CN103204515A - Preparation method for high-dispersion zeolite molecular sieves - Google Patents

Preparation method for high-dispersion zeolite molecular sieves Download PDF

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CN103204515A
CN103204515A CN2013100810076A CN201310081007A CN103204515A CN 103204515 A CN103204515 A CN 103204515A CN 2013100810076 A CN2013100810076 A CN 2013100810076A CN 201310081007 A CN201310081007 A CN 201310081007A CN 103204515 A CN103204515 A CN 103204515A
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molecular sieve
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zeolite
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CN103204515B (en
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郭洪臣
刘春燕
钱吉
郑步梅
李海龙
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Dalian University of Technology
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  • Silicates, Zeolites, And Molecular Sieves (AREA)

Abstract

The invention relates to a preparation method for high-dispersion zeolite molecular sieves. The preparation method includes preparing gel and performing hydrothermal crystallization on nanometer molecular sieves, pressing organochlorosilane in a crystallization kettle filled with crystallized matter through pressurization of nitrogen under the condition of stirring when the crystallization of the molecular sieves is finished so as to enable the organochlorosilane to fully contact and react with the surfaces of the molecular sieves, and collecting products after reaction of the organochlorosilane and the crystallized matter is finished. The mass ratio of the added organochlorosilane R is R/SIO2=0.01-2, the reaction time is no more than 100 hours, and the reaction temperature ranges from room temperature to 200 DEG C. The organochlorosilane is added when the crystallization of the molecular sieves is finished, and the condensation reaction of the organochlorosilane and the surface hydroxyl groups of the molecular sieves is utilized to block agglomeration among the molecular sieves, so that the defect that prior methods affect crystallization kinetics of the molecular sieves is overcome. Obtained molecular sieve products have good dispersibility and large specific surface areas, and are easy to filter.

Description

A kind of preparation method of high dispersive zeolite molecular sieve
Technical field
The invention belongs to the zeolite molecular sieve preparation field, relate to a kind of method that is conducive to prepare the little crystal grain zeolite molecular sieve of high dispersive.
Background technology
Zeolite molecular sieve is the most important component in the inorganic poromerics, is can be at the crystalline material of molecular level screening material, and its skeleton is by TO 4Share the multidimensional four syndetons composition that the summit forms between the tetrahedron, wherein T refers to Si, Al or other heteroatoms.Zeolite molecular sieve is because regular pore passage structure, unique ion exchangeable, select the shape adsorptivity, form and the easy modulation of character, the high reactivity of numerous small molecules catalyzed reactions and selectivity etc., it is widely used, especially the research fields such as catalysis, absorption and ion-exchange in refining of petroleum, petrochemical complex and fine chemistry industry and the daily-use chemical industry in many fields such as commercial run and high-tech material.It wherein is the MFI family zeolite molecular sieve of representative with ZSM-5 and ZSM-11, ZSM-8, TS-1, be the MWW family of representative and be the BEA family of representative with Beta with MCM-22 and MCM-49, because unique pore passage structure and good catalytic performance become the very important catalytic material of several classes.
(1) the ZSM-5 zeolite (USP 3702886) of U.S. Mobil oil company invention becomes a kind of very important shape selective catalysis material with its unique pore passage structure and good catalytic performance.Famous technology with the exploitation of ZSM-5 zeolite has: the Mobil intermediate distillates takes off cured technology (MDDW), lubricating oil takes off cured technology (MLDW), catalytic reforming process, the selectoforming of gasoline and M-reforming process, by the Cyclar technology (LPG BTX) of the synthetic aromatic hydrocarbons of light hydrocarbons, Mobil-Badger synthesizing ethyl benzene technology, toluene gasifying process (MTDP), xylene isomerization process (MVPI), preparing gasoline by methanol technology (MTG) and p-methyl-ethylbenzene synthesis technique (PET).
(2) (GB2071071A is with the Ti atom Al atom among the ZSM-5 to be substituted USP4410501), thereby has the selective oxidation active centre, and has the new catalytic material of ZSM-5 shape selective catalysis performance titanium-silicon molecular sieve TS-1.TS-1 has the katalysis of not replacing in a series of low temperature selective oxidation reactions that participated in by rare hydrogen peroxide such as epoxidation of propylene and phenol hydroxylation.What is particularly worth mentioning is that: the application of TS-1 in epoxidation of propylene, be expected to thoroughly break away from the contamination type production model that has technology now, huge industrial application potentiality are arranged.
(3) Beta zeolite (US 3308069) is a kind of supersiliceous zeolite with three-dimensional twelve-ring intersection pore passage structure, using in refining of petroleum such as hydrocracking, hysomer, dewaxing, alkylating aromatic hydrocarbon and olefin hydration and petrochemical process because its particular structure and good thermostability, hydrothermal stability are used as catalyzer, is a kind of important industrial zeolite molecular sieve.
(4) MCM-22 molecular sieve (US 4954325) is the layer molecule sieve with MWW topological framework, synthetic under hexamethylene imine template system first in nineteen ninety by Mobil company, it has two and overlaps independently pore canal system: interlayer ten-ring (the twelve-ring hole (0.71 * 0.71 * 1.82nm) of the ten-ring sinusoidal pore canal system of two dimension and crystal outside surface in 0.40 * 0.59nm) pore canal system that is connected, the layer.Afterwards, people had synthesized MCM-49, MCM-56, MCM-36, ITQ-1 and ITQ-2 equimolecular sieve again under hexamethylene imine template system, and found that they are the layer molecule sieve with MWW structure equally.Therefore, people are referred to as the MCM-22 family molecular sieves with these molecular sieves.The MCM-22 family molecular sieves has broad application prospects in reactions such as alkylation, aromizing, catalytic cracking and isomerization because of its unique pore passage structure.
These a few class zeolite catalysis materials belong to micro-pore zeolite, and the duct size is less, and there is bigger diffusional resistance in macromole in zeolite pore, so limited its application in the bulky molecular catalysis reaction to a certain extent.At present, solution to this problem mainly contains two kinds: a kind ofly be to introduce meso-hole structure in the zeolite micropore structure or be micropore with the crystallization of pore wall of mesoporous material, be formed with the transmission path that is beneficial to the macromolecular cpd diffusion; Another kind method is exactly synthetic superfine molecular sieves with nanoscale.Material with zeolite Jie micropore composite structure can improve the diffusion of product, has remedied the deficiency of micro porous molecular sieve, and for macromolecular reaction provides favourable sterie configuration, problem exists always but the more weak and hydrothermal stability of its acidity is relatively low etc.And the crystal size of molecular sieve is reduced to nano level from micron order, performances such as its mass transfer, absorption and catalysis all can change.With micron order zeolite facies ratio, nano zeolite has the intracrystalline rate of diffusion of bigger outer surface area and Geng Gao, the duct is short, and there is a large amount of intracrystalline pores, improve the utilization ratio of catalyzer, strengthening the macromole conversion capability, reducing deep reaction, improving aspects such as selectivity and all show more superior performance, in some hydro carbons catalytic conversion reactions, showing better active, selectivity and strong anti-coking deactivation ability.
Following patent and document have been introduced the application of little crystal grain (nanometer) molecular sieve.
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Because nano zeolite all shows huge application potential in numerous reactions, make and produce the focus that nano zeolite becomes domestic and international research always.Existing a lot of about the synthetic report of this respect at present.
The following discloses patent has been introduced the preparation method of ZSM-5 molecular sieve with small crystal grains.
Chinese patent application number: 201210141312.5(2012-05-09) disclosed a kind of high dispersive submicron ZSM-5 synthesis method of zeolite molecular sieve.Its technical characterictic is, under the system of no template, add the method for alkali by add segmentation in pre-crystallization liquid and the hydro-thermal building-up process in crystallization mother liquor, syntheticly obtained the ZSM-5 zeolite molecular sieve that size distribution mainly concentrates on 400～500nm.This method is to utilize pre-crystallization liquid and segmentation to add the method synthesizing small-grain zeolite molecular sieve of alkali.
Chinese patent application number: 201010261877.8(2010-08-23) disclosed a kind of preparation method of small crystal grain molecular sieve.Its technical characterictic is, makes synthetic good big crystal grain molecular screen primary material enter disintegrating apparatus, carries out the physics fragmentation, after the grading, obtains small crystal grain molecular sieve.
Chinese patent application number: 201010261597.7(2010-08-23) disclosed a kind of small-grain ZSM-5 prepare zeolite method.Its technical characterictic is, the sial bead of 10～200 μ m that spray drying forming is obtained mix with template, mineral alkali, template and water obtain raw mix after, the directed agents that adds raw mix weight 0.5～20% mixes the back at 100～200 ℃ of crystallization 10～360h, and obtaining grain-size is the ZSM-5 zeolite of 200～1000nm.This method is to utilize directed agents and prefabricated sial bead synthesizing small-grain zeolite molecular sieve.
Chinese patent application number: 201010261929.1(2010-08-23) disclosed a kind of small-grain ZSM-5 synthesis method of zeolite molecular sieve.Its technical characterictic is, the directed agents that in spray slurry, adds slurry weight 0.5～20%, be that 20～50% the spray-dried moulding of slurries obtains 10～200 μ m sial beads with solid content, again sial bead and template, mineral alkali and water are mixed and obtain raw mix, through hydrothermal crystallizing, obtaining grain-size is 200～1000nm small-grain ZSM-5 zeolite molecular sieve.This method also is to utilize directed agents and prefabricated sial bead synthesizing small-grain zeolite molecular sieve.
Chinese patent application number: 200910248667.2(2009-12-23) disclosed a kind of synthetic method of fine grain rare earth ZSM-5/ZSM-11 cocrystallization zeolite.Its technical characterictic is, with silicon source, aluminium source, mineral alkali (or mineral acid), 1, the salt of 6-hexanediamine, rare earth element, additive and deionized water are synthesis material, handle 4～30h through 60～98 ℃ of low temperature agings earlier, again under 160～195 ℃, through hydrothermal crystallizing 15～70h, obtain mean particle size less than the fine grain rare earth ZSM-5/ZSM-11 cocrystallization zeolite of 500nm.This method mainly utilizes the low temperature aging measure to reduce the grain fineness number of molecular sieve.
Chinese patent application number: 200810043970.4(2008-11-21) disclosed a kind of synthetic method of ZSM-5 molecular sieve with small crystal grains.Its technical characterictic is, is template with the 4-propyl bromide, after aged at room temperature, obtains SiO by the two-stage method crystallization again 2/ Al 2O 3Be not less than 200, particle diameter is less than the ZSM-5 zeolite molecular sieve of 300nm.This method is mainly utilized low temperature aging measure increase nucleus, is reduced the grain fineness number of molecular sieve.
