CN101722022A - Alkali treatment modifying method of Y-shaped molecular sieve - Google Patents
Alkali treatment modifying method of Y-shaped molecular sieve Download PDFInfo
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Abstract
The invention provides an alkali treatment modifying method of a Y-shaped molecular sieve, which comprises the following steps of: beating and uniformly mixing the Y-shaped molecular sieve and a strong alkali aqueous solution according to the mass ratio of the molecular sieve, a strong alkali and distilled water as (0.1-2): (0.05-2): (4-15), and carrying out alkali treatment for 0.1-24 hours at the temperature of 0-120 DEG C; compared with a parent Y-shaped molecular sieve, the obtained molecular sieve has the advanced performance of higher N2 adsorptive capacity, larger water absorbing capacity and the like. On the basis of modified treatment, the invention also provides a preparation method of an NH4 molecular sieve and an ultrastable Y-shaped molecular sieve, which comprises ammonium exchange treatment and hydrothermal ultrastable treatment implemented for a modified NaY molecular sieve after alkali treatment, and the obtained NH4 molecular sieve has lower metallic ion residues; an obtained USY molecular sieve has more abundant secondary holes while keeping high degree of crystallinity, thereby improving the catalytic activity of the USY molecular sieve.
Description
Technical field
The present invention relates to a kind of method of modifying, further say so about the method for modifying that adopts aqueous slkali that Y zeolite is carried out skeleton desiliconization processing at Y zeolite, and the preparation method of relevant modified Y molecular sieve, the sieve technology field belonged to.
Background technology
Y zeolite is a kind of crystalline microporous material with regular skeleton structure.It is an architecture basics with the sodalite cage, arrange in order at three dimensions according to adamantine frame mode, each sodalite cage interconnects with four hexatomic rings sodalite cage adjacent with it that it is in the positive tetrahedron zenith directions, thereby forms the crystal structure of Y molecular sieve.At its crystals, form the 3 D pore canal system together by bug hole, geode and duct, skeleton internal structure spaciousness, specific area are big, are the excellent materials of preparation catalyst (carrier) and adsorbent; The metal cation of balance skeleton negative electrical charge is present in aluminum-oxygen tetrahedron (AlO
4 -) near, can be exchanged by other cation, thus the character of change Y zeolite; In addition, silicon (oxygen) the aluminium skeleton that constitutes Y molecular sieve crystal structure variation of character such as recurring structure, kind, number under certain condition such as framework dealumination, skeleton are mended silicon, structure cell contraction etc., correlation theory and content can referring to: Chen Junwu, Cao Hanchang chief editor, " catalytic cracking process and engineering ", chapter 3, Sinopec publishing house, nineteen ninety-five version.The feasible modulation to its structure and character of the above-mentioned performance of Y zeolite becomes possibility.
Similar with other kinds molecular sieve analog (as A type, X type), Y zeolite has bigger surface area, pore volume and adjustable surface field, has very strong absorption property, can than the little Molecular Adsorption of orifice diameter to bug hole, therefore, this type of material can be used as the main component of adsorbent, drier, also can be used as activity of such catalysts component or carrier material.When absorption takes place, adsorbate passing hole channel and geode, inside " warehouse "---the bug hole that enters molecular sieve.Therefore, the number of bug hole has determined its adsorption capacity to a great extent in the y-type zeolite---inner available " warehouse " is many more, and adsorption capacity is big more.Know, have three kinds of cagelike structures in the Y molecular sieve skeleton: hexagonal prism cage (maximum open is hexa-atomic annular distance, and bore dia is 0.24nm), sodalite cage (hexatomic ring orifice diameter 0.24nm; Cage chamber diameter 0.66nm), octahedral zeolite cage.Can play the bug hole of " warehouse " effect under normal conditions and have only octahedral zeolite cage: its cage chamber diameter can reach 1.2nm, and the twelve-ring aperture that is about 0.74nm by four bore dias of positive tetrahedron zenith directions between two octahedral zeolite cages is interconnected.And for sodalite cage and hexagonal prism cage, because the hexatomic ring aperture is less, gas molecule that size is big slightly such as N
2(kinetic diameter 0.364nm), CO (kinetic diameter 0.376nm), CH
4(kinetic diameter 0.38nm) or cation such as NH
4 +(kinetic diameter 0.28nm) just is difficult to enter cage inside.Therefore, though sodalite cage inside also has than large space (cage chamber diameter 0.66nm), the aperture effect of hexatomic ring has restricted it and brought into play " warehouse " effect in adsorption process.So, when Y zeolite during as materials such as catalysis material or adsorbent/drier, if a part of sodalite cage in the Y molecular sieve skeleton can be opened, to enlarge the passage that reactant molecule or adsorption molecule enter the sodalite cage undoubtedly, make that bigger molecule can pass in and out the sodalite cage, also make little molecule turnover more smooth and easy, and then (apparent effect is: when adopting conventional nitrogen cryogenic absorption desorption method to measure its specific area also to have increased the space in available " warehouse ", specific area increases, because a part of sodalite cage is opened, passage enlarges, and nitrogen molecule can enter the sodalite cage), this will improve the utilization ratio of Y molecular sieve.
