CN1724359A - Synthesis method of molecular sieve - Google Patents
Synthesis method of molecular sieve Download PDFInfo
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- CN1724359A CN1724359A CN 200410076671 CN200410076671A CN1724359A CN 1724359 A CN1724359 A CN 1724359A CN 200410076671 CN200410076671 CN 200410076671 CN 200410076671 A CN200410076671 A CN 200410076671A CN 1724359 A CN1724359 A CN 1724359A
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Abstract
A process for synthesizing molecular sieve features that the culture medium containing the skeleton elements (Al, Si, etc) needed by crystal seed growth is added to the crystal seed slurry, the adding speed is controlled to be equal to the speed of crystal growing to prevent generation of new crystal nucleus, the crystal seed is same as the culture medium or not to obtain laminated molecular sieve, and the crystals with desired size is conventionally separated out.
Description
Invention field
The present invention relates to a kind of method of synthesis of molecular sieve.This method is particularly related to and adds for example substratum of skeleton structure such as aluminium and silicon element (raw material) in the seed slurry of molecular sieve.The speed that the control substratum adds makes it be substantially equal to control the speed of crystal growth.
Background of invention
The molecular sieve of crystal manosil AS zeolite type is known in the field, has comprised natural formation above 150 kinds and synthetic zeolite at present.Generally speaking, the crystal zeolite is by AlO
2And SiO
2Tetrahedron interconnects by shared Sauerstoffatom and forms, feature is to have hole of the same size and significant ion-exchange capacity, can also reversibly discharge the absorption that is dispersed in the whole crystals space and can not make the atom of forming constant crystalline structure produce displacement significantly mutually.
It is special living that the crystal microporous compositions of other known nonzeolite structure has also demonstrated the ion-exchange and/or the absorption of zeolite.They comprise: 1) at US-A-4, the disclosed pure zirconia that had not both had positively charged ion also not have the neutral backbone at positively charged ion position in 061,724,, silicate; 2) at US-A-4, disclosed crystalline aluminumphosphate compostions in 310,440; 3) at US-A-440, disclosed silicon replaces aluminum phosphate in 871; 4) at US-A-4, the aluminum phosphate that disclosed titanium replaces in 500,651.
Molecular sieve is normally synthetic by the reaction mixture hydrothermal method in the batch reactor.In such method, all components join and form gel in the reactor.And then stir gel, get zeolite through enough adding thermal crystalline for a long time.The shortcoming of traditional method comprises the limitation to crystallographic dimension, morphology Control, and the limitation of solids content produces unrenewable waste material and needs a large amount of investments.Therefore, in the industrial production of constantly being devoted to study the improvement molecular sieve.
For example, US-A-4314979 discloses the continuous preparation method of a kind of zeolite A.This method be will contain the solution of aluminium and silicon mix, again mixture is flowed into that crystallization obtains zeolite A in the crystallization reactor.US-A-5389358 discloses a kind of nucleus of formation earlier, adding comprises the aging zeolite synthesis that forms zeolite in solution, back of each reactant again.At last, US-A-3425800 has described the continuous processing of a kind of synthetic zeolite A or X, and the aqueous solution formation gel with reactant is filled into the layering crystallizing field and forms crystal after the gel heating.
C.S.Cundy et al., in Zeolites, Vol.15,353-372 (1995) discloses the method for synthetic zeolite ZSM-5.This method is to inject the seed slurry of suitable fluid in reactor.In reaction mixture, add aluminium source and silicon source constantly, shift out product simultaneously off and on and make maintenance constant liquid level in the reactor.(Zeolites, Vol.15,400-407 (1995) disclose when aluminium and silicon fashionablely can be seen very high nucleation rate to add than crystal growth faster rate another of same authors piece document.
Opposite with above-mentioned reference, the applicant has found a kind of method that can allow crystal seed grow up to the expection size.This method is the substratum that adds framework of molecular sieve element source in seed slurry, as Al, Si etc.The speed that substratum adds is substantially equal to crystal growth rate, therefore just can not form gel, does not also have new crystal nucleation basically.Substratum can provide the backbone element that is different from crystal seed, but the skeleton structure of its formation is identical with crystal seed.The mixing of slurry controlled to obtain monocrystalline or cohesive body.Adding that substratum reaches up to the size of crystal that obtains or particle can be by conventional means with molecular sieve isolating degree from liquid.