Chinese patent application number: 200710087075.8(2007-03-19) disclosed a kind of synthetic method of fine grain strong acid type ZSM-5 molecular sieve.Its technical characterictic is do not use any organic formwork agent, and the pre-treatment of introducing ultrasonic wave again through hydrothermal crystallizing, to obtain ZSM-5 molecular sieve with small crystal grains.This method utilizes ultrasonication to control the grain fineness number of molecular sieve.
Chinese patent application number: 200610118536.9(2006-11-21) disclosed a kind of preparation method of small-grain ZSM-5/mordenite composite molecular sieve.Its technical characterictic is, adds ZSM-5 and the mordenite crystal seed that contains the suitable silicon aluminum ratio in sieve synthesis procedure, and the pH value of regulating synthesized gel rubber is 9～14, through hydrothermal crystallizing, obtains the ZSM-5/ mordenite composite molecular sieve.Wherein used crystal seed is that silica alumina ratio is 20～100, and particle diameter is the amorphous article of 10～100nm, and this method reduces ZSM-5/ mordenite composite molecular sieve grain fineness number by the control to crystal seed and pH of latex gel value.
Chinese patent application number: 200610097462.5(2006-11-10) disclosed a kind of method of synthetic ZSM-5 zeolite.Its technical characterictic is, adopting silicone grease or silane is raw material, and 4-propyl bromide is template, regulate with acid solution silicon source and deionized water mixed solution pH value and stir hydrolysis, the adding crystal seed through hydrothermal crystallizing, obtains the product that grain fineness number is 100～400nm.
Chinese patent application number: 200510028781.6(2005-08-15) disclosed a kind of method for preparing the small-grain ZSM-5 zeolite.Its technical characterictic is, is the silicon source with water glass, silicon sol or white carbon black, and aluminium salt or aluminate are the aluminium source, adds the small amount of seeds directed agents in crystallization forward direction crystallization mother liquor, again through hydrothermal crystallizing, obtains the ZSM-5 zeolite of little crystal grain.This method also is to utilize directed agents method synthesizing small-grain zeolite molecular sieve.
Chinese patent application number: 200510028782.0(2005-08-15) disclosed the small-grain ZSM-5 zeolite synthesis method of crystallization after a kind of first moulding.Its technical characterictic is, adopting with diatomite or white carbon black is main raw material, adds the crystal seed directed agents, and with silicon sol or water glass as the binding agent moulding, handle mutually with organic amine and water vapor gas-solid then and be converted into integrated small-grain ZSM-5.
Chinese patent application number: 200510200328.9(2005-06-14) disclosed a kind of high silica alumina ratio small-grain ZSM-5 synthesis method of zeolite molecular sieve.Its technical characterictic is, Virahol, propyl carbinol, the trimethyl carbinol or isopropylcarbinol tensio-active agent are joined in the aluminum salt solution of acidifying, to be added drop-wise in the aluminum salt solution at leisure by water glass, template, the formed basic solution of crystal seed again, through hydrothermal crystallizing, obtain the small-grain ZSM-5 zeolite molecular sieve again.
Chinese patent application number: 200410048354.X(2004-06-29) disclosed a kind of small-grain ZSM-5 prepare zeolite method.Its technical characterictic is, with SiO 2/ Al 2O 3Mol ratio 20～600, granularity are the aqueous solution of 20～300 purpose alumino silica gel particles and organic formwork agent, through hydrothermal crystallizing, obtain silica alumina ratio and be 15～200, elementary crystal grain particle is the ZSM-5 zeolite of 0.1～0.5 μ m.
Chinese patent application number: 02155482.X(2002-12-16) disclosed a kind of method of fast synthetic strong acid type ZSM-5 zeolite molecular sieve.Its technical characterictic is by a certain percentage directed agents to be made in silicon source and template, aluminium source, mineral acid, deionized water; By a certain percentage silicon source and template, aluminium source, mineral acid, deionized water are configured to crystallization mother liquor again, in mother liquor, add the directed agents that accounts for cumulative volume 5～10%.The gained gel is small-grain ZSM-5 zeolite about 100nm through obtaining crystal grain behind the hydrothermal crystallizing.This method also is to utilize directed agents method synthesizing small-grain zeolite molecular sieve.
Chinese patent application number: 00109593.5(2000-06-28) disclosed a kind of method of directing agent method quickly synthesizing small crystal grain ZSM-5-5 molecular sieve.Its technical characterictic is that with directed agents replacement organic amine template, through hydrothermal crystallizing 65-75h, obtaining median size is the ZSM5 molecular sieve of 0.1 μ m.This method also is to utilize directed agents method synthesizing small-grain zeolite molecular sieve.
Chinese patent application number: 99102700.0(1999-04-21) disclosed the method for a kind of synthetic ZSM-5.Its technical characterictic is, is template with the n-Butyl Amine 99, and water glass, Tai-Ace S 150 and sodium hydroxide are raw material, by the grain-size of using an alkali metal salt to regulate zeolite molecular sieve, obtains ZSM-5 and the ZSM-11 zeolite of 10～500nm.
US Patent No. 19980218191(1998-12-22) disclosed a kind of method of synthetic ZSM-5 zeolite molecular sieve.Its technical characterictic is, is raw material with a kind of amorphous silicon aluminum, and template adopts Tri N-Propyl Amine, adds crystal seed, under 100～200 ℃, through hydrothermal crystallizing, obtains crystal grain less than the ZSM-5 zeolite molecular sieve of 500nm.
Chinese patent application number: 98123933.1(1998-11-07) disclosed a kind of preparation method of small-grain FeZSMS zeolite molecular sieve.Its technical characterictic is that adopting silicon-containing material, inorganic molysite, inorganic sodium, organic amine, mineral acid and deionized water is raw material, through the low-temperature hydrothermal dynamic crystallization, obtains crystal grain less than the hetero-atom molecular-sieve that contains Fe of 1 μ m.
US Patent No. 19920882015(1992-05-13) disclosed the method for a kind of synthetic ZSM-5.Its technical characterictic is, contains the nucleus slurries and raw material carries out mixture with prefabricated, through hydrothermal crystallizing, obtains the ZSM-5 molecular sieve of the about 100～500nm of granularity.
European patent EP 19850110256(1985-08-16) disclosed the method for a kind of synthetic ZSM-5.Its technical characterictic is, with raw mix at 80 ℃ of following pre-treatment 6h, again with the pre-treatment thing with 15% ratio with newly join raw mix under 175 ℃, through hydrothermal crystallizing 8h, obtaining silica alumina ratio is 60, and grain-size is about the ZSM-5 zeolite molecular sieve of 100～300nm.This method also is to utilize directed agents method synthesizing small-grain zeolite molecular sieve.
US Patent No. 19850694536(1985-01-24) disclosed the method for a kind of synthetic ZSM-5.Its technical characterictic is, on the basis of patent US 3702886, in the reaction system that contains a large amount of template, add with tetrapropyl quaternary ammonium salt or the previously prepared amorphous silicon alumina gel of quaternary ammonium hydroxide directed agents, through hydrothermal crystallizing, can obtain the above ZSM-5 molecular sieve of 100nm.
US Patent No. 19830520746(1983-08-05) disclosed the method that a kind of low sodium synthesizes ZSM-5.Its technical characterictic is, adopts alkylamine and alkyl halide composite mould plate agent to substitute quaternary ammonium hydroxide and quaternary ammonium salt, and behind hydrothermal crystallizing, obtaining grain fineness number is the ZSM-5 molecular sieve of 50nm～20 μ m.
US Patent No. 19730330925(1973-02-09) disclosed a kind of method of synthetic ZSM-5 zeolite.Its technical characterictic is that with TPAOH, 4-propyl bromide or both mixtures adopt violent stirring to reach high mass transfer velocity as template, through hydrothermal crystallizing, obtain the ZSM-5 zeolite molecular sieve of 5～100nm on the basis of patent US D3702886.
The following discloses patent has been introduced the preparation method of little crystal grain TS-1 molecular sieve.
Chinese patent application number: 201010552093.0(2010-11-17) disclosed a kind of preparation method of little crystal grain MFI structure titanium silicon molecular sieve.Its technical characterictic is, the little crystal grain MFI structure titanium silicon molecular sieve that synthesizes contains the skeleton organic group, and this organosilicon is at 1213～1278cm of infrared spectra -1There is corresponding absorption peak at the place.
Chinese patent application number: 201010235977.3(2010-07-20) disclosed a kind of in cheap system the method for quickly synthesizing small-crystallite titanium-silicon molecular sieve.Its technical characterictic is, is the silicon source with the silicon sol, and titanium tetrachloride or tetrabutyl titanate are the titanium source, 4-propyl bromide is template, and organic amine is alkali source, and adopts nano level TS-1 mother liquor as crystal seed, through hydrothermal crystallizing, obtain particle size less than the HTS of 1 μ m.This method also is to utilize crystal seed method synthesizing small-grain zeolite molecular sieve.
Chinese patent application number: 200910217756.0(2009-10-26) disclosed a kind of synthetic method of TS-1 molecular sieve.Its technical characterictic is, is the silicon source with the tetraethoxy, and tetrabutyl titanate is the titanium source, and TPAOH is template, and water and Virahol are solvent, H 2O 2Be inorganic additives, through hydrothermal crystallizing, obtain the TS-1 molecular sieve.
Chinese patent application number: 02132325.9(2003-03-12) disclosed a kind of synthetic method of small-crystallite titanium-silicon molecular sieve.Its technical characterictic is, adopt the self-control 4-propyl bromide through the strongly basic anionic resin exchange, concentrate that to obtain TPAOH be template, tetraethoxy is the silicon source, and tetrabutyl titanate is done the titanium source, obtains the HTS that crystal grain is 0.1 μ m behind the hydrothermal crystallizing.
Chinese patent application number: 01145256.0(2001-12-28) disclosed a kind of small-crystallite titanium-silicon molecular sieve Preparation of catalysts method.Its technical characterictic is, adopting the tetraalkyl brometo de amonio is template, and organic amine is alkali source, and silicon sol is the silicon source, and the alcoholic solution of titanium tetrachloride is done the titanium source, and through the alternating temperature hydrothermal crystallizing, obtaining grain size is the HTS of 0.85 μ m * 0.4 μ m * 0.15 μ m.
Chinese patent application number: 99122123.0(2001-05-09) disclosed a kind of synthetic method of small-crystallite titanium-silicon molecular sieve.Its technical characterictic is, the employing TPAOH is template, and tetraethyl orthosilicate is the silicon source, and inorganic titanium salt or organic titanium ester are done the titanium source, joins glue under 0 ℃ by alternating temperature hydrothermal crystallizing repeatedly, obtains crystal grain less than the HTS of 0.3 μ m.
