol/L stirs and is warmed up to 40～120 ℃, is preferably 70～100 ℃, then the weight ratio by aluminum saline solution and molecular sieve is 3: 1～50: 1, add the molecular sieve that step (4) obtains, constant temperature stirred 0.5～8 hour, preferred 1～3 hour, filter, wash, the washing until washings pH value near neutrality, then under 100～120 ℃ condition the drying 3～6 hours, obtain Y zeolite of the present invention.Wherein aluminium salt can be in aluminum chloride, aluminum nitrate and the Tai-Ace S 150 one or more in the aluminum saline solution.
Stirring described in the inventive method is to adopt conventional stirring means, generally adopts mechanical stirring.
The following examples are used for illustrating in greater detail the present invention, but scope of the present invention is not only limited to the scope of these embodiment.
Analytical procedure of the present invention: specific surface, pore volume and Extra specific surface area adopt the 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.
Crystallization reservation degree definition: the peak height of 5 characteristic peaks and as foundation in the X-ray diffracting spectrum of Y zeolite, with through the peak height of 5 characteristic peaks of Y zeolite after the modification and divided by the peak height of 5 characteristic peaks of raw materials used Y zeolite and per-cent; 5 characteristic peaks of the X-ray diffracting spectrum of Y zeolite are as follows respectively: 2 θ are the corresponding characteristic peaks of 15.8,20.7,24.0,27.4 and 31.8 peak positions.
Embodiment 1
The present embodiment is the raw materials small crystal grain NaY molecular sieve.
Used feedstock property is as follows:
High alkali deflection aluminium acid sodium: Na
2O content 291g/L, Al
2O
3Content 42g/L; Low alkali sodium metaaluminate: Na
2O content 117g/L, Al
2O
3Content 77g/L; Water glass: SiO
2Content 250g/L, modulus 3.2; Tai-Ace S 150: Al
2O
3Content 90g/L.
The preparation of LY-1:
The preparation of A, directed agents: under 10 ℃ of temperature, under agitation condition, the water glass of 1200ml is slowly joined in the 800ml high alkali deflection aluminium acid sodium, after water glass added, constant temperature stirred 40 minutes.Stop stirring mixed solution is enclosed within the container, under 5 ℃ of temperature, constant temperature burin-in process 12 hours.Constant temperature finishes to add in the backward mixed solution water purification of 667ml, and is stand-by as directed agents.
The preparation of B, gel: temperature is under 5 ℃, agitation condition, the low sodium metaaluminate and the 42.2ml directed agents that add successively 59.4ml Tai-Ace S 150,62.7ml in the water glass of 208ml, then the constant temperature constant speed stirred 1.5 hours, the synthetic liquid that then will obtain is static wearing out 8 hours under said temperature, obtains gel.
C, crystallization: under agitation condition, in 20 minutes the gel in the synthesis reactor is raised to 70 ℃, constant temperature stirred crystallization 7 hours; After the low temperature crystallized end, in 20 minutes the temperature in the synthesis reactor is brought up to 110 ℃, then constant temperature stirred 6 hours.After the high temperature crystallization finishes, fast with the cold water cooling, and open synthesis reactor and take out synthetic molecular sieve, after filtration, washing and dry, obtain product LY-1.
The preparation of LY-2:
The preparation of A, directed agents: under 8 ℃ of temperature, under agitation condition, the water glass of 1200ml is slowly joined in the 800ml high alkali deflection aluminium acid sodium, after water glass added, the constant temperature constant speed stirred 40 minutes.Stop stirring mixed solution is enclosed within the container, under 8 ℃ of temperature condition, constant temperature burin-in process 12 hours.After finishing, constant temperature in mixed solution, adds the water purification of 667ml, and stand-by as directed agents.
The preparation of B, gel: temperature is under 2 ℃, agitation condition, in the water glass of 208ml, add successively the low sodium metaaluminate of 59.4ml Tai-Ace S 150,62.7ml and the directed agents of 56.3ml, then the constant temperature constant speed stirred 1.5 hours, the synthetic liquid that then will obtain is static wearing out 8 hours under said temperature, obtains gel.