Detailed Description Of The Invention
Method of the present invention relates to by crystal seed and grows up to molecular sieve crystal, can not form new crystal basically.In one embodiment of the invention, grow up to the molecular sieve identical with crystal seed around the crystal seed, promptly backbone element is identical with structure and ratio between element need not identical.In another embodiment, the molecular sieve of growth has identical skeleton structure with crystal seed around crystal seed, but the backbone element difference promptly has at least a kind of element inequality.
Therefore, a crystal seed that fundamental is exactly a molecular sieve of the present invention.Molecular sieve is a kind of microporous compositions of three-dimensional framework, and all holes of crystalline are arranged.Molecular sieve is divided into zeolite and non-zeolite molecular sieve.Zeolite molecular sieve is a silico-aluminate, and its skeleton structure is by tetrahedral oxide SiO
2And AlO
2Form.Non-zeolite molecular sieve has comprised the element except that aluminium and silicon.For example comprise aluminosilicophosphate and aluminium phosphate molecular sieve.Can prepare the zeolite and the non-zeolite molecular sieve of three-dimensional framework structure by method of the present invention, shown in its skeleton general formula composed as follows:
(El
WAl
x′P
ySi
z)O
2 (I)
Here El is a kind of element that can form three-dimensional framework oxide unit as described below, and P, Al and Si are the backbone elements of tetrahedral oxide units.The molar fraction of El is expressed as 0～0.5 by " w ", the molar fraction of the Al of " x " expression is 0～0.5, and the molar fraction of " y " expression P is 0～0.5, is represented that by " z " molar fraction of Si is 0～1, w+x+y+z=1, and " y " and " z " is not zero simultaneously.When " El " comprised two or more elements, " w " represented above-mentioned element (El
1, El
2, El
3, El
4Deng) molar fraction, " w " equals to represent separately El
1, El
2, El
3, El
4" w etc. molar fraction
1", " w
2", " w
3", " w
4" etc. sum.These molecular sieves be abbreviated as ElAPSO, at-US-A-4, concrete description is arranged in 793,948.' also disclosed choice criteria in 984 in patent to the El element.The feature of element El is to meet following a kind of standard at least:
1) feature of " El " is that its electronic orbit configuration (configuration) is selected from d
0, d
1, d
2, d
5, d
6, d
7Or d
10, wherein metal ligand " O-El " small-crystalline field stabilization energy helps element El and O
2-Tetrahedral coordination, be discussed in " Inorganic Chemistry " J.E.Huheey, harper Row, p.348 (1978):
2) feature of " El " is to form stable oxygenate or hydrogen-oxygen compound kind (oxo orhydroxo species), its first hydrolytic constant K in the aqueous solution
11Greater than 10
-14, be discussed in " The Hydrolysis of Cations ", C.F.Baes, R.E.Mesmer, John Wiley ﹠amp; Sons (1976);
3) " El " element of being selected from is present in the stereo crystal structure that relates to different silicon oxide distortion such as quartz, cristobalite and tridymite, be discussed in E.Parthe and show " Crystal Chemistry of TetrahedralStructures ", Gordon and Breach, New York, London, pp.66-68 (1964); With
4) " El " is a kind of element, and its cationic form is by Pearson. (J.E.Huheey, " InorganicChemistry ", Harper ﹠amp; Row, p.276 (1978) are called " firmly " acid or " edge " acid, compare itself and " firmly " alkali O with the positively charged ion that is called " soft " sour element
2-Reaction forms more stable chemical bond.Concrete element includes but not limited to arsenic, beryllium, boron, chromium, cobalt, nickel, gallium, germanium, iron, lithium, magnesium, manganese, titanium, vanadium, tin and zinc.