Chinese patent application number: 99107790.3(2000-12-06) disclosed a kind of synthetic method of small-crystallite titanium-silicon molecular sieve.Its technical characterictic is, the employing organic bases is template, and the tetraalkyl silicon ester is the silicon source, and the alcoholic solution of titanium tetrachloride is done the titanium source, and crystallization in microwave radiation field obtains the HTS that grain size is 0.10～0.25 μ m.
US Patent No. 19950380724(1995-01-30) disclosed a kind of method of the TS-1 of preparation molecular sieve.Its technical characterictic is, positive silicon ester and the TPAOH aqueous solution are packed in the container, replenishes a spot of water, mixture is warming up to 80 ℃ again, remove pure 2h after, again mixture is cooled to 35 ℃ after, adding TiF 4, stirred 5 minutes, through hydrothermal crystallizing, obtain little crystal grain TS-1 molecular sieve.
The following discloses patent has been introduced the preparation method of little crystal grain MCM-22 molecular sieve.
Chinese patent application number: 201010221287.2(2010-07-07) disclosed a kind of preparation method of little crystal grain MCM-22 molecular sieve.Its technical characterictic is, adopts the mode that leaves standstill to separate the little crystal grain MCM-22 molecular sieve mixture after the crystallization, gets the upper strata suspension liquid as the raw material of synthesizing small-grain MCM-22 molecular sieve.
Chinese patent application number: 02132508.1(2002-06-28) disclosed a kind of preparation method of nano level MCM-22 zeolite molecular sieve.Its technical characterictic is, adopts patent US 4954325 used template and other raw material, and the water yield, alkali number and crystallization temperature by in the control raw mix through hydrothermal crystallizing, obtain the nano-grade MCM-22 molecular sieve that crystal diameter is lower than 900nm.This patent is mainly utilized under the condition of low wash water, makes gel keep hypersaturated state in crystallization process, is conducive to a large amount of formation of nucleus, and under higher temperature, is conducive to the growth of crystal, obtains the MCM-22 zeolite molecular sieve of nanometer at short notice.
The following discloses patent has been introduced the preparation method of small-crystallite beta molecular sieve.
Chinese patent application number: 201110294304.X(2011-10-06) disclosed a kind of synthetic method of Beta zeolite.Its technical characterictic is, at first the Beta zeolite seed crystal carried out high-temperature water thermal treatment, Beta zeolite seed crystal dip treating in acid solution of under agitation hydrothermal treatment consists being crossed then, and the crystal seed after the acid treatment washes with water to neutrality; At last, silicon source, aluminium source, sodium source, tetraethylammonium cation source and water are mixed with even gel, add pretreated Beta zeolite seed crystal then, the even gel that obtains obtains the Beta zeolite through hydrothermal crystallizing.
Chinese patent application number: 201110008767.5(2011-01-17) disclosed a kind of synthetic method of Beta zeolite.Its technical characterictic is, make crystal seed by the Beta zeolite powder that adds cryodrying, and when the preparation gel, crystal seed is carried out high speed shear emulsification and disperse, given full play to the structure-directing effect of Beta zeolite seed crystal, thereby widened the crystal seed scope that is suitable for, can be under low template consumption, in the wideer silica alumina ratio scope, through hydrothermal crystallizing, obtain the good Beta zeolite product of degree of crystallinity.
Chinese patent application number: 201010552179.3(2010-11-17) disclosed a kind of synthetic method of nanometer Beta zeolite.Its technical characterictic is with the mixed reaction mixture that gets of silicon source, aluminium source, alkali MOH, composite mould plate agent RN and water, through hydrothermal crystallizing, to obtain crystallization liquid; Wherein said composite mould plate agent RN is R 1And R 2Mixture, R 1Be selected from least a in tetraethyl ammonium hydroxide and triethylamine or the diethylamine, R 2Be selected from the tetraethyl-ammonium halide, R 1With R 2Mol ratio be 0.05～2.0; Add acidic cpd again in crystallization liquid, regulate crystallization liquid pH value less than 11, obtain the Beta zeolite of 10～100nm after separation, washing, drying, wherein said acidic cpd is selected from least a in mineral acid, organic acid or the ammonium chloride.
Chinese patent application number: 200910130913.4(2009-04-17) disclosed a kind of synthetic method of full-silicon beta zeolite with small crystal grains molecular sieve.Its technical characterictic is, silicon source, fluoride sources, tetraethyl ammonium ion source and deionized water are mixed by specific composition, through hydrothermal crystallizing, obtains crystal grain less than the full-silicon beta zeolite molecular sieve of 5 μ m.
Chinese patent application number: 200810228359.9(2008-10-28) disclosed a kind of method with the synthetic small-particle beta-zeolite molecular sieve of polynite.Its technical characterictic is, activation treatment is carried out in polynite, and the polynite with activation treatment is that raw material provides all or part of aluminium source again, through hydrothermal crystallizing, obtains the small-particle beta-zeolite molecular sieve.This method is by synthetic beta-molecular sieve being grown in closely the surface of polynite, form the structure of similar nucleocapsid, thereby improve catalyzed reaction efficient to shorten reactant and product molecule in the path of zeolite molecular sieve internal diffusion, but the gained zeolite molecular sieve is coacervate.
Chinese patent application number: 200810152303.X(2008-10-10) disclosed a kind of preparation method of nanometer high specific surface Beta zeolite.Its technical characterictic is, the tetraethyl-ammonium halide, and tetraethyl ammonium hydroxide, mixed templates mixes, silicon source, an amount of crystal seed, alkali metal halide, organic solvent through hydrothermal crystallizing, obtains the nano level Beta zeolite than high-ratio surface after mixing.This patent is introduced organic solvents such as alkali metal chloride, methyl alcohol in synthetic mixture.
Chinese patent application number: 200710064979.9(2007-03-30) disclosed a kind of nano aluminum-rich Beta prepare zeolite method.Its technical characterictic is, the silicon source and the hydrolytic reagent that are soluble in alcohols are mixed into glue, aging drying obtains silica gel, mix with hydrated aluminum oxide, acid again and obtain the mixed glue of sial, aging back and tetraethylammonium cation compound, contain the F-ionic compound and water mixes, through hydrothermal crystallizing, obtain low silica-alumina ratio, particle diameter is less than the Beta zeolite of 100nm.
The following discloses document also relates to the preparation method of small-grain ZSM-5 zeolite molecular sieve.
Open source literature SCI, 33(2012) 453～457 methods of having introduced a kind of synthetic Mn-ZSM-5 nano molecular sieve.Be characterized in, in classical formalism, synthesized particle diameter and about 80nm, contained the manganese hetero-atom molecular-sieve, but the method for dispersing molecule sieve is not provided.
Open source literature Catalysis Today, 116(2006) 82～87 methods of having introduced a kind of synthetic ZSM-5.Be characterized in, in the gelling system of white carbon black and sodium metaaluminate, respectively with Tetramethylammonium hydroxide, tetraethyl-hydrogenation ammonium, TPAOH, TBAH is template, under 230 ℃, through hydrothermal crystallizing, obtain 159.9nm, 76.3nm, the ZSM-5 zeolite of 55.8nm and 87.2nm, this method is not added other organism.
Open source literature petrochemical complex Journal of Chinese Universities, 18(2005) 20～23 methods of having introduced a kind of synthetic ZSM-5.Be characterized in, aluminum isopropylate and TPAOH solution in certain proportion are mixed, clarify fully with magnetic stirrer to solution.Above-mentioned settled solution is joined in a certain amount of silica gel, until the silica gel complete wetting.Wetting silica gel is completely added in the crystallizing kettle, through hydrothermal crystallizing, obtain the ZSM-5 zeolite of 100nm.
Open source literature Materials Letters, 59(2005) 3827-3430 has introduced the method for a kind of synthetic ZSM-5.Being characterized in, under the condition of not using organic formwork agent, is raw material with silicon sol, sodium metaaluminate and sodium hydroxide, and proportioning raw materials is 12Na 2O:100SiO 2: 2Al 2O 3: 2500H 2O.Aging 12h at normal temperatures, under 180 ℃, through hydrothermal crystallizing, obtaining with the grain-size is the ZSM-5 zeolite coacervate that 15nm forms again.
Open source literature petrochemical complex Journal of Chinese Universities, 18(2005) 17～19 methods of having introduced a kind of synthetic ZSM-5.Being characterized in, adopting mesoporous carbon to receive the material pipe for inertial base, is raw material with tetraethoxy, n-Butyl Amine 99, the vitriol oil, sodium hydroxide, dehydrated alcohol.Prepare the nano-ZSM-5 molecular sieve that mean grain size is 27nm by restriceted envelope size method.
Open source literature Microporous Mesoporous Materials, 75(2004) 41-49 has introduced the method for a kind of synthetic ZSM-5.Be characterized in that employing TPAOH is template, TEOS is raw material, sec.-propyl aluminium be the aluminium source under 70～90 ℃ of low temperature, through hydrothermal crystallizing, obtain the ZSM-5 zeolite coacervate of forming with 10～20nm.
Open source literature Langmuir, 20(2004) 8301-8306 has introduced the method for a kind of synthetic ZSM-5.Be characterized in, adopt the clear liquid method under 165 ℃, through hydrothermal crystallizing 120h, obtained the small-grain ZSM-5 zeolite coacervate of 100～600nm.
Open source literature Microporous Mesoporous Materials, 57(2003) 83-92 has introduced a kind of method based on the synthetic ZSM-5 zeolite molecular sieve of two-step approach.Be characterized in, under the condition that does not add the aluminium source, at first synthetic total silicon zeolite (silicalile-1).Be that crystal seed, Tai-Ace S 150 are that aluminium source, silicon oxide are that silicon source, TPAOH are template with the total silicon zeolite, adopt the synthetic method of clear liquid, 80 ℃ of following normal pressures, backflow, synthesizing grain-size is the ZSM-5 zeolite molecular sieve of 100～300nm.
Open source literature Chem Mater, 15(2003) 1664-1668 has introduced the synthetic method of a kind of ZSM-5.Be characterized in, after the mixing of raw materials such as aluminum isopropylate, tetraethyl silicate, water, TPAOH and ethanol, be impregnated on the gluey charcoal template, again under 180 ℃, through hydrothermal crystallizing 48h, obtaining the homogeneous grain-size is the ZSM-5 zeolite molecular sieve of 13nm, 22nm, 42nm and 90nm.
Open source literature Microporous Mesoporous Materials, 39(2000) 135-147 has introduced the synthetic method of a kind of ZSM-5.Being characterized in, is raw material with TEOS and aluminum isopropylate, and TPAOH is that template adopts no sodium clear liquid method to synthesize the ZSM-5 zeolite molecular sieve that elementary crystal grain is 10～100nm under higher basicity.
