CN105084388A - Method for preparing and modifying Y-type molecular sieve - Google Patents
Method for preparing and modifying Y-type molecular sieve Download PDFInfo
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- CN105084388A CN105084388A CN201410213442.4A CN201410213442A CN105084388A CN 105084388 A CN105084388 A CN 105084388A CN 201410213442 A CN201410213442 A CN 201410213442A CN 105084388 A CN105084388 A CN 105084388A
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Abstract
The invention relates to a method for preparing and modifying a Y-type molecular sieve, wherein the method comprises the steps of ammonia exchange on a NaY molecular sieve, treatment under a hydrothermal condition, modification by adding a silica sol, a alcohol substrate and a citric acid solution, and the like. The NaY molecular sieve is obtained by successively adding a guiding agent, a silicon source, an aluminum source and water into a mixing pot to obtain a mixture A for hydrothermal crystallization, wherein, the guiding agent is obtained by the following processes: mixing sodium metaaluminate and water glass to make the mole concentration of the aluminum element in the water glass be increased from zero so as to form a mixture B having a mole ratio of (6-25)Na2O: Al2O3:(6-25)SiO2, sequentially carrying out dynamic aging and standing aging, and adding water. According to the molecular sieve product, the cell parameter is 2.461-2.467 nm, the molecular sieve has higher crystallization retention degree, and the average diameter of the crystalline grain is 50-800 nm.
Description
Technical field
What the present invention relates to a kind of Y zeolite prepares method of modifying, the present invention relates in particular to prepare method of modifying under a kind of non-template agent of Y zeolite.
Background technology
The fifties end, Milton and Breck successfully synthesizes Y zeolite.Due to SiO in the structure of Y zeolite
2with Al
2o
3ratio be greater than X-type molecular sieve, thus thermostability and hydrothermal stability improve.Early seventies, Grace development of company directing agent method synthesis NaY molecular sieve, raw material instead of expensive silicon sol with water glass, and technique is simplified, growth cycle shortens, thus makes NaY molecular sieve be widely applied to petrochemical complex especially cracking of oil catalytic field rapidly.Up to now, in hundreds of molecular sieve developed, what industrially usage quantity was maximum is Y zeolite.At present, the synthesis of Y zeolite industrially mainly adopts crystal seed glue method.Due to the Application and improvement of crystal seed glue, greatly shortened, for the industrialization of Y zeolite is laid a good foundation the time of the synthesis crystallization of Y zeolite.
Industrial application and development is had higher requirement to the synthesis of molecular sieve and products thereof performance, also promotes the further investigation of Zeolite synthesis technology conversely.To the requirements at the higher level of Y zeolite synthesis mainly concentrate on synthesizing small-grain and ultra-fine grain zeolite product, improve silica alumina ratio and synthesizing high-silicon aluminum ratio ratio and three aspects such as the zeolite product of little crystal grain and ultra-fine grain.
The Y zeolite of little grain-size is owing to having larger outer surface area and higher micropore diffusion speed, improving in conversion macromole ability, the secondary cracking reducing product and the coking of reduction catalyzer etc., show the performance more more superior than conventional die size Y zeolite, therefore the study on the synthesis of the Y zeolite of little crystal grain becomes focus.The Y zeolite synthesized in conventional manner generally has the grain-size of about 1000nm, and the synthesis report that little crystal grain even can reach nano level (<100nm) grain-size this respect is still less.
With hot crushing technology process Y zeolite, although its grain fineness number can be made to be reduced to 100nm, the mode of this physical pulverization process not only expends comparatively macro-energy, and destroys the crystalline structure of molecular sieve, makes it part amorphous.If can direct synthesizing small-grain Y zeolite, it be the most simple and feasible method, therefore, must will optimize the synthesis condition of conventional Y zeolite, by improving and increase guiding dosage, improving the method reduction molecular sieve particle diameters such as the basicity that feeds intake, to obtain small crystal grain Y-shaped molecular sieve product and the business-like top condition of applicable molecular sieve.
The optimization of synthesis condition generally includes the condition as the preparation of crystal seed glue, the impact of digestion time, the preparation of silica-alumina gel and hydrothermal crystallizing, comprises basicity, crystallization temperature and crystallization time etc.The composition of silica-alumina gel generally causes molecular sieve different by the impact of crystallization condition; Hydrothermal crystallizing condition more immediate influence the synthesis of molecular sieve, and they both restricted mutually, the silica alumina ratio of the molecular sieve that influences each other again, degree of crystallinity and grain fineness number.The basicity of silica-alumina gel is a very crucial factor in sieve synthesis procedure, and the basicity improving synthetic system can prepare Microsize NaY Zeolite.The water glass containing poly state silicon due to industrial most employing is silicon source, improves system basicity, not only can increase the depolymerization of poly state silicon, and be conducive to forming more nucleus in silica-alumina gel, thus grain-size is reduced.Schhoeman etc. (SehoemanBJ, SterteJ, ChemicalCommunications, 1993:994 ~ 99) adopt the method for high alkalinity, high silica alumina ratio, have directly synthesized the NaY molecular sieve that grain-size is less than 150nm from liquid phase.But along with the increase of system basicity, the yield of synthetic product declines.The people such as Bi-ZengZ also find under study for action as synthetic system n (Na
2o)/n (Al
2o
3)=6 ~ 15, and be greater than the high-speed stirring of 3000r/min at rotating speed under, prepare homogeneous phase, mobility alumino silica gel, the Y zeolite of particle diameter at below 100nm can be obtained, but silica alumina ratio is generally less than 4.5 (Bi-ZengZ, MaryA.W, MiehaelL.ControlofParticlesizeandsurfaceProPertlesofCrys taIsofNaXZeolite, ChemistryofMaterials, 2002,14:363-3642).
In the synthetic method of Y zeolite, include the directing agent method based on commercial synthesis and the clear liquid synthesis method based on template.Based in the directing agent method of commercial synthesis, by adding the additives such as rare earth ion, aluminum complexing agent and tensio-active agent in synthetic system, the median size of NaY molecular sieve can be reduced, but its shortcoming to be size distribution wider.(the LindnerT. such as Linder, LechertH., Zeolites, 1996,16:196-206) study mineralizer on faujusite synthesize affect time find, in synthetic system, add a small amount of can form the organic complexing agent of stable comple with aluminium, generally can promote the nucleation of molecular sieve and the growth of crystal, thus make the grain-size of molecular sieve reduce, narrow particle size distribution, and framework of molecular sieve silica alumina ratio can not be reduced.Maher etc. disclose a kind of method of synthetic faujasites type molecular sieve in US3516786, before synthetic system intensification crystallization steps, add in synthetic system on a small quantity can be miscible with water organic solvent, as dimethyl sulfone, N, dinethylformamide, tetrahydrofuran (THF), methyl alcohol, ethanol, acetone etc., final zeolite crystal is of a size of 0.01 ~ 0.1 μm.Ambs etc. in order to reduce the volatilization of the organic solvent brought because of intensification, employ glucose in US4372931, and final grain-size is 0.035 ~ 0.069 μm.But, after adding organic solvent, the skeleton SiO of molecular sieve
2/ Al
2o
3lower, generally lower than 2.5.And another kind is based on the clear liquid synthesis method of template, this method can obtain nano level NaY molecular sieve, and has the advantage of crystal particle diameter narrow distribution, but its product yield is very low, and cost is very high.Holmberg etc. by adding 4 bromide and Tetramethylammonium hydroxide double template, by optimize TMA
+y zeolite grain-size and yield is controlled with the concentration of negatively charged ion, finally synthesize the Y zeolite that granularity is 37nm, but the very low and very high (HolmbergB.A. of cost of its product yield, WangH., ControllingsizeandyieldofzeoliteYnanocrystalsUsingtetram ethylammoniumbromide, MicroPorousandMesoPorousMaterial, 2003,59:13-28).