Several molecular sieves can be described and prepare to foundation as above shown in the general formula.For example, when " w " and " y " was zero, molecular sieve was zeolite or zeolite-type molecular sieve.Formula (I) is in this case
(Al
xSi
1-x)O
2 (II)
Wherein x is 0～0.5.The specific embodiments of the zeolite that the present invention can prepare includes but not limited to zeolite A, X zeolite, mordenite, silicite, zeolite beta, zeolite Y, zeolite L, ZSM-12, UZM-4 and UZM-5.UZM-4 and UZM-5 all have description respectively in WO 02/36491 and WO 02/36489.When x was zero, zeolite was silicite.X is greater than obtaining formula (III) under zero the situation in formula (I)
(El
wAl
x′P
y′Si
z)O
2 (III)
The definition cotype (I) of " w ", " y " and " z " wherein, x ' is greater than 0 to 0.5.In addition, when " w " and " z " in the formula (III) be zero or when " w " and " z " in the formula (I) be zero and " x " when zero, obtain at US-A-4 specifically described ALPO family non-zeolite molecular sieve in 310,440 and 4,500,651.In addition, when formula (I) or " w " (III) be 0 and " z " greater than 0 time (" x " is greater than 0 in the formula (I)), obtain the non-zeolite molecular sieve of SAPO family, be not limited to US-A-4, SAPO-34 that describes in 440,871 and the embodiment of SAPO-11.When " z " be 0 and formula (I) or (III) in other subscript all obtain the non-zeolite molecular sieve of ElAPO family greater than 0 the time.At last, all subscripts promptly are foregoing ElAPSO family non-zeolite molecular sieves all greater than 0 the time when formula (I) or (III), and one of example is MAPSO-31.
Except that backbone element, under the anhydrous state when synthetic, can contain the template that some are used for its preparation in the hole of molecular sieve.Template in the art includes but not limited to basic metal, alkaline-earth metal and organic compound.These organic compound can be any compound known in the field and include but not limited to amine, for example piperidines, tripropylamine, dipropylamine, diethanolamine, trolamine, encircle amine etc., and for example halogenide of tetramethyl-ammonium, TBuA, tetraethyl ammonium and tetrapropyl ammonium ion etc. or the quaternary ammonium compound of oxyhydroxide.
The crystal seed that can make above-mentioned molecular sieve by ordinary method has been described in patent cited above, reactant is mixed, for example the aluminium source in the same container, silicon source and formwork structure directed agents are mixed, be heated to certain temperature (pressurization or not pressure) and obtain crystallized product.The aluminium source comprises aluminum alcoholate, pseudo-boehmite, gibbsite, colloidal alumina, alumina sol, sodium aluminate, aluminum chloride and Wickenol CPS 325.In the middle of these aluminium sources, preferred pseudo-boehmite, sodium aluminate and as the aluminum alcoholate of aluminum isopropylate (aluminum isoproxide).The silicon source comprises the alkalimetal silicate of silicon dioxide gel, silicon dioxide colloid, fumed silica, silica gel, alcoholization silicon, silicic acid and for example water glass.The phosphorus source comprises phosphoric acid and the phosphatic organophosphate of for example tetraethyl-.
Element " El " can be introduced reaction system with arbitrary form with this element, and it allows the activity form of generting element on the spot, can react the skeleton oxide unit of forming element " El ".The compound of the element that can adopt " El " comprises oxide compound, oxyhydroxide, alcoholate, nitrate, vitriol, halogenide, carboxylate and their mixture.The representative compounds that can adopt is including but not limited to the carboxylate salt of arsenic and beryllium; Cobalt chloride hexahydrate, α cobaltous iodide; Rose vitriol; Cobaltous diacetate; Cobaltous bromide, cobalt chloride, alcoholization boron, chromium acetate, alcoholization gallium, zinc acetate, zinc bromide, zinc formate, zinc iodide, Zinc vitriol, germanium dioxide, iron acetate (II), Lithium Acetate, magnesium acetate; Magnesium bromide; Magnesium chloride; Magnesium iodide; Magnesium nitrate; Sal epsom; Manganese acetate; Manganese dibromide; Manganous sulfate; Titanium tetrachloride; The carboxylic acid titanium; The acetic acid titanium; Zinc acetate; Tin chloride etc.As mentioned above, also to add into plate reagent/structure direction agent for example the water of sodium hydroxide, tetramethyl ammonium chloride and capacity obtain the available mixture.