The interchangeability of the outer metal cation of Y molecular sieve skeleton adds the spacious skeleton structure that Y molecular sieve itself is had, and makes it can become effective catalyst activity component or catalyst carrier material, also can be used as drier or adsorbent etc.An important use of Y molecular sieve is as acid catalyzed reaction (reactions such as for example commonly used catalytic cracking of petroleum refining industry, hydrocracking, isomerization) activity of such catalysts component, and the acid centre on this moment molecular sieve and the shape selectivity of pore passage structure thereof will play crucial catalytic action.But, metal cation of in the Y molecular sieve building-up process, introducing such as Na
+, K
+Though Deng having played the effect of keeping the skeleton charge balance, simultaneously also " neutralization " the acid active sites of molecular sieve, make it can't directly apply to acid catalyzed reaction.So before using, need be with these cations NH
4 +Replace (also being referred to as the exchange of ammonium ion exchange or ammonium) and roasting and make HY; Or after ammonium ion exchange, continue above-mentioned Y zeolite further to be made ultra-steady Y molecular sieve (USY) by all super stabilizing methods; Also can on Y molecular sieve, exchange in addition and introduce other polyvalent cation (as Ca
2+, rare earth ion) etc., produce Bronsted acid center etc. by its polarization to water.Above-mentioned different ion exchange process all will relate to Na
+The exchange degree problem: it is thorough more that ion-exchange is carried out, Na
+Residual quantity is low more, and the acid centre number is many more, catalytic activity is high more; For the preparation of USY molecular sieve, Na
+Residual quantity is low more, and the super stabilizing degree of Y molecular sieve product is high more under the same hydrothermal treatment consists condition.Therefore, Y molecular sieve is being applied in the Preparation of catalysts process, how more effective Na
+, K
+Deng metal cation exchange the becoming research objective that other needed ion is this area.
In order to improve the exchange degree of depth of sodium ion, a lot of research reports is to take repeatedly exchange process or continuous exchange process.In Chinese patent CN1055063C, in order to make the Na of molecular sieve
2O content is reduced to below the 2.0 heavy %, and the mode that is adopted is that same ammonium exchange process is repeated repeatedly.But it is found that when adopting the mode that repeatedly exchanges to improve ion-exchange degree, after first and second exchange, when proceeding to exchange again, exchange degree improves very little, exchange efficiency reduces; And when adopting continuous exchange process, then to consume a large amount of exchange solution.Adopt the mode that ion-exchange and high-temperature roasting hocket to improve exchange degree and exchange efficiency, but the HY molecular sieve that roasting generates is extremely unstable, hydrolysis easily takes place in wet environment cause structural deterioration.Thereby in the middle of adopting the mode of roasting to improve the ion-exchange degree of depth be not most economical effective method.Employing adds acid and promotes that with the method that reduces exchange pH value of solution value removing of sodium ion is a kind of method preferably in ion exchange process.In Chinese patent CN1078819C, promptly taked the pH value that ammonium exchanges slurries to be adjusted to 3.0 mode with watery hydrochloric acid.So exchange result once can make the Na of initial Y molecular sieve
2O content is reduced to 5 heavy %.But the acid resistance of NaY type molecular sieve is relatively poor, and the potentiality that further improve the ion-exchange degree of depth by the mode that continues reduction exchange pH value of solution value are little.Adopted following ammonium switching method among the Chinese patent CN 1220238A: earlier Y zeolite is contacted with a kind of acid solution, contact with further exchange sodium ion with a kind of solution that contains the ammonium radical ion again.Because the NaY molecular sieve is carried out in the pretreated process with acid solution, the part framework aluminum can be by sour extracting, and a small amount of structural failure will appear in sodalite cage aperture, thereby help to improve the sodium ion exchange efficiency to a certain extent.But, be great test to the exchange of molecular sieve, the acid resistance of filter plant because the required acid amount of this method is bigger.
In Hydrothermal Preparation ultra-steady Y molecular sieve process, it must also be simultaneously one of key factor of the final modified product character of influence through link that in the Y molecular sieve modifying process first is not only in the ammonium of initial NaY molecular sieve exchange.Improve the sodium ion exchange degree of depth, the framework dealumination that not only helps Y molecular sieve is mended silicon, structure cell shrinks, and also helps strengthening the acid of product simultaneously and helps improving product secondary pore content.
The basic reason that the ammonium ion exchange of Y molecular sieve can not the degree of depth be carried out is that in ion exchange process the sodium ion of little cage (sodalite cage and hexagonal prism cage) position is difficult for and extraneous cation generation exchange reaction on the Y molecular sieve skeleton.This is because the electric field action of little cage inside has limited moving freely of sodium ion on the one hand; On the other hand because the kinetic diameter of ammonium ion is 0.28nm, and the diameter in sodalite cage hexatomic ring aperture has only 0.24nm in the Y molecular sieve skeleton, ammonium ion will meet with " ion sieve " effect in the ion exchange process, ammonium ion is difficult to enter sodalite or hexagonal prism cage and sodium ion and carries out ion-exchange reactions, and this degree of depth that will influence ion-exchange is to a certain extent carried out.For reducing ammonium exchange number of times and reaching the purpose that deep ion exchanges, the mode that usually adopts ion-exchange and high-temperature roasting to replace improves the exchange degree of depth and exchange efficiency, high-temperature calcination process has been considered to promote sodium ion from the migration of sodalite cage to octahedral zeolite cage, but this process is destroyed the part framework of molecular sieve easily, and energy consumption is very big.
