CN101186312B - Nano-crystallite and non-ionic surface active agent microwave self-assembling preparation method for mesopore and micropore molecular sieve - Google Patents
Nano-crystallite and non-ionic surface active agent microwave self-assembling preparation method for mesopore and micropore molecular sieve Download PDFInfo
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- CN101186312B CN101186312B CN2007100322823A CN200710032282A CN101186312B CN 101186312 B CN101186312 B CN 101186312B CN 2007100322823 A CN2007100322823 A CN 2007100322823A CN 200710032282 A CN200710032282 A CN 200710032282A CN 101186312 B CN101186312 B CN 101186312B
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Abstract
The invention discloses a preparation method of medium and micro sized diplopore molecular sieve by microwave auto-assmebly of nano microcrystal and nonionic surfactant, which comprises the steps that: deionized water is added into a cone-shaped bottle and then microporous template agent and aluminum source agent are added and stirred for 2 -5 hours, and then the pH value is adjusted; the reaction liquid is put into a reactionary pot to be crystallized for 1 to 3 hours, so as to obtain the microporous molecular sieve nanometer microcrystal; the nonionic surfactant is dissolved into the deionized water and is dripped into the obtained microporous molecular sieve nanometer microcrystal to be stirred, and then the pH value is adjusted; the reaction liquid is sent into polytetrafluoroethylene reaction pitcher to be crystallized for 0.5 to 2 hours; the obtained material is washed, dried, baked and demouded, and the medium and micro sized diplopore molecular sieve is finally made. By using different template agent and nonionic surfactant, the invention realizes bimodal pore structure of material and control of pore diameter, thus enhancing acidity of mesopore material and hydrothermal stability, ensuring nucleation of the nano micro crystal to be more uniform and the crystallized time to be shorter with high repeatability.
Description
Technical field
The present invention relates to the method for fine diplopore molecular sieve in a kind of preparation, the method for fine diplopore molecular sieve in particularly a kind of nano microcrystalline and the non-ionic surface active agent microwave self-assembly preparation.
Background technology
Micro porous molecular sieve has the microvoid structure and the strongly-acid of even prosperity, it is the type of selecting catalyzer important in the modern petroleum industry, yet because the aperture is less, the major diameter molecule enters the duct difficulty on the one hand, the macromole that forms in the duct on the other hand can not be overflowed fast, often cause side reaction to take place, and its range of application is dwindled greatly.Along with the modern chemistry industrial expansion, the heaviness of oil, the catalytic cracking of resolving heavy oil, residual oil becomes the controlling factor of petroleum catalytic cracking technological process, simultaneously, because the needs of Coal Chemical Industry and biomacromolecule repercussion study, the wide aperture molecular sieve catalyst that development research adapts with it just seems very important.
1992, people (C.T.Kresge such as the Beck of Mobil company, M.E.Leonowicz, W.J.Roth, J.C.Vartuli, J.S.Beck.Ordered mesoporous molecular sieves synthesized by a liquid-crystal templatemechanism. (based on liquid crystal templated theoretical synthetic ordered mesoporous molecular sieve) .Nature, 1992,359,710-712; J.S.Beck, J.C.Vartuli, W.J.Roth, M.E.Leonowicz, C.T.Kresge, K.D.Schmitt, C.T.W.Chu, D.H.Olson, E.W.Sheppard, S.B.McCullen, J.B.Higgins, J.L.Schienker.A New Family ofMesoporous Molecular Sieves Prepared with Liquid Crystal Templates. (liquid crystal templated method prepares novel mesopore molecular sieve) .Journal of the American Chemical Society, 1992,114,10834-10843.) reported first a kind of aperture adjustable novel mesoporous zeolite M41S of family in 1.5～10nm scope, these mesopore molecular sieves have regular pore passage structure, aperture size is adjustable, and have high-specific surface area and big loading capacity, the rapid diffusion that helps organic molecule, this makes it to select the type reaction for macromole (especially heavy oil organic molecule in the petrochemical process) unrivaled favourable space and effective acid active centre is provided, and adjustment aperture and acid intensity as required, so this class mesopore molecular sieve is at residual oil catalytic cracking, heavy-oil hydrogenation, lube oil hydrogenation, has sizable potential using value in the sepn process of acid catalysis fields such as alkylating separation and petrochemical complex.But the practice in, mesopore molecular sieve exists its fatal weakness: character is similar to unformed silico-aluminate, acidity a little less than, hydrothermally stable is also poor, catalytic activity is not enough.Limited the practical application of mesopore molecular sieve so greatly.