Collect the crystal seed of target molecule sieve, in water, stir into slurries (under suitable pH value).Yet, preferably crystal seed being dispersed in (water base) mixture that comprises the required total overall reaction thing of preparation target molecule sieve, its concentration is less than oversaturated threshold concentration.More preferably, the mixture of reactant or substratum is the balance saturation concentration.Mixture is preferably especially leaching target molecule sieve afterreaction and finishes the water that moment obtains.Can expect in advance that this water can be by cycle applications repeatedly in the preparation of molecular sieve.The substratum that adds as hereinafter mention in the source slurries of the element of expected structure can make to grow up to molecular sieve on the crystal seed.Thereby substratum that is added or substratum combination can be any forms that can grow up to molecular sieve.These combinations are: 1) silicon source; 2) aluminium and silicon source; 3) aluminium, phosphorus and silicon source; 4) aluminium and phosphorus source; 5) El, aluminium and phosphorus source; 6) El, aluminium, silicon and phosphorus source.It is to be noted simultaneously, may need to add extra template and structure direction agent.Add or get final product as a branch of adding separately the reagent source of expection and a kind of substratum wherein are common.In addition, initial seed slurry can contain excessive expection reagent.
The substratum that adds will generate the molecular sieve identical or different with crystal seed.Even formed the molecular sieve identical with crystal seed, the ratio that changes substratum also can make framework of molecular sieve element ratio thereby the change that generates subsequently on crystal seed.As described in embodiment, at Si/Al than being to add Si/Al on the crystal seed of 2.5 X zeolite can form X zeolite than the silicon and the aluminium source that are 2.0.
Under the different situation of the framework of molecular sieve element that crystal seed is grown on it, crystal seed or molecular sieve internal layer must have identical skeleton structure with the molecular sieve skin.And only need the internal layer of molecular sieve to have at least a kind of backbone element different with skin.For example, molecular sieve internal layer ALPO-34, molecular sieve skin can be SAPO-34, chabazite, CoAPO-44, LZ-218, GaAPO-34, zeolite φ etc.The molecular sieve of determining to have same structure can be by consulting W.M.Meier, D.H.Olson and Ch.Baulocher, Atlas of ZeoliteStructure Types, Fifth Revised Edition, Elsevier, Amsterdam, 2001 or Ch.Baulocher and L.B.McCusker, Database of Zeolite Structures, http://www.iza-structure.org/databases/.
Therefore, can be prepared into the different multilayer molecular sieves of forming.Like this, the internal layer molecular sieve can be formed by several layers, and its last one deck is outer molecular sieve.By this method fast, can obtain crystalline framework element consistent all the time but the different molecular sieve of each layer backbone element ratio, for example the ratio difference of Si/Al.Therefore, be internal layer with ZSM-5 when beginning to react, in each layer, progressively increase the ratio of Si/Al, can obtain the skin of silicate layer at last.
No matter select which kind of substratum, they can be all add in the mode of any routine.These modes comprise the solution for preparing substratum, and preparation solids suspension or slurries directly add solid and add clean substratum.Certain a kind of substratum can be with a kind of adding method, and other substratum can be used method for distinguishing.In addition, special substratum need add the pH value that extra acid or alkali arrive expection.For example when using water glass, need to add the acid issuable sodium hydroxide that neutralizes as substratum or silicon source.
