CN102963907A - Pentasil type zeolite molecular sieve synthetic method - Google Patents
Pentasil type zeolite molecular sieve synthetic method Download PDFInfo
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Abstract
The invention belongs to the field of molecular sieve catalytic materials and discloses a pentasil type zeolite molecular sieve synthetic method. The pentasil type zeolite molecular sieve synthetic method comprises the following steps of mixing an aluminum-source compound, an alkali-source compound, a silicon-source compound, an additive, an organic template agent and water, and uniformly stirring to form a reaction mixture; and carrying out hydrothermal crystallization, filtering, washing and drying to obtain pentasil type zeolite molecular sieve, wherein the additive is polyether type compound. The pentasil type zeolite molecular sieve synthetic method disclosed by the invention has the advantages of high crystallization speed, low cost, low template agent consumption and the like, and the synthesized pentasil type zeolite molecular sieve has high degree of crystallinity and purity.
Description
Technical field
The invention belongs to the molecular sieve catalytic Material Field, be specifically related to a kind of synthetic method of pentasil type zeolite molecular sieve, adopt polyether compound to carry out the synthetic of molecular sieve as additive.
Background technology
Because zeolite molecular sieve has good thermostability, hydrothermal stability; Regulatable acidity; And unique features such as pore passage structure, (structure of Tu Kun hilllock zeolite molecular sieve is with synthetic for Xu Ruren, Pang Wenqin to be widely used in the fields such as fractionation by adsorption, ion-exchange, heterogeneous catalyst; Press of Jilin University, 1987.; The Xu Ruren, Pang Wenqin, Yu Jihong, Huo Qisheng, old connecing won molecular sieve and porous material chemistry, 2004.; Chinese Academy of Sciences's Dalian zeolite molecular sieve that materialization is shown, Science Press, 1978.).Except silicon source, aluminium source, titanium source, alkali source and water, template also is must be obligato in molecular sieve synthetic.In the prior art, usually rely on when other characteristics of molecular sieve of expensive template regulatory molecule sieve crystal morphology structure, modulation system silica alumina ratio or silicon titanium, increased largely the difficulty of Zeolite synthesis cost and adjustability.Simultaneously, mostly template is the organism of nitrogenous or longer carbochain, has increased to a certain extent the Zeolite synthesis cost, and roasting can produce oxynitrides when removing template, to environment.
The general general formula of polyoxyethylene glycol is H (OCH
2CH
2)
nOH is called for short PEG.Because polyoxyethylene glycol (PEG) exists the differing molecular polymerization degree to make its molecular weight controlled, thus the state of regulation and control peg molecule chain in the different solutions environment: when anhydrous state, be zigzag long chain molecule, but then form indentation after water-soluble.Therefore, utilize each Subjective and Objective molecular interaction in the different states of molecular chain and the solution, can change various materials synthetic mechanism and result.
Impact research in porous material is synthetic mainly comprises the following aspects for polyoxyethylene glycol (PEG) at present: the class crown ether of (1) polyoxyethylene glycol.Contain ether-oxygen bond in the PEG structure, have the class Crown properties, energy and metal ion generation complexing action.The people such as Jiao add PEG the TiO of preparation porous structure in the siliceous titanium precursor liquid solution
2/ SiO
2Material (Jiao, J.; Xu, Q.; Li, L.; Tsubasa, T.; Kobayashi, T.Colloid ﹠amp; Polymer Science 2008,286,1485.; Jiao, J.; Xu, Q.; Li, L.Journal of Colloid and Interface Science 2007,316,596.).(2) reductibility of polyoxyethylene glycol.Thereby polymkeric substance and metal interaction form micella as the stablizer of metal ion, stop accumulation and the precipitation of metal ion.The PEG molecule can interact with metal ion and form class crown ether hole and serve as reductive agent (Krishnan, C.V.; Chen, J.; Burger, C.; Chu, B.The Journal of Physical Chemistry B 2006,110,20182.; Chen, D.-H.; Huang, Y.-W.Journal of Colloid and Interface Science 2002,255,299.).(3) to the control of molecular sieve structure silica alumina ratio.Delprato group the obstructed process such as dealuminzation of processing later directly synthesizes Si/Al greater than the molecular sieve of 3 FAU structure by adding organic formwork agent crown ether molecule.Similarly, adding-OCH in the building-up process of y-type zeolite
2CH
2-organic species is conducive to synthetic high SiO
2/ Al
2O
3Zeolite (Delprato, F.; Delmotte, L.; Guth, J.L.; Huve, L.Zeolites, 10,546.; Dougnier, F.; Patarin, J.; Guth, J.L.; Anglerot, D.Zeolites 1992,12, and 160.).(4) to morphology control and cutting out.Crystal morphology determines that by the crystal face growth velocity different crystal faces have the different surfaces energy, therefore adds organism or inorganics and can change apparent surface's energy of different crystal faces and can change crystal morphology.Polyoxyethylene glycol PEG can be used as cosolvent control Transition metal substituted AIPO