Therefore, a kind of novel matrix material that has mesopore and micropore simultaneously of urgent hope development, make its existing strong acidic site that the weak acid position be arranged again, can make the mutual supplement with each other's advantages of mesopore and micro porous molecular sieve like this, the dual acid position of this multiplet structure and have the molecular sieve of overlaying function, can avoid the defective of single pore structure, suitability is stronger when handling the mixture that differs such as component complexity such as vehicle exhaust, plant gas, molecule pore size, with its Application Areas of further expansion.Obviously, if make the amorphous hole wall crystallization or the partial crystallization of mesoporous material, its physico-chemical property will obtain the improvement of essence.Desirable material is when keeping meso-hole structure, to synthesize the even mesoporous of existing larger aperture, has the promptly middle fine diplopore molecular sieve of strongly-acid matrix material of zeolite type hole wall structure again.Middle fine diplopore molecular sieve has micropore and mesoporous dual model pore distribution, combine the duct advantage of mesoporous material and the strongly-acid and the high hydrothermal stability of micro porous molecular sieve, can make two kinds of material advantage complementations, synergy, but and aperture and acid all modulations, promptly be optimized compoundly, can prepare configuration of different holes and the acid matrix material that distributes by two kinds of materials selecting different pore passage structures and acid matter.The type material that this kind has dual pore passage structure will be expected to be used for the reaction of high order that macromole participates in, as heavy oit pyrolysis.At first macromole is to realize selecting the shape cracking at central hole structure, and the micropore canals that the small molecules that cracking obtains enters in the mesopore hole wall is more further selected the shape cracking, thereby improves the effect of catalytic cracking reaction.This class composite molecular screen has dual acidic site in a word, dual pore passage structure, and specific surface area is big, the thermostability advantages of higher, in petrochemical complex, fine chemistry industry and environmental protection field will have the excellent development prospect.
Summary of the invention
The object of the present invention is to provide the method for fine diplopore molecular sieve in a kind of nano microcrystalline and the non-ionic surface active agent microwave self-assembly preparation.
The method of fine diplopore molecular sieve in nano microcrystalline of the present invention and the non-ionic surface active agent microwave self-assembly preparation is characterized in that preparation process is as follows:
(1) preparation of micro porous molecular sieve nano microcrystalline: in the Erlenmeyer flask of clean dried, add 10～15ml deionized water, stir and add 0.01～0.05mol micropore template and 0.001～0.005mol aluminium source reagent with 200～300 rev/mins of speed, slowly drip 0.05～0.2mol silicon source reagent, stirred 2～5 hours with 300～500 rev/mins of speed, regulating the pH value is 9～12; Reaction solution is put into the tetrafluoroethylene retort, set microwave reaction power 90～480W, temperature rise rate is 10～40 ℃/minute, and 100～160 ℃ of following crystallization 30～105 minutes obtain the micro porous molecular sieve nano microcrystalline;
(2) self-assembly of nano microcrystalline and nonionogenic tenside: 0.005～0.05mol nonionogenic tenside is dissolved in 15～20ml deionized water, slowly be added drop-wise in (1) resulting micro porous molecular sieve nano microcrystalline, stirred 2～5 hours with 300～500 rev/mins speed, regulating the pH value is 3～10; Reaction solution is put into the tetrafluoroethylene retort, set microwave reaction power 90～480W, temperature rise rate is 10～40 ℃/minute, 100～160 ℃ of following crystallization 0.5～2 hour, with product take out remove residual reaction impurities with distilled water wash after, 100～120 ℃ of dried overnight, 500～600 ℃ of roasting demouldings 3～10 hours obtain middle fine diplopore molecular sieve;
Wherein, the proportioning of nonionogenic tenside and silicon source reagent is 0.1～0.5: 1.
The general formula of the micropore template of described step (1) is:
(R
1)
4NR
2
R wherein
1Be any alkyl among C1～C4, R
2Be OH, Cl or Br.
