CN101239322B - Method for preparing montmorillonite/molecular sieve composite material - Google Patents
Method for preparing montmorillonite/molecular sieve composite material Download PDFInfo
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- CN101239322B CN101239322B CN 200710010389 CN200710010389A CN101239322B CN 101239322 B CN101239322 B CN 101239322B CN 200710010389 CN200710010389 CN 200710010389 CN 200710010389 A CN200710010389 A CN 200710010389A CN 101239322 B CN101239322 B CN 101239322B
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Abstract
The present invention provides a montmorillonite/beta molecular sieve composite material and its preparing method. The montmorillonite/beta molecular sieve composite material is prepared by evenly mixing montmorillonite with beta molecular sieve gelatin, then processing home position crystallization, and via filtering, washing and drying. In the composite material, the montmorillonite disperses in the base material of the molecular sieve, the molecular sieve crystal grain ''grows'' around the montmorillonite, so the composite catalyzing material organically combined by montmorillonite and molecular sieve are obtained. The invention uses directing agent having high activity act with the montmorillonite, the molecular sieve crystal is induced generation on the surface of the montmorillonite, the preparing method is simple, the easily separating, the molecular sieve composite material has better water-heat stability. The composite material are mainly used for all kinds of catalysts and absorption agents, especially the preparing of hydrogenation catalyst.
Description
Technical field
The present invention relates to a kind of preparation method of new catalytic material, specifically, is the preparation method about imvite/molecular sieves compound material.
Background technology
Layer silicate mineral with swelling properties as terre verte family clay, is a kind of natural inorganic catalysis material.This clay mineral is at the nature ubiquity, and reserves are big.Because their small particle size (＜2 μ m) but and special interlayer interpolation property, for the absorption and the catalytic action of organic species provides certain surface area and space.The catalytic action of terre verte family clay is recognized in many " nature " process, forms reaction comprising oil, the transformation of chemical substance in soil and the differentiation reaction of relevant chemical substance.Because clay has the acidity of more weak or moderate strength, itself as catalyst industrial be far from being enough.Think and satisfy the needs of clay in different application, often need that it is carried out modification to handle, perhaps form composition and be used for the catalytic hydrocarbon conversion reaction with other inorganic oxide, for example be used for alkylation, cracking, oligomeric, isomerization and transalkylation reaction.
Zeolite molecular sieve (as β, ZSM-5 and Y molecular sieve) is as effectively solid acid catalyst or acidic components have been widely used in fields such as petroleum refining, fine chemistry industry and adsorbing separation.Zeolite molecular sieve has the pore structure of homogeneous and stronger acidity, and its outstanding feature is can modulation acidity, and the ducts that different sizes can be provided simultaneously and hole are played and selected shape and act on.Yet for some reaction, the acidity of molecular sieve is still very strong, therefore need find a kind of method of modulation.Lamellar clay has more weak acidity, and its hydrothermal stability is better.The researcher finds, can obtain effect preferably with molecular sieve supported to lamellar clay.
US4493902 disclose a kind of on kaolin microsphere the method for in-situ crystallization synthesis zeolite Y crystal grain, be characterized in before the kaolin microsphere moulding, adding so-called crystal seed, in-situ crystallization forms Y zeolite molecular sieve then.
CN1334142A is disclosed be a kind of be the method for the synthetic NaY molecular sieve of raw material with kaolin.This method is raw material with the protokaolin, a part of protokaolin is obtained high-temperature roasting soil at 940-1000 ℃ of roasting 1-3h, another part protokaolin obtains higher territory at 700-900 ℃ of roasting 1-3h, when two kinds of kaolin mix back or a kind of roasting kaolin therein by a certain percentage and exist, carry out crystallization under hydrothermal condition, obtaining a kind of NaY molecular sieve content is that 40～90wt%, silica alumina ratio are the crystallization product of 3.5-5.5.
CN1393402A discloses a kind of preparation method of nano Y zeolite molecular sieve carried by kaolin microspheres, be characterized in preparation directed agents earlier, in directed agents, add natrium citricum, then the kaolin microsphere after the roasting is joined aforementioned solution crystallization, make nano Y zeolite molecular sieve product by carried by kaolin microspheres.