4The pattern of-5 (AFI) molecular sieve.The adding polyoxyethylene glycol has suppressed significantly the Me-AFI crystal and has grown in the c-axis direction; And along with PEG/H
2The increase of O ratio, the transverse and longitudinal of Cr-AFI crystal is than reducing (Tian, D.; Yan, W.; Cao, X.; Yu, J.; Xu, R.Chemistry of Materials 2008,20,2160.).Simultaneously, polyoxyethylene glycol is used as the synthetic SAPO-34 crystal morphology of crystal growth inhibitor (crystal growth inhibitors, CGIs) control, the crystal inhibitor at first with aluminium phosphorus Species interaction, shorten nucleation time, increase nucleation quantity (Venna, S.R.; Carreon, M.A.The Journal of PhysicalChemistry B 2008,112,16261.).(5) polyoxyethylene glycol is on the impact of crystal particle diameter.The acidic site, high-ratio surface and the short characteristics such as the evolving path that have more exposure just because of nano zeolite are paid close attention to it widely.The people such as Wang add polyoxyethylene glycol and CTAB in the system of synthetic IM-5 nano zeolite, attempt to add to come modulation molecular sieve particle diameter (Wang, L. by tensio-active agent; Yang, W.; Xin, C.; Ling, F.; Sun, W.; Fang, X.; Yang, R.Materials Letters 2012,69,16.).(6) application of polyoxyethylene glycol in the multistage composite duct is synthetic.People's sol-gel methodes such as Tanaka prepare multistage composite pore passage structure material (Tanaka, N. in conjunction with phase separation; Kobayashi, H.; Ishizuka, N.; Minakuchi, H.; Nakanishi, K.; Hosoya, K.; Ikegami, T.Journal of Chromatography A 2002,965,35.; Ishizuka, N.; Minakuchi, H.; Nakanishi, K.; Soga, N.; Tanaka, N.Journal of Chromatography A 1998,797,133.; Ishizuka, N.; Minakuchi, H.; Nakanishi, K.; Hirao, K.; Tanaka, N.Colloids and Surfaces A:Physicochemical andEngineering Aspects 2001,187-188,273.).PEG is joined in the TMOS solution, obtain the silicon materials of crosslinked macroporous structure by hydrolysis and condensation, owing to PEG affects silicon species being separated in from colloidal sol to the gelation process, can control the diameter of macropore by the amount of modulation PEG; And mesoporous size mainly obtains with the ammonia soln aftertreatment.
In addition, relative wetting ability and the lipophilicity of polyether compound can be adjusted by substituted radical, and have cheap, easy synthetic, characteristics such as toxicity is little.Not yet propose polyether compound is used for the synthetic preparation of pentasil type zeolite molecular sieve in the prior art.
Summary of the invention
The invention provides molecular sieve and the synthetic method thereof of alkali metal containing ion in a kind of skeleton structure.It is synthetic that the present invention adopts the polyoxyethylene glycol of nonnitrogenous element of environmental protection and polypropylene glycol type polyether compound to carry out pentasil type zeolite molecular sieve, and crystallization that can the acceleration molecular sieve reduces the consumption of template; Realized synthetic higher pure silicon molecular sieve or the Si-Al molecular sieve of relative crystallinity under low consumption of template agent.
The present invention aims to provide a kind of innovative approach that adopts the zeolite molecular sieve of the synthetic pure silicon molecular sieve of polyether compound additive or silicon-aluminum containing structure, aluminum source compound, alkali source compound, silicon source compound, additive, organic formwork agent and water are mixed, stir, form reaction mixture; Described reaction mixture is carried out hydrothermal crystallizing, after filtration, washing, drying obtain described pentasil type zeolite molecular sieve; Wherein, described additive is polyether compound.
Described aluminium source comprises sodium metaaluminate, Tai-Ace S 150, aluminum nitrate and aluminum isopropylate.Described alkali source comprises potassium hydroxide and sodium hydroxide.Described silicon source comprises silicon sol, silica gel, water glass and white carbon black.Described polyether compound comprises polyoxyethylene glycol [HO (CH
2CH
2O)
nH, PEO], polypropylene glycol [HO (CH (CH
3) CH
2O)
nH, PPO] and contain the polymkeric substance of EO and PO structural unit.Wherein, the structural formula that contains the polymkeric substance of EO and PO structural unit is EO
mPO
nEO
t, wherein, m, n, t can be from 0 to ∞.
Among the present invention, described polyether compound is SiO in whole synthetic system
2: the polyether compound mass ratio is 1: (5-100%).
Among the present invention, in described reaction mixture, can also add Si-Al molecular sieve or guiding glue as crystal seed, SiO in the whole synthetic system
2: the SiO2 mass ratio is 1 in the crystal seed: (0-10%).
Among the present invention, Al in the described aluminum source compound
2O
3Molar equivalent: SiO
2Molar equivalent: alkali source compound: organic formwork agent: the mol ratio of water is (0-0.05): 1: (0.05-0.5): (0-0.5): (5-100).
Among the present invention, the temperature of described hydrothermal crystallizing is 100-200 ℃, and the time is 5-48 hour.
Particularly, the order of the interpolation of aluminium source, alkali source, silicon source, polyether compound and water and mixing is unrestricted among the present invention.
Among the present invention, the aluminium source also can be added and can not added.In reaction mixture, can select to add Si-Al molecular sieve or guiding glue as crystal seed.