Open source literature Zeolites, 15(1995) 611-619 has introduced the method for the synthetic ZSM-5 zeolite of a kind of clear liquid method.Be characterized in, under certain condition, ammoniacal liquor and Tai-Ace S 150, TPAOH are prepared tetrapropyl aluminium, make tetraethyl silicate hydrolysis 10～24h in the TPAOH aqueous solution then, again with the preparation tetrapropyl aluminium under strong stirring, join in the hydrolyzed solution of tetraethyl orthosilicate, mixed clear liquid refluxes down at 98 ℃, and obtaining grain-size is the nano-ZSM-5 zeolite molecular sieve of 130～230nm.
Open source literature Zeolites, 14(1994) 643-649 has introduced the synthetic method of a kind of ZSM-5.Being characterized in, is that silicon source, 4-propyl bromide are that template, sodium hydroxide are that alkali source, aluminum nitrate are the aluminium source with silicon sol or the silicon that obtains from GEOTHERMAL WATER, under 160 ℃, through dynamic hydrothermal crystallizing, obtains the ZSM-5 zeolite aggregate of 30～50nm.
The open source literature refining of petroleum, 12(1983) 744-748 has introduced the synthetic method of a kind of ZSM-5.Be characterized in, by adding inorganic salt modulation zeolite particle diameter, discover that the content that increases NaCl can make its crystal grain be decreased to about 70nm.
Open source literature chemistry journal, 12(1978) 85-87 has introduced the synthetic method of a kind of ZSM-5.Be characterized in, must add NaCl when synthetic, and make NaCl/A1 2O 3Scope 30～60, the too high or too low small-grain ZSM-5 zeolite that all can not get utilizes the ZSM-5 zeolite grain of this method preparation less than 100nm.
Open source literature Journal of the Indian chemical society, 83(2006) 686-691 has introduced a kind of method of synthetic ZSM-5 zeolite molecular sieve.Being characterized in, is template with the quadrol, synthesizes the spherical ZSM-5 zeolite molecular sieve that crystal grain is about 500nm.
The following discloses document also relates to the preparation method of little crystal grain TS-1.
Open source literature Catalysis today, 158(2010) 510-514 has introduced a kind of method of synthetic TS-1 molecular sieve.Be characterized in, use tetraethyl orthosilicate and tetrabutyl titanate respectively as silicon source and titanium source, TPAOH is used three kinds of method dissolving tetrabutyl titanates respectively: 1. make solvent with ethanol, and keep always as template in crystallization process; 2. make solvent with Virahol, in crystallization process, keep always; 3. make solvent with Virahol, but before crystallization, remove alcohol.This method can access the TS-1 zeolite molecular sieve of little crystal grain.
The following discloses document also relates to the preparation method of MCM-22 zeolite molecular sieve.
The open source literature chemical research, 2009,20(1): introduced a kind of method of utilizing sucrose to prepare meso-porous carbon molecular sieve among the 24-28.Be characterized in, at first adopt the vitriol oil that the sucrose carbonization of dewatering is prepared into carbon source, as template, prepare the bigger meso-porous carbon molecular sieve of specific surface area and pore volume with SBA-15.
Open source literature Microporous and Mesoporous Materials has introduced a kind of synthetic method of MCM-22 molecular sieve among 2009, the 118:1-10.Being characterized in, is that silicon source, sodium aluminate are the aluminium source with silicon-dioxide, and hexamethylene imine is template, through the hydro-thermal dynamic crystallization, obtains silica alumina ratio and is respectively 9,21,30,46 MCM-22 molecular sieve.
The open source literature chemical engineer, 2009,163(4): the synthetic method of having introduced a kind of MCM-22 molecular sieve among the 18-19.Be characterized in that adopting silicon sol and sodium metaaluminate is silicon source and aluminium source, is template with hexamethylene imine and piperazine diamine, through the hydro-thermal dynamic crystallization, obtains the MCM-22 molecular sieve.
Open source literature catalysis journal, 2006,27(7): the method for having introduced the synthetic MCM-22 molecular sieve of a kind of different silica sources among the 585-590.Be characterized in that as the silicon source, intending pellicular water aluminium masonry is the aluminium source with industrial columns layer silica gel, white carbon black or silicon sol, hexamethylene imine through hydrothermal crystallizing, obtains the MCM-22 molecular sieve as template.This method has promoted the synthetic of MCM-22 molecular sieve by aging to the silica-alumina gel ultrasonic wave, has shortened the crystallization time of MCM-22 molecular sieve, but has enlarged synthesizing Si-Al than scope, has changed the pattern of MCM-22 molecular sieve.
Open source literature catalysis journal, 2005,26(10): the method for having introduced a kind of synthetic MCM-22 molecular sieve among the 851-854.Being characterized in, is the silicon source with the solid silicone, and sodium aluminate is the aluminium source, and hexamethylene imine and hexahydroaniline diamine are template, through the hydro-thermal dynamic crystallization, obtains the MCM-22 molecular sieve.This method utilizes hexahydroaniline to the stabilization of skeleton, has improved the degree of crystallinity of MCM-22 molecular sieve.
Wherein method therefor comprises: gel is aging, ultrasonic pretreatment, prefabricated directed agents, various each high dispersive silicon source, special attachments matrix, post-modification, multistage intensification crystallization, dampening and the special salt of introducing or fluorochemical etc., adds special organism but do not relate to.
The following discloses patent has been introduced and added organic method in the preparation process of little crystal grain MCM-22 molecular sieve.
Chinese patent application number: 201010264235.3(2010-08-24) disclosed a kind of method of synthesizing small-grain MCM-22 zeolite molecular sieve.Its technical characterictic is, silicon source, aluminium source, alkali source, water, lignin salt's compounds and template hexamethylene imine are mixed, through hydrothermal crystallizing, obtain the MCM-22 zeolite molecular sieve of little crystal grain, and prepared molecular sieve particle diameter is 100～500nm, and thickness is 20～50nm.The lignin salt's compounds that adopts in this method mainly is xylogen sodium sulfate, xylogen vitriolate of tartar, sodium lignosulfonate, lignosulfonic acid potassium etc.Lignin salt is a kind of anion surfactant, and xylogen is a kind of complicated phenol polymer that is formed by alcohol monomer.
Chinese patent application number: 200510025147.7(2005-04-18) disclosed a kind of synthetic method of MCM-22 molecular sieve.Its technical characterictic is that adopting hexamethylene imine and piperidines is mixed templates, regulates the composition of template, synthetic through hydro-thermal, can control the grain size of MCM-22 molecular sieve.Wherein be that the synthetic zeolite crystal of template is bigger with the hexamethylene imine, along with the increase of piperidines amount, the crystal grain of molecular sieve can reduce gradually.
Chinese patent application number: 200410043273.0(2004-05-17) disclosed a kind of preparation method of little crystal grain MCM-22 zeolite molecular sieve.Its technical characterictic is, adopt hexanolactam shortening product directly as template, and in reaction gel, add organic additives such as Sodium dodecylbenzene sulfonate, polyethylene glycols tensio-active agent, through hydrothermal crystallizing, obtain particle diameter less than 600nm, the thickness stratiform MCM-22 zeolite molecular sieve less than 100nm.
The following discloses patent has been introduced and added organic method in the preparation process of β small crystal grain molecular sieve.
Chinese patent application number: 200810204229.1(2008-12-09) disclosed a kind of preparation method of beta zeolite in small crystal grain molecular sieve.Its technical characterictic is that the aqueous precursor gel that will contain secondary structure unit of beta zeolite joins as synthesis material in the mixing solutions that contains alcohol, tensio-active agent, through hydrothermal crystallizing, obtains little crystal grain zeolite molecules.Used alcohol is liquid alcohols such as propyl carbinol, isopropylcarbinol, hexanol in this method, and used tensio-active agent is cetyl trimethylammonium bromide cationoid tensio-active agent.
Chinese patent application number: 00107486.5(2000-05-19) disclosed a kind of synthetic method of beta zeolite in small crystal grain molecular sieve.Its technical characterictic is, with aluminium source, tetraethylammonium cation and the alkali source working solution that is made into soluble in water, be that 20～300 purpose silica gel particles mix mutually with working solution again with granularity, and add a kind of organic additive, through hydrothermal crystallizing, obtain the beta zeolite in small crystal grain molecular sieve.Wherein organic additive is polyol-based non-ionic surfactant, polyether class lubricating oil or their mixture.This method is by adding the surface energy that organic additive reduces raw material template to be accelerated silica gel particle surface " nibbling ", and reduces the viscosity of gel, accelerates nucleus growth, reduces grain size.
The following discloses patent has been introduced and added organic method in the preparation process of other small crystal grain molecular sieve.
Chinese patent application number: 200710304470.7(2007-12-28) disclosed a kind of synthetic method of small crystal grain NaY molecular sieve.Its technical characterictic is Al in introducing and the gel in synthesized gel rubber or crystallization process 2O 3Weight ratio be 0.1-3: 1 chitin and or oligosaccharides.This method be by add chitin and or oligosaccharides made big crystal grain (200～800nm), be that to synthesize silica alumina ratio be 5.5 small crystal grain NaY molecular sieve for 5 system at silica alumina ratio; Chitin and or joining day of oligosaccharides can be synthetic in or in the crystallization process.And adding fashionablely in the crystallization process, the preferred joining day is after the crystallization 8-16 hour, but crystallization time must not be less than 10 hours after introducing additive.
Chinese patent application number: 200480034919.7(2004-10-29) disclosed the preparation method of a kind of little crystal grain SSZ-32.Its technical characterictic is that this patent is with reference to the method for patents such as US 5252527, through hydrothermal crystallizing, obtains the small crystal grain molecular sieve product.Wherein add N, N '-di-isopropyl imidazolium hydroxide or N-methyl-N '-isopropylimdazole oxyhydroxide and alkylamine play template and fill the effect of duct rock steady structure.
Chinese patent application number: 200410077908.9(2004-09-17) disclosed a kind of preparation method of ZSM-35 molecular sieve.Its technical characterictic is, silicon source, aluminium source, alkali source, hexahydroaniline, organic additive and deionized water are prepared into gel, under 140～190 ℃, through hydrothermal crystallizing, gets the ZSM-35 molecular sieve of little crystal grain.Wherein organic additive is Sodium dodecylbenzene sulfonate, polyethylene glycols tensio-active agent or their mixture, but adds the degree of crystallinity that organic purpose is to improve molecular sieve.