When adding more than a kind of substratum, for example Si and Al, they can add simultaneously or add successively.Add successively fashionable, if every kind of substratum of the situation of liquid or slurries only needs a pump.Adding simultaneously fashionablely can have dual mode again.At first, each substratum is delivered in the reactor that comprises seed slurry by separately port or injector.In addition, each substratum is transported in the receiving tank and mixes, and comprises the reactor of seed slurry then as one injection.A kind of method in preferred back.At last, can be continuously or add substratum off and on.If add with gap, can be rule or erratic its pitch time.No matter substratum is to add continuously or intermittently add, it all will keep certain speed to make crystal seed or nucleus growth, and don't can have more than needed to such an extent that cause more new crystal nucleation or generate amorphous solid." new crystal nucleation " is meant that mixture can generate crystal when the concentration of substratum surpasses the supersaturation threshold concentration.Crystal seed grows up to macrocrystal and does not think " new crystal nucleation ".In order successfully to add substratum, its speed must be substantially equal to the speed of crystal growth.A kind of method of definite feeding rate is at first to determine the grain size of crystal seed by electron microscope scanning methods such as (SEM).Predict that then crystalline growth (judging according to experience) is the homogeneous linearity, crystal is a cubes.Calculate feeding rate thus.
The method that another kind of control adds the quantity of substratum is to keep the concentration of each substratum to be higher than saturation limit, but is lower than critical saturation limit.If concentration surpasses critical supersaturation limit, then can begin has new crystal nucleation, if instead concentration is equal to or less than saturation limit, crystal is not just grown.
The reaction conditions of crystal growth is identical with ordinary method, comprise autogenous pressure and from room temperature (20 ℃) to 250 ℃ temperature.Higher pressure can be applied, 300psig can be reached usually.Continue to add substratum and reach expection up to crystallographic dimension.The size of crystal seed can have very big variation range, and it is not a key parameter of the present invention.Though arbitrarily the crystal seed of size can both use, the typical range of crystal seed size is from 10 nanometers to 5 micron.The last crystallite size of product does not have the upper limit yet, yet the crystallite size that need obtain is 10 microns.Will stop to add substratum in case obtain the crystallographic dimension of expection, and can utilize methods such as filtration well known in the art, centrifugation that molecular sieve solid is separated from water or mother liquor.
The crystalline size is decided by the amount that adds substratum, and crystal itself also can attached collection or is gathered into particulate.Therefore, particulate can be all bigger than any independent crystal.Apply shearing to reaction mixture and can control particle size, promptly attached collection degree.Shearing can provide by mechanical process, waterpower method etc.Provide the concrete grammar of shearing to include but not limited to agitator, rotor, ultrasonic wave, opposed jets etc.These methods can be disperseed attached collection thing, simultaneously various crystal that also can the dispersion energy further growth.Dispersed each crystal just can not nucleation.
The distribution of crystallographic dimension and/or particle size can be controlled by add more crystal seed in preparation.Can once finish, also can or add constantly on whole process discontinuous ground.In addition, the crystal seed of Jia Ruing can be bigger compared with the crystal seed of beginning afterwards, can obtain narrow crystal and/or particle size distribution like this.Another kind of select be the crystal seed that added afterwards less than initial crystal seed, can obtain wideer crystal and or particle size distribution like this.
Following listed examples is used to explain the present invention.It should be explicitly made clear at this point a kind of mode that these embodiment just explain, rather than to the unnecessary restriction of the protection domain of the present invention of being set forth in the claim.
Embodiment 1
Prepare 2.5NaX (Si/Al
2=2.5) crystal seed, its average crystallite granularity are 1.2 μ m.Add the NaOH solution of 125g 2.5NaX crystal seed and 733g 15wt.% in the container of a 2L, container is stirred and heated to 70 ℃.Reactant in the container is constantly extracted out from the port of container bottom with the speed of 5L/min by opposed jets, and the port from container top turns back to the container again.Sodium silicate aqueous solution (29wt.%SiO
2And 9wt.%Na
2O) and sodium aluminate aqueous solution (24wt.%Al
2O
3And 20wt.%Na
2O) speed of the continuous increase shown in the following table joins in the container.
Time silicate drops into the speed aluminate and drops into speed
(hr) (mL/hr) (mL/hr)
0 64 65
1 88 89
2 115 116
3 145 147
4 179 181
Add after four hours, product is filtered, washing, dry down at 100 ℃ then.Average size of products is determined as 5.2 μ m, and the X-ray diffraction analysis shows the X zeolite of this product for no crystalline impurities.At last, chemical analysis shows its Si/Al
2Ratio be 2.1.