Among the present invention, be SiO as the prescription of the guiding glue of crystal seed
2: 0.10-0.35TPAOH: 6-35H
2O: 4EtOH directly uses behind 80-185 ℃ of lower crystallization 2-72h.Molecular sieve as crystal seed can be identical or different with the molecular sieve structure that target is synthesized.
Can prepare pentasil type zeolite molecular sieve according to the inventive method, be the molecular sieve with MFI or MEL structure.Among the present invention, adopt polyether compound as the molecular sieve of the synthetic pure silicon of additive and silicon-aluminum structure, reduce synthetic cost by adding the polytrimethylene ether compounds, reduce simultaneously itrogenous organic substance to the pollution of environment.Utilize the polyether compound complexing action stronger to alkalimetal ion among the present invention, promote Crystallization of Zeolite, shorten crystallization time; Simultaneously, reduce the consumption of organic formwork agent by adding polyoxyethylene glycol.Reduced the cost of synthesis technique among the present invention by reducing consumption of template agent and two aspects of shortening crystallization time.
The inventive method has the advantages such as crystallization rate is fast, cost is low, the template consumption is little, and pentasil type zeolite molecular sieve degree of crystallinity and the purity of being synthesized are higher.
Description of drawings
Figure 1 shows that among the present invention the XRD comparison diagram of polyoxyethylene glycol as the synthetic pure silicon ZSM-5 molecular sieve of additive.
Figure 2 shows that among the present invention the crystallization graphic representation of polyoxyethylene glycol as the synthetic pure silicon ZSM-5 molecular sieve of interpolation.
Figure 3 shows that among the present invention the shape appearance figure of polyoxyethylene glycol as the synthetic pure silicon ZSM-5 molecular sieve of interpolation.
Figure 4 shows that among the present invention the XRD comparison diagram (SiO of polyoxyethylene glycol as the synthetic ZSM-5 molecular sieve of additive
2/ Al
2O
3Be 30).
Figure 5 shows that among the present invention the crystallization graphic representation (SiO of polyoxyethylene glycol as the synthetic ZSM-5 molecular sieve of additive
2/ Al
2O
3Be 30).
Embodiment
In conjunction with following specific embodiments and the drawings, the present invention is described in further detail.Implement process of the present invention, condition, reagent, experimental technique etc., except the following content of mentioning specially, be universal knowledege and the common practise of this area, the present invention is not particularly limited content.
The synthetic method of pentasil type zeolite molecular sieve of the present invention is that aluminum source compound, alkali source compound, silicon source compound, additive, organic formwork agent and water are mixed, and stirs, and forms reaction mixture; Reaction mixture is carried out hydrothermal crystallizing, after filtration, washing, drying obtain pentasil type zeolite molecular sieve; Wherein, additive is polyether compound.
(1) aluminum source compound, alkali source compound, silicon source compound, additive, organic formwork agent, water and polyether compound are mixed, stir, form reaction mixture.Wherein reinforced order is unrestricted.
(2) reaction mixture that obtains is transferred to carries out hydrothermal crystallizing in the autoclave, the controlling crystallizing temperature and time is respectively 100-200 ℃ and 0-48 hour, and the reaction mixture after the crystallization after filtration, deionized water wash, drying etc. obtain the zeolite molecular sieve of silicon-aluminum containing structure.
Wherein, the aluminium source comprises sodium metaaluminate, Tai-Ace S 150, aluminum nitrate, aluminum isopropylate.Alkali source comprises potassium hydroxide, sodium hydroxide.
The silicon source comprises silicon sol, silica gel, water glass, white carbon black.Polyether compound comprises polyoxyethylene glycol [HO (CH
2CH
2O)
nH, PEO], polypropylene glycol [HO (CH (CH
3) CH
2O)
nH, PPO] and contain the polymkeric substance of EO and PO structural unit.Wherein, the structural formula that contains the polymkeric substance of EO and PO structural unit is EO
mPO
nEO
t, wherein, m, n, t can be from 0 to ∞.
Among the present invention, polyether compound is SiO in whole synthetic system
2: the polyether compound mass ratio is 1: (5-100%).
Among the present invention, in reaction mixture, can also add Si-Al molecular sieve or guiding glue as crystal seed, SiO in the whole synthetic system
2: crystal seed amount mass ratio is 1: (0-10%).
Among the present invention, Al in the aluminum source compound
2O
3Molar equivalent: SiO
2Molar equivalent: alkali source compound: organic formwork agent: the mol ratio of water is (0-0.05): 1: (0.05-0.5): (0-0.5): (5-100).
Among the present invention, the temperature of hydrothermal crystallizing is 100-200 ℃, and the time is 5-48 hour.
Among the present invention, be SiO as the prescription of the guiding glue of crystal seed
2: 0.10-0.35TPAOH: 6-35H
2O: 4EtOH directly uses behind 80-185 ℃ of lower crystallization 2-72h.Molecular sieve as crystal seed can be identical or different with the molecular sieve structure that target is synthesized." guiding glue " among the present invention is through 50-150 ℃ of resulting colloidal sol or the molecular sieve pulp with siliceous or sial of structure-directing effect of lower crystallization.