In sum, if sodalite cage hexatomic ring aperture in the Y molecular sieve skeleton can be opened, then will further improve the adsorption capacity of Y molecular sieve, and improve its ion-exchanging efficiency, thereby a kind of raw material of function admirable will be provided for adsorbent industry, catalyst industry etc.But in the Y molecular sieve post-modification method at present on the books, all be the Y zeolite raw material directly to be carried out post-modification handle, and without be intended to reaming, especially by taking off the molecular sieve preprocessing process of framework silicon reaming.CN1055256C discloses a kind of high water absorption molecular sieve adsorbent and preparation method thereof as Chinese patent, and the Y zeolite of wherein using is commodity molecular sieve of directly buying or the product that utilizes routine techniques to synthesize.Described Y zeolite did not relate to skeleton reaming preprocessing process before using.Chinese patent CN 1220238A discloses a kind of preparation method of overstable gamma zeolite, and ammonium exchange process has wherein adopted elder generation that y-type zeolite is contacted with a kind of acid solution to carry out suitable dealuminzation preliminary treatment, again with a kind of NH that contains
4 +The ion solution contact is with the invalid cation Na of further exchange
+This method has adopted sour dealuminzation preliminary treatment to the NaY molecular sieve, and the part framework aluminum is by sour extracting, and a small amount of structural failure can take place in sodalite cage aperture, thereby helps to improve the sodium ion exchange efficiency to a certain extent.But the preliminary treatment medium that this method adopted is a kind of acid solution, and Y molecular sieve can preferentially remove the framework aluminum atom in this solution, and framework silicon is then kept.The silicon that it is pointed out that the aluminium that removes on molecular sieve (the comprising Y molecular sieve) skeleton and remove on the skeleton has essential difference.Therefore because the aluminium on the skeleton provides an electronegative center, the silicon on the skeleton then is the environment that is in a neutrality, molecular sieve is carried out framework dealumination or skeleton desiliconization and handles resulting product and have diverse character.Framework dealumination will make the framework si-al ratio of molecular sieve improve, to increase its hydrophobicity (or increasing its lipophile), and the skeleton desiliconization will make the framework si-al ratio of molecular sieve reduce, to increase its hydrophily (or increasing its water imbibition), can be about this character instruction of molecular sieve referring to Sun Dekun etc., " Chinese Journal of Inorganic Chemistry ", 1993, the 2nd phase, 194-198 page or leaf and relevant books.
Preferentially removed these characteristics about the silicon species on the framework of molecular sieve in alkaline solution and be used for other high-silica zeolite such as ZSM-5 by people, post-modification (the Masaru O of Beta equimolecular sieve, Shin-yaS, Junko T, et al.Alkali-treatment technique-new method for modification ofstructural and acid-catalytic properties of ZSM-5zeolites.Applied Catalysis A:General, 2001,219:33-43.Effects of large pore zeolite additions in the catalyticpyrolysis catalyst on the light olefins production.Catalysis Today, 2007,125:270-277.).In the alkali treatment process, the silicon species on these high-silica zeolite skeletons is removed from zeolitic frameworks by selectivity, and products molecule sieve ratio surface area increases and form the skeleton secondary pore, and simultaneously a large amount of microcellular structures are kept.The evaluation of cumene catalytic cracking activity shows that the cracking activity of this material strengthens.Think that the secondary pore that produces behind the alkali treatment modifying has changed the absorption and the diffusion of raw material and product, thereby cause the improvement of catalytic activity.
People such as Halimaton reported (Halimaton H, Bogdan S, Jacek K, Journal ofPhysical Chemistry, 1989,93,350-356) adopt alkaline solutions such as NaOH, KOH to handle the USY type molecular sieve that has than high silica alumina ratio.But this work purpose is not to expand the passage of ion-exchange or increase its available space, its objective is USY framework of molecular sieve sial distribution carrying out modulation.This work makes non-framework aluminum in the dealuminzation USY molecular sieve come back to the skeleton of USY molecular sieve by alkali treatment.The Y molecular sieve product of this calorize is again compared with employing synthetic method Y molecular sieve that obtain, that have similar silica alumina ratio has different framework silicon-aluminum distributions.That is to say that the purpose of this research is the framework aluminum redistribution that makes the USY molecular sieve, its all work is all carried out around this starting point.
Adopt the silica alumina ratio of the synthetic NaY molecular sieve of routine techniques can be between 3.0～5.2 modulation, the consideration for material structure stability aspect is subjected to the restriction of synthetic level simultaneously, normally used NaY silica alumina ratio is about 5.0.If directly this NaY is carried out the alkali treatment desiliconization, the silica alumina ratio of gained sample will further reduce, and its skeleton stability will be difficult to be guaranteed.Based on present result of study, though being beneficial to, alkali treatment forms the skeleton secondary pore, obtain a large amount of micropores and even mesoporous feature, this is that the skeleton destroy integrity can cause the suitable reduction of molecular sieve silica alumina ratio simultaneously because the part framework silicon is preferably removed.Framework si-al ratio descends has directly influenced skeleton stability, this also is present alkali modification research and uses the reason that mainly concentrates on the high silica alumina ratio molecular sieve, obviously runs in the opposite direction with traditional concept and the relatively low molecular screen material of this silica alumina ratio of Y zeolite is directly implemented the highly basic processing.Therefore before the present invention, do not adopt the alkali treatment desilication method directly to handle the research report of NaY molecular sieve and the enlightenment of specific embodiments.
Summary of the invention
The objective of the invention is to propose a kind of alkali treatment modifying method to Y zeolite, alkali treatment by felicity condition changes the lower Y molecular sieve skeleton structure of silica alumina ratio to some extent, the absorption property of Y molecular sieve and ion-exchange performance etc. are improved, and help further the further modification of this molecular sieve being handled.
