CN101439298B - Method for preparing layered molecular screen composition - Google Patents
Method for preparing layered molecular screen composition Download PDFInfo
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- CN101439298B CN101439298B CN2007103068612A CN200710306861A CN101439298B CN 101439298 B CN101439298 B CN 101439298B CN 2007103068612 A CN2007103068612 A CN 2007103068612A CN 200710306861 A CN200710306861 A CN 200710306861A CN 101439298 B CN101439298 B CN 101439298B
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Abstract
The invention relates to a preparation method of a bedded molecular sieve compound. The compound comprises an inner core and an outer layer comprising a molecular sieve. The method comprises: providing slurry containing the grains of the inner core and a molecular sieve skeleton element source. Nutriment, namely the skeleton element source is added into the slurry, thereby forming a molecular sieve crystal accumulated on the inner core. The process proceeds for a time long enough to form the needed thickness.
Description
Background technology
The present invention relates to a kind of preparation method of laminar composition, wherein molecular sieve layer forms on inner core particles.This method comprises a kind of slurries that contain inner core particles of preparation, and adds the reactive sources of framework of molecular sieve element therein, forms the molecular sieve crystal of reuniting on kernel thus, makes molecular sieve layer.
Background technology
Molecular sieve can be used as the catalyst of multiple hydrocarbon conversion process.In most of processes, molecular sieve can form article shaped, like sphere, extrudate etc.Have now found that some processes receive diffusion restriction, the inner molecular sieve of article shaped is unemployed in reaction thus.Perhaps, because the evolving path is long, further reaction can take place in compound, causes generating not hoping the accessory substance that obtains.In addition, use the binding agent of some catalytically inactives to form these shaped granules, therefore can't obtain can be used for the pure molecular sieve of catalytic reaction.
There is a large amount of lists of references to disclose layered catalyst.For example, US 4,283, and 583 disclose a kind of coating zeolite catalyst, are made up of kernel and the external coating that contains the active catalytic zeolitic material.Soak into kernel, drying, should examine and contact then through part, make catalyst with zeolite powder.US 4,482, and 774 disclose a kind of composite zeolite, contain as the crystalline silica polymorph of nuclear material and in fact to have an improved silica of same crystal structure outer.Under crystallization condition, the particle of preformed silica core is joined in the crystallization gel, thereby make zeolite on nuclear crystallization to form skin.US 4,088, and 605 disclose the shell that is substantially free of aluminium is grown on the aluminium that contains zeolite.US 5,895, and 769 disclose the polycrystalline zeolite is deposited on the porous matrix.US 5,935, and 889 disclose and apply nuclear particle with the atomization slurry that contains coating material and prepare catalyst granules.At last, US6,013,851 discloses a kind of nuclear zeolite that contains deposition top layer on it, and the Si/Al ratio of its mesexine is higher than nuclear.
Contrast these lists of references, the applicant has developed molecular sieve layer has been grown in the method on the kernel.This method comprises: the slurries that contain inner core particles are provided, add in slurries in order to form molecular sieve crystal then the framework of molecular sieve element reactive sources (nutrients, nutrient).Along with the formation of crystal, they are reunited on nuclear, form required bed thickness after the time enough.Preferred technical process comprises: at first intermittently add nutrients and form crystal, add the crystal growth of nutrients agglomerated on nuclear then continuously.
Summary of the invention
As stated, the invention relates to the preparation method of laminar composition, this laminar composition contains kernel and skin, and skin comprises the molecular sieve with three-dimensional microporous framework structure, and skeleton is formed and represented with following empirical formula:
(El
wAl
xP
ySi
z)O
2 (1)
Wherein El, Al, P and Si are the backbone elements that exists with tetrahedral oxide units, the mole fraction of " w " expression El, value 0-0.5; " x " is the mole fraction of Al, and value 0-0.5, " y " are the mole fractions of P; Value 0-0.5, " z " are the mole fractions of Si, value 0-1; W+x+y+z=1 and " y " and " z " are not zero simultaneously; This method comprises: a kind of slurries are provided under reaction condition, and these slurries contain the inner core particles that is dispersed in the liquid, contain the reactive sources corresponding to El, Al, P, Si in the formula (1) in the liquid; Add nutrients obtaining the backbone element according to the molecular sieve of formula (1) to the slurries discontinuous, thereby form molecular sieve crystal, crystal is reunited on kernel, and add the intermittence of carrying out first period then, on kernel, forms first molecular sieve layer.