Embodiment 1
A kind of preparation method of pure silicon Silicalite-1 molecular sieve, its concrete steps are as follows:
(1) with deionized water dissolved solids NaOH, stirs after the clarification, add polyoxyethylene glycol (PEG400) and form settled solution; In mentioned solution, add solid silicone, stirred 30-60 minute, add at last and contain TPA
+Guiding glue stirs.In the above-mentioned reaction mixture, Al in the aluminum source compound
2O
3Molar equivalent: SiO
2Molar equivalent: alkali source compound: H
2The mol ratio of O is 0: 1: 0.055: 12.SiO wherein
2: the mass ratio of guiding glue: PEG400 is 1: 5%: 20%.
(2) reaction mixture that obtains is transferred to carries out hydrothermal crystallizing in the autoclave, in 175 ℃ of crystallization 12 hours, the product after the crystallization after filtration, deionized water wash, drying etc. obtain containing the pure silicon zeolite molecular sieve of MFI structure.
Comparative Examples 1
A kind of preparation method of pure silicon Silicalite-1 molecular sieve, its concrete steps are as follows:
(1) with deionized water dissolved solids NaOH, stirs settled solution; In mentioned solution, add solid silicone, stirred 30-60 minute, add at last and contain TPA
+Guiding glue stirs.In the above-mentioned reaction mixture, Al in the aluminum source compound
2O
3Molar equivalent: SiO
2Molar equivalent: alkali source compound: H
2The mol ratio of O is 0: 1: 0.055: 12.SiO wherein
2: the mass ratio of guiding glue is 1: 5%.
(2) reaction mixture that obtains is transferred to carries out hydrothermal crystallizing in the autoclave, in 175 ℃ of crystallization 12 hours, the product after the crystallization after filtration, deionized water wash, drying etc. obtain containing the pure silicon zeolite molecular sieve of MFI structure.
According to experimental result as can be known, not adding the prepared sieve sample of PEG is 85% in its degree of crystallinity of 12h, and according to after the present embodiment method interpolation PEG, behind the same crystallization time, the degree of crystallinity of pure silicon Silicalite-1 molecular sieve reaches 100%.In conjunction with Fig. 1 as seen, the Silicalite-1 that adds PEG is the MFI structure of pure phase, occurs without any dephasign.As shown in Figure 2, compare the crystallization curve of two samples as seen, the adding of PEG can obviously promote the crystallization of Silicalite-1.The pattern of above sample as shown in Figure 3, two samples all are 100-200nm size coffin shape crystal, do not have more less crystal grain or amorphous substance but add the prepared sieve sample of PEG; The adding of PEG promotes crystallization, and crystal grain disperses than homogeneous.
A kind of preparation method of silicon-aluminum containing ZSM-11 molecular sieve, its concrete steps are as follows:
(1) with deionized water dissolved solids NaOH, stirs after the clarification, add polyoxyethylene glycol (PEG400) and form settled solution; In mentioned solution, add solid silicone, stirred 30-60 minute, add at last TBAH (TBAOH), stir.In the above-mentioned reaction mixture, Al in the aluminum source compound
2O
3Molar equivalent: SiO
2Molar equivalent: alkali source compound: TBAOH: H
2The mol ratio of O is 0: 1: 0.055: 0.2: 12.SiO wherein
2: the mass ratio of PEG400 is 1: 20%.
(2) reaction mixture that obtains is transferred to carries out hydrothermal crystallizing in the autoclave, in 175 ℃ of crystallization 24 hours, the product after the crystallization after filtration, deionized water wash, drying etc. obtain containing the pure silicon zeolite molecular sieve of MEL structure.
Comparative Examples 2
A kind of preparation method of silicon-aluminum containing ZSM-11 molecular sieve, its concrete steps are as follows:
(1) with deionized water dissolved solids NaOH, stirs settled solution; In mentioned solution, add solid silicone, stirred 30-60 minute, add at last TBAOH, stir.In the above-mentioned reaction mixture, Al in the aluminum source compound
2O
3Molar equivalent: SiO
2Molar equivalent: alkali source compound: TBAOH: H
2The mol ratio of O is 0: 1: 0.055: 0.2: 12.
(2) reaction mixture that obtains is transferred to carries out hydrothermal crystallizing in the autoclave, in 175 ℃ of crystallization 24 hours, the product after the crystallization after filtration, deionized water wash, drying etc. obtain containing the pure silicon zeolite molecular sieve of MEL structure.
Embodiment 3
A kind of preparation method of pure silicon Silicalite-1 molecular sieve, its concrete steps are as follows:
(1) diluting concentrated sulfuric acid is formed sulfuric acid dilute solution A; Simultaneously, with hot water dissolving nine water water glass (Na
2SiO
39H
2O) form clarification B solution.Under mechanical stirring, settled solution A dropwise is added drop-wise in the B solution, after acid dropwises fully, above-mentioned turbid liquid filtration is obtained amorphous filter cake, this filter cake is fed intake according to the following formulation Al in the aluminum source compound
2O
3Molar equivalent: SiO
2Molar equivalent: alkali source compound: H
2The mol ratio of O is 0: 1: 0.055: 35, and add at last and contain TPA
+Guiding glue stirs 30-60 minute to evenly getting final product.SiO wherein
2: the mass ratio of guiding glue: PEG400 is 1: 5%: 20%.
(2) reaction mixture that obtains is transferred to carries out hydrothermal crystallizing in the autoclave, in 175 ℃ of crystallization 12 hours, the product after the crystallization after filtration, deionized water wash, drying etc. obtain containing the pure silicon zeolite molecular sieve of MFI structure.