The general formula of the nonionogenic tenside of described step (2) is:
CH
3R
1-(OCH
2CH
2) or CH
3R
1NH (CH
3)
2
R wherein
1Be any alkyl among C11～C17.
The micropore size scope of fine diplopore molecular sieve is 0.4～1nm in described; The mesopore pore diameter range is 2～20nm.
The crystallization time of described step (1) is 30～105 minutes.
The present invention compared with prior art has following advantage and beneficial effect:
(1) microwave can guarantee even heating in whole reactor, makes that the nucleation of nano microcrystalline is more even, and crystallization time is shorter, and the consuming time of entire synthesis process shortened 3～4 times than traditional water thermal synthesis technology;
(2) building-up process need not used complicated hydro-thermal synthetic technology, and device makes the easier control of building-up process parameter and guarantee repeatability;
(3) during microwave radiation, the kinetics of reactant may change reaction mechanism in the liquid phase (water or other dielectric materials), thereby the new possibility of regulatory molecule sieve nano microcrystalline size, structure is provided;
(4) can realize the reasonable distribution of Molecular Sieve Pore by isoparametric accurate control of temperature and pressure and optimum combination;
(5) entire synthesis process was finished by the two relatively independent steps, be the self-assembly of nanocrystal and tensio-active agent under oxide compound (comprising zeolite) nanocrystal preparation under the microwave action and the microwave action, guaranteed that pore structure mesoporous, micropore can be according to the independence regulation and control respectively of practical application needs.
The middle fine diplopore molecular sieve that the present invention obtains is a kind of the even mesoporous of larger aperture that both had, the molecular screen material that has the zeolite type hole wall structure again, be widely used in fields such as absorption, catalysis, medicament slow release, the dual pore passage structure of its distinctive mesopore/micropore has application potential for the reaction of high order that has macromole to participate in.
Embodiment
In order to understand the present invention better, the present invention is done to describe further below in conjunction with embodiment.
Embodiment one
(1) preparation of micro porous molecular sieve nano microcrystalline: in the Erlenmeyer flask of clean dried, add the 10ml deionized water, stir and adding 0.025mol tetraethyl ammonium hydroxide and 0.0016mol aluminum isopropylate with 200 rev/mins speed, slowly drip the 0.075mol tetraethoxy, stirred 2 hours with 300 rev/mins speed, regulating the pH value is 11 again.Reaction solution is put into the tetrafluoroethylene retort, and setting MARS-5 microwave workstation power is 300W, and temperature rise rate is 20 ℃/minute, 100 ℃ of following crystallization 1 hour.
(2) self-assembly of nano microcrystalline and nonionogenic tenside: the 0.03mol polyoxyethylene lauryl ether is dissolved in the 16.5ml deionized water, slowly be added drop-wise in (1) resulting micro porous molecular sieve nano microcrystalline, stirred 2 hours with 200 rev/mins speed, regulating the pH value is 8 again.Reaction solution is put into the tetrafluoroethylene retort, setting MARS-5 microwave workstation power is 300W, temperature rise rate is 20 ℃/minute, 100 ℃ of following crystallization 40 minutes, with product take out remove residual reaction impurities with distilled water wash after, 100 ℃ of dried overnight, 550 ℃ of roasting demouldings 5 hours promptly prepare middle fine diplopore molecular sieve.
Fine diplopore molecular sieve has mesopore and the dual pore passage structure of micropore through XRD and pore structure Analysis and Identification in the gained, concrete structure parameter: mesopore aperture: 19.89nm, mesopore volume: 1.6ml/g, micropore size: 0.52nm, micropore pore volume: 2.45ml/g, BET specific surface area: 455.82m
2/ g.
Embodiment two
(1) preparation of micro porous molecular sieve nano microcrystalline: in the Erlenmeyer flask of clean dried, add the 12ml deionized water, stir and add 0.01mol Tetramethylammonium hydroxide (TMAOH) and the 0.001mol aluminic acid is received with 250 rev/mins speed, slowly drip the 0.05mol tetraethoxy, stirred 2 hours with 400 rev/mins speed, regulating the pH value is 11.Reaction solution is put into the tetrafluoroethylene retort, and setting MARS-5 microwave workstation power is 90W, and temperature rise rate is 10 ℃/minute, 140 ℃ of following crystallization 90 minutes.