The invention still further relates to laminar composition, comprise Alpha-alumina kernel and the skin that contains molecular sieve, molecular sieve has three-dimensional microporous framework structure, representes the skeleton composition with following empirical formula:
(El
wAl
xP
ySi
z)O
2 (1)
Wherein El, Al, P and Si are the backbone elements that exists with tetrahedral oxide units, the mole fraction of " w " expression El, value 0-0.5; " x " is the mole fraction of Al, and value 0-0.5, " y " are the mole fractions of P; Value 0-0.5, " z " are the mole fractions of Si, value 0-1; W+x+y+z=1 and " y " and " z " are not zero simultaneously, and wherein molecular sieve layer is combined on the kernel through the reunion of molecular sieve crystal.
Through following detailed description of the present invention, can more be expressly understood these purposes of the present invention and other purposes and embodiment.
Can obtain other guide of the present invention, the specific embodiment and details from following detailed description of the present invention.
Detailed Description Of The Invention
A requisite item of the present invention is a kernel.This kernel is an inertia, and wherein the implication of inertia is: on nuclear, form in layer or the treatment step subsequently, chemical change can not take place in kernel basically.The unrestriced example of nuclear composition is white sand quartz, bead, amorphous silica, aluminium oxide, gibbsite, mullite, silica-alumina and cordierite in can be used as.Should be understood that silica-alumina is not the physical mixture of silica and aluminium oxide, but a kind of acid amorphous materials that has passed through cogelled or co-precipitation.This term is known in the art, for example referring to US 3,909,450; US3,274,124 with US 4,988,659, all these are incorporated herein by reference.Preferred aluminium oxide is an Alpha-alumina.The shape of these kernels is the shape of any expectation, includes but not limited to sphere, irregularly shaped particles, leafy particle, ball type etc.Effective average diameter of these kernels can change to the millimeter level from nanoscale, just, and 10
-9M to 10
-3M.Although each independent crystal can be used as kernel, its average diameter is 0.01 μ m-5mm usually, preferred .10 μ m-5mm.Said effective diameter representes that the shape with arbitrary expectation is compression molded into the diameter of spherical getable spheroid.
Inner core particles is formed slurries (under suitable pH value condition) in water, preferably be dispersed in the water solution mixture that contains necessary all reactants of preparation desired molecule sieve, but its concentration is less than critical supersaturation concentration.Most preferably this mixture contains reactant or the nutrients that is in equilibrium saturation.A preferred especially mixture is a water, and it obtains after required layered component thing filters in this process at last.Can imagine that this water can be recycled several times, and utilize again with preparation stratiform molecular sieve.
Being deposited on the molecular sieve that forms molecular sieve layer on the kernel is the three-dimensional framework microporous compositions with crystallography homogeneous hole.These molecular sieves can be categorized as zeolite type or non-zeolitic molecular sieves.Zeolite is aluminium-silicate compositions, and its skeleton structure is by SiO
2And AlO
2Tetrahedral oxide is formed.Non-zeolite molecular sieve is except that aluminium and silicon, also contains those of other element.Example comprises silicoaluminophosphate and aluminophosphate molecular sieve.Have the three-dimensional framework structure with the zeolite of method preparation of the present invention with molecular sieve nonzeolite, represent the skeleton composition with following general empirical formula:
(El
wAl
xP
ySi
z)O
2 (1)
Wherein El is a kind of element that can form three-dimensional framework (tetrahedron) oxide unit that is described below, and P, Al and Si also are the backbone elements that exists with tetrahedral oxide units.The molar fraction of El is represented with w, and value 0-0.5, x are the molar fractions of Al, and value 0-0.5, y are the molar fractions of P, and value 0-0.5, z are the molar fractions of Si, and value 0-1, w+x+y+z=1 and " y " and " z " are not zero simultaneously.When El comprised two kinds or more kinds of element, " w " represented said element (El
1, El
2, El
3, El
4Deng) molar fraction, " w " equals " w
1", " w
2", " w
3", " w
4" wait with, it is represented respectively and represents El respectively
1, El
2, El
3, El
4Deng molar fraction.The acronym of these molecular sieves is EIAPSO, and US 4,793, detailed description is arranged in 984, introduces its full content as a reference.' also introduced the standard of selecting the El element in 984 in patent.El has the characteristic of following at least a standard:
1) " El " is characterised in that and has the d of being selected from
0, d
1, d
2, d
5, d
6, d
7, or d
10The electron orbit structure, wherein the small crystals field stable energy of metal ligand " O-El " helps element El and O
2-The tetrahedral coordination effect, like " Inorganic Chemistry " J.E.Huheey, Harper Row, p.348 disclosed in (1978);
2) " El " is characterised in that and can in the aqueous solution, forms stable oxygenate or hydroxylated material, and these can be by greater than 10
-14The first hydrolysis constant K
11Prove, like " The Hydrolysis of Cations ", C.F.Baesand R.E.Mesmer, John Wiley&Sons (1976) is disclosed;
3) " El " is selected from the known element in the crystal structure type that is present in, and the geometrical configuration of this crystal structure type relates to the modification of different oxidation silicon body, quartz, cristobalite or tridymite.Like E.Parthe, " Crystal Chemistry of Tetrahedral Structures ", Gordon and Breach, NewYork, London, pp.66-68 (1964) is said; And
4) " El " is a kind of element, its cationic form be categorized as Pearson. (J.E.Huheey, " Inorganic Chemistry ", Harper & Row, p.276 (1978) described " firmly " or " edge " acid, its with " by force " alkaline O
2-Effect forms than is categorized as the more stable key of cation of " soft " acid.Concrete element includes but not limited to arsenic, beryllium, boron, chromium, cobalt, nickel, gallium, germanium, iron, lithium, magnesium, manganese, titanium, vanadium, tin and zinc.
