CN103172081B - High-molecular organic polymer template synthesized compound pore structure molecular sieve and preparation method thereof - Google Patents
High-molecular organic polymer template synthesized compound pore structure molecular sieve and preparation method thereof Download PDFInfo
- Publication number
- CN103172081B CN103172081B CN201310114100.2A CN201310114100A CN103172081B CN 103172081 B CN103172081 B CN 103172081B CN 201310114100 A CN201310114100 A CN 201310114100A CN 103172081 B CN103172081 B CN 103172081B
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- mixing solutions
- total mass
- accounts
- source
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention relates to a high-molecular organic polymer template synthesized compound pore structure molecular sieve and a preparation method thereof and belongs to the technical field of compound pore structure molecular sieve preparation. The technical scheme is that the preparation method comprises the following steps of: forming molecular sieve gel, wherein a certain amount of silicon source, aluminum source, template agent and deionized water are uniformly mixed under room temperature; and a certain amount of PEI (Polyethyleneimine) is added to the uniformly mixed molecular sieve gel as a mesoporous structure guide agent for being uniformly stirred; carrying out hydrothermal reaction, wherein the hydrothermal reaction temperature is 100 DEG C to 250 DEG C, the hydrothermal reaction is carried out directly or under stirring conditions and the reaction time is 12 hours to 168 hours; drying, wherein the drying is carried out for 6 hours to 48 hours under 50 DEG C to 150 DEG C; and roasting to obtain the molecular sieve with the compound pore structure, wherein the roasting is carried out for 1 hour to 24 hours under 300 DEG C to 800 DEG C.
Description
Technical field
The present invention relates to a kind of polymer organic polymer templated synthesis and there is composite pore structural molecular sieve and preparation method thereof, belong to composite pore structural technical field of molecular sieve preparation.
Background technology
Regular and the uniform pore passage structure of zeolitic molecular sieve, comprise the size and shape in duct, and it has higher specific surface and pore volume, higher hydrothermal stability makes it be widely used in refining of petroleum and the catalysis engineering in processing, the cracking of such as hydrocarbon polymer, alkylation, hydrocracking, isomerization, secondly they are also widely used in adsorption separation process, as drying, the de-CO of Sweet natural gas, splitting gas etc.
2, the field of purification such as desulfurization.Wherein most is representational is the synthetic work that ZSM-5 Series Molecules sieves.But because the aperture of zeolite molecular sieve is less, strongly limit the application [Corma, A. Chem. Rev. 97, (1997), 2373.] of the velocity of diffusion of catalyzed reaction and the catalyzed reaction in macromole participation.
Mobil company in 1992 uses quaternary ammonium alkyl cationic surfactants to successfully synthesize mesostructured material series [Kresge for template first, C. T., Leonowicz, M. E., Roth, W. J., Vartuli, J. C. & Beck, J. S. Nature 352, (1992), 710.], this kind of molecular screen material with regular mesopore orbit is conducive to macromolecular absorption and diffusion, in catalysis, membrane separation technique and molecular engineering etc., have bright prospects.Mesoporous material is widely used at catalytic field, nowadays petroleum refining process, fine chemicals conversion, particularly have macromole to participate in catalyzed reaction in demonstrate especially excellent catalytic performance.In refining of petroleum, conventional catalyst material is generally micro porous molecular sieve, as Y type, type ZSM 5 molecular sieve.But, along with the increasing gradually of petroleum resources heavy oil composition in worldwide day by day exhausted and crude oil, traditional micro porous molecular sieve catalytic material due to aperture less, heavy oil molecules can not enter duct, thus limits the carrying out of catalyzed reaction.Ordered mesoporous material then provides mesoporous pore passage structure, and this catalyzed conversion for heavy oil molecules provides a good opportunity.But mesoporous material is compared with microporous zeolitic material, the reasons such as lower hydrothermal stability, more weak strength of acid and its preparation cost are high limit its application in catalysis.In view of the demand of petrochemical complex and fine chemistry industry, a lot of research is devoted to find a kind of novel material in conjunction with both microporous zeolitic material and mesoporous material advantage, not only there is high hydrothermal stability and comparatively high acid strength but also include larger aperture, larger application can have been obtained at catalytic field.