C, crystallization: under agitation condition, in 20 minutes with synthesis reactor in the temperature of gel be raised to 80 ℃, constant temperature stirred crystallization 6 hours; After the low temperature crystallized end, in 20 minutes the temperature in the synthesis reactor is brought up to 120 ℃, then constant temperature stirred 5 hours.After the high temperature crystallization finishes, fast with the cold water cooling, and open synthesis reactor and take out synthetic molecular sieve, after filtration, washing and dry, obtain product LY-2.
Embodiment 2
At first raw material small crystal grain NaY molecular sieve LY-1 is carried out the ammonium exchange.Compound concentration is 10 liters of 0.5mol/l aqueous ammonium nitrate solutions.Take by weighing small crystal grain NaY molecular sieve 2000 grams, be dissolved in 10 liters of aqueous ammonium nitrate solutions that prepare, mixing speed is 300rpm, stirs 1 hour at 90 ℃ of lower constant temperature, then filters molecular sieve, and stays sample, analyzes Na
2O content; Repeat aforesaid operations, until Na in the molecular sieve
2O content reach 2.5～5wt%, obtaining dried sample number into spectrum is LNY-1.
Measure 1 liter of water purification and with 1000 the gram LNY-1 be dissolved in the water purification, the stirring that is rapidly heated, temperature is 95 ℃, mixing speed is 300rpm.Within 2 hours time, at the uniform velocity in the molecular sieve slurry, add the hexafluorosilicic acid aqueous ammonium, add altogether 50 gram ammonium hexafluorosilicate, then the constant temperature constant speed stirred 2 hours, filtered, and drying obtains production code member LNY-2, and character is listed in table 1.
Embodiment 3
At first raw material small crystal grain NaY molecular sieve LY-2 is carried out the ammonium exchange.Compound concentration is 10 liters of 0.7mol/l aqueous ammonium nitrate solutions.Take by weighing small crystal grain NaY molecular sieve 1000 grams, be dissolved in 10 liters of aqueous ammonium nitrate solutions that prepare, mixing speed is 300rpm, stirs 1 hour at 90 ℃ of lower constant temperature, then filters molecular sieve, and stays sample, analyzes Na
2O content; Repeat aforesaid operations, until Na in the molecular sieve
2O content reach 2.5～5wt%, obtaining dried sample number into spectrum is LNY-3.
Measure 1 liter of water purification and with 200 the gram LNY-3 be dissolved in the water purification, the stirring that is rapidly heated, temperature is 95 ℃, mixing speed is 300rpm.Within 2 hours time, at the uniform velocity in the molecular sieve slurry, add the hexafluorosilicic acid aqueous ammonium, add altogether 50 gram ammonium hexafluorosilicate, then the constant temperature constant speed stirred 2 hours, filtered, and drying obtains production code member LNY-4, and character is listed in table 1.
Embodiment 4
Take by weighing 100g LNY-2 molecular sieve and put into the pipe type water heat treatment furnace, temperature programming to 570 ℃, under gauge pressure 0.2MPa, processed 2.0 hours, after hydrothermal treatment consists finishes, take out molecular sieve and put into reflux and flask that can be airtight, add and contain concentration 0.6mol/L aluminum sulfate aqueous solution 2000ml, stirred 1.0 hours at 1 00 ℃ of lower constant temperature, filter, and use the hot deionized water washing leaching cake, stop to wash after 7 with the pH value of washings.Filter cake 120 ℃ of dryings 5 hours in baking oven obtain Y zeolite of the present invention, and it numbers LNYA-1, and molecular sieve character sees Table 1.
Embodiment 5
Take by weighing 100g LNY-2 molecular sieve and put into the pipe type water heat treatment furnace, temperature programming to 600 ℃, under gauge pressure 0.2MPa, processed 2.5 hours, then put into reflux and flask that can be airtight, add and contain concentration 0.8mol/L aluminum sulfate aqueous solution 900ml, stirred 2 hours at 90 ℃ of lower constant temperature, filter, and use the hot deionized water washing leaching cake, after 7, stop washing with the pH value of washings.Filter cake 120 ℃ of dryings 5 hours in baking oven.Numbering LNYA-2, molecular sieve character sees Table 1.