In said method, all with kaolin as the silicon source, and adopt caustic soda and sodium aluminate to replenish sodium source and aluminium source and synthesized the composition that kaolin supports Y molecular sieve.Because kaolin has participated in the regrouping process of Y molecular sieve skeleton as the silicon source, therefore kaolinic structure has inevitably been suffered destruction.Compare with kaolin, more weak Van der Waals force and have exchange cation between cheating engaging layer, but and special interlayer interpolation property, for the absorption of organic species, the load and the catalytic action of reactive metal provide extra surface area and space.Therefore be compounding ingredients as if replacing kaolin, and take special method to synthesize, will obtain a kind of novel composite material with imvite.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of preparation method of compound catalyze material, i.e. the preparation method of imvite/molecular sieves compound material.
The technical scheme of the inventive method is: imvite and molecular sieve gel are mixed, carry out in-situ crystallization then, and make described imvite/molecular sieves compound material through Separation of Solid and Liquid, washing and drying.Wherein the weight ratio of imvite and molecular sieve gel is (1～8): (2～9) are preferably (3～7): (7～3), the mole proportioning of described molecular sieve gel are (4～100) SiO
2: Al
2O
3: (2～180) Na
2O: (0～20) R
1: (160～1000) H
2O, " R in the formula
1" be the template agent.Described crystallization condition is: 90～160 ℃ of crystallization temperatures, crystallization time 1～8 day.
In imvite/molecular sieves compound material that the present invention makes, imvite is dispersed in and forms the compound that imvite is wrapped up by molecular sieve matrix in the molecular sieve matrix.In this composite, the content of imvite is 10wt%～90wt%, is preferably 30wt%～70wt%.This composite has porous and the crystal structure of the XRD of imvite and institute's composite molecular screen simultaneously.
The method of testing of sample among the present invention: porous is carried out on the ASAP2400 physical adsorption appearance that U.S. Mai Ke company produces.Experiment condition is: sample is at 300 ℃, and 0.1MPa handled 4 hours down, treats to take off sample after sample bottle charges into the nitrogen of 101.325KPa, accurately analyzes after the weighing.Crystal structure mainly characterizes with D/max2500 type X-ray diffraction (XRD) instrument that Japanese company of science produces, and experiment condition is: voltage 40Kv, electric current 80mA, 6 °/min scanning.In addition, characterize with the microstructure of SEM (SEM) to sample segment, experiment is carried out on the JSM-6301F of company of NEC awkward silence at a meeting emission scan Electronic Speculum, and before the experiment, sample ultrasonic wave in ethanol disperses.
Compared with prior art, preparation method's of the present invention characteristics are:
(1) composite of the inventive method preparation had both had the acid of zeolite and hole, basket structure and the stable skeleton structure of the uniqueness that possessed, compare with kaolin simultaneously, imvite provides extra volume for the load of metal cation on carrier, improved the load capacity of reactive metal, for chemical reactant provides enough reaction compartments.
(2) because imvite is 2: 1 layer structures, have characteristics such as interlayer is pillared, interlayer absorption, interlayer catalysis, also have the adjustable big pore property of pore structure (from the super large micropore to the mesopore scope) simultaneously, therefore the composite of preparation has possessed great character changeability.
(3) composite is as catalytic component the time, and imvite can be played good molding bonded effect.The inventive method is that molecular sieve is coated on outer surface with the nuclear of imvite as composite, has fully improved the catalytic effect of unit formula sieve.
(4) preparation process is simple, and product separates easily, and the bedded clay/molecular sieve composite material good hydrothermal stability that makes is mainly used in all kinds of catalyst and adsorbent, especially the catalyst of hydrogenation aspect.
Description of drawings
Fig. 1 is the XRD spectra of the embodiment of the invention 1 gained sample
Fig. 2 is the SEM spectrogram of the embodiment of the invention 1 gained sample
Fig. 3 is the XRD spectra of the embodiment of the invention 2 gained samples
Fig. 4 is the SEM spectrogram of the embodiment of the invention 2 gained samples
The specific embodiment
The concrete preparation process of imvite/molecular sieves compound material of the present invention is:
(1) preparation of molecular sieve gel:
With silicon source, aluminium source, NaOH, template agent and water according to (4～100) SiO
2: Al
2O
3: (2～180) Na
2O: (0～20) R
1: (160～1000) H
2The mole proportioning of O is mixed under room temperature and stirring condition, continues to be stirred to reaction mass and mixes, and obtains the gel that the colloidal sol shape has better flowability.Described silicon source is white carbon, Ludox, waterglass or silicic acid; Described aluminium source is aluminum sulfate, aluminium chloride or sodium aluminate; Dissimilar according to institute's composite molecular screen, template agent R
1Can be tetraethyl ammonium hydroxide, tetraethylammonium bromide, TPAOH, 4-propyl bromide or softex kw.