Mould plate technique is widely used in the preparation of nanoassemble material, and this technology can realize the control of shape, structure and size to assembled material by the shape and size changing corresponding template.Utilize restricted clearance legal system for nano zeolite be by the growth limitation of zeolite grain in the small duct of inert media carbon black [Schmidt I. Inorg. Chem., 2000, (39): 2279-2283].Jacobsen [Jacobsen C J H, J. Am. Chem. Soc., 2000,122 (29): 7116-7117.] by after the gel of ZSM-5 micro porous molecular sieve and carbon black are carried out hydro-thermal reaction, zeolite can by the growth of the charcoal particle encapsulation of inertia within zeolite grain, by mesopore orbit can be left in zeolite crystal after roasting removing carbon black template, define the ZSM-5 with composite pore structural.Yousheng Tao [Tao, Y. J. Am. Chem. Soc. 2003,125,6044.] by utilizing the carbonization superpolymer aerosol template with high mesoporous porosity, successfully carbon template is loaded in ZSM-5 molecular sieve, roasting, except after carbon elimination template, obtains having the ZSM-5 zeolite material of comparatively homogeneous mesopore orbit.Liu Zhicheng [Liu Zhicheng, Xie Ku. petroleum journal (refining of petroleum) .2008,24:124.] etc. people by starch being joined in ZSM-5 molecular sieve gel, obtain the ZSM-5 molecular sieve with composite pore structural finally by calcining, and mesoporous quantity can be regulated by regulating the ratio of starch.The people such as Xie Ku [Zhu H B, Xie Z K. Chem Mater, 2008,20:1134.] have also successfully prepared the Silicate-1 molecular sieve with meso-hole structure by using nano-calcium carbonate as hard template.
Supermolecular module is the normally used method of synthesising mesoporous molecular sieve, selects the suitable supermolecular module with ad hoc structure also can cause mesoporous generation when synthetic zeolite.Utilize micromolecular organic ammonium and the effect of cationic polymers pore-creating agent dual mould plate, the Mesoporous Zeolite Materials with composite holes pore passage structure can be synthesized.Xiao [Xiao F S. Angew. Chem. Int. Ed., 2006,45 (19): 3090-3093] ZSM-5 molecular sieve with meso-hole structure has been synthesized under etc. people uses the multipolymer (PDD2AM) of TPAOH (TPAOH) and Poly Dimethyl Diallyl Ammonium Chloride and acrylamide to exist.Korean science man [Choi M, Cho H S, Srivastava R, et al. Nat. Mater., 2006,5 (9): 718-723] devises a kind of molecules surfactant [(CH of novel texture
3o)
3siC
3h
6n (CH
3)
2c
16h
33] Cl, this tensio-active agent one end has can at the end group of the methoxy silane of zeolite synthesis Water Under solution, the other end is then the end group of organic ammonium, to be added to by this tensio-active agent in synthetic system of zeolite and can have the zeolitic material of high mesoporous content by single sintering.Ryong Ryoo [M. Choi, R. Srivastava and R. Ryoo, Chem. Commun., 2006,4380.] uses close both sexes organosilane [(CH
3o)
3siC
3h
6n (CH
3)
2c
16h
33] Cl synthesized the multiple phosphate aluminium molecular sieve with composite pore structural.Xie Ku [Zhu H B, Xie Z K. J Phys Chem C, 2008,112 (44): 17257.] by using PVB(polyvinyl butyral acetal) as mesoporous directed agents, successfully synthesize and had without ordered meso-porous structure beta-molecular sieve and ZSM-11 molecular sieve.Wang [H. Wang and T. J. Pinnavaia, Angew. Chem., Int. Ed., 2006,45,7603.] by using PEI(polymine) organic high molecular polymer of Si modification as template, successfully synthesized the ZSM-5 with meso-hole structure, and its mesoporous pore size size can by adjustment PEI(polymine) molecular weight control.But wherein much relate to the price of method due to its template and the complexity of synthesis condition of high molecular polymer, be difficult to apply to industrial circle, therefore synthesizing high-stability, acid intensity high and low cost, composite pore structural, the molecular sieve of high catalytic activity has important practical significance and industrial value.