Embodiment 2
Make among the crystal seed of X zeolite such as the embodiment 1.In the container of a 10L, add 3040g 15wt.% solution and 720g crystal seed, heated and stirred to 90 ℃.Reactant in the container is 6 by operating rate, and the high shearing agitator of 000rpm is constantly extracted out from the container bottom port with the speed of 1.6L/min, and the port from container top turns back to the container again.The speed of the continuous increase shown in water glass and the sodium aluminate following table joins in the container.
Time silicate drops into the speed aluminate and drops into speed
(hr) (mL/hr) (mL/hr)
0 1485 1500
0.27 2058 2080
0.47 2559 2585
0.64 3025 3056
0.78 3434 3469
0.91 3821 3860
1.00 4125 4168
Behind reinforced the end, product is filtered, washing, dry down at 100 ℃ then.Average size of products is determined as 10.8 μ m.The X-ray diffraction analysis shows the X zeolite of this product for no crystalline impurities.At last, chemical analysis shows its Si/Al
2Ratio be 2.1.
Embodiment 3
Make the crystal seed that median size is the mordenite of 1.2 μ m by routine techniques.In the reactor of 2L, add 320.3g deionized water, 5.0g NaOH particle, 174.7g sodium silicate solution and 60g mordenite crystal seed.Apply the air pressure of 125psig in the reactor, the speed of stirring is 1, and 000rpm is heated to 125 ℃.Use the airhood pipeline, add water glass, sodium aluminate and sulfuric acid (96%H according to the speed that constantly increases shown in the following table
2SO
4) aqueous solution.
| Time (hr) | Silicate drops into speed (mL/hr) | Aluminate drops into speed (mL/hr) | Sulfosalt drops into speed (mL/hr) |
| 0 | 24.1 | 3.3 | 2.0 |
| 1.5 | 27.9 | 3.8 | 2.3 |
| 3.0 | 31.9 | 4.4 | 2.7 |
| 4.5 | 36.2 | 5.0 | 3.0 |
| 6.0 | 40.8 | 5.6 | 3.4 |
Add after six hours,, filter the product cooling, washing, dry down in 100 ℃.The X-ray diffraction analysis shows the complete mordenite of this product for no crystalline impurities.Average size of products is 2.2 μ m.
Embodiment 4
Adding 354.2g deionized water, 58.8g 4-propyl bromide, 256.0g 40wt.% TPAOH, 110.5g tetraethyl orthosilicate salt and 1.0g average crystalline particle diameter in the reactor of 2L is the silicate crystal seed of 0.5 μ m.Reactor is sealed to be heated to 170 ℃, with the stirring of 250rpm speed.702.3 silica gel (Ludox
LS30) speed that constantly increases and shown in the 37.7g 40wt.% TPAOH following table adds.
| Time (hr) | Drop into speed (mL/hr) |
| 0 | 11.6 |
| 1 | 46.6 |
| 2 | 104.7 |
| 3 | 186.2 |
| 4 | 290.0 |
Add after four hours, with the product cooling, centrifugation, washing, dry down at 100 ℃.The X-ray diffraction analysis shows the complete silicate zeolite of this product for no crystalline impurities.Particle diameter is 4.8 μ m.
Claims (10)
1. a skeleton is formed the synthetic method of the molecular sieve of being represented by following empirical formula with three-dimensional microporous framework structure:
(El
wAl
xP
ySi
z)O
2
Wherein El, Al, P and Si are the backbone elements of tetrahedral oxide units, its value of molar fraction of " w " expression El is 0～0.5, its value of molar fraction of " x " expression Al is 0～0.5, its value of molar fraction of " y " expression P is 0～0.5, its value of molar fraction of " z " expression Si is 0～1, and w+x+y+z=1 and " y " and " z " are not zero simultaneously; This method is included under the reaction conditions seed slurry is provided; Add the nutrition source slurries, provide seeded growth required backbone element; The speed with crystal growth is consistent basically for reinforced speed, and the reinforced time will be enough to generate molecular sieve.