From above-mentioned general-purpose type, can know, can describe and prepare several molecular sieve analogs, for example, when " w " and " y " is zero simultaneously, molecular sieve is zeolite or zeolite-type molecular sieves.Formula (1) is changed in this case
(Al
xSi
1-x)O
2 (2)
X value 0-0.5 wherein.The concrete example of molecular sieve prepared in accordance with the present invention includes but not limited to zeolite A, X zeolite, mordenite, siliceous salt (silicalite), zeolite beta, zeolite Y, zeolite L, ZSM-12, UZM-4 and UZM-5.WO 02/36491 and WO 02/36489 have described UZM-4 and UZM-5 respectively, introduce its full content as a reference.When x was zero, zeolite was siliceous salt.In this case, " x " in the formula (1) can get formula (3) greater than zero:
(El
wAl
x’P
ySi
z)O
2 (3)
Wherein " w ", " y " and " z " be suc as formula defining in (1), x ' value greater than zero to 0.5.In addition, " w " and " z " is zero in formula (3), or " w " and " z " is zero in formula (1), and " x " is when zero; Can obtain like US 4,310,440 with US 4; 500, the 651 ALPO family non-zeolite molecular sieves described in detail are introduced this full content of two pieces as a reference.In addition, " w " in formula (1) or formula (3) is zero, and " z " greater than zero time (" x " in the formula (1) is greater than zero); Can obtain SAPO family non-zeolite molecular sieve, unrestriced example is US 4,440; 871 described SAPO-34 and SAPO-11 introduce its full content as a reference.Be zero as " z " in formula (1) or (3), other subscripts greater than zero the time, can obtain ElAPO family non-zeolite molecular sieve.At last, when all subscripts in formula (1) or (3) all greater than zero the time, can obtain ElAPSO family non-zeolite molecular sieve as stated, one of them example is MAPSO-31.
Like this, contain inner core particles and backbone element source and template/structure directing agent and water in the slurries.These template are known in the art, include but not limited to alkali metal, alkaline-earth metal and organic compound.Organic compound is known in the art any; Include but not limited to amine, like piperidines, tripropyl amine (TPA), di-n-propylamine, diethanol amine, triethanolamine, cyclohexylamine and quaternary ammonium compound (like the halide of tetramethyl-ammonium, TBuA, tetraethyl ammonium, tetrapropyl ammonium, ethyl trimethyl ammonium, diethyl-dimethyl ammonium or hydroxide etc.).Aluminium known in the art source includes but not limited to aluminium alkoxide, pseudobochmite, gibbsite, colloidal alumina, alumina sol, sodium aluminate, aluminum sulfate, alchlor and aluminum chlorohydrate.Preferably pseudobochmite, aluminum sulfate, sodium aluminate and aluminium alkoxide such as aluminium isopropoxide in the above-mentioned aluminium source.The silicon source includes but not limited to silica sol, colloidal silica, pyrogenic silica, silica gel, silicon alkoxide, silicic acid and alkali silicate such as sodium metasilicate.The phosphorus source includes but not limited to phosphoric acid and organophosphorus ester such as triethyl phosphate.
But element El source can be any reaction formation that allows the reaction formation original position formation of element, just reacts the skeleton oxide unit of generting element El.The compound of adoptable element El comprise oxide, hydroxide, alkoxide, nitrate, sulfate, halide, carboxylate, and composition thereof.Spendable representational compound includes but not limited to: the carboxylate of arsenic and beryllium; Cobalt chloride hexahydrate, the inferior cobalt of alpha-iodineization; The inferior cobalt of sulfuric acid; Cobalt acetate; Cobalt dibromide; Cobalt chloride; Alkoxylate boron; Chromic acetate; The gallium alkoxide; Zinc acetate; Zinc bromide; Zinc formate; Zinc iodide; Six zinc sulphate hydrates; Germanium dioxide; Ferric acetate (II); Lithium acetate; Magnesium acetate; Magnesium bromide; Magnesium chloride; Magnesium iodide; Magnesium nitrate; Magnesium sulfate; Manganese acetate; Manganous bromide; Manganese sulfate; Titanium tetrachloride; The carboxylic acid titanium; The acetate titanium; Zinc acetate; Stannic chloride; Or the like.