The main character of the height of framework si-al ratio and the structures shape in duct thereof molecular sieve and function.In general, the molecular sieve that silica alumina ratio is higher often has stronger heat-resisting, resistance to water vapour and capacity antacid; In addition, dissimilar molecular sieve is to some catalyzed reaction, and the change with its silica alumina ratio also shows different specific regularity.Therefore, by directly synthesizing or obtained by the method (i.e. secondary synthesis) of modification the silica alumina ratio of dissimilar molecular sieve, thus its character and function can be regulated and controled.
Be less than 5.0 with the silica alumina ratio of Y zeolite of ordinary method synthesis, generally silica alumina ratio is greater than 6.0 be high-Si Y-type molecular sieve.The conventional method obtaining high-Si Y-type molecular sieve has two kinds: a kind of is the method for directly synthesizing, and another kind is on the basis of single sintering, is adopted by product specific route to reprocess, and namely improves framework si-al ratio by the method for secondary synthesis.At present, two-step fabrication mainly contains: high temperature hydrothermal method (US3449370), high temperature gas-phase reaction method (US4701313), ammonium silicofluoride liquid phase reaction method (US4093560) etc., the shortcoming of these methods be that preparation process is numerous and diverse, zeolite crystallinity loss is comparatively large, preparation technology's process CIMS is complicated, yield is low and environmental pollution larger etc.
And need to consider more factor in the method for directly synthesizing, such as: the preparation of the composition of reaction mixture, preparation method, reactant source, directed agents, whether stir, gel potential of hydrogen and crystallization condition etc.The Y zeolite that usual silica alumina ratio is lower more easily obtains, otherwise the preparation condition of silica alumina ratio more high request is harsher, more difficultly synthesizes desirable sample.In the method for directly synthesis, the conventional approach improving silica alumina ratio mainly contains following several: a kind of approach extends crystallization time, but this approach is after silica alumina ratio is greater than 5.5, crystallization velocity exponentially form decline, make synthesis because of consuming time, cost is high and be not suitable for industrial production; Another kind of approach uses organic amine (US5116590, US4965059, CN96105159.7, or inorganic salt (US4333859 CN97196899), US4309313) as template, but the problem such as this exists equally that cost is high, crystallization time long, the utilization ratio of silicon is on the low side, simultaneously, the silicon waste liquid of a large amount of high density is discharged, and has both wasted also contaminate environment.
In the method for direct synthesizing high-silicon aluminum ratio Y zeolite, adopt non-template agent method to be the focus and difficult point studied always.CN102198950A discloses a kind of preparation method of high silica alumina ratio NaY molecular sieve; By silicon source, aluminium source and deionized water mixing, get the directed agents of two kinds of different mol ratio, water glass, acid aluminium salt and sodium aluminate solution according to following gel masses mol ratio and mix obtained two kinds of gels, respectively crystallization; Gel masses mol ratio is: (1.0 ~ 6.5) Na
2o:Al
2o
3: (5.0 ~ 18) SiO
2: (100 ~ 280) H
2o, the wherein Al of directed agents
2o
3account for Al
2o
30.01 ~ 15% of gross weight; Two kinds of gels are 1:(0.1 ~ 10 according to mass ratio) Homogeneous phase mixing, obtained mixed gel; By obtained mixed gel crystallization 2 ~ 50 hours at 80 ~ 120 DEG C, obtained NaY molecular sieve.Under the condition that molar ratio is identical, the method can prepare the NaY molecular sieve of high silica alumina ratio within the shorter time.Method disclosed in CN1785807A and CN1785808A is at 15 ~ 60 DEG C, stir ageing 0.5 ~ 48 hour obtained directed agents in advance, then reaction mixture is made in directed agents, water, silicon source, aluminium source, by reaction mixture crystallization in two steps after stirring, the first step dynamic crystallization, second step static crystallization, finally by filtration, washing, dry, obtained relative crystallinity is greater than 80%, framework si-al ratio and SiO
2/ Al
2o
3mol ratio is between 6.0 ~ 7.0, and the high silicon aluminium ratio small crystal NaY molecular sieve of average crystal grain between 300 ~ 800nm.The preparation method of the NaY molecular sieve of high silica alumina ratio, little crystal grain disclosed in CN1789125, first synthesize NaY molecular sieve directed agents, then gel is obtained with water glass, directed agents, acid aluminium salt and sodium metaaluminate, by gel at 50 ~ 100 DEG C after crystallization 0 ~ 70h, add silicon source, at 90 ~ 120 DEG C, continue crystallization 0.5 ~ 50h again, finally by filtration, washing, dry, obtain that silica alumina ratio is 5.2 ~ 7.0, crystal grain is the NaY molecular sieve of 100 ~ 400nm.
Y zeolite will carry out modification to it before application, obtained having different SiO
2/ Al
2o
3the molecular sieve of ratio, acidity and pore structure.Content normally by changing aluminium realizes the modification of molecular sieve, and wherein sour dealuminzation is an important method of Y zeolite modification.Acid-treated condition is general gentleer, can not saboteur's sieve structure, optionally removes the non-framework aluminum in molecular sieve.But for the difficult non-framework aluminum removed of part, adopt general acid treatment it effectively, uniformly can not be removed, if by improving acid concentration, then can cause removing of part framework aluminum, make modified molecular sieve structure destruction, degree of crystallinity declines, sour irrational distribution, thus directly cause the decline of catalytic performance.Another kind of method of modifying with salicide processes molecular sieve.CN1382632A discloses a kind of super stabilizing method of small-grain Y-type zeolite, the method uses dry gas and the fine grain NaY zeolitic contact of silicon tetrachloride, obtain after washing, due to the heat of its raw material self and hydrothermal stability just poor, this inventive method is the mode process molecular sieve adopting gas phase dealumination complement silicon simultaneously, this make the heat of product and hydrothermal stability poorer, active low; To there is batch in the industrial production little for this gas phase treatment method in addition, and the shortcoming such as consume energy higher.CN101941713A discloses a kind of preparation method of little grain high-Si Y-type molecular sieve, and the method selects suitable modifying process, i.e. ammonium exchange, ammonium hexafluorosilicate dealumination complement silicon, hydrothermal treatment consists and aluminum saline solution process etc. obtain product; CN102311129A discloses a kind of preparation method of high-Si Y-type molecular sieve, and first the method carries out silicofluoric acid process to molecular sieve pulp, directly adds ammonium salt after silicofluoric acid process, obtains modification high-Si Y-type molecular sieve.Though above-mentioned two kinds of method of modifying can improve the framework si-al ratio of molecular sieve, the fluorion that additive is introduced is difficult to wash-out from slurries, and the fluorion that the liquid residue after molecular sieve washing is a large amount of causes environmental issue in industrial production.