Comparative Examples 3
A kind of preparation method of pure silicon Silicalite-1 molecular sieve, its concrete steps are as follows:
(1) diluting concentrated sulfuric acid is formed sulfuric acid dilute solution A; Simultaneously, with hot water dissolving nine water water glass (Na
2SiO
39H
2O) form clarification B solution.Under mechanical stirring, settled solution A dropwise is added drop-wise in the B solution, after acid dropwises fully, above-mentioned turbid liquid filtration is obtained amorphous filter cake, this filter cake is fed intake according to the following formulation Al in the aluminum source compound
2O
3Molar equivalent: SiO
2Molar equivalent: alkali source compound: H
2The mol ratio of O is 0: 1: 0.055: 35, and add at last and contain TPA
+Guiding glue stirs 30-60 minute to evenly getting final product.SiO wherein
2: the mass ratio of guiding glue is 1: 5%.
(2) reaction mixture that obtains is transferred to carries out hydrothermal crystallizing in the autoclave, in 175 ℃ of crystallization 24 hours, the product after the crystallization after filtration, deionized water wash, drying etc. obtain containing the pure silicon zeolite molecular sieve of MFI structure.
By the contrast of embodiment 3 and Comparative Examples 4, in identical synthetic system, and produce brilliant degree of crystallinity and be about under 99% the condition, adding quantitative PEG can directly foreshorten to 12 hours from 24 hours with crystallization time, had reduced production cost consumption largely.
A kind of preparation method of ZSM-5 molecular sieve, its concrete steps are as follows:
(1) solid NaOH and sodium metaaluminate are dissolved in deionized water, stir after the clarification, add polyoxyethylene glycol (PEG400) and form settled solution; In mentioned solution, add solid silicone, stirred 30-60 minute, add at last and contain TPA
+Guiding glue, stir.Al in the above-mentioned aluminum source compound
2O
3Molar equivalent: SiO
2Molar equivalent: alkali source compound: the guiding glue: PEG400: H
2The mol ratio of O is 0.033: 1: 0.055: 12; SiO wherein
2: the mass ratio of guiding glue: PEG400 is 1: 5%: 20%.
(2) reaction mixture that obtains is transferred to carries out hydrothermal crystallizing in the autoclave, in 175 ℃ of crystallization 12 hours, the product after the crystallization after filtration, deionized water wash, drying etc. obtain containing the Si-Al zeolite molecular sieve of MFI structure.
Comparative Examples 4
A kind of preparation method of ZSM-5 molecular sieve, its concrete steps are as follows:
(1) solid NaOH and sodium metaaluminate are dissolved in deionized water formation settled solution; In mentioned solution, add solid silicone, stirred 30-60 minute, add at last and contain TPA
+Guiding glue, stir.Al in the above-mentioned aluminum source compound
2O
3Molar equivalent: SiO
2Molar equivalent: alkali source compound: H
2The mol ratio of O is 0.033: 1: 0.055: 12; SiO wherein
2: the mass ratio of guiding glue is 1: 5%.
(2) reaction mixture that obtains is transferred to carries out hydrothermal crystallizing in the autoclave, in 175 ℃ of crystallization 12 hours, the product after the crystallization after filtration, deionized water wash, drying etc. obtain containing the Si-Al zeolite molecular sieve of MFI structure.
Than the pure silicon system, obviously increase the inductive phase of Si-Al molecular sieve, and the adding of PEG further significantly promotes nucleation and the crystallization of molecular sieve.According to experimental result as can be known, not adding the prepared ZSM-5 molecular sieve sample crystalline substance of PEG is 89% in the degree of crystallinity of 12h, and according to after the present embodiment method interpolation PEG, behind the bar crystallization time, the degree of crystallinity of ZSM-5 molecular sieve reaches 100%.In conjunction with Fig. 4 as seen, the ZSM-5 that adds PEG is the MFI structure of pure phase, occurs without any dephasign.As shown in Figure 5, relatively different brilliant crystallization curve as seen, the adding of PEG can obviously promote the crystallization of ZSM-5.
A kind of preparation method of ZSM-5 molecular sieve, its concrete steps are as follows:
(1) Tai-Ace S 150 is dissolved in the dilute sulfuric acid aqueous solution, stirs and form clarification A solution; Simultaneously, with hot water dissolving nine water water glass (Na
2SiO
39H
2O) form clarification B solution.Under mechanical stirring, settled solution A dropwise is added drop-wise in the B solution, after acid dropwises fully, above-mentioned turbid liquid filtration is obtained filter cake, the amorphous filter cake of this sial is fed intake.Al in the above-mentioned aluminum source compound
2O
3Molar equivalent: SiO
2Molar equivalent: alkali source compound: TPAOH: H
2The mol ratio of O is 0.033: 1: 0.055: 0.1: 35, and SiO wherein
2: the mass ratio of PEG400 is 1: 20%.
(2) reaction mixture that obtains is transferred to carries out hydrothermal crystallizing in the autoclave, in 175 ℃ of crystallization 24 hours, the product after the crystallization after filtration, deionized water wash, drying etc. obtain containing the Si-Al zeolite molecular sieve of MFI structure.