The template agent plays important effect in the crystallization process of synthetic zeolite, be mainly reflected in three aspects; (1) skeleton of support zeolite; (2) electric charge of balance zeolitic frameworks; (3) formation of guiding zeolite nucleus.Different molecular sieves needs different template agent, therefore can also add the effect that potassium chloride plays certain specific molecular sieve template agent, is (4～100) SiO with preparation mole proportioning
2: Al
2O
3: (2～180) Na
2O: (2～200) K
2O: (0～20) R
1: (160～1000) H
2The molecular sieve gel of O.
Usually, in order to save template agent or to shorten crystallization time, and the purpose of synthetic even sieve particle, added the structure directing agent of 2v%～10v% in the molecular sieve gel in the past.The preparation method of described structure directing agent is generally: with silicon source, aluminium source, template agent, NaOH and water according to (12～150) SiO
2: (0～1) Al
2O
3: (0～40) R
2: (10～80) Na
2O: (160～1000) H
2The mole proportioning of O is mixed under room temperature and stirring condition, continues to stir to mix until reaction mass, changes over to then in the synthesis reactor, makes directed agents down in aging 1～3 day at 30 ℃～150 ℃.Described aluminium source can be aluminum sulfate, aluminium chloride or sodium aluminate; Described silicon source can be white carbon, waterglass, Ludox or silicic acid; Described template agent R
2Can be tetraethyl ammonium hydroxide, tetraethylammonium bromide, TPAOH or 4-propyl bromide.
(2) with the imvite microballoon according to (1～8): the weight ratio of (2～9) joins in the molecular sieve gel that step (1) makes, after stirring, 90～160 ℃ of crystallization 1～8 day, carry out Separation of Solid and Liquid then, wash and be drying to obtain imvite/molecular sieves compound material.Described Separation of Solid and Liquid can adopt centrifugation or suction filtration to separate; Described washing is meant and spends deionised water 1～6 time; Described drying is meant at 50～180 ℃ following dry 10～30 hours.
The imvite component that the present invention is used is generally the refining imvite after the flotation.Described method for floating is: get natural montmorillonite by weight 1: (5～20) add deionized water and are mixed with slurries, stirred 0.5～24 hour down in room temperature～95 ℃ then, sedimentation 0.5～24 hour, get supernatant liquid, add flocculant, isolate refining imvite, ℃ following drying for standby in room temperature～150.
The present invention is preferred to carry out one of by the following method imvite after the modification as compounding ingredients:
The sodium modification: get natural calcium base montmorillonite or redistilled calcium base montmorillonite, add deionized water and sodium agent and be mixed with slurries, ℃ following the stirring 30 minutes～24 hours in room temperature～95 isolated the refining sodium-base imvite, ℃ following drying for standby in room temperature～150 then.Sodium agent commonly used comprises NaCl, NaNO
3, Na
2SO
4Deng reagent, calcium-base montmorillonite: sodium agent: the ratio of deionized water weight is 1: (0.1～0.6): (5～20).
The acid modification: imvite, deionized water and ammonium salt (or acid) are with weight ratio 1: (0.1～0.6): (5～20) make slurries, ℃ stir 30 minutes～24 hours down in room temperature～95, separate, and washing, ℃ dry down in room temperature～150.Wherein ammonium salt comprises NH
4Cl, NH
4NO
3, (NH
4)
2SO
4Deng, acid is hydrochloric acid, sulfuric acid, nitric acid etc.If what add is ammonium salt, need be standby after 1～5 hour 300～700 ℃ of following roastings
Organically-modified: with imvite, quaternary ammonium salt and deionized water with weight ratio 1: (0.1～0.6): (5～20) make slurries, ℃ stir 30 minutes～24 hours down in room temperature～95, separate, washing, ℃ dry down in room temperature～150.Wherein organic ammonium salt comprises softex kw, OTAC etc.