Summary of the invention
The object of the invention is for the deficiencies in the prior art, the raising silica alumina ratio of a kind of environmental friendliness, low cost be provided, have better crystallization reservation degree small crystal grain Y-shaped molecular sieve prepare method of modifying.
Contriver finds in the synthetic test of a large amount of Y zeolites, optimize directed agents contact raw state, dynamic aging, static-aging, the composition of directed agents and the raw material addition sequence of add-on, reaction mixture and the parameter such as crystallization temperature and time in the reactive mixture simultaneously, unexpectedly can obtain high silica alumina ratio, median size is the NaY molecular sieve of 50-800nm, and molecular sieve stability is better, based on it, carry out Si modification further operate the high silica alumina ratio molecular sieve obtained, crystallization reservation degree is better.
Therefore, Y zeolite provided by the invention prepare method of modifying, it is characterized in that comprising the steps: that (1) prepares NaY molecular sieve; (2) NaY molecular sieve being exchanged through ammonium the weight content obtaining sodium oxide is the NH of 2.5-5%
4naY molecular sieve; (3) NH is processed under hydrothermal conditions
4naY molecular sieve; (4) by NH
4after NaY molecular sieve making beating, add the organic alcohols material of silicon sol that pH is 2-4 and C2-C4 and adjust pH to be 3-6 with citric acid solution, fully mixing at temperature is 80-120 DEG C, then obtaining modified product through washing and drying; Wherein, in said step (1), the process of preparation NaY molecular sieve is under the condition of synthesis NaY molecular sieve, the mixture A obtained after order according to directed agents, silicon source, aluminium source and water is added mixing tank successively carries out hydrothermal crystallizing and also reclaims the product obtained, said directed agents is mixed with water glass by sodium metaaluminate, and the volumetric molar concentration of aluminium element in water glass is edged up to forming mol ratio for (6 ~ 25) Na by zero
2o:A1
2o
3: (6 ~ 25) SiO
2mixture B, then sequentially pass through dynamic ageing, still aging, then add that water obtains.
In the present invention, the process of the said preparation NaY molecular sieve of step (1) uses direct synthesis technique: first prepare directed agents, then preparation feedback mixture, finally by crystallization, filtration, washing, drying and obtain middle high silicon aluminium ratio small crystal NaY molecular sieve.In said reaction mixture, not adding any template or additive, also need not carry out chemistry to synthesizing the molecular sieve that obtain or physical method carries out dealuminzation, or dealumination complement silicon and secondary synthesis improve silica alumina ratio.Raw materials used inexpensive, be easy to get, simple for process, be conducive to reduce manufacturing cost.
In the present invention, silicon source and aluminium source (mix with any order by the preparation process that the preparation of step (1) said directed agents is different from conventional method synthesis NaY molecular sieve directed agents, aging under quiescent conditions after mixing), be also different from and saidly in CN1785807A, CN1785808A at 15 ~ 60 DEG C, stir aging obtained directed agents.The preparation of the directed agents in the present invention is mixed with water glass by sodium metaaluminate, and the volumetric molar concentration of aluminium element in water glass is edged up to forming mol ratio for (6 ~ 25) Na by zero
2o:A1
2o
3: (6 ~ 25) SiO
2mixture B, then sequentially pass through dynamic ageing, still aging, then add that water obtains.Preparation process comprises the following steps more specifically: sodium metaaluminate, at 15 ~ 60 DEG C of temperature and agitation condition, adds by (1) in water glass, and forming mol ratio is (6 ~ 25) Na
2o:A1
2o
3: (6 ~ 25) SiO
2said mixture B; (2) by mixture B dynamic ageing 5 ~ 48 hours at 15 ~ 60 DEG C, then at 15 ~ 60 DEG C still aging 5 ~ 48 hours; (3) after ageing, under the condition stirred, add water, make the final mol ratio of directed agents for (6 ~ 25) Na
2o:A1
2o
3: (6 ~ 25) SiO
2: (200 ~ 400) H
2o.
Obtain after directed agents through said process, the further step of preparing of step of the present invention (1) said NaY molecular sieve is: at room temperature add water, silicon source, aluminium source, directed agents obtain mixture A, the mol ratio of mixture A is (2 ~ 6) Na
2o:A1
2o
3: (8 ~ 20) SiO
2: (200 ~ 400) H
2o, the add-on of directed agents accounts for 3 ~ 30% calculating of total aluminium element mole number according to the mole number of aluminium element in directed agents.Said mixture A obtains after adding mixing tank successively according to the order of directed agents, silicon source, aluminium source and water.Wherein, said water is deionized water or distilled water, silicon source can be one or more the mixture in water glass, silicon sol, silica gel and white carbon black, and said aluminium source is one or more the mixture in sodium metaaluminate, Tai-Ace S 150, aluminum chloride, aluminum nitrate, aluminium hydroxide and pseudo-boehmite.The hydrothermal crystallizing of said mixture A carries out 15-48 hour in closed reactor at 90-100 DEG C.
Adopt the directed agents preparation process being different from prior art in step (1) and the NaY molecular sieve obtained in conjunction with specific raw materials order Hydrothermal Synthesis, there is the feature of middle high silica alumina ratio and little crystal grain, skeleton SiO
2/ Al
2o
3mol ratio is between 5.0 ~ 6.0, and average crystal grain at 50 ~ 800nm, and can adjust between 50 ~ 200nm, 200 ~ 500nm, 500 ~ 800nm.This step need not additionally add template or additive, raw materials used inexpensive, be easy to get, simple for process, be conducive to reduce manufacturing cost.
In method of the present invention, NaY molecular sieve is exchanged through ammonium the weight content obtaining sodium oxide by (2) also is in steps the NH of 2.5-5%
4naY molecular sieve.The process that said ammonium exchanges carries out one or many, it is the ammonium salt solution of 0.1 ~ 1.0mol/L that the process that said ammonium exchanges comprises employing ammonium concentration, under temperature 50 ~ 100 DEG C, solvent and solute weight ratio are the condition of 8 ~ 15:1, constant temperature process 0.5 ~ 1.5 hour.Said ammonium salt is one or more in ammonium nitrate, ammonium sulfate, ammonium chloride and ammonium acetate.
In method of the present invention, process NH under (3) hydrothermal condition also in steps further
4naY molecular sieve.The process processed under said hydrothermal condition processes 1 ~ 3 hour at 100% water vapour, gauge pressure 0.1 ~ 0.2MPa, temperature 500 ~ 650 DEG C.
In method of the present invention, further also in steps (4) by NH
4after NaY molecular sieve making beating, add the small molecules organic alcohols material of silicon sol that pH is 2-4 and C2-C4 and adjust pH to be 3-6 with citric acid solution, fully mixing at temperature is 80-120 DEG C, then obtaining modified product through washing and drying.Said making beating, solvent and solute weight ratio is 3-10:1; Said pH is the silicon sol of 2-4 is add at making beating 80-120 DEG C, slurry, adds according to every 100 mol sieves with SiO
2the ratio counting the silicon sol of 0.1-10 gram adds.The organic alcohols material of said C2-C4 can reduce the high surface energy of silicon sol as dispersion agent, add the repulsion between micelle, ensure that the good distribution of micelle, one or more in the preferred glycerol of organic alcohols material of said C2-C4, ethylene glycol and Virahol.The organic alcohols material of said C2-C4 adds according to the ratio of the alcohols material of every 100g molecular sieve 1-30g.Regulating pH to be 3-6 is adopt citric acid solution, and the concentration of said citric acid solution can be 0.1-0.3mol/L; Said abundant mixing can be stir 0.5-5 hour under constant temperature constant speed.The present invention adds acidic silicasol, make the silicon in silicon sol be supplemented in molecular sieve surface and skeleton because of hydrothermal aging produce some lattice defects, improve the crystallization reservation degree of molecular sieve, and the silica alumina ratio of Y zeolite can be increased considerably.