Except above-claimed cpd, can optionally contain the crystal seed that is deposited on the molecular sieve on the kernel in the slurries.The use of crystal seed is it can reunite on kernel, and allows the one-tenth kernel effect of growth, and maybe can look bigger.Available these crystal seeds of methods known in the art preparation; Adopt the conventional method of these patents descriptions of being quoted and introduce above-mentioned patent; This method comprises the mixed reactant source; For example, in container, add aluminium source, silicon source and formwork structure directed agents, heat up (pressurize or need not and pressurize) is until the temperature that obtains the crystallization product.
Add required backbone element source to above-mentioned slurries discontinuous, hereinafter all is called nutrients, thereby nutraceutical concentration surpasses critical saturated concentration, when critical saturated concentration, can become the kernel effect, forms crystal.Along with the formation of crystal with grow up, their can be reunited around inner core particles, form the skin of kernel.
Nutrients that adds or nutraceutical combination are to form any one of molecular sieve.These combinations include but not limited to: 1) silicon source; 2) aluminium and silicon source; 3) aluminium, phosphorus and silicon source; 4) aluminium and phosphorus source; 5) El and silicon source; 6) El, aluminium and phosphorus source; 7) El, aluminium, silicon and phosphorus source.Should be understood that to need to add in addition template/structure directing agent.This can be through adding required reagent source with a kind of nutrients, or add as independent logistics.In addition, initial slurry can contain excessive required reagent.
No matter select which kind of nutrients, can use the method for any routine to add.These methods comprise preparation nutrient solution, preparation solid suspension or slurries, directly add solid and add pure nutrients.Certainly, available a kind of method adds a kind of nutrients, and adds other nutrients with method for distinguishing.In addition, according to concrete nutrients,, possibly need to add in addition acid or alkali for reaching required pH value.For example, when using sodium metasilicate, need to add the NaOH that acid produces with neutralization as nutrients or silicon source.
When adding more than a kind of nutrients, for example, Si and Al can add simultaneously or sequentially.Order adds fashionable, for liquid or slurries, only need use a pump.A kind of adding simultaneously in the available dual mode.The first, use independent mouth or syringe, every kind of nutrients is joined in the reactor that contains seed slurry.The second, every kind of nutrients is joined in the accumulator tank, mix, join in the reactor that contains slurries as a kind of logistics then.A kind of method in preferred back.
Intermittence or pulse add nutrients, surpass critical supersaturation concentration and the kernel effect has taken place up to nutraceutical concentration in reactant mixture, thereby form molecular sieve crystal.Along with the formation of crystal, they are reunited on kernel, form the ground floor on the nuclear.Control uniformity of mixture and reunion through shearing the introducing reactant mixture.Can wait through mechanical means, fluid power method and implement to shear.The concrete grammar of implement shearing includes but not limited to agitator, impeller, ultrasonic, relative injection etc.The amount that needs control to shear, thus excessive reunion can not take place, but can not excessive shear, to avoid peeling off the layer on the kernel.
Although nutrients can intermittently join in the reactant mixture up to the layer that forms desired thickness, preferably adopt following method adding nutrients.At first, intermittently add nutrients, on kernel, form one deck molecular sieve crystal.So handle very first time section, it can change in the scope of broad, is generally 0.1 hour to 72 hours.Add the stage in this pulse, sustainable 1 second to 5 minutes of pulse, be 10 seconds to 3 hours the blanking time of pulse.Next step adds nutrients continuously, makes nutrient concentrations subcritical supersaturation concentration but is higher than saturated concentration.In this case, be deposited on the molecular sieve crystal meeting continued growth on the kernel, but the further one-tenth kernel effect of new crystal can not take place substantially.So handled for second time period, it typically is 1 hour-72 hours.In the continuous adding stage, need the nutraceutical adding speed of control, make its allomeric growth speed identical substantially.Adopt the growth rate of the analysis means experience mensuration crystal as ESEM (SEM).A kind of in addition method of controlling continuous adding speed is measurement and keeps every kind of nutraceutical concentration to be between saturated concentration and the critical supersaturation concentration.Can carry out repeatedly intermittence or continuous adding, as it is necessary to obtain required bed thickness.Yet molecular sieve bed thickness amplitude of variation broad is usually from 0.1 μ m to 150 μ m.