Summary of the invention
The technical problem to be solved in the present invention is, use macromolecule organic amine polymkeric substance as meso-hole structure directed agents, preparation has certain compound pore passage structure, comparatively high-ratio surface, the molecular sieve of high catalytic activity, with applicable industrial production and application.
Zeolite molecular sieve involved in the present invention is primary is that the molecular sieve being applied in various structure in refining of petroleum and chemical engineering industry field is not only only Si-Al molecular sieve (as MFI-type molecular sieve, L-type molecular sieve, Y zeolite), wherein also comprise silica zeolite (as Silicalite-1 molecular sieve), HTS (as TS-1 molecular sieve), phosphate aluminium molecular sieve (as AFI type molecular sieve), aluminium silicophosphate molecular sieve (as SAPO Series Molecules sieve).
The preparation method with the Si-Al molecular sieve material of composite pore structural that the present invention relates to: silicon source and aluminium source are added to the water and stir, and add using polymine and organic amine or organic quaternary ammonium salt as composite shuttering, and by NaOH(sodium hydroxide), KOH(potassium hydroxide) come Molecular regulator sieve mixing solutions pH be in 12 ~ 14, prepare the molecular sieve containing composite pore structural; Polymine add-on is 1% ~ 30% of mixing solutions total mass; The temperature of hydrothermal treatment consists is 100 ~ 200 DEG C, and crystallization time is 1 ~ 7 day; Again by molecular screen material 300 ~ 800 DEG C of calcinings 5 ~ 24 hours thus obtain the molecular sieve with open duct in atmosphere.
Si-Al molecular sieve synthetic ratio: wherein silicon source accounts for 25% ~ 50% of molecular sieve mixing solutions total mass, aluminium source accounts for 0.75% ~ 4% of molecular sieve mixing solutions gross weight, template accounts for 3% ~ 8% of molecular sieve mixing solutions total mass, and water accounts for 42% ~ 72% of molecular sieve mixing solutions total mass.
Silicon source is tetraethoxy, water glass, white carbon black, water glass or silicon sol etc.;
Aluminium source is aluminum isopropylate, KAlO
2(potassium metaaluminate), NaAlO
2(sodium metaaluminate), pseudo-boehmite, aluminum oxide and Al
2(SO
4)
3(Tai-Ace S 150) etc.;
Organic amine or organic quaternary ammonium salt are TPABr(4-propyl bromide), TPAOH(TPAOH), triethylamine, quadrol, n-Butyl Amine 99;
Macromolecule organic amine polymkeric substance is polymine (PEI), and the molecular weight of polymine can regulate from 600 ~ 700000;
The preparation method with the silica zeolite material of composite pore structural that the present invention relates to: silicon source is added to the water, be stirred to evenly, in water-heat process, using polymine and organic amine or organic quaternary ammonium salt as composite shuttering, prepare the molecular sieve containing composite pore structural, hydrothermal treatment consists temperature is 150 DEG C ~ 200 DEG C, and crystallization time is 2 ~ 5 hours.Finally by filtration, wash to about pH=7, and within 5 ~ 24 hours, obtain the pure silicon molecular sieve with composite pore structural in 300 DEG C ~ 500 DEG C calcinings after dry 4 hours at 110 DEG C.
Silica zeolite synthetic ratio: wherein silicon source accounts for 10% ~ 20% of molecular sieve mixing solutions total mass, template accounts for 10% ~ 20% of molecular sieve mixing solutions total mass, and water accounts for 60% ~ 80% of molecular sieve mixing solutions total mass.
Wherein silicon source is tetraethoxy, water glass, white carbon black, water glass or silicon sol;
Organic amine or organic quaternary ammonium salt are TPABr(4-propyl bromide), TPAOH(TPAOH), quadrol, n-Butyl Amine 99;
Macromolecule organic amine polymkeric substance is polymine (PEI), and the molecular weight of polymine can regulate from 600 ~ 700000.