The present invention also provides a kind of NH on this basis
4The preparation method of Y molecular sieve, i.e. it is residual that alkali treatment by in advance can make the NaY molecular sieve have a lower metal ion after the ammonium ion exchange of the same terms is handled, and improved the exchange degree of depth, thereby a kind of NH with good ion-exchange performance is provided
4Y molecular sieve is for the modification work of Y molecular sieve provides a kind of novel material.
The present invention also provides a kind of preparation method of super-stable Y molecular sieves, makes the USY molecular sieve that obtains have abundant more secondary pore when keeping high-crystallinity, thereby has improved the catalytic activity of this USY molecular sieve.
This case inventor is when adopting alkaline solution directly to handle Y zeolite, and the discovery products obtained therefrom is compared with its parent Y molecular sieve without alkali treatment, has bigger specific area and the water absorption capacity of Geng Gao, to hydrone, N
2The adsorption capacity of probe molecules such as molecule increases.Show Y zeolite is carried out suitable alkali treatment, can further promote its adsorption capacity, improve its absorption, drying property.Aspect ion-exchange performance, after the ammonium exchange processing through similarity condition, alkali-treated Y zeolite is compared with its parent Y molecular sieve and is had lower Na earlier
+(K
+) residual quantity.
So, the present invention at first provides a kind of method of modifying of Y zeolite, comprise: according to molecular sieve (butt): alkali: water=(0.1～2): (0.05～2): the mass ratio of (4～15), the aqueous solution making beating of Y molecular sieve and alkali is mixed, and the temperature conditions of keeping 0～120 ℃ stirs down and implements alkali treatment 0.1～24h, and this alkali treatment process is at least once.
Y molecular sieve raw material used in the present invention can be NaY, KY, NH
4In Y, REY, the HY type molecular sieve any; Especially can be from synthetic back of crystallization and the NaY molecular sieve that separates with crystallization mother liquor, that is, and the former powder of NaY that synthesizes according to conventional method; Also can be the NaY molecular sieve mixture that includes crystallization mother liquor, that is, directly use still contains the molecular sieve and the crystallization mother liquor mixture of crystallization mother liquor, the crystallization slurries that just separate behind the crystallization.
Consider the preferred silica alumina ratio of NaY molecular sieve used in the present invention (SiO on the phalanges frame from the stability requirement of satisfying Y molecular sieve
2/ Al
2O
3Mol ratio, down together) be not less than 5.0; Preferably be not less than 5.5; Especially use framework si-al ratio to be not less than 5.8 Y molecular sieve.
The method according to this invention, when molecular sieve was implemented alkali treatment, at the character characteristics of Y molecular sieve, the use amount of alkali and the concentration of solution should be according to Y zeolite (butts): alkali: H
2O=(0.1～2): (0.05～2): the mass ratio relation of (4～15) is definite, preferably Y zeolite (butt): alkali: H
2O=(0.5～2): (0.075～1): (4～10); Earlier alkali is mixed with aqueous slkali during concrete operations, the temperature and time of alkali treatment can be adjusted according to the concentration and the degree of treatment needs of aqueous slkali, and preferably, the temperature of alkali treatment is controlled at 20-100 ℃, and the processing time can be controlled stir process 0.1～12h.The present invention manages the quality of related molecular sieve of stage or mass ratio throughout all in butt.
The operation of alkali treatment described in the method provided by the invention is well known to those of ordinary skill in the art, and there is no particular limitation to it in the present invention.The aqueous slkali that adopts both can be any in NaOH, the KOH solution, also can be the mixing of above-mentioned two kinds of alkali.NaOH solution preferably.
Alkali treatment process described in the method provided by the invention can be carried out one or many.After last alkali treatment finishes, the gained molecular sieve pulp is filtered, washes processing, its filtrate pH is reduced to less than 10, both finished modification and handled, obtain the Y molecular sieve that is changed by alkali modification, skeleton structure.Experiment showed, Y molecular sieve through the inventive method modification, its ion-exchange performance and absorption property be improved significantly, reason should be because the suitable desiliconization of skeleton, the inner duct of molecular sieve is more unimpeded.
On the basis of The above results, the present invention also provides a kind of NH
4The preparation method of Y molecular sieve, this method comprises: according to the method described above NaY type molecular sieve is carried out alkali treatment modifying, then the NaY molecular sieve of this alkali modification is implemented ammonium ion exchange and handle (also claiming the ammonium exchange).
Ammonium ion exchange method to Y molecular sieve is well known to those of ordinary skill in the art, and there is no particular limitation to it in the present invention.Particularly, described ammonium ion exchange process is: with the NaY molecular sieve pulp after the alkali treatment filter, wash to pH less than 10, then the gained filter cake is mixed with ammonium salt solution and carry out ammonium ion exchange, add the pH of acid solution regulation system in the exchange process in the 2.0-7.0 scope; Perhaps, add acid solution in the NaY molecular sieve pulp after alkali treatment, the pH of regulation system adds ammonium salt and carries out ammonium ion exchange in the 2.0-7.0 scope.Promptly, can use the filter cake that molecular sieve is carried out obtaining after the alkali treatment to mix and carry out ammonium ion exchange with ammonium salt solution, also can directly in the alkali treatment slurries of Y molecular sieve, add a kind of acid solution, the pH value is transferred to the required pH value of ammonium ion exchange scope, directly add ammonium salt then and carry out ammonium ion exchange.Preferably adopt the former, described ammonium ion exchange process is: with the Y molecular sieve dope filtration after the alkali treatment, wash to pH less than 10, then with the gained filter cake according to alkali treatment Y molecular sieve (butt), ammonium salt and water with 1: (0.5～2): the mass ratio of (5～30) making beating mixes, stir exchange 0.5～2h down at 60～95 ℃, and regulate slurries pH in the exchange process in 2～7 scopes, this ion exchange process can repeat 1～3 time.