The formation of crystal and the reaction condition of growth comprise that with used identical in the conventional method self-generated pressure and room temperature (20 ℃) are to 250 ℃ temperature.Can use high pressure, usually can be up to 300psig.In case reach required bed thickness, stop to add nutrients, from water or mother liquor, isolate layer composition with methods known in the art, like filtration, centrifugal process etc.
The crystal seed that optionally in building-up process, adds the desired molecule sieve.The adding of crystal seed helps the control table area, because if reunite, the total surface area of particle can reduce.Like this, adding little crystal seed can increase specific area, can offset the result of the minimizing surface area that is caused by reunion like this.Can help nutrients is added the control of speed conversely to the control of surface area.That is to say that if particle agglomeration, the average diameter of particle increases, just need to reduce nutraceutical adding speed.Along with the increase of speed, the more difficult control that can become increases surface area like this and allows better control to add speed.
Although foregoing has been described the method for deposition one deck molecular sieve, this process can repeat repeatedly to obtain multi-layered product.Like this, the pulp in reactant mixture of the laminar composition of separation contains the reactive sources according to El, Al, P and Si in the formula (1) in this mixture.Again, intermittently add reactive sources, optionally variation between intermittently or continuously adding with the 3rd time period.Unique restriction for forming the second layer is that molecular sieve and ground floor (or being close to the one deck under it) have various structure; Perhaps have identical structure, and have at least a kind of backbone element different.For example, ground floor is siliceous salt, and the second layer can be the Y zeolite.Perhaps, ground floor can be ALPO-34, and the second layer is SAPO-34.
In the another one specific embodiment of the present invention, the second layer can also be except being the composition the molecular sieve.The example of these other composition includes but not limited to aluminium oxide, silica, silica-alumina, zirconia, titanium oxide, aluminium oxide-phosphate, zinc oxide, tin oxide, iron oxide, ruthenium-oxide and its mixture.Can oxide precipitation original position on the laminated composites be generated these compounds by the slurries that contain the laminar composition particle and the solution that contains oxide precursor.These oxides can form multilayer on multi-layer composition.As stated, the sole criterion of one deck of laminar composition is that contiguous layer does not have identical structure and composition.
Laminar composition of the present invention can come the isolated molecule mixture according to the degree of polarity of molecular size (kinetic diameter) or molecule.When the separation of molecule during, got rid of big material and realize separating through making little molecule get into the intercrystalline space based on molecular size.D.W.Breck, Zeolite MolecularSieve, p.636 John Wiley and Sons (1974) provides the kinetic diameter of multiple molecule, like oxygen, nitrogen, carbon dioxide, carbon monoxide.
Laminar composition of the present invention is perhaps used as synthetic catalyst or the catalyst carrier that perhaps after modification, is used as hydrocarbon conversion process.Hydrocarbon conversion process is known in the art, comprises that alkylation, isomerization, polymerization, reformation, dewaxing, hydrogenation, dehydrogenation, alkyl exchange, dealkylation, hydration, dehydration, hydrotreatment, hydrodenitrogeneration, hydrodesulfurization, methanation and the synthesis gas of open loop, cracking, hydrocracking, aromatic compounds and isoparaffin rotated (syngas shift) process.The type that can be used for concrete reaction condition and the charging of these processes can be referring to US 4,310,440 with US 4,440,871, these documents are hereby incorporated by.
Usually hydrocracking condition comprises the temperature of 400-1200
(204-649 ℃) scope, preferred 600-950
(316-510 ℃).Reaction pressure is an atmospheric pressure to 3, and 500 psig (24,132kPa), preferred 200-3000psig (1379-20,685kPa).Usually time of contact, its scope was 0.1hr corresponding in liquid hourly space velocity (LHSV) (LHSV)
-1-15hr
-1, preferred 0.2hr
-1-3hr
-1Hydrogen circulation rates is every barreled material 1,000-50,000 standard cubic feet (scf) (178-8,888std.m
3/m
3), preferred every barreled material 2,000-30,000scf (355-5,333std.m
3/ m
3).Normally suitable hydroprocessing condition is in the above-mentioned wide hydrocracking condition scope of listing.
Usually the reaction zone effluent is shifted out from beds, carry out partial condensation and steam-fluid separation applications, different components is reclaimed in fractionation then.Hydrogen and part or all of if necessary unconverted heavy material loop back reactor.Perhaps use two sections flow processs, unconverted material is fed second reactor.Catalyst of the present invention can only be used for a stage of said method, or can be used for the double-reactor section.