Pillared modification: with between bigger inorganic hydroxyl cation and argillic horizon as Na
+, K
+And Ca
+Exchange, these hydroxyl species are the polymerization that formed by Al, Zr, Cr, Ca, Si, Ti, Fe and their hybrid metal salt hydrolysis or oligomeric hydroxy metal cation, sample after the exchange reaction passes through careful heat treatment again, make it dehydrogenation and dehydration, form stable metal oxide post, thereby lamella is strutted, form two-dimentional duct with an opening.
The modification of porous isomery: get acidity or organo montmorillonite, add organic amine, behind the vigorous stirring reaction 30min, add TEOS, stirring reaction 2～8h under the room temperature separates, drying, and 300～700 ℃ of roasting 3～8h remove organic matter, obtain porous isomery material.Wherein imvite: organic amine: the TEOS mol ratio is 1: 50: (50～200).
The present invention compound molecular sieve comprise existing various micropore, mesoporous molecular sieve, as Y molecular sieve, ZSM-5 molecular sieve, beta-molecular sieve, SAPO-11, MCM-22, MCM-41 molecular sieve etc.Composite provided by the invention is mainly used in all kinds of catalyst and adsorbent, especially the catalyst of hydrogenation aspect.
By the following examples technical scheme of the present invention is further elaborated.
Embodiment 1
The flotation of imvite is refining: get 10g natural calcium base montmorillonite, add the 90ml deionized water, at room temperature stirred 5 hours, supernatant liquid is got in sedimentation 2 hours, adds flocculant, isolates the redistilled calcium base montmorillonite, 110 ℃ of following drying for standby.
Synthesizing of composite:
(1) takes by weighing 2.78g potassium chloride respectively and 1.69g sodium chloride joins in the 20g deionized water, be stirred to molten entirely;
(2) measuring concentration is that 20% tetraethyl ammonium hydroxide solution 90ml fully mixes with solution (1);
(3) under agitation the white carbon black of 9.8g is joined in the solution (2) gradually, stir;
(4) take by weighing the 4.31g sodium aluminate and 1.2g NaOH joins in the deionized water, be stirred to molten entirely;
(5) solution (3) is mixed mutually with solution (4), stir 5～30min to thick;
(6) take by weighing the 3.5g imvite and join in the mixed liquor (5) mechanical agitation 15min.
(7) (6) are placed autoclave 120 ℃ of following thermostatic crystallizations 6 days;
(8) treat that autoclave cools off in air or water after, separation, suction filtration, washing 70 ℃ of dryings, and obtain imvite/beta molecular sieve composite material in 550 ℃ of roasting 5h.
The XRD spectra of this composite as shown in Figure 1.The characteristic peak of imvite and the characteristic peak of beta-molecular sieve exist simultaneously, and because the content of beta-molecular sieve is bigger, the characteristic peak of beta-molecular sieve is more obvious.Fig. 2 is the stereoscan photograph of gained composite, can find out obviously that beta-molecular sieve wraps up imvite fully, and imvite cannot see fully as the nuclear of composite material granular.
Embodiment 2
The redistilled calcium base montmorillonite of getting 10g natural calcium base montmorillonite or preparing according to embodiment one scheme adds the 400ml deionized water, is mixed with slurries, add 4g NaCl then, 60 ℃ of following mechanical agitation 4 hours, centrifugation went out sodium-based montmorillonite, 80 ℃ of following drying for standby.
(1) takes by weighing 3.65g potassium chloride respectively and 1.54g sodium chloride joins in the 32g deionized water, be stirred to molten entirely;
(2) measuring concentration is that 25% tetraethyl ammonium hydroxide solution 105ml fully mixes with solution (1);
(3) under agitation the white carbon black of 12.8g is joined in the solution (2) gradually, stir;
(4) take by weighing the 3.6g sodium aluminate and 2.11g NaOH joins in the deionized water, be stirred to molten entirely;
(5) solution (3) is mixed mutually with solution (4), stir 5～30min to thick;
(6) take by weighing the 5.8g imvite and join in the mixed liquor (5) mechanical agitation 18min.