Identical with routine operation, used ammonium salt can be selected from one or more in ammonium sulfate, ammonium chloride, ammonium nitrate, ammonium carbonate, ammonium acetate, ammonium oxalate, ammonium citrate and the ammonium phosphate etc. in the ammonium exchange process, use ammonium salt aqueous solution, but the kind of ammonium salt does not influence enforcement of the present invention, so the present invention is not particularly limited this and requirement.
The acid solution that is used for regulation system pH in the described ammonium ion exchange operation then can be selected from one or more of the aqueous solution such as hydrochloric acid, sulfuric acid, nitric acid, carbonic acid, acetic acid, oxalic acid and citric acid.
On the basis that above-mentioned alkali modification is handled, further the molecular sieve of alkali treatment is implemented ammonium ion exchange and hydrothermal treatment consists, can obtain a kind of active super-stable Y molecular sieves that improves.
For obtaining needed super stable molecular sieve (USY), wherein, above-mentioned preparation method also can comprise the process of the molecular sieve after super steady processing of hydro-thermal being implemented once more the ammonium ion exchange processing, promptly, the ammonium ion exchange process can be only carried out before steady in that molecular sieve water heat is super, also can before and after the super steady processing of hydro-thermal, all carry out the ammonium exchange and handle, especially advise all carrying out the ammonium exchange in the super steady front and back of hydro-thermal.
The super steady processing procedure of described hydro-thermal, comprise and to place 500～700 ℃ hydro-thermal stove through the molecular sieve that the ammonium exchange is handled, roasting is 1～24 hour under 20～100% (volume) water vapour atmosphere, and roasting is 1～4 hour under preferably 550 ℃～700 ℃, 50～100% steam.And this water-heat process can carry out 1-2 time.
Can sum up the beneficial effect that the invention process produces according to above description:
By Y molecular sieve is carried out suitable alkali treatment, increased the adsorption capacity of Y molecular sieve, improved the ion-exchanging efficiency of Y molecular sieve, a kind of novel initiation material can be provided for the post processing modification of Y molecular sieve, thereby a kind of raw material of function admirable are provided for adsorbent industry, catalyst industry etc.The reason that this effect is provided is that Y molecular sieve skeleton top silicon atom hydrolysis takes place in strong base solution removes, hexatomic ring aperture on the part sodalite basket structure unit is also opened simultaneously, these damaged apertures can make adsorbate transmission, the diffusion more quick, the inner space of sodalite cage also can obtain more effectively utilizing; The expansion in aperture also makes how external cation or molecule (as ammonium ion, nitrogen molecule etc.) can enter sodalite cage inside, inner ion is easier moves out by the aperture.Adopting common instrument (physical adsorption appearance) promptly to can observe this reaming effect of alkali treatment---the nitrogen adsorption amount of mensuration increases.And alkali modification implementation process of the present invention is simple, consumption is low, does not need existing equipment is carried out any transformation, has also just had favorable industrial application prospect.
According to method of the present invention,, improved the effective aperture of Y molecular sieve inner passage, and then improved the ion-exchange performance and the absorption property of NaY molecular sieve by the alkali treatment means in early stage.And, the present invention is by alkali treatment, suitably destroyed NaY framework of molecular sieve structure, the destruction of this active to skeleton structure, not only be beneficial to and improve the ammonium exchange capacity, the secondary pore content of hydro-thermal ultra-steady Y molecular sieve that more helped increase successful in the post-processed process has improved the structure cell contraction level of product.Experimental result shows, with original NaY molecular sieve is directly handled the USY molecular sieve that obtains and is compared according to the exchange of conventional ammonium, hydrothermal method, the USY molecular sieve that adopts the method for the invention to prepare has abundant more secondary pore when keeping high-crystallinity.When being used for the residual oil cracking reaction, this USY molecular sieve has stronger heavy oil conversion performance and the yield of light oil of Geng Gao.
The specific embodiment
The following examples are used for that the present invention will be further described, but not thereby limiting the invention.
In each embodiment and Comparative Examples:
The N of molecular sieve
2Adsorption capacity low temperature nitrogen determination of adsorption method (because the kinetic diameter and the N of following toxic gas molecule
2Molecule is close: SO
2(0.360nm), CH
4(0.380nm), CO (0.376nm), CO
2(0.330nm), consider that simultaneously nitrogen molecule is a most frequently used probe molecule in the BET surface area measuring process, by N before and after the alkali treatment of contrast Y molecular sieve
2Adsorption capacity can recognize intuitively whether alkali treatment helps to improve the gas purification performance of Y molecular sieve);
Water absorption is measured in order to following method: reference literature (R.Dimitrijevic at first, W.Lutz, A.Ritzmann.Journal of Physics and Chemistry of Solids, 2006 (67): 1741-1748) described method, with molecular sieve behind 120 ℃ of dry 2h, 450 ℃ of heat treatment 3h, place drying box to be cooled to 25 ℃, be placed on then in the steam atmosphere of 25 ℃ of saturated nacl aqueous solutions and adsorb 24h, adopt gravimetric method to record adsorbance at last;
The lattice constant and the relative crystallinity of molecular sieve are measured with x-ray powder diffraction, adopt the RIPP145-90 standard method (referring to " petrochemical industry analytical method " (RIPP test method), volumes such as Yang Cuiding, Science Press, nineteen ninety version); Framework si-al ratio (SiO
2/ Al
2O
3Mol ratio) adopt following formula to calculate: SiO
2/ Al
2O
3=2 * (25.8575-α
0)/(α
0-24.191);
In each embodiment and Comparative Examples, constituent content x-ray fluorescence spectrometries such as the surface silicon aluminum ratio of product, sodium, potassium; Body phase silica alumina ratio adopts chemical analysis to measure; Lattice avalanche temperature is measured by differential thermal analysis.