Embodiment 6
Take by weighing 100g LNY-4 molecular sieve and put into the pipe type water heat treatment furnace, temperature programming to 650 ℃, under gauge pressure 0.1MPa, processed 1.5 hours, then put into reflux and flask that can be airtight, add and contain concentration 0.6mol/L aluminum sulfate aqueous solution 800ml, stirred 2.0 hours at 90 ℃ of lower constant temperature, filter, and use the hot deionized water washing leaching cake, after 7, stop washing with the pH value of washings.Filter cake 120 ℃ of dryings 5 hours in baking oven.Numbering LNYA-3, molecular sieve character sees Table 1.
Comparative Examples 1
Fine grain NaY with the preparation of CN1785807A patented method.
Restrain sodium hydrate solids with 1053 and be dissolved in the 3095 gram water, be cooled to room temperature, add sodium metaaluminate 220 grams, and add 3673 gram water glass, mix 40 ℃ of stirring ageings and made directed agents in 4 hours.
1421 gram water are joined in the beaker, and temperature is 60 ℃ in the control beaker, adds simultaneously 1279 gram alum liquors and 3191 gram water glass under the rapid stirring.After stirring, add 190 gram directed agents, the pH value of gel is 12.5, after stirring, in its stainless steel cauldron of packing into, stirred crystallization 6 hours at 60 ℃, then be warming up to 100 ℃ of static crystallizations 60 hours, then filter, wash, drying obtains fine grain NaY.Be numbered DL-1.
Compound concentration is 10 liters of 0.5mol/l aqueous ammonium nitrate solutions.Take by weighing DL-1 molecular sieve 500 grams in the Comparative Examples 1, be dissolved in 10 liters of aqueous ammonium nitrate solutions that prepare, mixing speed is 300rpm, stirs 1 hour at 90 ℃ of lower constant temperature, then filters molecular sieve, and stays sample, analyzes Na
2O content; Repeat aforesaid operations, until Na in the molecular sieve
2O content reach 2.5～5wt%, obtaining dried sample number into spectrum is DLN-1.
Measure 1 liter of water purification and with 200 the gram DLN-1 be dissolved in the water purification, the stirring that is rapidly heated, temperature is 95 ℃, mixing speed is 300rpm.Within 2 hours time, at the uniform velocity in the molecular sieve slurry, add the hexafluorosilicic acid aqueous ammonium, add altogether 50 gram ammonium hexafluorosilicate, then the constant temperature constant speed stirred 2 hours, filtered, and drying obtains production code member DLN-2, and character is listed in table 1.
Comparative Examples 2
Take by weighing 100g DLN-2 molecular sieve and put into the pipe type water heat treatment furnace, temperature programming to 570 ℃, under gauge pressure 0.2MPa, processed 2.0 hours, after hydrothermal treatment consists finishes, take out molecular sieve and put into reflux and flask that can be airtight, add and contain concentration 0.6mol/L aluminum sulfate aqueous solution 2000ml, stirred 1.0 hours at 100 ℃ of lower constant temperature, filter, and use the hot deionized water washing leaching cake, stop to wash after 7 with the pH value of washings.Filter cake 120 ℃ of dryings 5 hours in baking oven obtain Y zeolite of the present invention, and it numbers DLNA-1, and molecular sieve character sees Table 1.