(7) (6) are placed autoclave 130 ℃ of following thermostatic crystallizations 5 days;
(8) treat that autoclave cools off in air or water after, separation, suction filtration, washing 60 ℃ of dryings, and obtain containing the composite of β zeolite in 500 ℃ of roasting 5h.
The XRD spectra of this composite as shown in Figure 3.The characteristic peak of imvite and the characteristic peak of beta-molecular sieve exist simultaneously, and because the content of imvite is bigger, its characteristic peak is more obvious.Fig. 4 is the stereoscan photograph of gained composite.Can obviously find out because beta-molecular sieve content is less, and beta-molecular sieve can not wrap up imvite fully, imvite with beta-molecular sieve loose be attached on its surface.
Embodiment 3
Get the 10g calcium-base montmorillonite, add the 400ml deionized water, adding 5ml concentration is the hydrochloric acid of 36% (mass fraction), and at room temperature mechanical agitation is 5 hours, and centrifugation or suction filtration separate, and washs then to filtrate and does not have Cl
-Till (checking) with silver nitrate, 130 ℃ of following drying for standby.
(1) takes by weighing 4.2g potassium chloride respectively and 2.15g sodium chloride joins in the 36g deionized water, be stirred to molten entirely;
(2) measuring concentration is that 30% tetraethyl ammonium hydroxide solution 138ml fully mixes with solution (1);
(3) under agitation the white carbon black of 13.7g is joined in the solution (2) gradually, stir;
(4) take by weighing the 3.71g sodium aluminate and 1.62g NaOH joins in the deionized water, be stirred to molten entirely;
(5) solution (3) is mixed mutually with solution (4), stir 30min to thick;
(6) take by weighing the 5.65g imvite and join in the mixed liquor (5) mechanical agitation 25min.
(7) (6) are placed autoclave 140 ℃ of following thermostatic crystallizations 3 days;
(8) treat that autoclave cools off in air or water after, separation, suction filtration, washing 70 ℃ of dryings, and obtain containing the composite of β zeolite grain in 600 ℃ of roasting 5h.
Embodiment 4
Get the 10g calcium-base montmorillonite, add the 400ml deionized water, add 4g NH
4Cl, at room temperature mechanical agitation is 5 hours, and centrifugation or suction filtration separate, and wash then to filtrate and do not have Cl
-Till (checking) with silver nitrate, down dry, standby after 4 hours 500 ℃ of following roastings then at 70 ℃.
(1) with 4.07gNaOH, 2.09g sodium aluminate and 19.95g water mix put be stirred to molten entirely;
(2) with above-mentioned solution and 22.72g sodium silicate solution (28.7wt%SiO
2, 8.9wt%Na
2O) stir 10min, ageing one day;
(3) with 0.14g NaOH, 13.09g sodium aluminate and 130.97g water mix be stirred to molten entirely;
(4) above-mentioned solution is mixed mutually with the 142.43g sodium silicate solution, strong agitation to gel evenly generates;
(5) directed agents in (4) addings (2);
(6) in (5), add the 2g imvite, stir 1h;
(7) material is sealed room temperature ageing diel, then in 100 ℃ of following crystallization 24 hours.At room temperature wash 3 times, obtain the composite of imvite/Y zeolite after the 105 ℃ times oven dry.
Embodiment 5
The flotation of imvite is refining: get 10g natural calcium base montmorillonite, add the 90ml deionized water, at room temperature stirred 5 hours, supernatant liquid is got in sedimentation 2 hours, adds flocculant, isolates the redistilled calcium base montmorillonite, 110 ℃ of following drying for standby.
(1) with 710.3gH
2O, 13.8gNaOH and 117.0gTPAOH solution (20% solution) fully dissolving are mixed to evenly;
(2) under agitation 158.9g silicic acid is progressively added in the above-mentioned solution in batches, the 1h that at room temperature fully vibrates is at 100 ℃ of following ageing 16h;
(3) with 867.8gH
2O, 8.8gNaOH fully mix with the 10.3g sodium aluminate and mix;
(4) under fully stirring, progressively add in the solution (3) 113.1g silicic acid and the 1h that at room temperature fiercely vibrates in batches;
(5) the colloidal state crystal seed 50g that makes in the step (2) is added the 1h that vibrates again in (4);
(6) the 2.0g imvite is joined the 1h that vibrates again in (5);
(7) (6) are placed reactor, filter behind 180 ℃ of following crystallization 40h, fully wash with deionized water, 105 ℃ promptly obtain imvite/ZSM-5 composite behind the dry 24h down.