(2) self-assembly of nano microcrystalline and nonionogenic tenside: 0.005mol polyoxyethylene myristyl ether is dissolved in the 16.5ml deionized water, slowly be added drop-wise in (1) resulting micro porous molecular sieve nano microcrystalline, stirred 2 hours with 300 rev/mins speed, regulating the pH value is 5.Reaction solution is put into the tetrafluoroethylene retort, setting MARS-5 microwave workstation power is 300W, temperature rise rate is 20 ℃/minute, 100 ℃ of following crystallization 40 minutes, with product take out remove residual reaction impurities with distilled water wash after, 100 ℃ of dried overnight, 550 ℃ of roasting demouldings 5 hours promptly prepare middle fine diplopore molecular sieve.
Fine diplopore molecular sieve has mesopore and the dual pore passage structure of micropore through XRD and pore structure Analysis and Identification in the gained, concrete structure parameter: mesopore aperture: 12.5nm, mesopore volume: 1.58ml/g, micropore size: 0.40nm, micropore pore volume: 1.77ml/g, BET specific surface area: 560.19m
2/ g.
Embodiment three
(1) preparation of micro porous molecular sieve nano microcrystalline: in the Erlenmeyer flask of clean dried, add the 15ml deionized water, stir and adding 0.03mol tetrabutylammonium chloride (TBAC) and 0.005mol aluminum isopropylate with 300 rev/mins speed, slowly drip the 0.2mol methyl silicate, stirred 5 hours with 500 rev/mins speed, regulating the pH value is 12.Reaction solution is put into the tetrafluoroethylene retort, and setting MARS-5 microwave workstation power is 480W, and temperature rise rate is 40 ℃/minute, 160 ℃ of following crystallization 105 minutes.
(2) self-assembly of nano microcrystalline and nonionogenic tenside: 0.05mol polyoxyethylene octadecyl ether is dissolved in the 20ml deionized water, slowly be added drop-wise in (1) resulting micro porous molecular sieve nano microcrystalline, stirred 4 hours with 400 rev/mins speed, regulating the pH value is 10.Reaction solution is put into the tetrafluoroethylene retort, setting MARS-5 microwave workstation power is 480W, temperature rise rate is 40 ℃/minute, 160 ℃ of following crystallization 120 minutes, with product take out remove residual reaction impurities with distilled water wash after, 120 ℃ of dried overnight, 600 ℃ of roasting demouldings 10 hours promptly prepare middle fine diplopore molecular sieve.
Fine diplopore molecular sieve has mesopore and the dual pore passage structure of micropore through XRD and pore structure Analysis and Identification in the gained, concrete structure parameter: mesopore aperture: 8.16nm, mesopore volume: 0.98ml/g, micropore size: 0.97nm, micropore pore volume: 1.37ml/g, BET specific surface area: 577.78m
2/ g.
Embodiment four
(1) preparation of micro porous molecular sieve nano microcrystalline: in the Erlenmeyer flask of clean dried, add the 12ml deionized water, stir and adding 0.05mol 4-propyl bromide (TPABr) and 0.003mol Tai-Ace S 150 with 200 rev/mins speed, slowly drip the 0.075mol tetraethoxy, stirred 3 hours with 350 rev/mins speed, regulating the pH value is 9.Reaction solution is put into the tetrafluoroethylene retort, and setting MARS-5 microwave workstation power is 300W, and temperature rise rate is 20 ℃/minute, 120 ℃ of following crystallization 60 minutes.
(2) self-assembly of nano microcrystalline and nonionogenic tenside: 0.05mol polyoxyethylene cetyl ether is dissolved in the 15ml deionized water, slowly be added drop-wise in (1) resulting micro porous molecular sieve nano microcrystalline, stirred 5 hours with 300 rev/mins speed, regulating the pH value is 4.Reaction solution is put into the tetrafluoroethylene retort, setting MARS-5 microwave workstation power is 90W, temperature rise rate is 10 ℃/minute, 120 ℃ of following crystallization 30 minutes, with product take out remove residual reaction impurities with distilled water wash after, 110 ℃ of dried overnight, 500 ℃ of roasting demouldings 3 hours promptly prepare middle fine diplopore molecular sieve.