Chinese patent application number: 01135686.3(2001-10-19) disclosed a kind of method of synthesizing small-grain A-type molecular sieve.Its technical characterictic is, utilizes alumino silica gel, oil, tensio-active agent and cosurfactant to prepare stable W/O microemulsion, at last with microemulsion under 90-120 ℃, through hydrothermal crystallizing, obtain average grain size less than the A type molecular sieve of 400nm.This method mainly is to utilize in specific water-in-oil (W/O) microemulsion system to carry out, and crystal growth is limited by the finite space in the small water that oil phase wrapped up, and has avoided excessively growing up of crystal.Used oil is hexanaphthene, sherwood oil; Tensio-active agent is Triton X-100, sodium laurylsulfonate; Cosurfactant is Pentyl alcohol, n-hexyl alcohol.This method is to utilize surfactant-based material and oil phase to form water in oil micro emulsion liquid, and provides the place for the crystallization of molecular sieve.
Chinese patent application number: 01135684.7(2001-10-19) disclosed a kind of method for preparing small crystal grain Y-shaped molecular sieve.Its technical characterictic is, under optimal conditions, utilizes in specific water-in-oil (W/O) microemulsion system and carrying out, and crystal growth is limited by the finite space in the small water that oil phase wrapped up, and has avoided excessively growing up of crystal.Used oil is hexanaphthene, sherwood oil; Tensio-active agent is Triton X-100, sodium laurylsulfonate; Cosurfactant is Pentyl alcohol, n-hexyl alcohol.
Chinese patent application number: 00111065.9(2000-06-02) disclosed a kind of synthetic method of fine grain NaY type molecular sieve.Its technical characterictic is, at first adopts special method to prepare directed agents, joins in the building-up process of molecular sieve again, through hydrothermal crystallizing, obtains the NaY type molecular sieve of small particle size.This method adds glycerol, ethylene glycol or Virahol as organic dispersing agent when the preparation directed agents, organic dispersing agent can also be methyl alcohol, ethanol, dimethyl sulfoxide (DMSO) and left dextrose etc.Dispersion agent plays the reduction gel viscosity in this patent, the nucleus of directed agents is disperseed fully and expose, increase grain density, reach the purpose that reduces the zeolite crystal size, and the best introducing time of organic dispersing agent is after the silicon source adds for the first time, and introduces the purpose that does not all reach abundant dispersion directed agents nucleus in aging and crystallization process.
Application No.: US19810325457(1981-11-27) disclosed a kind of method of synthesizing small-grain faujasite molecular sieve.Its technical characterictic is to become glue at zero point to 10 under ℃ low temperature, and add monose or disaccharides, synthesizing small-grain faujasite molecular sieve in synthetic system.
Following patent has also been introduced and added organic method in molecular sieve is synthetic.
Chinese patent application number: 201010501473.1(2010-10-0) disclosed the preparation method of a kind of multi-stage porous titanium-silicon zeolite TS-1.Its technical characterictic is, the synthetic colloidal sol of TS-1 molecular sieve that will contain sugar prepares dried glue through thermal treatment, in this process, sugar is heated and partially carbonized dehydration forms hard template, so the molecular sieve of preparing has the mesoporous of 4-50nm simultaneously and greater than the TS-1 molecular screen material that is interconnected between the macropore of 50nm and the multistage pore canal.This method is to synthesize multilevel hole material as hard template after utilizing organic carbon.
Chinese patent application number: 200910187933.5(2009-10-16) disclosed a kind of synthetic method of MCM-22 molecular sieve.Its technical characterictic is, the employing hexamethylene imine is template (mould silicon is than being 0.15-1.0), and add the dimethylene imines, also dimethylene imines and hydro carbons, organic amine, alcohols, ketone etc. are prepared the MCM-22 molecular sieve of pure phase as auxiliary organic formwork agent.But this method just reaches the shortening crystallization time by adding auxiliary organism, reduces the effect of crystallization temperature.
Chinese patent application number: 200710062872.0(2007-01-19) disclosed a kind of preparation method of MCM-22 molecular sieve.Its technical characterictic is in conventional synthesized gel rubber, to add proper C 2-C 9Alcohols, C 2-C 6Branched paraffin substituted benzene organic additive, through hydrothermal crystallizing, obtain the MCM-22 molecular sieve.This method mainly utilizes the selection of organic additive kind and consumption to come the pore structure of modulation molecular sieve, makes the most probable pore size distribution can reach 0.65nm, and the pore volume maximum can be by 0.346m 3/ g increases to 0.435m 3/ g.
The following discloses patent has been introduced the method for adding organosilane in the preparation process of molecular sieve.
Chinese patent application number: 200710011690.0(2007-06-11) disclosed a kind of preparation method who contains the ordered meso-porous structure zeolite molecular sieve.Its technical characterictic is, utilizes tensio-active agent and organosilane mixing solutions to be template, and the crystallization process of the ratio control zeolite molecular sieve by regulating the two finally obtains the MFI zeolite molecular sieve of order mesoporous structure.
Chinese patent application number: 201010519498.4(2010-10-26) disclosed a kind of preparation method of small crystal grain NaY molecular sieve.Its technical characterictic is that adopting chlorosilane is the silicon source, through hydrothermal crystallizing, obtains the NaY molecular sieve about granularity～100nm.
Chinese patent application number: 201010546164.6(2010-11-16) disclosed a kind of preparation method of ZSM-5 zeolite molecular sieve.Its technical characterictic is that the employing 4-propyl bromide is template, is that silicon source, Tai-Ace S 150 are the aluminium source with water glass that the commercialization silane coupling agent directly joins in the synthetic system of traditional Z SM-5 zeolite, obtains having the zeolite product of hierarchical porous structure.
Chinese patent application number: 201110182984.6(2011-06-30) disclosed a kind of preparation method of y-type zeolite molecular sieve.Its technical characterictic is, being to be the silicon source with water glass, is the aluminium source with Tai-Ace S 150 and sodium aluminate, with molecules surfactant N, N-diethyl-N-hexadecyl-N-(3-methoxy silane propane) ammonium iodide is template, has synthesized the Y zeolite that contains meso-hole structure by traditional hydrothermal method.When the zeolite product that this method obtains has traditional microporous molecular sieve structure, also has a large amount of meso-hole structures.
Chinese patent application number: 201210011147.1(2012-01-13) disclosed a kind of preparation method of mesoporous MFI zeolite molecular sieve.Its technical characterictic is to utilize organosilane or organosilane and surfactant mixtures to be template, synthetic multistage pore canal zeolite molecular sieve under the microwave-assisted heating condition.The material that this method synthesizes combines the advantage of micro-pore zeolite and mesoporous material, has both kept strongly-acid, highly selective and the high hydrothermal stability of micro-pore zeolite, also possesses the advantage that the mesoporous material aperture is conducive to molecular diffusion greatly simultaneously.
Chinese patent application number: 201210073742.8(2012-03-20) disclosed a kind of preparation method of ZSM-5 zeolite molecular sieve microballoon.Its technical characterictic is, utilize methylic organo-siloxane and tetraethoxy to make silicon source single stage method and prepare ZSM-5 zeolite molecular sieve microballoon, microballoon is made up of tiny ZSM-5 zeolite grain, changes the addition that contains methylsiloxane, and the big I of microballoon is regulated at 3-8 μ m.The ZSM-5 zeolite molecular sieve microballoon size that this method obtains is even, good dispersity, and preparation process is simple, is easy to a large amount of preparations.
From patent, document, the method for synthesizing small-grain (nanometer) zeolite is more at present.For example: use directed agents, nanometer crystal seed, inorganic salt, or use the inertia mesoporous material that hard template is provided, or when crystallization, adopt stirring, microwave, ultrasonic and multi-stage type crystallization etc.But the more little then plane of crystal of zeolite crystal size can be more big, the problem that inevitably exists molecular sieve product to reunite.All can reunite in the filtration of molecular sieve crystallization process (especially crystallization later stage) and zeolite product, washing, drying, the roasting, finally cause the outer surface area effective rate of utilization low, molecular sieve nanometer advantage seriously reduces.And in the existing method, add some organism (as: oligosaccharides, polyoxyethylene glycol, tensio-active agent) and can reach and reduce zeolite crystal size and certain dissemination by adding at synthesized gel rubber or crystallization initial stage.But the amount that adds organic additive hour can not play the effect of dispersion; When add-on is big slightly, the crystallization of molecular sieve there is serious inhibition again, causes crystallization time obviously to prolong, increased the production cost of molecular sieve.And add polyhydroxy substance at synthesized gel rubber or crystallization initial stage, hindered the growth of molecular sieve crystal because organic hydroxyl is elementary with molecular sieve or secondary structure combines, the zeolite product inside that obtains inevitably exists defective, causes the degradation of molecular sieve.Therefore, directly prepare the little crystal grain zeolite molecular sieve of high dispersive and have very important meaning.
Summary of the invention
The invention provides a kind of method of the directly synthetic little crystal grain zeolite molecular sieve of high dispersive.We discovered at MFI, Beta, MWW family molecular sieves synthesized gel rubber or crystallization initial stage, add organochlorosilane and can influence the zeolite molecular sieve process of growth, (wherein T refers to Si to limiting structure hydroxyl T-OH, Al, P or other heteroatoms) between dehydration form the T-O-T key, thereby the effect that disperses the zeolite molecular sieve particle is played in the polymerization of restriction zeolite molecular sieve.But the amount that adds organochlorosilane hour can not play obvious dissemination, when add-on is big then the crystallization process to molecular sieve serious inhibition is arranged.We especially introduce organochlorosilane and can obtain the little crystal grain zeolite molecular sieve of high dispersive through a large amount of discovering in the zeolite molecular sieve crystallization later stage when crystallization just finishes.This be because, behind the hydrolyzing organochlorosilanes hydroxyl can with molecular sieve surface hydroxyl generation condensation, hinder T-OH dehydration between the molecular sieve in conjunction with forming the T-O-T key, and then stop the polymerization of zeolite molecular sieve.Simultaneously, the combination between silane species and the structural hydroxyl can also reduce the wetting ability of molecular sieve, makes that molecular sieve is easy to filter, and is conducive to product and collects, and make product keep dispersed preferably after roasting.In the crystallization later stage, add organochlorosilane when especially crystallization has just finished, not only can not change brilliant looks and the composition of molecular sieve, and normal crystallization that can the disturbing molecule sieve, the product that obtains not only has polymolecularity, has also kept the performance of little crystal grain product preferably.