Embodiment 1
Take by weighing 30 gram NaOH and be dissolved in the 970 gram distilled water, be warming up to 85 ℃ after stirring.Get 200 gram NaY molecular sieve (sample name Y-A; Degree of crystallinity: 95%; Framework si-al ratio: 6.15; Body phase silica alumina ratio: 6.24; Surface silicon aluminum ratio: 5.12; Na
2The heavy % of O:12.1; N
2Adsorption capacity: 295.01cc/g; Water adsorption amount 295mg/g; System is synthetic voluntarily with reference to patent CN 1785808 described methods), join in the above-mentioned aqueous slkali, in 85 ℃ of following stir process after 2 hours, filtration, washing, drying, (measurement result is: degree of crystallinity: 92% to obtain the alkali treatment sample; Framework si-al ratio: 5.43; Body phase silica alumina ratio: 5.56; Surface silicon aluminum ratio: 4.72; Na
2The heavy % of O:12.0; N
2Molecular Adsorption amount: 323.08cc/g; Water adsorption amount: 320mg/g).
The water adsorption amount of having measured framework si-al ratio under the similarity condition and be 4.8～5.5 common NaY molecular sieve is 295mg/g～306mg/g.
This shows that the NaY that adopts the highly basic processing has the big advantage of adsorbance as adsorbent (drier) material, will be beneficial to the drying effect that improves the Unit Weight adsorbent.
Embodiment 2
Get the alkali treatment products of 30 grams among the embodiment 1, join in the 300 gram distilled water with 30 gram ammonium chlorides and stir, under 90 ℃ of conditions, stir exchange 1h then.The pH value that adopts the 1mol/L hydrochloric acid solution will exchange slurries in the exchange process transfers to 3.0 and also keeps.After exchange finishes, filter, wash Na in the ammonium trade-to product that obtains
2The O residual quantity is 4.3 heavy %.
Comparative Examples 1
Get used NaY molecular sieve Y-A among the 30 gram embodiment 1, by condition described in the embodiment 2 it is carried out ion-exchange treatment, Na in the ammonium trade-to product that obtains
2The O residual quantity is 4.8 heavy %.
(industrial goods, the Lanzhou catalyst plant produces, degree of crystallinity 96%, framework si-al ratio 5.0, Na to get the conventional NaY molecular sieve of 30 grams
2O content 13.2%), it is carried out ion-exchange treatment, Na in the ammonium trade-to product that obtains by condition described in the embodiment 2
2The O residual quantity is 5.2 heavy %.
Embodiment 3
Taking by weighing 40 gram NaOH is dissolved in the 960 gram distilled water, be warming up to 65 ℃ after stirring, getting the NaY molecular sieve Y-A described in the 150 gram embodiment 1 joins in the above-mentioned aqueous slkali for preparing, stirred 3 hours down in 65 ℃, filter, spend deionised water to filtrate pH=10, with the collection of gained filter cake, drying for standby.
The NaY sieve sample of getting the above-mentioned alkali treatment of 30 gram processes joins in the 300 gram distilled water with 30 gram ammonium chlorides and stirs, under 90 ℃ of conditions, stir exchange 1h then, filter, repeat above-mentioned exchange process secondary after, with sample filtering and fully washing, Na in the ammonium ion exchange sample that obtains
2The O residual quantity is 2.0 heavy %.
Comparative Examples 2
With NaY molecular sieve Y-A used among the embodiment 1 is initiation material, getting this NaY sample 30 grams (butt) and 30 gram ammonium chlorides joins 300 together and restrains in the distilled water and stir, under 90 ℃ of conditions, stir exchange 1h then, filter, after repeating above-mentioned exchange process secondary, with sample filtering and fully washing, obtain Na in the ammonium ion exchange sample
2The O residual quantity is 3.0 heavy %.
Embodiment 4
(industrial goods, the Lanzhou catalyst plant produces, degree of crystallinity 96%, framework si-al ratio 5.0, Na to get conventional NaY molecular sieve used in the 30 gram Comparative Examples 1
2O content 13.2%), it is carried out alkali treatment, washing and drying etc., obtain the alkali treatment sample of conventional NaY molecular sieve by condition described in the embodiment 1.
The lattice avalanche temperature that adopts differential thermal analysis to record above-mentioned alkali treatment product is 903 ℃, and the lattice avalanche temperature that records alkali treatment product among the embodiment 1 under the similarity condition is 938 ℃.