The inventive method preparation process is simple, and production cost is low, little to the pollution of environment in production process.
Through the Y zeolite prepared method of modifying and obtain provided by the invention, be small crystal grain Y-shaped molecular sieve, average crystal grain can adjust between 50-800nm, body phase SiO
2/ Al
2o
3mol ratio 5-10, crystallization reservation degree is greater than 85%, and relative crystallinity is 85%-95%, and product structure cell only has minimal shrink, and unit cell parameters is 2.461-2.467nm, sodium oxide weight content≤0.1wt%.
Embodiment
Below by embodiment, the present invention is further illustrated, but scope not thereby limiting the invention.
In each embodiment and comparative example, sample topography is provided by electromicroscopic photograph, is observed by JSM-5610LV type scanning electron microscope instrument.
NaY molecular sieve silica alumina ratio is the lattice constant a calculating NaY molecular sieve by SH/T0339-92 standard method (" standard of chemical industry compilation ", China Standards Press publish for 2000), then according to Breck-Flanigen formula S iO
2/ Al
2o
3=2 (25.858-a)/(a-24.191) draws.Relative crystallinity measures (" standard of chemical industry compilation ", China Standards Press publish for 2000) according to SH/T0340-92 standard method.Modified sieve sample body phase SiO
2/ Al
2o
3mol ratio adopts XRF method to measure, crystallization reservation degree: Y zeolite XRD figure spectrum in 5 characteristic peaks peak height and be foundation, with the per-cent of the peak height sum of 5 characteristic peaks of the Y zeolite sample after modification divided by the peak height sum of raw material Y zeolite 5 characteristic peaks, 5 characteristic peaks are 2 θ is respectively 15.8,20.7,24.0, characteristic peak corresponding to 27.4 and 31.8 peak positions.XRD spectra SIMADUXRD6000 type X-ray diffractometer measures, and (experiment condition is: CuKa radiation, pipe pressure 40kv, tube current 40mA.)。
Embodiment 1
By 50.39g high alkali deflection aluminium acid sodium solution, (limited-liability company of China Petrochemical Industry catalyzer Chang Ling branch office provides, Al
2o
3content is 40.2g/L, Na
2o content is 255g/L, and proportion is 1.324) (limited-liability company of China Petrochemical Industry catalyzer Chang Ling branch office provides, SiO to join 65.56g water glass
2content is 260.6g/L, Na
2o content is 81.6g/L, and proportion is 1.2655, and modulus is 3.3) in, at room temperature stir ageing 48 hours, then static ageing 5 hours at 60 DEG C of temperature, finally under the condition stirred, add 15g deionized water, the final mol ratio of the directed agents obtained is 15Na
2o:A1
2o
3: 15SiO
2: 320H
2o.
Obtained directed agents is all for the preparation of following reaction mixture, and the add-on of directed agents, accounts for 3% of total aluminium element mole number according to the mole number of aluminium element in directed agents and calculate.
Under the condition of room temperature and high-speed stirring, according to directed agents (abovementioned steps preparation), 1682.6g water glass (the same), 134.19g low alkali aluminium acid sodium solution, (limited-liability company of China Petrochemical Industry catalyzer Chang Ling branch office provides, Al
2o
3content is 194g/L, Na
2o content is 286.2g/L, and proportion is 1.413), (limited-liability company of China Petrochemical Industry catalyzer Chang Ling branch office provides 448.02g Tai-Ace S 150, Al
2o
3content is 88.9g/L, and proportion is 1.2829) and the order of 150.4g water add successively in mixing tank, total molar ratio of reaction mixture is 3Na
2o:A1
2o
3: 12SiO
2: 209H
2o.After stirring, loaded in stainless steel cauldron, 100 DEG C of static crystallizations 24 hours, then filter, wash, dry NaY molecular sieve product.
It is 5.8 that XRD spectra surveys its silica alumina ratio, and relative crystallinity is 93.7%, and electromicroscopic photograph display average grain size is 300nm.
Compound concentration is 0.5mol/L aqueous ammonium nitrate solution 10 liters.Take small crystal grain NaY molecular sieve 1000 grams, be dissolved in 10 liters of aqueous ammonium nitrate solutions prepared, mixing speed is 300rpm, and at 90 DEG C, constant temperature stirs 1 hour, then filtering molecular sieve.Repeat aforesaid operations, until Na in molecular sieve
2the content of O reaches 2.5wt%.Obtain dried sample at 500 DEG C, the Water Under thermal treatment 1.5h of 100% water vapour gauge pressure 0.1MPa.Measure 1 liter of water purification and be dissolved in water purification by 200 grams of above-mentioned samples, be rapidly heated stirring, and temperature is 80 DEG C, and mixing speed is 300rpm.In molecular sieve slurry, add acidic silicasol, glycerol fast, add with SiO altogether
2count the acidic silicasol solution of 18 grams, 36g glycerol, be 3.0 with the pH of the citric acid solution regulator solution of 0.1mol/L, then constant temperature constant speed stirs 2 hours, filters, and dry, obtain production code member NY-1, character lists in table 1.
Comparative example 1
This comparative example illustrates is synthesizing in directed agents process the situation changing directed agents aging condition, only adopt feeding sequence that is still aging and reaction mixture to change.
Each raw material sources are with embodiment 1.
50.39g high alkali deflection aluminium acid sodium solution is joined in 65.56g water glass, at room temperature still aging 28 hours, then to add the final mol ratio of directed agents that 15g deionized water obtains be 15Na
2o:A1
2o
3: 15SiO
2: 320H
2o.
Obtained directed agents is all for the preparation of following reaction mixture, and the add-on of directed agents, accounts for 3% of total aluminium element mole number according to the mole number of aluminium element in directed agents and calculate.
In mixing tank, 1682.6g water glass is first added under the condition of room temperature and high-speed stirring, add 150.4g water, 134.19g low alkali aluminium acid sodium solution, directed agents (abovementioned steps preparation) and 448.02g Tai-Ace S 150 more successively, total molar ratio of reaction mixture is 3Na
2o:A1
2o
3: 12SiO
2: 209H
2o.After stirring, loaded in stainless steel cauldron, 100 DEG C of static crystallizations 24 hours, then filter, wash, dry NaY molecular sieve product.
It is 4.8 that XRD spectra surveys its silica alumina ratio, and relative crystallinity is 88.7%, and electromicroscopic photograph display average grain size is 1000nm.