Claims (18)
1. the preparation method of a small crystal grain Y-shaped molecular sieve, the character of small crystal grain Y-shaped molecular sieve is as follows: SiO
2/ Al
2O
3Mol ratio is 10.0～120.0, and average grain diameter is 100～700nm; Unit cell parameters is 2.420～2.445nm, and crystallization reservation degree is greater than 95%, sodium oxide weight content≤0.1wt%; Described crystallization reservation degree is the peak height of 5 characteristic peaks in the X-ray diffracting spectrum of Y zeolite and as foundation, with the peak height of 5 characteristic peaks of small crystal grain Y-shaped molecular sieve and divided by the peak height of 5 characteristic peaks of raw materials used fine grain NaY type molecular sieve and per-cent; 5 characteristic peaks of the X-ray diffracting spectrum of Y zeolite are as follows respectively: 2 θ are the corresponding characteristic peaks of 15.8,20.7,24.0,27.4 and 31.8 peak positions;
Its preparation method comprises the steps:
(1) preparation of fine grain NaY type molecular sieve;
(2) the fine grain NaY type molecular sieve with step (1) gained becomes little crystal grain NH
4NaY;
(3) with (NH
4)
2SiF
6In the aqueous solution to the little crystal grain NH of step (2) gained
4NaY carries out dealumination complement silicon to be processed;
(4) step (3) gained Y zeolite is carried out hydrothermal treatment consists;
(5) with the molecular sieve of aluminum saline solution treatment step (4) gained, drying and obtain small crystal grain Y-shaped molecular sieve then;
Wherein the preparation method of fine grain NaY type molecular sieve is as follows in the step (1):
A, preparation directed agents: more than 0 ℃ and under less than 15 ℃ temperature, high alkali deflection aluminium acid sodium solution and water glass are mixed, then more than 0 ℃ and under less than 15 ℃ temperature, static aging 10～14 hours, make directed agents; Na in the described high alkali deflection aluminium acid sodium solution
2O content is 260～320g/L, Al
2O
3Content is 30～50g/L;
B, preparation gel: under 0 ℃～10 ℃ temperature, the prepared directed agents of water glass, alum liquor, low alkali aluminium acid sodium solution and steps A is mixed, the synthetic liquid that then will obtain is static wearing out 5～10 hours under said temperature, obtains gel; The Al in the directed agents wherein
2O
3Weight accounts for the middle Al that always feeds intake
2O
33wt%～the 10wt% of weight; Na in the described low alkali aluminium acid sodium solution
2O content is 100～130g/L, Al
2O
3Content is 60～90g/L;
C, crystallization: the gel that step B is obtained was 50 ℃～90 ℃ and the Water Under thermal crystallisation that stirs 5～10 hours, then heat up, hydrothermal crystallizing 5～10 hours again under 80 ℃～120 ℃ and the condition that stirs, crystallization obtains fine grain NaY type molecular sieve by filtration, washing, drying.
2. according to preparation method claimed in claim 1, it is characterized in that the described high alkali deflection aluminium acid sodium solution of steps A and water glass are by Na
2O: Al
2O
3: SiO
2: H
2The mol ratio of O=10～20: 1: 10～20: 300～400 feeds intake; The described water glass of step B, alum liquor, low alkali aluminium acid sodium solution and the prepared directed agents of steps A are pressed Na
2O: Al
2O
3: SiO
2: H
2The mol ratio of O=2～4: 1: 6～12: 150～300 feeds intake.
3. according to preparation method claimed in claim 1, after it is characterized in that in the steps A water glass and high alkali deflection aluminium acid sodium solution mixed, under mixing temperature, constant temperature stirred 0.5～2 hour, then wore out.
4. according to preparation method claimed in claim 1, after it is characterized in that among the step B that directed agents with water glass, alum liquor, low alkali aluminium acid sodium solution and steps A gained mixes, under mixing temperature, constant temperature stirred 0.5～2 hour, then wore out.
5. according to preparation method claimed in claim 1, when it is characterized in that the described preparation directed agents of steps A, the raw material mixing temperature is 0 ℃～10 ℃, and aging temperature is 0 ℃～10 ℃.
6. according to preparation method claimed in claim 1, it is characterized in that SiO in steps A and the described water glass of step B
2Content be 200～300g/L, modulus is 2.8～3.5; Al in the described alum liquor of step B
2O
3Content be 80～100g/L.
7. according to preparation method claimed in claim 1, it is characterized in that steps A gained directed agents adds the water purification that accounts for directed agents weight 20%～40% before use.
8. according to preparation method claimed in claim 1, the feeding sequence that it is characterized in that the water glass described in the step B, alum liquor, low alkali aluminium acid sodium solution and steps A gained directed agents is the order adding according to water glass, alum liquor, low alkali aluminium acid sodium solution and steps A gained directed agents.