Comparative Examples 5
A kind of preparation method of ZSM-5 molecular sieve, its concrete steps are as follows:
(1) Tai-Ace S 150 is dissolved in the dilute sulfuric acid aqueous solution, stirs and form clarification A solution; Simultaneously, with hot water dissolving nine water water glass (Na
2SiO
39H
2O) form clarification B solution.Under mechanical stirring, settled solution A dropwise is added drop-wise in the B solution, after acid dropwises fully, above-mentioned turbid liquid filtration is obtained filter cake, the amorphous filter cake of this sial is fed intake.Al in the above-mentioned aluminum source compound
2O
3Molar equivalent: SiO
2Molar equivalent: alkali source compound: TPAOH: H
2The mol ratio of O is 0.033: 1: 0.055: 0.35: 35.
(2) reaction mixture that obtains is transferred to carries out hydrothermal crystallizing in the autoclave, in 175 ℃ of crystallization 24 hours, the product after the crystallization after filtration, deionized water wash, drying etc. obtain containing the Si-Al zeolite molecular sieve of MFI structure.
A kind of preparation method of ZSM-5 molecular sieve, its concrete steps are as follows:
(1) with deionized water dissolved solids NaOH and sodium metaaluminate (NaAlO
2), stir after the clarification, add polyoxyethylene glycol (PEG400) and form clarification A solution; In mentioned solution, add solid silicone, stirred 30-60 minute, continue adding and contain TPA
+Guiding glue stirs.Al in the above-mentioned aluminum source compound
2O
3Molar equivalent: SiO
2Molar equivalent: alkali source compound: TPAOH: H
2The mol ratio of O is 0.033: 1: 0.055: 0.1: 12, and SiO wherein
2: the mass ratio of PEG400 is 1: 100%.
(2) reaction mixture that obtains is transferred to carries out hydrothermal crystallizing in the autoclave, in 175 ℃ of crystallization 12 hours, the product after the crystallization after filtration, deionized water wash, drying etc. obtain containing the Si-Al zeolite molecular sieve of MFI structure.
A kind of preparation method of ZSM-5 molecular sieve, its concrete steps are as follows:
(1) with deionized water dissolved solids NaOH and sodium metaaluminate (NaAlO
2), stir after the clarification, add polyoxyethylene glycol (PEG6000) and form clarification A solution; In mentioned solution, add solid silicone, stirred 30-60 minute, continue adding and contain TPA
+Guiding glue stirs.Al in the above-mentioned aluminum source compound
2O
3Molar equivalent: SiO
2Molar equivalent: alkali source compound: quadrol: the mol ratio of water is 0.033: 1: 0.055: 0.28: 12, SiO wherein
2: the mass ratio of PEG6000 is 1: 50%.
(2) reaction mixture that obtains is transferred to carries out hydrothermal crystallizing in the autoclave, in 175 ℃ of crystallization 12 hours, the product after the crystallization after filtration, deionized water wash, drying etc. obtain containing the Si-Al zeolite molecular sieve of MFI structure.
Embodiment 7
A kind of preparation method of ZSM-5 molecular sieve, its concrete steps are as follows:
(1) with deionized water dissolved solids NaOH and sodium metaaluminate (NaAlO
2), stir after the clarification, add polyoxyethylene glycol (PEG20000) and form clarification A solution; In mentioned solution, add solid silicone, stirred 30-60 minute, continue adding and contain TPA
+Guiding glue stirs.Al in the above-mentioned aluminum source compound
2O
3Molar equivalent: SiO
2Molar equivalent: alkali source compound: quadrol: H
2The mol ratio of O is 0.033: 1: 0.055: 0.28: 12, and SiO wherein
2: the mass ratio of PEG20000 is 1: 20%.
(2) reaction mixture that obtains is transferred to carries out hydrothermal crystallizing in the autoclave, in 140 ℃ of crystallization 24 hours, the product after the crystallization after filtration, deionized water wash, drying etc. obtain containing the Si-Al zeolite molecular sieve of MFI structure.
A kind of preparation method of ZSM-5 molecular sieve, its concrete steps are as follows:
(1) with deionized water dissolved solids NaOH and sodium metaaluminate (NaAlO
2), stir after the clarification, add polyoxyethylene glycol (PEG400) and form clarification A solution; In mentioned solution, add solid silicone, stirred 30-60 minute, continue adding and contain TPA
+Guiding glue stirs.Al in the above-mentioned aluminum source compound
2O
3Molar equivalent: SiO
2Molar equivalent: alkali source compound: TPAOH: the guiding glue: H
2The mol ratio of O is 0.033: 1: 0.055: 0.1: 12, and SiO wherein
2: the mass ratio of guiding glue: PEG400 is 1: 1%: 100%.
(2) reaction mixture that obtains is transferred to carries out hydrothermal crystallizing in the autoclave, in 175 ℃ of crystallization 12 hours, the product after the crystallization after filtration, deionized water wash, drying etc. obtain containing the Si-Al zeolite molecular sieve of MFI structure.