Compound concentration is 0.5mol/L aqueous ammonium nitrate solution 10 liters.Take small crystal grain NaY molecular sieve 1000 grams, be dissolved in 10 liters of aqueous ammonium nitrate solutions prepared, mixing speed is 300rpm, and at 90 DEG C, constant temperature stirs 1 hour, then filtering molecular sieve.Repeat aforesaid operations, until Na in molecular sieve
2the content of O reaches 2.5wt%.Obtain dried sample at 500 DEG C, the Water Under thermal treatment 1.5h of 100% water vapour gauge pressure 0.1MPa.Measure 1 liter of water purification and be dissolved in water purification by 200 grams of above-mentioned samples, be rapidly heated stirring, and temperature is 80 DEG C, and mixing speed is 300rpm.In molecular sieve slurry, add acidic silicasol, glycerol fast, add with SiO altogether
2count the acidic silicasol solution of 20 grams, 40g glycerol, be 3.0 with the pH of the citric acid solution regulator solution of 0.1mol/L, then constant temperature constant speed stirs 2 hours, filters, and dry, obtain production code member NY-D-1, character lists in table 1.
Embodiment 2
By 50.39g high alkali deflection aluminium acid sodium solution, (limited-liability company of China Petrochemical Industry catalyzer Chang Ling branch office provides, Al
2o
3content is 40.2g/L, Na
2o content is 255g/L, and proportion is 1.324) (limited-liability company of China Petrochemical Industry catalyzer Chang Ling branch office provides, SiO to join 65.56g water glass
2content is 260.6g/L, Na
2o content is 81.6g/L, and proportion is 1.2655, and modulus is 3.3) in, ageing 5 hours is stirred at 60 DEG C of temperature, then static ageing 5 hours at 60 DEG C of temperature, finally under the condition stirred, add 15g deionized water, the final mol ratio of the directed agents obtained is 15Na
2o:A1
2o
3: 15SiO
2: 320H
2o.
Obtained directed agents is all for the preparation of following reaction mixture, and the add-on of directed agents, accounts for 3% of total aluminium element mole number according to the mole number of aluminium element in directed agents and calculate.
According to directed agents (abovementioned steps preparation), 1682.6 under the condition of room temperature and high-speed stirring
g(limited-liability company of China Petrochemical Industry catalyzer Chang Ling branch office provides, Al for water glass (the same), 134.19g low alkali aluminium acid sodium solution
2o
3content is 194g/L, Na
2o content is 286.2g/L, and proportion is 1.413), (limited-liability company of China Petrochemical Industry catalyzer Chang Ling branch office provides 448.02g Tai-Ace S 150, Al
2o
3content is 88.9g/L, and proportion is 1.2829) and the order of 1419.4g water add successively in mixing tank, total molar ratio of reaction mixture is 3Na
2o:A1
2o
3: 12SiO
2: 350H
2o.After stirring, loaded in stainless steel cauldron, 100 DEG C of static crystallizations 32 hours, then filter, wash, dry NaY molecular sieve product.
It is 5.9 that XRD records its silica alumina ratio, and relative crystallinity is 90.6%, and electromicroscopic photograph display average grain size is 800nm.
Ammonium exchanges.Compound concentration is 0.2mol/L ammonium sulfate solution 10 liters.Take small crystal grain NaY molecular sieve 1000 grams, be dissolved in 10 liters of aqueous ammonium nitrate solutions prepared, mixing speed is 300rpm, and at 90 DEG C, constant temperature stirs 1 hour, then filtering molecular sieve.Repeat aforesaid operations, until Na in molecular sieve
2o content reach 3wt%.Obtain dried sample at 580 DEG C, the Water Under thermal treatment 2.0h of 100% water vapour gauge pressure 0.2MPa.Measure 1 liter of water purification and be dissolved in water purification by the sample of 300 grams of abovementioned steps gained, be rapidly heated stirring, and temperature is 90 DEG C, and mixing speed is 300rpm.Be rapidly in molecular sieve slurry and add acidic silicasol and ethylene glycol, add with SiO altogether
2count the acidic silicasol solution of 20 grams, 50g ethylene glycol, be 4.0 with the pH of the citric acid solution regulator solution of 0.2mol/L, then constant temperature constant speed stirs 2 hours, filters, and dry, obtain production code member NY-2, character lists in table 1
Comparative example 2
This comparative example illustrates the situation of the order of addition(of ingredients) changing silicon source, aluminium source in directed agents preparation.
Each raw material sources are with embodiment 2.
65.56g water glass is joined in 50.39g high alkali deflection aluminium acid sodium solution, ageing 5 hours is stirred at 60 DEG C of temperature, then static ageing 5 hours at 60 DEG C of temperature, finally under the condition stirred, add 15g deionized water, the final mol ratio of the directed agents obtained is 15Na
2o:A1
2o
3: 15SiO
2: 320H
2o.
Obtained directed agents is all for the preparation of following reaction mixture, and the add-on of directed agents, accounts for 3% of total aluminium element mole number according to the mole number of aluminium element in directed agents and calculate.
Add successively in mixing tank according to the order of directed agents (abovementioned steps preparation), 1682.6g water glass, 134.19g low alkali aluminium acid sodium solution, 448.02g Tai-Ace S 150 and 1419.4g water under the condition of room temperature and high-speed stirring, total molar ratio of reaction mixture is 3Na
2o:A1
2o
3: 12SiO
2: 350H
2o.After stirring, loaded in stainless steel cauldron, 100 DEG C of static crystallizations 32 hours, then filter, wash, dry NaY molecular sieve product.
It is 5.0 that XRD records its silica alumina ratio, and relative crystallinity is 87%, and electromicroscopic photograph display average grain size is 1000nm.
Compound concentration is 0.2mol/L ammonium sulfate solution 10 liters.Take small crystal grain NaY molecular sieve 1000 grams, be dissolved in 10 liters of aqueous ammonium nitrate solutions prepared, mixing speed is 300rpm, and at 90 DEG C, constant temperature stirs 1 hour, then filtering molecular sieve.Repeat aforesaid operations, until Na in molecular sieve
2o content reach 3wt%.Obtain dried sample at 580 DEG C, the Water Under thermal treatment 2.0h of 100% water vapour gauge pressure 0.2MPa.Measure 1 liter of water purification and be dissolved in water purification by the sample of 300 grams of abovementioned steps gained, be rapidly heated stirring, and temperature is 90 DEG C, and mixing speed is 300rpm.Be rapidly in molecular sieve slurry and add acidic silicasol and ethylene glycol, add with SiO altogether
2count the acidic silicasol solution of 20 grams, 50g ethylene glycol, be 4.0 with the pH of the citric acid solution regulator solution of 0.2mol/L, then constant temperature constant speed stirs 2 hours, filters, and dry, obtain production code member NY-D-2, character lists in table 1
Embodiment 3
By 164.54g high alkali deflection aluminium acid sodium solution, (limited-liability company of China Petrochemical Industry catalyzer Chang Ling branch office provides, Al
2o
3content is 40.2g/L, Na
2o content is 340g/L, and proportion is 1.297) (limited-liability company of China Petrochemical Industry catalyzer Chang Ling branch office provides, SiO to join 291.37g water glass
2content is 260.6g/L, Na
2o content is 81.6g/L, and proportion is 1.2655, and modulus is 3.3) in, stir ageing 20 hours at 30 DEG C of temperature, then static ageing 15 hours at 40 DEG C of temperature, finally under the condition stirred, add 60g deionized water.The final mol ratio of the directed agents obtained is 20Na
2o:A1
2o
3: 20SiO
2: 380H
2o.