Embodiment 6
Get the 10g calcium-base montmorillonite, add the 400ml deionized water, add the softex kw of 4g, 60 ℃ of following mechanical agitation 5 hours, centrifugation or suction filtration separate, wash then do not have Cl-to filtrate till (checking) with silver nitrate, 90 ℃ of following drying for standby.
(1) takes by weighing 3.65g potassium chloride respectively and 1.54g sodium chloride joins in the 32g deionized water, be stirred to molten entirely;
(2) measuring concentration is that 25% tetraethyl ammonium hydroxide solution 105ml fully mixes with solution (1);
(3) under agitation the white carbon black of 12.8g is joined in the solution (2) gradually, stir;
(4) take by weighing the 3.6g sodium aluminate and 2.11g NaOH joins in the deionized water, be stirred to molten entirely;
(5) solution (3) is mixed mutually with solution (4), stir 5～30min to thick;
(6) take by weighing the 5.8g organo montmorillonite and join in the mixed liquor (5) mechanical agitation 18min.
(7) (6) are placed autoclave 130 ℃ of following thermostatic crystallizations 5 days;
(8) treat that autoclave cools off in air or water after, separation, suction filtration, washing 60 ℃ of dryings, and obtain containing the composite of β zeolite in 500 ℃ of roasting 5h.
Embodiment 7
The sodium hydroxide solution that with 560ml concentration is 0.2mol/L is added drop-wise in the 0.3mol/L aluminum trichloride solution of 180ml with the speed of 2mL/min, and 45 ℃ of constant temperature and carry out vigorous stirring during dropping at 95 ℃ of following ageing 5h, make aluminum crosslinker again.Get the slurries that imvite after the purification is made into 3% (mass fraction), speed with 2.0mL/min splashes into the aluminum crosslinker solution for preparing in the above-mentioned slurries then, continue to stir 6h, separate with centrifugal process after leaving standstill 10h, its paste (is used AgNO till being washed till no Cl-with deionized water
3Check), after 0 ℃ of following drying standby behind the pillared montmorillonite.
(1) takes by weighing 4.2g potassium chloride respectively and 2.15g sodium chloride joins in the 36g deionized water, be stirred to molten entirely;
(2) measuring concentration is that 30% tetraethyl ammonium hydroxide solution 150ml fully mixes with solution (1);
(3) under agitation the white carbon black of 13.7g is joined in the solution (2) gradually, stir;
(4) take by weighing the 3.71g sodium aluminate and 1.5g NaOH joins in the deionized water, be stirred to molten entirely;
(5) solution (3) is mixed mutually with solution (4), stir 30min to thick;
(6) take by weighing the 5.65g cross-linked montmorillonite and join in the mixed liquor (5) mechanical agitation 25min.
(7) (6) are placed autoclave 140 ℃ of following thermostatic crystallizations 5 days;
(8) treat that autoclave cools off in air or water after, separation, suction filtration, washing 70 ℃ of dryings, and obtain containing the composite of β zeolite grain in 600 ℃ of roasting 5h.
Embodiment 8
Get the 0.2mol/L AlCl of 80ml
3Solution under constantly stirring, slowly drips the Na2CO3 solution (dripping the about 200mL/h of speed) of 0.1M, to Na
2CO
3With AlCl
3Mol ratio be 1.4 (calculated values), after dropwising, continue to stir 1h, at 120 ℃ of high temperature ageing 4.5h, standby then.
Get the 0.2mol/L FeCl3 of 60ml, the 0.2mol/L CrCl of 40ml
3After solution mixes, with the Na of 0.1M
2CO
3Titration under agitation slowly splashes in the hydroxy Al solution that has prepared to pH=4, drips off the back and continues to stir 1h, and room temperature is placed aging two weeks, promptly gets hydroxyl siderochrome aluminum crosslinker.
The above-mentioned crosslinking agent that makes of 60ml behind 120 ℃ of high temperature ageing 4.5h, is under agitation added respectively in the 3% prepared sodium-based montmorillonite slurries of 30ml, continue to stir 1.5h, in 120 ℃ of aging 2.5h, be washed with distilled water to no Cl then
-Till (AgNO with 1%
3The solution check), 0～150 ℃ dry down, pulverizes standby.