Embodiment 9
A kind of preparation method of ZSM-5 molecular sieve, its concrete steps are as follows:
(1) with deionized water dissolved solids NaOH and sodium metaaluminate (NaAlO
2), stir after the clarification, add polyoxyethylene glycol (PEG400) and form clarification A solution; In mentioned solution, add solid silicone, stirred 30-60 minute, continue adding and contain TPA
+Guiding glue stirs.Al in the above-mentioned aluminum source compound
2O
3Molar equivalent: SiO
2Molar equivalent: alkali source compound: TEABr: H
2The mol ratio of O is 0.033: 1: 0.055: 0.35: 12, and SiO wherein
2: the mass ratio of PEG400 is 1: 5%.。
(2) reaction mixture that obtains is transferred to carries out hydrothermal crystallizing in the autoclave, in 185 ℃ of crystallization 12 hours, the product after the crystallization after filtration, deionized water wash, drying etc. obtain containing the Si-Al zeolite molecular sieve of MFI structure.
A kind of preparation method of ZSM-5 molecular sieve, its concrete steps are as follows:
(1) with deionized water dissolved solids KOH and sodium metaaluminate (NaAlO
2), stir after the clarification, add polyoxyethylene glycol (PEG400) and form clarification A solution; In mentioned solution, add solid silicone, stirred 30-60 minute, continue adding and contain TPA
+Guiding glue stirs.Al
2O
3Molar equivalent: SiO
2Molar equivalent: alkali source compound: hexanediamine: H
2The mol ratio of O is 0.033: 1: 0.055: 0.35: 12, and SiO wherein
2: the mass ratio of PEG400 is 1: 20%.。
(2) reaction mixture that obtains is transferred to carries out hydrothermal crystallizing in the autoclave, in 185 ℃ of crystallization 12 hours, the product after the crystallization after filtration, deionized water wash, drying etc. obtain containing the Si-Al zeolite molecular sieve of MFI structure.
Embodiment 11
A kind of preparation method of ZSM-5 molecular sieve, its concrete steps are as follows:
(1) with deionized water dissolved solids KOH and sodium metaaluminate (NaAlO
2), stir after the clarification, add polyoxyethylene glycol (PPG2000) and form clarification A solution; In mentioned solution, add solid silicone, stirred 30-60 minute, continue adding and contain TPA
+Guiding glue stirs.Al
2O
3Molar equivalent: SiO
2Molar equivalent: alkali source compound: TPAOH: H
2The mol ratio of O is 0.033: 1: 0.055: 0.1: 12, and SiO wherein
2: the mass ratio of PEG400 is 1: 20%.
(2) reaction mixture that obtains is transferred to carries out hydrothermal crystallizing in the autoclave, in 200 ℃ of crystallization 12 hours, the product after the crystallization after filtration, deionized water wash, drying etc. obtain containing the Si-Al zeolite molecular sieve of MFI structure.
A kind of preparation method of ZSM-5 molecular sieve, its concrete steps are as follows:
(1) with deionized water dissolved solids NaOH and sodium metaaluminate (NaAlO
2), stir after the clarification, add polyoxyethylene glycol (PEG400) and form clarification A solution; In mentioned solution, add solid silicone, stirred 30-60 minute, continue adding and contain TPA
+Guiding glue stirs.Al
2O
3Molar equivalent: SiO
2Molar equivalent: alkali source compound: TPABr: H
2The mol ratio of O is 0.033: 1: 0.055: 0.1: 12, and SiO wherein
2: the mass ratio of PEG400 is 1: 20%.。
(2) reaction mixture that obtains is transferred to carries out hydrothermal crystallizing in the autoclave, in 185 ℃ of crystallization 12 hours, the product after the crystallization after filtration, deionized water wash, drying etc. obtain containing the Si-Al zeolite molecular sieve of MFI structure.
Embodiment 13
A kind of preparation method of ZSM-5 molecular sieve, its concrete steps are as follows:
(1) with deionized water dissolved solids NaOH and sodium metaaluminate (NaAlO
2), stir after the clarification, add polyoxyethylene glycol (PEG400) and form clarification A solution; In mentioned solution, add solid silicone, stirred 30-60 minute, continue adding and contain TPA
+Guiding glue stirs.Al
2O
3Molar equivalent: SiO
2Molar equivalent: alkali source compound: butylamine: PEG400: H
2The mol ratio of O is 0.033: 1: 0.055: 0.28: 12, and SiO wherein
2: the mass ratio of PEG400 is 1: 20%.。
(2) reaction mixture that obtains is transferred to carries out hydrothermal crystallizing in the autoclave, in 185 ℃ of crystallization 12 hours, the product after the crystallization after filtration, deionized water wash, drying etc. obtain containing the pure silicon zeolite molecular sieve of MFI structure.
The synthesis step of present embodiment ZSM-5 molecular sieve and embodiment 4 are basically identical.Present embodiment adopts hydrochloric acid as acid source.Its crystallization temperature is 175 ℃, can synthesize in crystallization 2-48 hour to obtain the former powder of ZSM-5 molecular sieve of the present invention, and its relative crystallinity can reach 108%.
The synthesis step of present embodiment ZSM-5 molecular sieve and embodiment 3 are basically identical.Present embodiment adopts white carbon black as the silicon source.Its crystallization temperature is 175 ℃, can synthesize in crystallization 2-48 hour to obtain the former powder of ZSM-5 molecular sieve of the present invention, and its relative crystallinity can reach 108%.