Obtained directed agents is all for the preparation of following reaction mixture, and the add-on of directed agents, accounts for 10% of total aluminium element mole number according to the mole number of aluminium element in directed agents and calculate.
Under the condition of room temperature and high-speed stirring, according to directed agents (abovementioned steps preparation), 1092.62g water glass (the same), 166.31 low alkali aluminium acid sodium solutions, (limited-liability company of China Petrochemical Industry catalyzer Chang Ling branch office provides, Al
2o
3content is 194g/L, Na
2o content is 286.2g/L, and proportion is 1.413), (limited-liability company of China Petrochemical Industry catalyzer Chang Ling branch office provides 332.87g Tai-Ace S 150, Al
2o
3content is 88.9g/L, and proportion is 1.2829) and the order of 479.4g water add successively in mixing tank, total molar ratio of reaction mixture is 4Na
2o:A1
2o
3: 9SiO
2: 220H
2o.After stirring, loaded in stainless steel cauldron, 95 DEG C of static crystallizations 24 hours, then filter, wash, dry NaY molecular sieve product.
It is 5.2 that XRD records its silica alumina ratio, and relative crystallinity is 95.1%, and electromicroscopic photograph display average grain size is 300nm.
Compound concentration is 0.5mol/L aqueous ammonium chloride solution 10 liters.Take small crystal grain NaY molecular sieve 1000 grams, be dissolved in 10 liters of aqueous ammonium nitrate solutions prepared, mixing speed is 300rpm, and at 90 DEG C, constant temperature stirs 1 hour, then filtering molecular sieve.Repeat aforesaid operations, until Na in molecular sieve
2o content reach 3.5wt%.Obtain dried sample at 550 DEG C, the Water Under thermal treatment 2.5h of 100% water vapour gauge pressure 0.2MPa.Measure 1 liter of water purification and be dissolved in water purification by the sample of above-mentioned experiment gained, be rapidly heated stirring, and temperature is 90 DEG C, and mixing speed is 300rpm.Be rapidly in molecular sieve slurry and add acidic silicasol and Virahol, add with SiO altogether
2count the acidic silicasol solution of 20 grams, 40g Virahol, be 5.0 with the pH of the citric acid solution regulator solution of 0.3mol/L, then constant temperature constant speed stirs 2 hours, filters, and dry, obtain production code member NY-3, character lists in table 1
Comparative example 3
The explanation of this comparative example changes directed agents aging condition in synthesis directed agents process, only adopts the situation of dynamic ageing.
Raw material sources are with embodiment 3.
Join in 291.37g water glass by 164.54g high alkali deflection aluminium acid sodium solution, stir ageing 20 hours at 30 DEG C of temperature, finally under the condition stirred, add 60g deionized water, the final mol ratio of the directed agents obtained is 20Na
2o:A1
2o
3: 20SiO
2: 380H
2o.
Obtained directed agents is all for the preparation of following reaction mixture, and the add-on of directed agents, accounts for 10% of total aluminium element mole number according to the mole number of aluminium element in directed agents and calculate.
Add successively in mixing tank according to the order of directed agents (abovementioned steps preparation), 1092.62g water glass, 166.31 low alkali aluminium acid sodium solutions, 332.87g Tai-Ace S 150 and 479.4g water under the condition of room temperature and high-speed stirring, total molar ratio of reaction mixture is 4Na
2o:A1
2o
3: 9SiO
2: 220H
2o.After stirring, loaded in stainless steel cauldron, 95 DEG C of static crystallizations 24 hours, then filter, wash, dry NaY molecular sieve product.
It is 5.0 that XRD records its silica alumina ratio, and relative crystallinity is 55.1%, and electromicroscopic photograph display average grain size is 1000nm.
Compound concentration is 0.5mol/L aqueous ammonium chloride solution 10 liters.Take small crystal grain NaY molecular sieve 1000 grams, be dissolved in 10 liters of aqueous ammonium nitrate solutions prepared, mixing speed is 300rpm, and at 90 DEG C, constant temperature stirs 1 hour, then filtering molecular sieve.Repeat aforesaid operations, until Na in molecular sieve
2o content reach 3.5wt%.Obtain dried sample at 550 DEG C, the Water Under thermal treatment 2.5h of 100% water vapour gauge pressure 0.2MPa.Measure 1 liter of water purification and be dissolved in water purification by the sample of above-mentioned experiment gained, be rapidly heated stirring, and temperature is 90 DEG C, and mixing speed is 300rpm.Be rapidly in molecular sieve slurry and add acidic silicasol and Virahol, add with SiO altogether
2count the acidic silicasol solution of 20 grams, 40g Virahol, be 5.0 with the pH of the citric acid solution regulator solution of 0.3mol/L, then constant temperature constant speed stirs 2 hours, filters, and dry, obtain production code member NY-D-3, character lists in table 1
Embodiment 4
By 251.76g high alkali deflection aluminium acid sodium solution, (limited-liability company of China Petrochemical Industry catalyzer Chang Ling branch office provides, Al
2o
3content is 40.2g/L, Na
2o content is 270g/L, and proportion is 1.323) (limited-liability company of China Petrochemical Industry catalyzer Chang Ling branch office provides, SiO to join 349.64g water glass
2content is 260.6g/L, Na
2o content is 81.6g/L, and proportion is 1.2655, and modulus is 3.3) in, stir ageing 15 hours at 40 DEG C of temperature, then static ageing 20 hours at 15 DEG C of temperature, finally under the condition stirred, add 78g deionized water.The final mol ratio of the directed agents obtained is 16Na
2o:A1
2o
3: 16SiO
2: 290H
2o.
Obtained directed agents is all for the preparation of following reaction mixture.The add-on of directed agents, accounts for 15% of total aluminium element mole number according to the mole number of aluminium element in directed agents and calculates.
Under the condition of room temperature and high-speed stirring, according to directed agents (abovementioned steps preparation), 1129.04g water glass (the same), 55.90g low alkali aluminium acid sodium solution, (limited-liability company of China Petrochemical Industry catalyzer Chang Ling branch office provides, Al
2o
3content is 194g/L, Na
2o content is 286.2g/L, and proportion is 1.413), (limited-liability company of China Petrochemical Industry catalyzer Chang Ling branch office provides 514.81g Tai-Ace S 150, Al
2o
3content is 88.9g/L, and proportion is 1.2829) and the order of 489.2g water add successively in mixing tank, total molar ratio of reaction mixture is 3Na
2o:A1
2o
3: 10SiO
2: 250H
2o.After stirring, loaded in stainless steel cauldron, 95 DEG C of static crystallizations 36 hours, then filter, wash, dry NaY molecular sieve product.
It is 5.8 that XRD records its silica alumina ratio, and relative crystallinity is 97.6%, and electromicroscopic photograph display average grain size is 100nm.