Technical scheme of the present invention is as follows:
Scheme one: directly add organochlorosilane when the gel crystallization is complete
The first step: preparation synthesized gel rubber
The slip-stick artist who is familiar with this area all can adopt the technological method of reporting in existing open source literature and the patent, and preparation is for the synthesis of the gel of little crystal grain or nano molecular sieve.As preparing required gel ZL200510200328.9, ZL200510028781.6, ZL01145256.0, ZL00107486.5, ZL200710064979.9, ZL200810204229.1, ZL200510025147.7, Zeolites according to the method for introducing in the following patent, 15 (1995) 611-619, Micropor.Mesopor.Mater, 57 (2003) 83-92, Chinese Journal of Inorganic Chemistry, 19 (2003) 396, Catalysis today, 158(2010) 510-514, Nankai University's journal (natural science edition), 39 (2006) 4.Be prepared small-grain ZSM-5 according to embodiment 1 among the patent ZL200510200328.9 as an example: take by weighing industrial aluminum sulphate 8.6 grams, make its dissolving to wherein adding deionized water 230 grams, add sulfuric acid 28 grams then, the basicity of regulator solution, add sodium-chlor 10 grams again, after constantly stirring is dissolved it fully, add Virahol 1.5 grams again, form A solution.With 100 gram deionized waters dilutions, 517 gram water glass, add homemade ZSM-5 crystal seed 2.5 grams then, constantly carry out mechanical stirring in the reinforced process, add n-Butyl Amine 99 at leisure after, form B solution.Under constantly stirring, B solution is joined in the A solution at leisure, used mulser emulsification then 15 minutes, again reaction mixture is installed in the reactor, stirred crystallization 24 hours at 100 ℃, be warming up to 170 ℃ then, crystallization 24 hours.
Second step: when the gel crystallization is complete, in the crystallization system, add organochlorosilane
When the molecular sieve crystallization finishes, under agitation by nitrogen pressure organochlorosilane is pressed in the crystallizing kettle that the crystallization thing is housed, make fully contact reacts of organochlorosilane and molecular sieve surface.Said molecular sieve crystallization refers to crystallization concluding time of determining by the crystallization curve of investigating molecular sieve when finishing, the slip-stick artist who is familiar with this area all can finish this operation; Any or its any mixture in the organochlorosilanes such as the optional METHYL TRICHLORO SILANE of selected organochlorosilane, methyl hydrogen dichlorosilane, trimethylchlorosilane; The amount that wherein adds organochlorosilane (R) is R/SiO 2=0.01～2(mass ratio).Reaction times is 0～100h, and the preferred reaction time is 2～10h.Temperature of reaction is room temperature～200 ℃, preferred 100～160 ℃.Suitable molecular sieve comprises MFI, Beta, MWW family molecular sieves etc.
The 3rd step: collect product
After treating that the reaction of organochlorosilane and crystallization thing finishes, adopt ordinary method to collect product.For example adopt Plate Filtration to carry out solid-liquid separation, with deionized water product is washed to pH=8～9, then at 110 ℃ of following dry 24h, and through 540 ℃ of roasting 6h, obtain the molecular sieve of Nano zeolite product of high dispersive.
Scheme two: gel crystallization back recovery mother liquor fully adds organic chlorosilane again
Iteration scheme one, but when the gel crystallization finishes, open the reducing valve of crystallizing kettle, part water and whole volatile organic component in the crystallization feed liquid are fully vaporized, obtain reclaiming mother liquor through condensation, reclaiming mother liquor can recycle.Then, under agitation in post-decompression crystallizing kettle, be pressed into organochlorosilane, make fully contact reacts of organochlorosilane and molecular sieve surface.In this method, post-decompression crystallization feed liquid is long-pending to be reduced, and temperature and pressure reduces, and is conducive to reduce the consumption of organochlorosilane, and is conducive to operation.
The invention has the beneficial effects as follows: by adding organochlorosilane in the molecular sieve crystallization later stage, the condensation that can reduce effectively between the molecular sieve is reunited, and the zeolite product good dispersity of gained, external surface area be big, be easy to filter.And hydrolyzing organochlorosilanes discharges hydrogenchloride can regulate the synthetic system pH value, and it is brilliant that inhibition system changes.Utilize the molecular sieve of present method preparation to have more catalytic active center to expose on the outer surface, be conducive to prepare high performance catalyst.
Embodiment
The present invention will be further described below by embodiment, but the present invention is not subjected to the restriction of these embodiment.
The comparative example 1
According to the report of patent ZL200510200328.9, choose a representative formula and carry out the synthetic of ZSM-5 molecular sieve.Be about to water glass (SiO 2), water, sulfuric acid, Tai-Ace S 150 (Al 2O 3), Virahol (IPA) and n-Butyl Amine 99 (NBA) be SiO by the mole proportioning 2/ Al 2O 3=178, OH -/ SiO 2=0.58, NBA/SiO 2=0.40, IPA/SiO 2=0.01, H 2O/SiO 2=15 are prepared into even gel, and add its SiO in gel 2The ZSM-5 molecular sieve crystal seed of gross weight 2%.Behind reaction gel usefulness mulser emulsification 15min, transfer in the high pressure water heating kettle, in 100 ℃ of aging 24h of stirring, be warming up to 170 ℃ of crystallization 24h again.Crystallization is opened reducing valve after finishing, and makes part water, vaporizable Virahol and n-Butyl Amine 99 in the crystallization material liquid, obtains reclaiming through condensation, reclaims liquid and can be used for synthetic ZSM-5 molecular sieve next time.The gained solid product to pH=8～9, at 110 ℃ of following dry 24h, and at 540 ℃ of following roasting 6h, obtains pure ZSM-5 molecular sieve through deionized water wash.The relative crystallinity of product is 100%.Characterize through SEM, product is the nano zeolite of highly assembling.Through N 2Physical adsorption characterizes, and its BET outer surface area is 50m 2/ g, product filters slowly.
The comparative example 2
According to open source literature Catalysis today, the 158(2010) report of 510-514 is chosen a representative formula and is carried out the synthetic of TS-1 molecular sieve.Being about to tetraethoxy (TEOS), water, tetrabutyl titanate (TBOT), ethanol (EtOH), Virahol (IPA) and TPAOH (TPAOH) is SiO by the mole proportioning 2/ TiO 2=30.0, H 2O/SiO 2=20.0, TPA +/ SiO 2=0.20, IPA/TiO 2=1.5 are prepared into even gel.With reaction gel 70 ℃ except behind the pure 4h, add equal-volume water again, stir 1h after, transfer in the high pressure water heating kettle, in 165 ℃ of dynamic crystallization 30h.Crystallization is opened reducing valve after finishing, and makes part water, vaporizable ethanol and Virahol in the crystallization material liquid, obtains reclaiming through condensation, reclaims liquid and can be used for synthetic TS-1 molecular sieve next time.The gained solid product to pH=8～9, at 110 ℃ of following dry 24h, and at 540 ℃ of following roasting 6h, obtains pure TS-1 molecular sieve through deionized water wash.The relative crystallinity of product is 100%.Characterize through SEM, the product pattern is coccoid about 120nm.Through N 2Physical adsorption characterizes, and its BET outer surface area is 70m 2/ g, product filters very difficult, adopts centrifugal collection.
The comparative example 3
According to the report of publication ZL00107486.5, choose a representative formula and carry out the synthetic of Beta molecular sieve.Being about to silochrom, water, sodium hydroxide, pseudo-boehmite, vacuum pump oil and tetraethyl ammonium hydroxide (TEAOH) is SiO by the mole proportioning 2/ Al 2O 3=30, Na 2O/SiO 2=0.075, TEAOH/SiO 2=0.09, H 2O/SiO 2=6.5, vacuum pump oil/SiO 2=0.5, be prepared into even gel.Behind reaction gel mechanical stirring 1h, transfer in the high pressure water heating kettle, under 120 ℃, crystallization 24h is warming up to 148 ℃ of crystallization 48h again.Crystallization is opened reducing valve after finishing, and makes the part water vapor in the crystallization material liquid, discharges through condensation.The gained solid product to pH=8～9, at 110 ℃ of following dry 24h, and at 540 ℃ of following roasting 6h, obtains pure Beta molecular sieve through deionized water wash.The relative crystallinity of product is 100%.Characterize through SEM, product is the nano zeolite of highly assembling.Through N 2Physical adsorption characterizes, and its BET external surface area is 80m 2/ g, product filters slowly, adopts centrifugal collection.
The comparative example 4
According to the report of publication ZL200510025147.7, choose a representative formula and carry out the synthetic of MCM-22 molecular sieve.Be about to NaAlO 2, NaOH, water, silicon sol and hexamethylene imine (HMI) be SiO by the mole proportioning 2/ A1 2O 3=30.0, OH -/ SiO 2=0.15, H 2O/SiO 2=15.0, Na +/ SiO 2=0.09, HMI/SiO 2=0.35 is prepared into even gel, adds the MCM-22 molecular sieve crystal seed that mixes butt gross weight 5% in gel.Behind reaction gel mechanical stirring 1h, transfer in the high pressure water heating kettle, in 140 ℃ of crystallization 120h.Crystallization is opened reducing valve after finishing, and makes part water and vaporizable U-4527 in the crystallization material liquid, obtains reclaiming through condensation, reclaims liquid and can be used for synthetic MCM-22 molecular sieve next time.The gained solid product to pH=8～9, at 110 ℃ of following dry 24h, and at 540 ℃ of following roasting 6h, obtains pure phase MCM-22 molecular sieve through deionized water wash.The relative crystallinity of product is 100%.Characterize through SEM, the product pattern is the serious flowers shape of reuniting.Through N 2Physical adsorption characterizes, and its BET outer surface area is 100m 2/ g, product filters extremely slow.
The comparative example 5
According to the report of patent ZL200510200328.9, choose a representative formula and carry out the synthetic of ZSM-5 molecular sieve.Be about to water glass (SiO 2), water, sulfuric acid, Tai-Ace S 150 (Al 2O 3), Virahol (IPA), trimethylchlorosilane (R) and n-Butyl Amine 99 (NBA) be SiO by the mole proportioning 2/ Al 2O 3=178, OH -/ SiO 2=0.58, NBA/SiO 2=0.40, IPA/SiO 2=0.01, H 2O/SiO 2=15 and mass ratio R/SiO 2=0.3 is prepared into even gel, and adds its SiO in gel 2The ZSM-5 molecular sieve crystal seed of gross weight 2%.Behind reaction gel usefulness mulser emulsification 15min, transfer in the high pressure water heating kettle, in 100 ℃ of aging 24h of stirring, be warming up to 170 ℃ of crystallization 24h.Crystallization is opened reducing valve after finishing, and makes part water, vaporizable Virahol and n-Butyl Amine 99 in the crystallization material liquid, obtains reclaiming through condensation, reclaims liquid and can be used for synthetic ZSM-5 molecular sieve next time.The gained solid product to pH=8～9, at 110 ℃ of following dry 24h, and at 540 ℃ of following roasting 6h, obtains pure ZSM-5 molecular sieve through deionized water wash.The relative crystallinity of product is 45%.