Embodiment 16
The synthesis step of present embodiment ZSM-5 molecular sieve and embodiment 4 are basically identical.Present embodiment adopts nitric acid and aluminum nitrate respectively as acid source and aluminium source.Its crystallization temperature is 175 ℃, can synthesize in crystallization 2-48 hour to obtain the former powder of ZSM-5 molecular sieve of the present invention, and its relative crystallinity can reach 102%.
Embodiment 17
The synthesis step of present embodiment ZSM-5 molecular sieve and embodiment 1 are basically identical.The crystallization temperature that present embodiment adopts is 185 ℃, can synthesize in crystallization 2-48 hour to obtain the former powder of ZSM-5 molecular sieve of the present invention, and its relative crystallinity can reach 100%.
The synthetic middle polyether compound that adds of pentasil type zeolite molecular sieve of the present invention, the crystallization of acceleration molecular sieve, the consumption of minimizing template can synthesize the higher molecular sieve of relative crystallinity under low consumption of template agent.
Protection content of the present invention is not limited to above embodiment.Under the spirit and scope that do not deviate from inventive concept, the variation that those skilled in the art can expect and advantage section are included in the present invention, and take appending claims as protection domain.
Claims (6)
1. the synthetic method of a pentasil type zeolite molecular sieve is characterized in that, aluminum source compound, alkali source compound, silicon source compound, additive, organic formwork agent and water are mixed, and stirs, and forms reaction mixture; Described reaction mixture is carried out hydrothermal crystallizing, after filtration, washing, drying obtain described pentasil type zeolite molecular sieve; Wherein, described additive is polyether compound.
2. the synthetic method of pentasil type zeolite molecular sieve as claimed in claim 1 is characterized in that, described aluminum source compound comprises sodium metaaluminate, Tai-Ace S 150, aluminum nitrate and aluminum isopropylate; Described alkali source compound comprises potassium hydroxide and sodium hydroxide; Described silicon source compound comprises silicon sol, silica gel, water glass and white carbon black; Described polyether compound comprises polyoxyethylene glycol, polypropylene glycol and contains EO and the polymkeric substance of PO structural unit; Described organic formwork agent comprises TPAOH, TPABr, amine and diamines.
3. the synthetic method of pentasil type zeolite molecular sieve as claimed in claim 1 is characterized in that, described polyether compound is SiO in whole synthetic system
2: the polyether compound mass ratio is 1: (5-100%).
4. the synthetic method of pentasil type zeolite molecular sieve as claimed in claim 1 is characterized in that, adds Si-Al molecular sieve or guiding glue as crystal seed in described reaction mixture, SiO in the whole synthetic system
2: the SiO2 mass ratio is 1 in the crystal seed: (0-10%).
5. the synthetic method of pentasil type zeolite molecular sieve as claimed in claim 1 is characterized in that, Al in the described aluminum source compound
2O
3Molar equivalent: SiO
2Molar equivalent: alkali source compound: organic formwork agent: the mol ratio of water is (0-0.05): 1: (0.05-0.5): (0-0.5): (5-100).
6. the synthetic method of pentasil type Si-Al zeolite molecular sieve as claimed in claim 1 is characterized in that, the temperature of described hydrothermal crystallizing is 100-200 ℃, and the time is 5-48 hour.
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| CN105460952A (en) * | 2014-08-19 | 2016-04-06 | 神华集团有限责任公司 | Preparation method of ZSM-5 molecular sieve material, and ZSM-5 molecular sieve material prepared by the method |
| CN107915234A (en) * | 2017-11-09 | 2018-04-17 | 华东师范大学 | A kind of preparation method of 1 nano zeolite aggregation molecular sieves of multi-stage porous TS |
| CN109264740A (en) * | 2018-09-30 | 2019-01-25 | 厦门大学 | A kind of preparation method and application of nanometer of SAPO-34 molecular sieve |
| CN110817899A (en) * | 2018-08-14 | 2020-02-21 | 中国科学院大连化学物理研究所 | Method for promoting synthesis of ZSM-11 molecular sieve |
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| CN105460952A (en) * | 2014-08-19 | 2016-04-06 | 神华集团有限责任公司 | Preparation method of ZSM-5 molecular sieve material, and ZSM-5 molecular sieve material prepared by the method |
| CN107915234A (en) * | 2017-11-09 | 2018-04-17 | 华东师范大学 | A kind of preparation method of 1 nano zeolite aggregation molecular sieves of multi-stage porous TS |
| CN107915234B (en) * | 2017-11-09 | 2020-10-16 | 华东师范大学 | Preparation method of hierarchical porous TS-1 nano zeolite aggregate molecular sieve |
| CN110817899A (en) * | 2018-08-14 | 2020-02-21 | 中国科学院大连化学物理研究所 | Method for promoting synthesis of ZSM-11 molecular sieve |
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| CN109264740A (en) * | 2018-09-30 | 2019-01-25 | 厦门大学 | A kind of preparation method and application of nanometer of SAPO-34 molecular sieve |
| CN111001436A (en) * | 2019-12-14 | 2020-04-14 | 中触媒新材料股份有限公司 | Intergrowth composite molecular sieve with AEI/KFI structure, preparation method thereof and SCR application thereof |
| CN111646485A (en) * | 2020-04-28 | 2020-09-11 | 北京泷涛环境科技有限公司 | Hierarchical pore molecular sieve and preparation method and application thereof |
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