Preferably with the operation of UZM-9 composition, used charging has such as gas oil, heavy naphtha, deasphalted crude residual oil etc. catalytic cracking process, and gasoline is main required product.Suitable temperature conditions is 850-1100
(454-593 ℃), LHSV value are 0.5-10hr
-1, pressure condition is 0-50psig (0-345kPa).
The alkylation of aromatic generally includes aromatic compounds, especially benzene, and monoolefine (C
2-C
12) prepared in reaction straight chained alkyl substituted arene.The operating condition of this method is: aromatic hydrocarbons: (benzene for example: alkene) ratio is 5: 1 to 30: 1 to alkene, and the LHSV value is 0.3-6hr
-1, temperature is 100 ℃-250 ℃, pressure is 200-1000psig (1379-6895kPa).The further details of used instrument can be hereby incorporated by referring to US 4,870,222.
Isoparaffin and olefin alkylation production are applicable to that the operation condition of the alkylates of fuel for motor vehicle component is: temperature is-30-40 ℃, and pressure is atmospheric pressure to 6, and (1,000psig), weight (hourly) space velocity (WHSV) (WHSV) is 0.1-120hr to 894kPa
-1The details of alkylation of paraffines can be referring to US5,157,196 with US 5,157,197, be hereby incorporated by.
Other reaction of available these laminar composition catalysis comprises that the dimerization and oligomeric, the alcohol of side chain alkylation, aldol condensation, olefines double bond isomerizing and acetylene isomerization, alcohol dehydrogenase, the alkene of base catalysis aromatic is converted into alkene.But NO in the ions with proper exchanging form catalysis automobile of these materials and the industrial waste gas logistics
xReduction generates N
2Reaction.Some reaction conditions and feed type used in these processes can be referring to US 5; 015,796 and H.Pines, The Chemistry Of CatalyticHydrocarbon Conversions; Academic Press (1981) pp.123-154 is hereby incorporated by.
Following embodiment is intended to set forth the present invention.Should understand embodiment and only be and be used for explaining, not as the improper restriction of the wide protection domain of the present invention that accompanying claims is explained.
Embodiment 1
In the reaction vessel that contains the 486g deionized water, add the 90g sodium hydrate particle while stirring, add 213g60 purpose sand again.Then mixture is heated to 81 ℃, respectively sodium aluminate and sodium metasilicate is pumped into container.The speed that pumps into solution with pulse mode is respectively 1100mL/hr and 1650mL/hr, is the time delay (at interval) that does not add solution then.Pulse length and blanking time are listed in the table below.
| Burst length (second) | Blanking time (branch) |
| 39 | 87 |
| 39 | 55 |
| 47 | 56 |
| 47 | 42 |
Experiment with the gained solid filtering, is used water washing after finishing.Find that gained solid product (270g) is made up of the sand and the zeolite A powder that apply zeolite A.Further analyze the zeolite A bed thickness that shows on the sand and be about 4 microns.
Embodiment 2
In the reaction vessel that contains the 485g deionized water, add and stir limit adding 90g sodium hydrate particle, add 230g 1.5mm soda lime bead again.Mixture is warming up to 81 ℃, in container, pumps into sodium aluminate and sodium silicate solution respectively then.The speed that pumps into solution with pulse mode is respectively 260mL/hr and 274mL/hr, is the time delay (at interval) that does not add solution then.Pulse length and blanking time are listed in the table below.
| Burst length (second) | Blanking time (minute) |
| 39 | 90 |
| 39 | 78 |
| 109 | 6 |
| 150 | 90 |
Experiment with the gained solid filtering, is used water washing after finishing.Analysis result shows that products therefrom is made up of bead that has applied zeolite N and zeolite N powder.Find that the zeolite N bed thickness on the bead is 1 micron.
Embodiment 3
In the 2L container, adding the 80g particle mean size is 70 μ m (Versal
TM900) alpha-alumina nuclei, 88g zeolite Y crystal seed (Si/Al
2=5, particle mean size is 1.0 μ m) and 616.4g circulating mother liquor solution (warp analysis H
2Contain 12.4 weight %Si, 0.21 weight %Al and 9.0 weight %Na among the O), mixture is heated to 95 ℃ while stirring.In container, add sodium silicate aqueous solution (29 weight %SiO with the pulse length that prolongs then
2With 9 weight %Na
2O) and sodium aluminate aqueous solution (24 weight %Al
2O
3With 20 weight %Na
2O).As shown in the table.
| Burst length (second) | Blanking time (branch) | The silicate feed rate (milliliter/hour) | The aluminate feed rate (milliliter/hour) |
| 31 | 15 | 3800 | 520 |
| 32 | 15 | 3800 | 520 |
| 33 | 15 | 3800 | 520 |
| 34 | 15 | 3800 | 520 |
| 35 | 15 | 3800 | 520 |
| 36 | 15 | 3800 | 520 |
| 37 | 15 | 3800 | 520 |
| 38 | 15 | 3800 | 520 |
| 39 | 15 | 3800 | 520 |
After pulse adds EOS, use the same sodium aluminate solution of same sodium silicate solution of 455.6mL and 62.3mL to continue to add nutrients 146 minutes continuously with constant rate of speed.After adding nutrients, filtration product, washing, at room temperature dry.Keep mother liquor and be used for recirculation.Wash solids, sieve, elutriation to be to keep the bead of 20-150 μ m.Produce 70.0g classification (sized) bead.