9. according to preparation method claimed in claim 1, it is characterized in that step B gained gel was warmed up to 50 ℃～90 ℃ with 3～8 ℃/minutes, after the first paragraph crystallization, be warmed up to 80 ℃～120 ℃ with 3～8 ℃/minutes and carry out the second segment crystallization.
10. according to preparation method claimed in claim 1, it is characterized in that step (2) process is as follows: adopting ammonium concentration is the ammonium salt solution of 0.1mol/L～1.0mol/L, it is 50～100 ℃ in temperature, solvent and solute weight ratio is under 8: 1～15: 1 the condition, constant temperature is processed fine grain NaY, time is 0.5～1.5 hour, after filtration, then repeat under these conditions the ammonium exchange, the product that obtains after filtration, stand-by after dry, wherein requiring the weight content of sodium oxide in the small crystal grain molecular sieve after the exchange of control ammonium is 2.5%～5.0%; Described ammonium salt is one or more in ammonium nitrate, ammonium sulfate, ammonium chloride and the ammonium acetate.
11. according to preparation method claimed in claim 1, it is characterized in that step (3) process is as follows: first the molecular sieve that obtains in the step (2) is pulled an oar in the aqueous solution, solvent and solute weight ratio is 3: 1～10: 1, and temperature is 80～120 ℃, and mixing speed is 200～400rpm; After temperature reaches to fixed temperature, add 10～60 gram (NH according to per 100 gram Y molecular sieves
4)
2SiF
6Amount, add 3～30 gram (NH with every 100gY type molecular sieve per hour
4)
2SiF
6Speed add (NH in the slurry
4)
2SiF
6The aqueous solution, add take disposed slurry temperature as 80～120 ℃ under, the constant temperature constant speed stirred 0.5～5 hour, then filtration drying.
12. according to preparation method claimed in claim 1, it is characterized in that the described hydrothermal treatment consists condition of step (4) is as follows: gauge pressure 0.05～0.4MPa, 450～750 ℃ of temperature, 0.5～5 hour treatment time.
13. according to preparation method claimed in claim 1, the process that it is characterized in that the described molecular sieve with gained in the aluminum saline solution treatment step (4) of step (5) is as follows: add aluminum saline solution in return-flow system and airtight container, wherein the aluminium salt concn is with Al
3+Count 0.2～4.0mol/L, stirring also is warmed up to 40～120 ℃, then the weight ratio by aluminum saline solution and molecular sieve is 3: 1～50: 1, the molecular sieve that adds step (4) gained, constant temperature stirred 0.5～8 hour, filter, washing, then under 100～120 ℃ condition dry 3～6 hours; Wherein aluminium salt is one or more in aluminum chloride, aluminum nitrate and the Tai-Ace S 150.
14. a small crystal grain Y-shaped molecular sieve is characterized in that according to the arbitrary described method preparation of claim 1～13.
15. according to the described Y zeolite of claim 14, it is characterized in that described SiO
2/ Al
2O
3Mol ratio is 15.0～80.0, and average grain diameter is 300～500nm, crystallization reservation degree 95%～120%.
16. according to the described Y zeolite of claim 14, it is characterized in that described crystallization reservation degree is 98%～110%.
17. according to the described Y zeolite of claim 14, it is characterized in that the specific surface area 750m of described small crystal grain Y-shaped molecular sieve
2/ g～980m
2/ g, pore volume 0.30ml/g～0.50ml/g, relative crystallinity are 90%～130%.
18. according to the described Y zeolite of claim 14, the specific surface that it is characterized in that described small crystal grain Y-shaped molecular sieve is 850～950m
2/ g, pore volume 0.30ml/g～0.50ml/g, relative crystallinity are 100%～130%.
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| CN104477938A (en) * | 2014-12-08 | 2015-04-01 | 上海大学 | Method for preparing small-size neodymium-doped Y-type zeolite through in-situ synthesis |
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| CN107344721B (en) * | 2016-05-05 | 2019-05-21 | 中国石油化工股份有限公司 | A kind of Modified Zeolite Y and its preparation method and application |
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