The comparative example 6
According to open source literature Catalysis today, the 158(2010) report of 510-514 is chosen a representative formula and is carried out the synthetic of TS-1 molecular sieve.Being about to tetraethoxy (TEOS), water, tetrabutyl titanate (TBOT), ethanol (EtOH), Virahol (IPA), trimethylchlorosilane (R) and TPAOH (TPAOH) is SiO by the mole proportioning 2/ TiO 2=30.0, TPA +/ SiO 2=0.20, IPA/TiO 2=1.5, H 2O/SiO 2=20.0 and mass ratio R/SiO 2=0.3 is prepared into even gel.With reaction gel 70 ℃ except behind the pure 4h, add equal-volume water again, stir 1h after, transfer in the high pressure water heating kettle, in 165 ℃ of dynamic crystallization 30h.Crystallization is opened reducing valve after finishing, and makes part water, vaporizable ethanol and Virahol in the crystallization material liquid, obtains reclaiming through condensation, reclaims liquid and can be used for synthetic TS-1 molecular sieve next time.The gained solid product to pH=8～9, at 110 ℃ of following dry 24h, and at 540 ℃ of following roasting 6h, obtains pure TS-1 molecular sieve through deionized water wash.The relative crystallinity of product is 50%.
The comparative example 7
According to the report of publication ZL00107486.5, choose a representative formula and carry out the synthetic of Beta molecular sieve.Being about to silochrom, water, sodium hydroxide, pseudo-boehmite, vacuum pump oil, trimethylchlorosilane (R) and tetraethyl ammonium hydroxide (TEAOH) is SiO by the mole proportioning 2/ Al 2O 3=30, Na 2O/SiO 2=0.075, TEAOH/SiO 2=0.09, H 2O/SiO 2=6.5, vacuum pump oil/SiO 2=0.5 and mass ratio R/SiO 2=0.3, be prepared into even gel.Behind reaction gel mechanical stirring 1h, transfer in the high pressure water heating kettle, under 120 ℃, crystallization 24h is warming up to 148 ℃ of crystallization 48h again.Crystallization is opened reducing valve after finishing, and makes the part water vapor in the crystallization material liquid, and discharges through condensation.The gained solid product to pH=8～9, at 110 ℃ of following dry 24h, and at 540 ℃ of following roasting 6h, obtains pure Beta molecular sieve through deionized water wash.The relative crystallinity of product is 40%.
The comparative example 8
According to the report of publication ZL200510025147.7, choose a representative formula and carry out the synthetic of MCM-22 molecular sieve.Be about to NaAlO 2, NaOH, water, silicon sol, trimethylchlorosilane (R) and hexamethylene imine (HMI) be SiO by the mole proportioning 2/ A1 2O 3=30.0, OH -/ SiO 2=0.15, Na +/ SiO 2=0.09, HMI/SiO 2=0.35, H 2O/SiO 2=15.0 and mass ratio R/SiO 2=0.3, be prepared into even gel, in gel, add the MCM-22 molecular sieve crystal seed that mixes butt gross weight 5%.Behind reaction gel mechanical stirring 1h, transfer in the high pressure water heating kettle, in 140 ℃ of crystallization 120h.Crystallization is opened reducing valve after finishing, and makes part water and vaporizable U-4527 in the crystallization material liquid, obtains reclaiming through condensation, reclaims liquid and can be used for synthetic MCM-22 molecular sieve next time.The gained solid product to pH=8～9, at 110 ℃ of following dry 24h, and at 540 ℃ of following roasting 6h, obtains pure phase MCM-22 molecular sieve through deionized water wash.The relative crystallinity of product is 43%.
Embodiment 1
Repeat comparative example 1, with water glass (SiO 2), water, sulfuric acid, Tai-Ace S 150 (Al 2O 3), Virahol (IPA) and n-Butyl Amine 99 (NBA) be SiO by the mole proportioning 2/ Al 2O 3=178, OH -/ SiO 2=0.58, NBA/SiO 2=0.40, IPA/SiO 2=0.01, H 2O/SiO 2=15 are prepared into even gel, and add its SiO in gel 2The ZSM-5 molecular sieve crystal seed of gross weight 2%.Behind reaction gel usefulness mulser emulsification 15min, transfer in the high pressure water heating kettle, in 100 ℃ of aging 24h of stirring, be warming up to 170 ℃ of crystallization 23h again.Wherein 23h is by investigating the crystallization curve of zeolite molecular sieve, the crystallization concluding time of definite zeolite molecular sieve.When the zeolite molecular sieve crystallization time reaches 23h, by nitrogen pressure trimethylchlorosilane (is pressed mass ratio R/SiO 2=0.5) is pressed in the crystallizing kettle that the crystallization thing is housed, stirs, under 170 ℃, react 2h again.The gained slurries are through Plate Filtration, and washing, dry, roasting obtain pure ZSM-5 molecular sieve.The relative crystallinity of product is 90.0%, characterizes through SEM, and product is the nano zeolite of dispersion.Through N 2Physical adsorption characterizes, and its BET outer surface area is 75m 2/ g, and the product filtration velocity is 10 times of comparative example 1.
Embodiment 2
Repeat to implement 1, but respectively with the alternative trimethylchlorosilane of METHYL TRICHLORO SILANE, methyl hydrogen dichlorosilane of equal in quality, the product that then obtains is pure ZSM-5 molecular sieve through the X-ray diffraction analysis proof, its relative crystallinity is respectively 86%, 90%.Characterize through SEM, product is the nano zeolite of dispersion.Through N 2Physical adsorption characterizes, and its BET outer surface area is respectively 70m 2/ g, 65m 2/ g, and the product filtration velocity is 10 times of comparative example 1.
Embodiment 3
Repeat embodiment 1, when the zeolite molecular sieve crystallization time reaches 23h, open reducing valve, make part water, vaporizable Virahol and n-Butyl Amine 99 in the crystallization material liquid, obtain reclaiming through condensation, reclaiming liquid can recycle.Be equipped with in the still of crystallization material liquid after the decompression and be pressed into trimethylchlorosilane, stir, at 100 ℃ of reaction 5h down.The gained solid product through washing, dry, roasting, obtains pure ZSM-5 molecular sieve through Plate Filtration.The relative crystallinity of product is 93.0%, characterizes through SEM, and product is the nano zeolite of dispersion.Through N 2Physical adsorption characterizes, and its BET outer surface area is 70m 2/ g, and the product filtration velocity is 10 times of comparative example 1.
Embodiment 4
Repeating comparative example 2, is SiO with tetraethoxy (TEOS), water, tetrabutyl titanate (TBOT), ethanol (EtOH), Virahol (IPA) and TPAOH (TPAOH) by the mole proportioning 2/ TiO 2=30.0, H 2O/SiO 2=20.0, TPA +/ SiO 2=0.20, IPA/TiO 2=1.5 are prepared into even gel.With reaction gel 70 ℃ except behind the pure 4h, add equal-volume water again, stir 1h after, transfer in the high pressure water heating kettle, in 165 ℃ of dynamic crystallization 29h.Wherein 29h is by investigating the crystallization curve of zeolite molecular sieve, the crystallization concluding time of definite zeolite molecular sieve.When the zeolite molecular sieve crystallization time reaches 29h, by nitrogen pressure trimethylchlorosilane (is pressed mass ratio R/SiO 2=0.5) is pressed in the crystallizing kettle that the crystallization thing is housed, stirs, under 165 ℃, react 3h again.The gained slurries are through Plate Filtration, and washing, dry, roasting obtain pure TS-1 molecular sieve.The relative crystallinity of product is 84%, characterizes through SEM, and the product pattern is coccoid about 120nm.Through N 2Physical adsorption characterizes, and its BET outer surface area is 90.0m 2/ g, and product can adopt conventional Plate Filtration method to collect.
Embodiment 5
Repeat embodiment 4, but respectively with the alternative trimethylchlorosilane of METHYL TRICHLORO SILANE, methyl hydrogen dichlorosilane of equal in quality, the product that then obtains is pure TS-1 molecular sieve through the X-ray diffraction analysis proof, its relative crystallinity is respectively 82%, 84%.Characterize through SEM, the product pattern is coccoid about 120nm.Through N 2Physical adsorption characterizes, and its BET outer surface area is respectively 95m 2/ g, 90.0m 2/ g, and product can adopt conventional Plate Filtration method to collect.
Embodiment 6
Repeating comparative example 3, is SiO with silochrom, water, sodium hydroxide, pseudo-boehmite, vacuum pump oil and tetraethyl ammonium hydroxide (TEAOH) by the mole proportioning 2/ Al 2O 3=30, Na 2O/SiO 2=0.075, TEAOH/SiO 2=0.09, H 2O/SiO 2=6.5, vacuum pump oil/SiO 2=0.5, be prepared into even gel.Behind reaction gel mechanical stirring 1h, transfer in the high pressure water heating kettle, under 120 ℃, crystallization 24h is warming up to 148 ℃ of crystallization 47h again.Wherein 47h is by investigating the crystallization curve of zeolite molecular sieve, the crystallization concluding time of definite zeolite molecular sieve.When the zeolite molecular sieve crystallization time reaches 47h, by nitrogen pressure trimethylchlorosilane (is pressed mass ratio R/SiO 2=0.5) is pressed in the crystallizing kettle that the crystallization thing is housed, stirs, under 148 ℃, react 5h again.The gained slurries obtain pure Beta molecular sieve through Plate Filtration, washing, drying, roasting.The relative crystallinity of product is 90%, characterizes through SEM, and product is the nano zeolite of dispersion.Through N 2Physical adsorption characterizes, and its BET outer surface area is 100m 2/ g, and product can adopt conventional Plate Filtration method to collect.
Embodiment 7
Repeat embodiment 6, but respectively with the alternative trimethylchlorosilane of METHYL TRICHLORO SILANE, methyl hydrogen dichlorosilane of equal in quality, the product that then obtains is pure Beta molecular sieve through the X-ray diffraction analysis proof, its relative crystallinity is respectively 88%, 90%.Characterize through SEM, product is the nano zeolite of dispersion.Through N 2Physical adsorption characterizes, and its BET outer surface area is respectively 105m 2/ g, 100m 2/ g, and product can adopt conventional Plate Filtration method to collect.