Compound concentration is 0.7mol/L aqueous ammonium chloride solution 10 liters.Take small crystal grain NaY molecular sieve 1000 grams, be dissolved in 10 liters of aqueous ammonium nitrate solutions prepared, mixing speed is 300rpm, and at 90 DEG C, constant temperature stirs 1 hour, then filtering molecular sieve.Repeat aforesaid operations, until Na in molecular sieve
2o content reach 4.5wt%.Obtain dried sample at 600 DEG C, the Water Under thermal treatment 1h of 100% water vapour gauge pressure 0.2MPa.Measure 1 liter of water purification and be dissolved in water purification by 200 grams, the sample of above-mentioned experiment gained, be rapidly heated stirring, and temperature is 95 DEG C, and mixing speed is 300rpm.Be rapidly in molecular sieve slurry and add acidic silicasol and glycerol, add with SiO altogether
2count the acidic silicasol solution of 10 grams, 20 grams of glycerol, be 5.0 with the pH of the citric acid solution regulator solution of 0.3mol/L, then constant temperature constant speed stirs 2 hours, filters, and dry, obtain production code member NY-4, character lists in table 1
Comparative example 4
This comparative example illustrates in preparation feedback mixture process, the situation of the addition sequence change of raw material.
Each raw material sources are with embodiment 4.
251.76g high alkali deflection aluminium acid sodium solution is joined in 349.64g water glass, at 40 DEG C of temperature, stirs ageing 15 hours, then static ageing 20 hours at 15 DEG C of temperature, finally under the condition stirred, add 78g deionized water.The final mol ratio of the directed agents obtained is 16Na
2o:A1
2o
3: 16SiO
2: 290H
2o.
Obtained directed agents is all for the preparation of following reaction mixture, and the add-on of directed agents, accounts for 15% of total aluminium element mole number according to the mole number of aluminium element in directed agents and calculate.
Add successively in mixing tank according to 55.90g low alkali aluminium acid sodium solution, 514.81g Tai-Ace S 150,1129.04g water glass, directed agents (abovementioned steps preparation) and the order of 489.2g water under the condition of room temperature and high-speed stirring, total molar ratio of reaction mixture is 3Na
2o:A1
2o
3: 10SiO
2: 250H
2o.After stirring, loaded in stainless steel cauldron, 95 DEG C of static crystallizations 36 hours, then filter, wash, dry NaY molecular sieve product.
It is 5.0 that XRD records its silica alumina ratio, and relative crystallinity is 87%, and electromicroscopic photograph display average grain size is 1000nm.
Compound concentration is 0.7mol/L aqueous ammonium chloride solution 10 liters.Take small crystal grain NaY molecular sieve 1000 grams, be dissolved in 10 liters of aqueous ammonium nitrate solutions prepared, mixing speed is 300rpm, and at 90 DEG C, constant temperature stirs 1 hour, then filtering molecular sieve.Repeat aforesaid operations, until Na in molecular sieve
2o content reach 4.5wt%.Obtain dried sample at 600 DEG C, the Water Under thermal treatment 1h of 100% water vapour gauge pressure 0.2MPa.Measure 1 liter of water purification and be dissolved in water purification by 200 grams, the sample of above-mentioned experiment gained, be rapidly heated stirring, and temperature is 95 DEG C, and mixing speed is 300rpm.Be rapidly in molecular sieve slurry and add acidic silicasol and glycerol, add with SiO altogether
2count the acidic silicasol solution of 10 grams, 20 grams of glycerol, be 5.0 with the pH of the citric acid solution regulator solution of 0.3mol/L, then constant temperature constant speed stirs 2 hours, filters, and dry, obtain production code member NY-D-4, character lists in table 1
Embodiment 5
By 335.69g high alkali deflection aluminium acid sodium solution, (limited-liability company of China Petrochemical Industry catalyzer Chang Ling branch office provides, Al
2o
3content is 40.2g/L, Na
2o content is 270g/L, and proportion is 1.323) (limited-liability company of China Petrochemical Industry catalyzer Chang Ling branch office provides, SiO to join 466.18g water glass
2content is 260.6g/L, Na
2o content is 81.6g/L, and proportion is 1.2655, and modulus is 3.3) in, stir ageing 10 hours at 50 DEG C of temperature, then static ageing 36 hours at 20 DEG C of temperature, finally under the condition stirred, add 104g deionized water.The final mol ratio of the directed agents obtained is 16Na
2o:A1
2o
3: 16SiO
2: 290H
2o.
Obtained directed agents is all for the preparation of following reaction mixture, and the add-on of directed agents, accounts for 20% of total aluminium element mole number according to the mole number of aluminium element in directed agents and calculate.
Under the condition of room temperature and high-speed stirring, according to directed agents (abovementioned steps preparation), 815.83g water glass (the same), 15.29g low alkali aluminium acid sodium solution, (limited-liability company of China Petrochemical Industry catalyzer Chang Ling branch office provides, Al
2o
3content is 194g/L, Na
2o content is 286.2g/L, and proportion is 1.413), (limited-liability company of China Petrochemical Industry catalyzer Chang Ling branch office provides 558.48g Tai-Ace S 150, Al
2o
3content is 88.9g/L, and proportion is 1.2829) and the order of 528.7g water add successively in mixing tank, total molar ratio of reaction mixture is 2.7Na
2o:A1
2o
3: 8.6SiO
2: 250H
2o.After stirring, loaded in stainless steel cauldron, 90 DEG C of static crystallizations 48 hours, then filter, wash, dry NaY molecular sieve product.
It is 5.6 that XRD records its silica alumina ratio, and relative crystallinity is 92.5%, and electromicroscopic photograph display average grain size is 100nm.
Compound concentration is 0.5mol/L aqueous ammonium chloride solution 10 liters.Take small crystal grain NaY molecular sieve 1000 grams, be dissolved in 10 liters of aqueous ammonium nitrate solutions prepared, mixing speed is 300rpm, and at 90 DEG C, constant temperature stirs 1 hour, then filtering molecular sieve.Repeat aforesaid operations, until Na in molecular sieve
2o content reach 4wt%.Obtain dried sample at 600 DEG C, the Water Under thermal treatment 1h of 100% water vapour gauge pressure 0.2MPa.Measure 1 liter of water purification and be dissolved in water purification by 200 grams, the sample of above-mentioned experiment gained, be rapidly heated stirring, and temperature is 100 DEG C, and mixing speed is 300rpm.Be rapidly in molecular sieve slurry and add acidic silicasol and ethylene glycol, add with SiO altogether
2count the acidic silicasol solution of 10 grams, 25 grams of ethylene glycol, be 4.0 with the pH of the citric acid solution regulator solution of 0.2mol/L, then constant temperature constant speed stirs 2 hours, filters, and dry, obtain production code member NY-5, character lists in table 1.
Comparative example 5
This comparative example illustrates that the preparation of directed agents is according to process of the present invention, but the situation that the raw material of reaction mixture adds simultaneously.
Each raw material sources are with embodiment 5
335.69g high alkali deflection aluminium acid sodium solution is joined in 466.18g water glass, ageing 10 hours is stirred at 50 DEG C of temperature, then static ageing 36 hours at 20 DEG C of temperature, finally under the condition stirred, add 104g deionized water, the final mol ratio of the directed agents obtained is 16Na
2o:A1
2o
3: 16SiO
2: 290H
2o.
Obtained directed agents is all for the preparation of following reaction mixture, and the add-on of directed agents, accounts for 20% of total aluminium element mole number according to the mole number of aluminium element in directed agents and calculate.
Under the condition of room temperature and high-speed stirring, in mixing tank, add directed agents (abovementioned steps preparation), 815.83g water glass, 15.29g low alkali aluminium acid sodium solution, 558.48g Tai-Ace S 150 and 528.7g water, total molar ratio of reaction mixture is 2.7Na simultaneously
2o:A1
2o
3: 8.6SiO
2: 250H
2o.After stirring, loaded in stainless steel cauldron, 90 DEG C of static crystallizations 48 hours, then filter, wash, dry NaY molecular sieve product.