Adding 88g zeolite Y crystal seed, 616.4g recycle in the 2L container mother liquor solution (containing 4.76 weight %Si, 0.06 weight %Al and 3.72 weight %Na) and 65g classification bead through dividing in the bleed.While stirring mixture is heated to 95 ℃.As shown in the tablely then in container, add sodium metasilicate (29 weight %SiO
2With 9 weight %Na
2O) and the aqueous solution of sodium aluminate (24 weight %Al
2O
3With 20 weight %Na
2O).The result is as shown in the table.
| Burst length (second) | Blanking time (branch) | The silicate feed rate (milliliter/hour) | The aluminate feed rate (milliliter/hour) |
| 31 | 15 | 3800 | 520 |
| 32 | 15 | 3800 | 520 |
| 33 | 15 | 3800 | 520 |
| 34 | 15 | 3800 | 520 |
| 35 | 15 | 3800 | 520 |
| 36 | 15 | 3800 | 520 |
| 37 | 15 | 3800 | 520 |
| 38 | 15 | 3800 | 520 |
| 39 | 15 | 3800 | 520 |
| 40 | 15 | 3800 | 520 |
| 41 | 15 | 3800 | 520 |
| 42 | 15 | 3800 | 520 |
| 43 | 15 | 3800 | 520 |
After pulse adds EOS, use the same sodium aluminate solution of same sodium silicate solution of 247.1mL and 33.1mL to continue to add nutrients 78.5 minutes continuously with constant rate of speed.After adding nutrients, product is filtered, washing, at room temperature dry.Keep mother liquor and be used for recirculation.With solids wash, sieve, elutriation to be to keep the bead of 20-150 μ m.Produce 84.9g classification bead.
Use 80g classification bead, 88g Y zeolite seed crystal and 616.4g circulating mother liquor, repeat said process.Produce 95.1g classification bead.
In reactor, add the preceding paragraph fall described 80g classification bead, 88g Y zeolite seed crystal and 616.4g circulating mother liquor solution, while stirring mixture is heated to 95 ℃.Pulse length to prolong adds sodium silicate solution (29 weight %SiO
2With 9 weight %Na
2O) and sodium aluminate solution (24 weight %Al
2O
3With 20 weight %Na
2O).As shown in the table.
| Burst length (second) | Blanking time (branch) | The silicate feed rate (milliliter/hour) | The aluminate feed rate (milliliter/hour) |
| 31 | 15 | 3800 | 520 |
| 32 | 15 | 3800 | 520 |
| 33 | 15 | 3800 | 520 |
| 34 | 15 | 3800 | 520 |
| 35 | 15 | 3800 | 520 |
| 36 | 15 | 3800 | 520 |
| 37 | 15 | 3800 | 520 |
| 38 | 15 | 3800 | 520 |
| 39 | 15 | 3800 | 520 |
After pulse adds EOS, use the same sodium aluminate solution of same sodium silicate solution of 455.6mL and 62.3mL to continue to add nutrients 146 minutes continuously with constant rate of speed.After adding nutrients, product is filtered, washing, at room temperature dry.Keep mother liquor and be used for recirculation.With solids wash, sieve, elutriation to be to keep the bead of 20-150 μ m.Produce 99.4g classification bead.
Under 75 ℃ of temperature, bead is carried out ammonium ion exchange with 10% ammonium nitrate solution.Through the bead of ion-exchange with 50% steam 600 ℃ of following vaporization process 2 hours, exchange again then.