Embodiment 5
Take by weighing 250 gram NaOH and be dissolved in the 400 gram distilled water, stir back cooling and constant temperature in 25 ℃ of water-baths.Get used NaY molecular sieve Y-A (degree of crystallinity: 95% among the 50 gram embodiment 1; Framework si-al ratio: 6.15; Body phase silica alumina ratio: 6.24; Surface silicon aluminum ratio: 5.12; Na
2The heavy % of O:12.1; N
2Adsorption capacity: 295.01cc/g) join in the above-mentioned NaOH strong base solution for preparing, after stirring 30min under 25 ℃,, obtain alkali treatment sample (degree of crystallinity: 77% with sample filtering, washing, drying; Framework si-al ratio: 4.35; Body phase silica alumina ratio: 4.64; Surface silicon aluminum ratio: 4.02; Na
2The heavy % of O:12.3; N
2Adsorption capacity: 373cc/g).
The lattice avalanche temperature that adopts differential thermal analysis to record above-mentioned alkali treatment product is 893 ℃.The lattice avalanche temperature that records sample Y-A under the similarity condition is 942 ℃.
As can be seen, when the alkali treatment condition is too harsh (as, alkali concn is too high, the alkali consumption is excessive), the degree of crystallinity of molecular sieve declines to a great extent, and molecular sieve structure is impaired serious.
Embodiment 6
Take by weighing 1 gram NaOH and be dissolved in the 999 gram distilled water, be warming up to 99 ℃ after stirring.Get used NaY molecular sieve Y-A (degree of crystallinity: 95% among the 50 gram embodiment 1; Framework si-al ratio: 6.15; Body phase silica alumina ratio: 6.24; Surface silicon aluminum ratio: 5.12; Na
2The heavy % of O:12.1; N
2Adsorption capacity: 295.01cc/g), join in the above-mentioned strong base solution for preparing, after stirring 5h under 99 ℃,, obtain alkali treatment sample (degree of crystallinity: 96% with sample filtering, washing, drying; Framework si-al ratio: 6.15; Body phase silica alumina ratio: 6.20; Surface silicon aluminum ratio: 5.13; Na
2The heavy % of O:12.0; N
2Adsorption capacity: 295.1cc/g).
Get the above-mentioned alkali treatment product of 30 grams, join 300 grams with 30 gram ammonium chlorides and stir in the distilled water, under 90 ℃ of conditions, stir exchange 1h then.The pH value that adopts the 1mol/L hydrochloric acid solution will exchange slurries in the exchange process transfers to 3.0 and also keeps.After exchange finishes, filter, wash Na in the ammonium trade-to product that obtains
2The O residual quantity is 4.8 heavy %.
The foregoing description shows that concentration of lye is low excessively, and effective desiliconization can not take place framework of molecular sieve.Thinking, is because the crystallization building-up process of Y molecular sieve itself just is in a high basicity system.Thereby cross when low when the concentration of lye of preparation, Y molecular sieve can keep skeleton to stablize in this environment of low basicity.
Embodiment 7
Ammonium among the embodiment 2 exchange sample is placed roasting 2h under 650 ℃, 100% water vapour atmosphere, and the gained sample is handled through an ammonium ion exchange again, promptly gets USY product finally.Molecular sieve (butt) in the ammonium exchange process for the second time: ammonium chloride: distilled water=1: 1: 10, adopt 1mol/L hydrochloric acid to regulate slurries pH=2.5 and also keep 1h.
Product lattice constant α
0=2.445nm, BET specific area 683.6m
2/ g, mesoporous volume 0.24cc/g (, choose diameter in the framework of molecular sieve calculates secondary pore in the hole of 2～60nm scope volume, down with) with reference to U.S. Pat P 5601798 described methods.
Embodiment 8
The 5g sodium hydrate solid is dropped into stirring and dissolving in the 397g distilled water, solution is warming up to 65 ℃ then.Take by weighing the NaY sieve sample described in the 60g embodiment 1 (sample name Y-A, degree of crystallinity 95%, silica alumina ratio 6.15), it is put in the above-mentioned aqueous slkali react 2h.Alkali treatment finishes, with dope filtration, gained molecular sieve filter cake is washed till filtrate pH value less than after 10, by method described in the embodiment 2 this alkali treatment sample is carried out the ammonium exchange first time, by method described in the embodiment 7 it is carried out hydro-thermal super stabilizing and the processing of ammonium exchange for the second time, promptly obtain final modification sample USY.
The lattice constant α 0=2.446nm of gained USY product, BET specific area 688.7m
2/ g, mesoporous volume 0.25cc/g.
Comparative Examples 3
Take by weighing NaY molecular sieve used among the 60g embodiment 1 (sample name Y-A, degree of crystallinity 95%, silica alumina ratio 6.15), pull an oar and mix with 60g ammonium chloride, 600g distilled water, in 90 ℃ of ion-exchange 1h, adopt 1mol/L hydrochloric acid solution adjusting slurry pH value to 3 in the exchange process.Ion-exchange finishes, and filters, washing, and the gained sample carries out hydro-thermal super stabilizing and ion-exchange treatment for the second time according to embodiment 7 described methods, promptly obtains the USY sample according to conventional " two hand over a roasting " method modification.
The lattice constant α of gained USY product
0=2.448nm, BET specific area 658.9m
2/ g, mesoporous volume 0.14cc/g.
Comparative Examples 4
" two hand over one roasting " USY molecular sieve in the Comparative Examples 3 is carried out 650 ℃, 100% steam treatment again one time, promptly obtain USY product according to conventional " two hand over two roastings " method modification.The lattice constant α of gained USY product
0=2.434nm, BET specific area 655.7m
2/ g, mesoporous volume 0.21cc/g.