Fine diplopore molecular sieve has mesopore and the dual pore passage structure of micropore through XRD and pore structure Analysis and Identification in the gained, concrete structure parameter: mesopore aperture: 11.36nm, mesopore volume: 0.9ml/g, micropore size: 0.53nm, micropore pore volume: 1.8ml/g, BET specific surface area: 329.62m
2/ g.
Embodiment five
(1) preparation of micro porous molecular sieve nano microcrystalline: in the Erlenmeyer flask of clean dried, add the 10ml deionized water, stir and adding 0.02mol tetraethyl ammonium hydroxide (TBAOH) and 0.00167mol aluminum isopropylate with 200 rev/mins speed, slowly drip the 0.05mol water glass, stirred 2 hours with 500 rev/mins speed, regulating the pH value is 11.Reaction solution is put into the tetrafluoroethylene retort, and setting MARS-5 microwave workstation power is 300W, and temperature rise rate is 20 ℃/minute, 120 ℃ of following crystallization 3 hours.
(2) self-assembly of nano microcrystalline and nonionogenic tenside: with 0.025mol N, N-dimethyl hexadecylamine is dissolved in the 16.5ml deionized water, slowly be added drop-wise in (1) resulting micro porous molecular sieve nano microcrystalline, stirred 2 hours with 500 rev/mins speed, regulating the pH value is 3.Reaction solution is put into the tetrafluoroethylene retort, setting MARS-5 microwave workstation power is 300W, temperature rise rate is 20 ℃/minute, 100 ℃ of following crystallization 40 minutes, with product take out remove residual reaction impurities with distilled water wash after, 100 ℃ of dried overnight, 550 ℃ of roasting demouldings 5 hours promptly prepare middle fine diplopore molecular sieve.
Fine diplopore molecular sieve has mesopore and the dual pore passage structure of micropore through XRD and pore structure Analysis and Identification in the gained, concrete structure parameter: mesopore aperture: 2.34nm, mesopore volume: 1.5ml/g, micropore size: 0.53nm, micropore pore volume: 0.94ml/g, BET specific surface area: 569.75m
2/ g.
Claims (2)
1. the method for fine diplopore molecular sieve in nano microcrystalline and the non-ionic surface active agent microwave self-assembly preparation is characterized in that preparation process is as follows:
(1) preparation of micro porous molecular sieve nano microcrystalline: in the Erlenmeyer flask of clean dried, add 10～15ml deionized water, stir and add 0.01～0.05mol micropore template and 0.001～0.005mol aluminium source reagent with 200～300 rev/mins speed, slowly drip 0.05～0.2mol silicon source reagent, stirred 2～5 hours with 300～500 rev/mins speed, regulating the pH value is 9～12 again; Reaction solution is put into the tetrafluoroethylene retort, set microwave reaction power 90～480W, temperature rise rate is 10～40 ℃/minute, and 100～160 ℃ of following crystallization 30～105 minutes obtain the micro porous molecular sieve nano microcrystalline;
(2) self-assembly of nano microcrystalline and nonionogenic tenside: 0.005～0.05mol nonionogenic tenside is dissolved in 15～20ml deionized water, slowly be added drop-wise in (1) resulting micro porous molecular sieve nano microcrystalline, stirred 2～5 hours with 300～500 rev/mins speed, regulating the pH value is 3～10 again; Reaction solution is put into the tetrafluoroethylene retort, set microwave reaction power 90～480W, temperature rise rate is 10～40 ℃/minute, 100～160 ℃ of following crystallization 0.5～2 hour, with product take out remove residual reaction impurities with distilled water wash after, 100～120 ℃ of dried overnight, 500～600 ℃ of roasting demouldings 3～10 hours obtain middle fine diplopore molecular sieve;
Wherein, the proportioning of nonionogenic tenside and silicon source reagent is 0.1～0.5: 1.
2. method according to claim 1 is characterized in that, the micropore size scope of described middle fine diplopore molecular sieve is 0.4～1nm; The mesopore pore diameter range is 2～20nm.
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