Claims (9)
1. one kind prepares the stratiform method for compositions, and said composition comprises kernel and skin, and skin contains molecular sieve, and this molecular sieve has three-dimensional microporous framework structure, and skeleton is formed and represented by following empirical formula:
(El
wAl
xP
ySi
z)O
2 (1)
Wherein El, Al, P and Si are the backbone elements that exists with tetrahedral oxide units, and " w " is the molar fraction of El, value 0-0.5; " x " is the molar fraction of Al, and value 0-0.5, " y " are the molar fractions of P; Value 0-0.5; And " z " be the molar fraction of Si, and value 0-1, w+x+y+z=1 and " y " and " z " are not zero simultaneously; This method comprises: under reaction condition, provide and contain the slurries that are dispersed in the inner core particles in the liquid, this liquid contains the reactive sources corresponding to El, Al, P and Si in the formula (1); Add nutrients to the slurries discontinuous; So that the backbone element according to the molecular sieve of formula (1) to be provided; Thereby formation molecular sieve crystal; Crystal is reunited on kernel, and add to form first molecular sieve layer on the kernel intermittence of carrying out very first time section, and wherein kernel is selected from aluminium oxide, silica-alumina, cordierite, mullite, white sand quartz, gibbsite, silica; And composition thereof, wherein El is selected from Mg, Ni, As, Ga, Ge, Mn, Co, Sn, Ti, Fe, Cr, Be, B, V, Zn and composition thereof.
2. according to the process of claim 1 wherein that kernel comprises Alpha-alumina.
3. according to the method for claim 1, also contain after very first time section, add second time period of nutrients continuously, wherein keep every kind of nutraceutical concentration to be between saturated concentration and the critical supersaturation concentration with the growth molecular sieve crystal.
4. according to the method for claim 3, its discontinuous and continuous adding step repeat 2 times at least.
5. according to the method for claim 1, also comprise the separation laminar composition, contain the slurries of laminar composition particle, on ground floor, generate the second layer through generation; Add nutrients to obtain backbone element to the slurries discontinuous according to the molecular sieve of formula (1); Thereby forming molecular sieve crystal and crystal reunites on ground floor; Add to form the second layer of second molecular sieve on the laminar composition intermittence of carrying out for the 3rd time period again, and wherein second layer molecular sieve has and ground floor molecular sieve various structure or different experience compositions.
6. according to the method for claim 5, also be included in for the 3rd time period after, add nutraceutical the 4th time period continuously, so that the molecular sieve crystal growth wherein adds speed continuously and equals crystal growth rate substantially.
7. a laminar composition contains Alpha-alumina kernel and the skin that contains molecular sieve, and this molecular sieve has three-dimensional microporous framework structure, and skeleton is formed and represented by following empirical formula:
(El
wAl
xP
ySi
z)O
2 (1)
Wherein El, Al, P and Si are the backbone elements that exists with tetrahedral oxide units, and " w " is the molar fraction of El, value 0-0.5; " x " is the molar fraction of Al, and value 0-0.5, " y " are the molar fractions of P; Value 0-0.5, and " z " be the molar fraction of Si, value 0-1; W+x+y+z=1 and " y " and " z " are not zero simultaneously, and wherein the reunion through molecular sieve crystal is attached on the kernel molecular sieve layer.
8. according to the composition of claim 7; Also contain at least one extra play, this layer contain the formula of seeing service that is selected from (1) but with next-door neighbour's one deck under it have the molecular sieve of various structure or composition composition, aluminium oxide, silica, silica-alumina, zirconia, aluminium oxide-phosphate, zinc oxide, tin oxide, iron oxide, ruthenium-oxide, and composition thereof.
9. a hydroconversion process comprises hydro carbons is contacted under the hydrocarbon conversion condition with the catalytic complex of the laminar composition that contains claim 7 or 8, to obtain conversion product.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3730910A (en) * | 1971-02-02 | 1973-05-01 | Grace W R & Co | Novel zeolite surfaces |
| US5895769A (en) * | 1994-07-08 | 1999-04-20 | Exxon Research And Engineering Company | In-situ crystallized zeolite containing composition (LAI-ISC) |
| CN1724359A (en) * | 2004-07-20 | 2006-01-25 | 环球油品公司 | Synthesis method of molecular sieve |
| US7112316B1 (en) * | 2005-08-08 | 2006-09-26 | Uop Llc | Process for preparing molecular sieves via continuous addition of nutrients |
-
2007
- 2007-11-23 CN CN2007103068612A patent/CN101439298B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3730910A (en) * | 1971-02-02 | 1973-05-01 | Grace W R & Co | Novel zeolite surfaces |
| US5895769A (en) * | 1994-07-08 | 1999-04-20 | Exxon Research And Engineering Company | In-situ crystallized zeolite containing composition (LAI-ISC) |
| CN1724359A (en) * | 2004-07-20 | 2006-01-25 | 环球油品公司 | Synthesis method of molecular sieve |
| US7112316B1 (en) * | 2005-08-08 | 2006-09-26 | Uop Llc | Process for preparing molecular sieves via continuous addition of nutrients |
Non-Patent Citations (1)
| Title |
|---|
| N. van der Puil et al..Preparation and catalytic testing of zeolite coatings on preshaped alumina supports.《Microporous and Mesoporous Materials》.1999,第27卷95-106. * |
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