It is 5.0 that XRD records its silica alumina ratio, and relative crystallinity is 88%, and electromicroscopic photograph display average grain size is 1000nm.
Compound concentration is 0.5mol/L aqueous ammonium chloride solution 10 liters.Take small crystal grain NaY molecular sieve 1000 grams, be dissolved in 10 liters of aqueous ammonium nitrate solutions prepared, mixing speed is 300rpm, and at 90 DEG C, constant temperature stirs 1 hour, then filtering molecular sieve.Repeat aforesaid operations, until Na in molecular sieve
2o content reach 4wt%.Obtain dried sample at 600 DEG C, the Water Under thermal treatment 1h of 100% water vapour gauge pressure 0.2MPa.Measure 1 liter of water purification and be dissolved in water purification by 200 grams, the sample of above-mentioned experiment gained, be rapidly heated stirring, and temperature is 90 DEG C, and mixing speed is 300rpm.Be rapidly in molecular sieve slurry and add acidic silicasol and ethylene glycol, add with SiO altogether
2count the acidic silicasol solution of 10 grams, 25 grams of ethylene glycol, be 4.0 with the pH of the citric acid solution regulator solution of 0.2mol/L, then constant temperature constant speed stirs 2 hours, filters, and dry, obtain production code member NY-D-5, character lists in table 1
From data in table 1, present method prepares the Y zeolite that modification obtains, and has that crystal grain is little, silica alumina ratio is high, the feature that crystallization reservation degree is high.
Claims (13)
1. Y zeolite prepare a method of modifying, it is characterized in that comprising the steps: that (1) prepares NaY molecular sieve; (2) NaY molecular sieve being exchanged through ammonium the weight content obtaining sodium oxide is the NH of 2.5-5%
4naY molecular sieve; (3) NH is processed under hydrothermal conditions
4naY molecular sieve; (4) by NH
4after NaY molecular sieve making beating, add the organic alcohols material of silicon sol that pH is 2-4 and C2-C4 and adjust pH to be 3-6 with citric acid solution, fully mixing at temperature is 80-120 DEG C, then obtaining modified product through washing and drying; Wherein, in said step (1), the process of preparation NaY molecular sieve is under the condition of synthesis NaY molecular sieve, the mixture A obtained after order according to directed agents, silicon source, aluminium source and water is added mixing tank successively carries out hydrothermal crystallizing and also reclaims the product obtained, said directed agents is mixed with water glass by sodium metaaluminate, and the volumetric molar concentration of aluminium element in water glass is edged up to forming mol ratio for (6 ~ 25) Na by zero
2o:A1
2o
3: (6 ~ 25) SiO
2mixture B, then sequentially pass through dynamic ageing, still aging, then add that water obtains.
2., according to the process of claim 1 wherein, the mol ratio of said directed agents is (6 ~ 25) Na
2o:A1
2o
3: (6 ~ 25) SiO
2: (200 ~ 400) H
2o.
3., according to the process of claim 1 wherein, said dynamic ageing carries out 5 ~ 48 hours at agitation condition, at 15 ~ 60 DEG C.
4. according to the process of claim 1 wherein, said still aging, be carry out 5 ~ 48 hours at static conditions, at 15 ~ 60 DEG C.
5., according to the process of claim 1 wherein, the mol ratio of said mixture A is (2 ~ 6) Na
2o:A1
2o
3: (8 ~ 20) SiO
2: (200 ~ 400) H
2o.
6., according to the process of claim 1 wherein, in directed agents, the mole number of aluminium element accounts for 3 ~ 30% of the mole number of total aluminium element in mixture A.
7., according to the process of claim 1 wherein, said hydrothermal crystallizing carries out 15 ~ 48 hours at 90 ~ 100 DEG C.
8., according to the process of claim 1 wherein, it is adopt ammonium concentration to be the ammonium salt solution of 0.1-1mol/L that the ammonium of said step (2) exchanges, and be 50-100 DEG C in temperature, solvent and solute weight ratio is carry out under the condition of 8-15:1.
9. according to the method for claim 8, wherein, said ammonium salt is one or more in ammonium nitrate, ammonium sulfate, ammonium chloride and ammonium acetate.
10., according to the process of claim 1 wherein, the hydrothermal condition of said step (3) is 100% water vapour, gauge pressure 0.1-0.2MPa, temperature 500-650 DEG C, treatment time 1-3 hour.
11. according to the process of claim 1 wherein, step (4) said making beating carries out at normal temperatures, and solvent and solute weight ratio is 3-10:1; Said pH is the silicon sol of 2-4 is add at making beating 80-120 DEG C, slurry, and every 100 mol sieves add with SiO
2count the silicon sol of 0.1-10 gram.
12. according to the process of claim 1 wherein, in step (4), the additional proportion of the organic alcohols material of C2-C4 is the organic alcohols material of every 100g molecular sieve 1-30g.
13. according to the method for claim 1 or 12, and wherein, in step (4), the organic alcohols material of said C2-C4 is selected from one or more in glycerol, ethylene glycol and Virahol.
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| CN107344721A (en) * | 2016-05-05 | 2017-11-14 | 中国石油化工股份有限公司 | A kind of Modified Zeolite Y and its preparation method and application |
| US11518684B2 (en) | 2018-05-28 | 2022-12-06 | China Petroleum & Chemical Corporation | NaY molecular sieve with an aluminum-rich surface and a process of preparing same |
| CN115722189A (en) * | 2021-08-31 | 2023-03-03 | 中国石油化工股份有限公司 | Adsorbent for removing oxygen-containing compounds in low-molecular hydrocarbons |
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|---|---|---|---|---|
| CN1354134A (en) * | 2001-10-19 | 2002-06-19 | 中国石油化工股份有限公司 | Method for synthesizing small-grain Y-type molecular sieve |
| CN101759198A (en) * | 2008-12-24 | 2010-06-30 | 中国石油化工股份有限公司 | Small crystal particle Y-shaped molecular sieve and preparation method thereof |
| CN102951655A (en) * | 2012-11-27 | 2013-03-06 | 华东师范大学 | Modified method of Y-type molecular sieve |
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2014
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1354134A (en) * | 2001-10-19 | 2002-06-19 | 中国石油化工股份有限公司 | Method for synthesizing small-grain Y-type molecular sieve |
| CN101759198A (en) * | 2008-12-24 | 2010-06-30 | 中国石油化工股份有限公司 | Small crystal particle Y-shaped molecular sieve and preparation method thereof |
| CN102951655A (en) * | 2012-11-27 | 2013-03-06 | 华东师范大学 | Modified method of Y-type molecular sieve |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107344721A (en) * | 2016-05-05 | 2017-11-14 | 中国石油化工股份有限公司 | A kind of Modified Zeolite Y and its preparation method and application |
| US11518684B2 (en) | 2018-05-28 | 2022-12-06 | China Petroleum & Chemical Corporation | NaY molecular sieve with an aluminum-rich surface and a process of preparing same |
| CN115722189A (en) * | 2021-08-31 | 2023-03-03 | 中国石油化工股份有限公司 | Adsorbent for removing oxygen-containing compounds in low-molecular hydrocarbons |
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