2. according to the process of claim 1 wherein that reaction conditions comprises that temperature is 20～250 ℃ and autogenous pressure.
3. according to the process of claim 1 wherein that " y " and " w " is zero.
4. according to the process of claim 1 wherein that the structure of molecular sieve is selected from zeolite A, X zeolite, mordenite, silicate, zeolite beta, zeolite Y, zeolite L, ZSM-12, UZM-4, UZM-5, SAPO-34, SAPO-11 and MAPSO-31.
5. according to arbitrary method of claim 1 to 4, wherein nutrition source adds for continuing.
6. according to arbitrary method of claim 1 to 4, wherein nutrition source is intermittently to add.
7. synthetic method that comprises the three-dimensional structure micro porous molecular sieve of internal layer molecular sieve with identical skeleton structure and outer molecular sieve, shown in the general formula composed as follows of its internal layer molecular sieve:
(El
wAl
xP
ySi
z)O
2
Wherein El, Al, P and Si are the backbone elements of tetrahedral oxide units, its value of molar fraction of " w " expression El is 0～05, its value of molar fraction of " x " expression Al is 0～0.5, its value of molar fraction of " y " expression P is 0～0.5, its value of molar fraction of " z " expression Si is 0～1, and w+x+y+z=1 and " y " and " z " are not zero simultaneously; This method is included in the seed slurry that the internal layer molecular sieve is provided under the reaction conditions; Add the nutrition source slurries, grow up to the required backbone element of outer molecular sieve on the crystal seed to be provided at, the skeleton structure of outer molecular sieve and internal layer molecular sieve is identical but they have a kind of different backbone element at least, shown in the empirical formula composed as follows of its outer molecular sieve:
(El
wAl
xP
ySi
z)O
2
Wherein El, Al, P and Si are the backbone elements of tetrahedral oxide units, its value of molar fraction of " w " expression El is 0～0.5, its value of molar fraction of " x " expression Al is 0～0.5, its value of molar fraction of " y " expression P is 0～0.5, its value of molar fraction of " z " expression Si is 0～1, and w+x+y+z=1 and " y " and " z " are not zero simultaneously; The speed with outer crystal growth is consistent basically for reinforced speed, and the reinforced time will be enough to generate molecular sieve.
8. according to the method for claim 7, wherein the skeleton structure of molecular sieve is selected from zeolite A, X zeolite, mordenite, silicate, zeolite beta, zeolite Y, zeolite L, ZSM-12, UZM-4, UZM-5, SAPO-34, SAPO-11 and MAPSO-31.
9. according to the method for claim 7, wherein nutrition source adds for continuing.
10. according to the method for claim 7, wherein nutrition source is intermittently to add.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101439298B (en) * | 2007-11-23 | 2012-04-25 | 环球油品公司 | Method for preparing layered molecular screen composition |
| CN108602054A (en) * | 2016-05-25 | 2018-09-28 | 环球油品公司 | High charge density metal phosphate molecular sieve |
| CN110183359A (en) * | 2019-06-11 | 2019-08-30 | 河南中医药大学 | A kind of preparation method of 2,2 '-dihydroxybiphenyls |
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| US4203869A (en) * | 1976-09-24 | 1980-05-20 | Mobil Oil Corporation | ZSM-5 Containing aluminum-free shells on its surface |
| US4112056A (en) * | 1977-05-02 | 1978-09-05 | Mobil Oil Corporation | Preparation of zeolites |
| US5989518A (en) * | 1998-12-29 | 1999-11-23 | Uop Llc | Process for synthesizing and controlling the particle size and particle size distribution of a molecular sieve |
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| CN101439298B (en) * | 2007-11-23 | 2012-04-25 | 环球油品公司 | Method for preparing layered molecular screen composition |
| CN108602054A (en) * | 2016-05-25 | 2018-09-28 | 环球油品公司 | High charge density metal phosphate molecular sieve |
| CN110183359A (en) * | 2019-06-11 | 2019-08-30 | 河南中医药大学 | A kind of preparation method of 2,2 '-dihydroxybiphenyls |
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| CN1331746C (en) | 2007-08-15 |
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