(1) takes by weighing 4.2g potassium chloride respectively and 2.15g sodium chloride joins in the 36g deionized water, be stirred to molten entirely;
(2) measuring concentration is that 30% tetraethyl ammonium hydroxide solution 150ml fully mixes with solution (1);
(3) under agitation the white carbon black of 13.7g is joined in the solution (2) gradually, stir;
(4) take by weighing the 3.71g sodium aluminate and 1.5g NaOH joins in the deionized water, be stirred to molten entirely;
(5) solution (3) is mixed mutually with solution (4), stir 30min to thick;
(6) take by weighing the 5.65g cross-linked montmorillonite and join in the mixed liquor (5) mechanical agitation 25min.
(7) (6) are placed autoclave 140 ℃ of following thermostatic crystallizations 5 days;
(8) treat that autoclave cools off in air or water after, separation, suction filtration, washing 70 ℃ of dryings, and obtain containing the composite of β zeolite grain in 600 ℃ of roasting 5h.
Embodiment 9
Getting molar concentration is 0.2mol/L FeCl
3, 0.2mol/L CrCl
3, 0.2mol/L AlCl
3The solution equal proportion is got above-mentioned solution 80ml after evenly mixing, and under agitation slowly splashes into the 0.15mol/L Na of 240ml
2CO
3, drip off the back and continue to stir 1h, in two weeks of aged at room temperature, obtain hydroxyl siderochrome aluminum crosslinker.
With the above-mentioned crosslinking agent that makes of 60ml behind 120 ℃ of high temperature ageing 4.5h, under agitation add respectively in the 3% prepared sodium-based montmorillonite slurries of 180ml, continue to stir 1.5h,, be washed with distilled water to (AgNO till the no Cl-with 1% then in 120 ℃ of aging 2.5h
3The solution check), 120 ℃ dry down, pulverizes standby.
(1) takes by weighing 4.2g potassium chloride respectively and 2.15g sodium chloride joins in the 36g deionized water, be stirred to molten entirely;
(2) measuring concentration is that 30% tetraethyl ammonium hydroxide solution 138ml fully mixes with solution (1);
(3) under agitation the white carbon black of 13.7g is joined in the solution (2) gradually, stir;
(4) take by weighing the 3.71g sodium aluminate and 1.62g NaOH joins in the deionized water, be stirred to molten entirely;
(5) solution (3) is mixed mutually with solution (4), stir 30min to thick;
(6) take by weighing the 5.65g cross-linked montmorillonite and join in the mixed liquor (5) mechanical agitation 25min.
(7) (6) are placed autoclave 140 ℃ of following thermostatic crystallizations 4 days;
(8) treat that autoclave cools off in air or water after, separation, suction filtration, washing 70 ℃ of dryings, and obtain containing the composite of β zeolite grain in 600 ℃ of roasting 5h.
Get the acid imvite of 10g, add the 20ml octylame, behind the vigorous stirring 30min, add 60ml TEOS.Stirring reaction 4h under the room temperature.Centrifugation, air drying, 500 ℃ of roasting 4h remove organic matter, obtain porous isomery material.
(1) takes by weighing 4.2g potassium chloride respectively and 2.15g sodium chloride joins in the 36g deionized water, be stirred to molten entirely;
(2) measuring concentration is that 30% tetraethyl ammonium hydroxide solution 138ml fully mixes with solution (1);
(3) under agitation the white carbon black of 13.7g is joined in the solution (2) gradually, stir;
(4) take by weighing the 3.71g sodium aluminate and 1.62g NaOH joins in the deionized water, be stirred to molten entirely;
(5) solution (3) is mixed mutually with solution (4), stir 30min to thick;
(6) take by weighing 5.65g porous isomery material and join in the mixed liquor (5) mechanical agitation 25min.
(7) (6) are placed autoclave 140 ℃ of following thermostatic crystallizations 4 days;
(8) treat that autoclave cools off in air or water after, separation, suction filtration, washing 70 ℃ of dryings, and obtain containing the composite of β zeolite grain in 600 ℃ of roasting 5h.