Embodiment 8
Repeat comparative example 4, with NaAlO 2, NaOH, water, silicon sol and hexamethylene imine (HMI) be SiO by the mole proportioning 2/ A1 2O 3=30.0, OH -/ SiO 2=0.15, H 2O/SiO 2=15.0, Na +/ SiO 2=0.09, HMI/SiO 2=0.35 is prepared into even gel, adds the MCM-22 molecular sieve crystal seed that mixes butt gross weight 5% in gel.Behind reaction gel mechanical stirring 1h, transfer in the high pressure water heating kettle, in 140 ℃ of crystallization 119h.Wherein 119h is by investigating the crystallization curve of zeolite molecular sieve, the crystallization concluding time of definite zeolite molecular sieve.When the zeolite molecular sieve crystallization time reaches 119h, by nitrogen pressure trimethylchlorosilane (is pressed mass ratio R/SiO 2=0.5) is pressed in the crystallizing kettle that the crystallization thing is housed, stirs, under 140 ℃, react 5h again.The gained slurries obtain pure MCM-22 molecular sieve through Plate Filtration, washing, drying, roasting.The relative crystallinity of product is 88%, characterizes through SEM, and it is the laminar of 20-50nm that the product pattern is thickness.Through N 2Physical adsorption characterizes, and its BET outer surface area is 150m 2/ g, and the product filtration velocity is 10 times of comparative example 4.
Embodiment 9
Repeat to implement 8, but respectively with the alternative trimethylchlorosilane of METHYL TRICHLORO SILANE, methyl hydrogen dichlorosilane of equal in quality, the product that then obtains is pure MCM-22 molecular sieve through the X-ray diffraction analysis proof, its relative crystallinity is respectively 86%, 89%.Characterize through SEM, the product pattern is thickness and is the laminar of 20-50nm.Through N 2Physical adsorption characterizes, and its BET outer surface area is respectively 155m 2/ g, 150m 2/ g, and the product filtration velocity is 10 times of comparative example 4.
Embodiment 10
Repeat to implement 8, with NaAlO 2, NaOH, water, silicon sol and hexamethylene imine (HMI) be SiO by the mole proportioning 2/ A1 2O 3=30.0, OH -/ SiO 2=0.15, H 2O/SiO 2=15.0, Na +/ SiO 2=0.09, HMI/SiO 2=0.35 is prepared into even gel, adds the MCM-22 molecular sieve crystal seed that mixes butt gross weight 5% in gel.Behind reaction gel mechanical stirring 1h, transfer in the high pressure water heating kettle, in 140 ℃ of crystallization 119h.Wherein 119h is by investigating the crystallization curve of zeolite molecular sieve, the crystallization concluding time of definite zeolite molecular sieve.When the zeolite molecular sieve crystallization time reaches 119h, by nitrogen pressure trimethylchlorosilane (is pressed mass ratio R/SiO respectively 2=0.1,0.3,0.8 and 1.0) be pressed in the crystallizing kettle that the crystallization thing is housed, stir, under 140 ℃, react 5h again.The gained slurries obtain pure MCM-22 molecular sieve through Plate Filtration, washing, drying, roasting.The relative crystallinity of product is respectively 95%, 92%, 86% and 86%, characterizes through SEM, and it is the laminar of 20-70nm that the product pattern is thickness.Through N 2Physical adsorption characterizes, and its BET outer surface area is respectively 130m 2/ g, 140m 2/ g, 155m 2/ g and 155m 2/ g, and the product filtration velocity is 10 times of comparative example 4.
Embodiment 11
Repeat to implement 8, with NaAlO 2, NaOH, water, silicon sol and hexamethylene imine (HMI) be SiO by the mole proportioning 2/ A1 2O 3=30.0, OH -/ SiO 2=0.15, H 2O/SiO 2=15.0, Na +/ SiO 2=0.09, HMI/SiO 2=0.35 is prepared into even gel, adds the MCM-22 molecular sieve crystal seed that mixes butt gross weight 5% in gel.Behind reaction gel mechanical stirring 1h, transfer in the high pressure water heating kettle, in 140 ℃ of crystallization 119h.Wherein 119h is by investigating the crystallization curve of zeolite molecular sieve, the crystallization concluding time of definite zeolite molecular sieve.When the zeolite molecular sieve crystallization time reaches 119h, by nitrogen pressure trimethylchlorosilane (is pressed mass ratio R/SiO 2=0.5) is pressed in the crystallizing kettle that the crystallization thing is housed, stirs, under 140 ℃, react 2h, 10h, 30h and 100h more respectively.The gained slurries obtain pure MCM-22 molecular sieve through Plate Filtration, washing, drying, roasting.The relative crystallinity of product is respectively 92%, 85%, 85% and 85%, characterizes through SEM, and it is the laminar of 20-50nm that the product pattern is thickness.Through N 2Physical adsorption characterizes, and its BET outer surface area is respectively 145m 2/ g, 150m 2/ g, 155m 2/ g and 155m 2/ g, and the product filtration velocity is 10 times of comparative example 4.
Embodiment 12
Repeat to implement 8, with NaAlO 2, NaOH, water, silicon sol and hexamethylene imine (HMI) be SiO by the mole proportioning 2/ A1 2O 3=30.0, OH -/ SiO 2=0.15, H 2O/SiO 2=15.0, Na +/ SiO 2=0.09, HMI/SiO 2=0.35 is prepared into even gel, adds the MCM-22 molecular sieve crystal seed that mixes butt gross weight 5% in gel.Behind reaction gel mechanical stirring 1h, transfer in the high pressure water heating kettle, in 140 ℃ of crystallization 119h.Wherein 119h is by investigating the crystallization curve of zeolite molecular sieve, the crystallization concluding time of definite zeolite molecular sieve.When the zeolite molecular sieve crystallization time reaches 119h, by nitrogen pressure trimethylchlorosilane (is pressed mass ratio R/SiO 2=0.5) is pressed in the crystallizing kettle that the crystallization thing is housed, stirs, under 40 ℃, 80 ℃, 120 ℃, 160 ℃, 180 ℃, react 5h more respectively.The gained slurries obtain pure MCM-22 molecular sieve through Plate Filtration, washing, drying, roasting.The relative crystallinity of product is respectively 90%, 90%, 90%, 90% and 90%, characterizes through SEM, and it is the laminar of 20-50nm that the product pattern is thickness.Through N 2Physical adsorption characterizes, and its BET outer surface area is respectively 140m 2/ g, 145m 2/ g, 150m 2/ g, 155m 2/ g and 155m 2/ g, and the product filtration velocity is 10 times of comparative example 4.

Claims (9)

1. the preparation method of a high dispersive zeolite molecular sieve is characterized in that following steps:
The first step: preparation gel, the hydrothermal crystallizing of nano molecular sieve;
Second step: when the molecular sieve crystallization finishes, under agitation by nitrogen pressure organochlorosilane is pressed in the crystallizing kettle that the crystallization thing is housed, makes fully contact reacts of organochlorosilane and molecular sieve surface; Perhaps when the molecular sieve crystallization finishes, open reducing valve, part water and whole volatile organic component in the crystallization material liquid are fully vaporized, obtain reclaiming through condensation, recovery liquid recycles, in post-decompression crystallizing kettle, be pressed into organochlorosilane then, stir, make the fully reaction of organochlorosilane and molecular sieve surface; The mass ratio that wherein adds organic chlorosilane R is R/SiO 2=0.01～2, the reaction times is for being not more than 100h, and temperature of reaction is room temperature～200 ℃; After treating that the reaction of organochlorosilane and crystallization thing finishes, collect product.
2. preparation method according to claim 1 is characterized in that, described organochlorosilane is a kind of or its any mixture in METHYL TRICHLORO SILANE, methyl hydrogen dichlorosilane, the trimethylchlorosilane.
3. preparation method according to claim 1 and 2 is characterized in that, temperature of reaction is 100～160 ℃.
4. preparation method according to claim 1 and 2 is characterized in that, described molecular sieve comprises MFI, Beta, MWW family molecular sieves.
5. preparation method according to claim 3 is characterized in that, described molecular sieve comprises MFI, Beta, MWW family molecular sieves.
6. according to claim 1 or 2 or 5 described preparation methods, it is characterized in that, after reaction finishes, adopt Plate Filtration to collect product.
7. according to claim 1 or 2 or 5 described preparation methods, the hydrothermal crystallizing step that it is characterized in that the preparation of gel and nano molecular sieve is as follows, industrial aluminum sulphate 8.6 grams, make its dissolving to wherein adding deionized water 230 grams, add sulfuric acid 28 grams then, the basicity of regulator solution, add sodium-chlor 10 grams again, after constantly stirring is dissolved it fully, add Virahol 1.5 grams again, form A solution.With 100 gram deionized waters dilutions, 517 gram water glass, add ZSM-5 crystal seed 2.5 grams then, constantly carry out mechanical stirring in the reinforced process, add n-Butyl Amine 99 at leisure after, form B solution; Under constantly stirring, B solution is joined in the A solution at leisure, used mulser emulsification then 15 minutes, again reaction mixture is installed in the reactor, stirred crystallization 24 hours at 100 ℃, be warming up to 170 ℃ then, crystallization 24 hours.
8. preparation method according to claim 3, the hydrothermal crystallizing step that it is characterized in that the preparation of gel and nano molecular sieve is as follows, industrial aluminum sulphate 8.6 grams, make its dissolving to wherein adding deionized water 230 grams, add sulfuric acid 28 grams then, the basicity of regulator solution, add sodium-chlor 10 grams again, after constantly stirring is dissolved it fully, add Virahol 1.5 grams again, form A solution.With 100 gram deionized waters dilutions, 517 gram water glass, add ZSM-5 crystal seed 2.5 grams then, constantly carry out mechanical stirring in the reinforced process, add n-Butyl Amine 99 at leisure after, form B solution; Under constantly stirring, B solution is joined in the A solution at leisure, used mulser emulsification then 15 minutes, again reaction mixture is installed in the reactor, stirred crystallization 24 hours at 100 ℃, be warming up to 170 ℃ then, crystallization 24 hours.
9. preparation method according to claim 4, the hydrothermal crystallizing step that it is characterized in that the preparation of gel and nano molecular sieve is as follows, industrial aluminum sulphate 8.6 grams, make its dissolving to wherein adding deionized water 230 grams, add sulfuric acid 28 grams then, the basicity of regulator solution, add sodium-chlor 10 grams again, after constantly stirring is dissolved it fully, add Virahol 1.5 grams again, form A solution.With 100 gram deionized waters dilutions, 517 gram water glass, add ZSM-5 crystal seed 2.5 grams then, constantly carry out mechanical stirring in the reinforced process, add n-Butyl Amine 99 at leisure after, form B solution; Under constantly stirring, B solution is joined in the A solution at leisure, used mulser emulsification then 15 minutes, again reaction mixture is installed in the reactor, stirred crystallization 24 hours at 100 ℃, be warming up to 170 ℃ then, crystallization 24 hours.
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