Embodiment 9
(the molecular sieve solid content is 10% to take out the fresh crystallization slurries of 1000g from the synthetic slurries of the NaY molecular sieve that just stops crystallization, degree of crystallinity is 93%, silica alumina ratio is 5.83), to wherein adding the 30g mass percentage concentration is 25% NaOH concentrated solution, be warming up to 95 ℃ of reaction 3h after stirring, filter, wash, the gained sieve sample carries out " two hand over two roastings " modification according to the exchange of conventional ion described in Comparative Examples 3 and the Comparative Examples 4, hydrothermal method to be handled, and obtains final modification sample USY.
The lattice constant α of gained USY product
0=2.434nm, BET specific area 686.3m
2/ g, mesoporous volume 0.30cc/g.
Comparative Examples 5
(the molecular sieve solid content is 10% with embodiment 9 described identical fresh crystallization slurries to get 1000g, degree of crystallinity is 93%, silica alumina ratio is 5.83), it is directly filtered, washs, gained NaY molecular sieve carries out routine " two hand over two roastings " modification according to method described in Comparative Examples 3 and the Comparative Examples 4 to be handled, and obtains final modification sample.
The lattice constant α of gained USY product
0=2.434nm, BET specific area 678.8m
2/ g, mesoporous volume 0.23cc/g.
Embodiment 10
With the foregoing description 7,9 and Comparative Examples 3,5 described each modified molecular screen is active component, be matrix with kaolin, be binding agent with aluminium colloidal sol, after molecular sieve (butt), kaolin (butt), aluminium colloidal sol (solid content) mixed in 35: 50: 15 ratio making beating, spraying, drying, after making microspherical catalyst, estimated the reactivity worth of each catalyst on the small fixed flowing bed catalytic cracking unit, its result is as shown in table 1.Wherein, through 800 ℃, 100% steam aging 4 hours, feedstock oil was mixed 30% decompression residuum for the grand celebration wax oil before the evaluating catalyst, and reaction temperature is 480 ℃, air speed 16h
-1, oil ratio 4.0.
Table 1 catalyst performance evaluation
Catalytic cracking evaluating data in the above-mentioned table 1 shows, comparing and adopt conventional ion exchange, the super steady catalyst that the USY molecular sieve that obtains is the active component preparation of handling of hydro-thermal, is that the catalyst that active component prepares has stronger heavy oil conversion performance and the yield of light oil of Geng Gao with alkali treatment method in conjunction with USY molecular sieve identical, that the conventional super steady means of ion-exchange, hydro-thermal obtain.
Claims (10)
1. the alkali treatment modifying method of a Y zeolite, it is characterized in that, described method of modifying comprises: according to Y zeolite (butt): alkali: water=(0.1～2): (0.05～2): the mass ratio of (4～15), the aqueous solution making beating of this Y zeolite and alkali is mixed, and the temperature conditions of keeping 0～120 ℃ stirs down and implements alkali treatment 0.1～24h, and this alkali treatment process is at least once.
2. according to the method for modifying of claim 1, the framework si-al ratio of wherein said Y zeolite is not less than 5.0.
3. according to the process of claim 1 wherein that described Y zeolite is the NaY molecular sieve, synthesize the NaY molecular sieve that separate with crystallization mother liquor the back, or include the molecular sieve mixture of crystallization mother liquor from crystallization.
4. according to the process of claim 1 wherein that described alkali treatment condition is: according to Y zeolite: alkali: water=(0.5～2): (0.075～1): the mass ratio of (4～10) mixes the aqueous solution making beating of molecular sieve and alkali, and keeps stirring.
5. according to the process of claim 1 wherein, described alkali is selected from one or both the mixture among NaOH, the KOH.
6. the preparation method of a NH4Y molecular sieve, this method comprises: according to each method of claim 1-5 NaY type molecular sieve is carried out alkali treatment modifying, then the NaY molecular sieve of this alkali modification is implemented ammonium ion exchange and handle.
7. according to the described preparation method of claim 6, wherein, described ammonium ion exchange process is: with the NaY molecular sieve pulp after the alkali treatment filter, wash to pH less than 10, then the gained filter cake is mixed with ammonium salt solution and carry out ammonium ion exchange, regulation system pH is in the 2.0-7.0 scope in the ammonium ion exchange process; Perhaps, add acid solution in the NaY of alkali treatment molecular sieve pulp, the pH of regulation system adds ammonium salt and carries out ammonium ion exchange in the 2.0-7.0 scope.
8. the preparation method of a super-stable Y molecular sieves, this method comprises: according to each method of claim 1-5 NaY type molecular sieve is carried out alkali treatment modifying, the NaY molecular sieve to this alkali modification carries out ammonium ion exchange and the super steady processing of hydro-thermal then.
9. according to the described preparation method of claim 8, wherein, described ammonium ion exchange process is: with the NaY molecular sieve pulp after the alkali treatment filter, wash to pH less than 10, then the gained filter cake is mixed with ammonium salt solution and carry out ammonium ion exchange, regulation system pH is in the 2.0-7.0 scope in this ammonium ion exchange process; Perhaps, add acid solution in the NaY molecular sieve pulp after alkali treatment, the pH of regulation system adds ammonium salt and carries out ammonium ion exchange in the 2.0-7.0 scope.
10. according to claim 8 or 9 described preparation methods, wherein, the super steady processing procedure of described hydro-thermal comprises placing 500～700 ℃ hydro-thermal stove with handling molecular sieve through ammonium ion exchange that roasting is 1～24 hour under 20～100% water vapour atmospheres.
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