Imvite/the molecular sieves compound material that obtains by this method not only has the mesopore and the interlamination region characteristic of imvite, and what also have micro porous molecular sieve selects shape, and cracking performance preferably.Resulting product specific area is at 300～700m
2, pore volume has acid preferably the distribution at 0.3～0.8ml/g, can be used for all kinds of catalyst and adsorbent, especially the catalyst of hydrogenation aspect.
Claims (10)
1. the preparation method of an imvite/molecular sieves compound material comprises the steps:
(1) with silicon source, aluminium source, NaOH, template agent and water according to (4～100) SiO
2: Al
2O
3: (2～180) Na
2O: 20R
1: (160～1000) H
2The mole proportioning of O is mixed under room temperature and stirring condition, continues to be stirred to reaction mass and mixes, and obtains the gel that the leucosol shape has better flowability, R in the formula
1Be the template agent;
(2) with the molecular sieve gel of imvite and step (1) according to (1～8): the weight ratio of (2～9) mixes, and carries out crystallization then, and makes described imvite/molecular sieves compound material through Separation of Solid and Liquid, washing and drying;
Described imvite is that natural montmorillonite obtains through organically-modified or the modification of porous isomery; Wherein organically-modifiedly be: with imvite, quaternary ammonium salt and deionized water with weight ratio 1: (0.1～0.6): (5～20) make slurries, ℃ following the stirring 30 minutes～24 hours in room temperature～95, separate, washing, ℃ following drying in room temperature～150, organic ammonium salt is selected from softex kw and OTAC;
Porous isomery method of modifying: get organo montmorillonite, add organic amine, behind the vigorous stirring reaction 30min, add TEOS, stirring reaction 2～8h under the room temperature separates, drying, and 300～700 ℃ of roasting 3～8h remove organic matter, obtain porous isomery material; Wherein imvite: organic amine: the TEOS mol ratio is 1: 50: (50～200).
2. preparation method according to claim 1 is characterized in that the mole proportioning of described molecular sieve gel is: (4～100) SiO
2: Al
2O
3: (2～180) Na
2O: (2～200) K
2O: 20R
1: (160～1000) H
2O.
3. preparation method according to claim 1 is characterized in that adding the mole proportioning and is (12～150) SiO in described molecular sieve gel
2: (0～1) Al
2O
3: (0～40) R
2: (10～80) Na
2O: (160～1000) H
2The directed agents of O, R in the formula
2Be the template agent.
4. preparation method according to claim 3, the addition that it is characterized in that described directed agents is 2%～10% of a molecular sieve gel volume.
5. preparation method according to claim 1 is characterized in that described crystallization condition is: 90 ℃～160 ℃ of crystallization temperatures, crystallization time 1～8 day.
6. preparation method according to claim 1 is characterized in that, described Separation of Solid and Liquid adopts centrifugation or suction filtration to separate, and described washing is meant and spends deionised water 1～6 time that described drying is dry 10h～30h under 50 ℃～180 ℃.
7. preparation method according to claim 1 is characterized in that described silicon source is white carbon, Ludox, waterglass or silicic acid, and described aluminium source is aluminum sulfate, aluminium chloride or sodium aluminate, described template agent R
1Be tetraethyl ammonium hydroxide, tetraethylammonium bromide, TPAOH, 4-propyl bromide or softex kw.
8. preparation method according to claim 3 is characterized in that described directed agents prepares by the following method: with silicon source, aluminium source, template agent, NaOH and water according to (12～150) SiO
2: (0～1) Al
2O
3: (0～40) R
2: (10～80) Na
2O: (160～1000) H
2The mole proportioning of O is mixed under room temperature and stirring condition, continues to stir to mix until reaction mass, changes over to then in the synthesis reactor, makes directed agents down in aging 1～3 day at 30 ℃～150 ℃.
9. preparation method according to claim 8 is characterized in that described aluminium source is aluminum sulfate, aluminium chloride, sodium aluminate, and described silicon source is waterglass, Ludox, white carbon black or silicic acid, described template agent R
2Be tetraethyl ammonium hydroxide, tetraethylammonium bromide, TPAOH or 4-propyl bromide.
10. preparation method according to claim 1 is characterized in that described molecular screening is from ZSM-5 molecular sieve, beta-molecular sieve or MCM-41 molecular sieve.
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