The preparation method with the titanium-silicon molecular screen material of composite pore structural that the present invention relates to: add using polymine and organic amine or organic quaternary ammonium salt as composite shuttering after silicon source and titanium source are added to the water stirring, the molecular sieve containing composite pore structural is obtained after hydrothermal crystallizing, hydrothermal temperature is 150 DEG C ~ 170 DEG C, and crystallization time is 2 days ~ 3 days.Finally by filtration, wash to about pH=7, and at 110 DEG C after dry 6 hours at 300 DEG C ~ 800 DEG C calcining within 5 ~ 12 hours, obtain the HTS with composite pore structural.
HTS synthetic ratio: wherein silicon source accounts for 5% ~ 15% of molecular sieve mixing solutions total mass, titanium source accounts for 1% ~ 5% of molecular sieve mixing solutions total mass, template accounts for 5% ~ 15% of molecular sieve solution total mass, and water accounts for 65% ~ 89% of molecular sieve mixing solutions total mass.
Wherein silicon source is tetraethoxy, water glass, white carbon black, water glass or silicon sol;
Organic amine or organic quaternary ammonium salt are TPABr(4-propyl bromide), TPAOH(TPAOH), quadrol, n-Butyl Amine 99;
Titanium source is TiO
2(titanium dioxide), isopropyl titanate, tetrabutyl titanate;
Macromolecule organic amine polymkeric substance is polymine (PEI), and the molecular weight of polymine can regulate from 600 ~ 700000.
The preparation method with the phosphate aluminium molecular sieve material of composite pore structural that the present invention relates to: aluminium source and phosphorus source are added to the water and carry out stirring and add using polymine and organic amine or organic quaternary ammonium salt as composite shuttering, the molecular sieve containing composite pore structural is obtained after hydrothermal crystallizing, hydrothermal temperature is 150 DEG C ~ 170 DEG C, and crystallization time is 1 day ~ 2 days.Finally by filtration, wash to about pH=7, and at 110 DEG C after dry 6 hours at 300 DEG C ~ 800 DEG C calcining within 5 ~ 12 hours, obtain the phosphate aluminium molecular sieve with composite pore structural.
Phosphate aluminium molecular sieve synthetic ratio: aluminium source accounts for 5% ~ 10% of molecular sieve mixing solutions total mass, phosphorus source accounts for 10% ~ 15% of molecular sieve mixing solutions total mass, template accounts for 10% ~ 15% of molecular sieve mixing solutions total mass, and water accounts for 60% ~ 75% of molecular sieve mixing solutions total mass.
Wherein silicon source is tetraethoxy, water glass, white carbon black, water glass or silicon sol;
Aluminium source is aluminum isopropylate, KAlO
2(potassium metaaluminate), NaAlO
2(sodium metaaluminate), pseudo-boehmite, aluminum oxide and Al
2(SO
4)
3(Tai-Ace S 150) etc.;
Organic amine or organic quaternary ammonium salt are triethylamine, diethylamine, di-n-propylamine, TPAOH;
Phosphorus source is the strong phosphoric acid of 85% massfraction;
Macromolecule organic amine polymkeric substance is polymine (PEI), and the molecular weight of polymine can regulate from 600 ~ 700000.
The preparation method with the aluminium silicophosphate molecular sieve material of composite pore structural that the present invention relates to: phosphorus source, silicon source and aluminium source are added to the water and stir, using polymine and organic amine or organic quaternary ammonium salt as composite shuttering, prepare the molecular sieve containing composite pore structural; Polymine add-on is 1% ~ 30% of mixing solutions total mass; , then crystallization 18 ~ 48 hours at 150 DEG C ~ 200 DEG C.Calcine at 300 ~ 600 DEG C after dry 6 hours at 100 DEG C after product washing and within 5 ~ 12 hours, obtain the SAPO-34 molecular sieve with composite pore structural.
Aluminium silicophosphate molecular sieve synthetic ratio: silicon source accounts for 2% ~ 5% of molecular sieve mixing solutions total mass, aluminium source accounts for 5% ~ 10% of molecular sieve mixing solutions total mass, phosphorus source accounts for 8% ~ 15% of molecular sieve mixing solutions total mass, template accounts for 15% ~ 20% of molecular sieve mixing solutions total mass, and water accounts for 50% ~ 70% of molecular sieve mixing solutions total mass.
Wherein silicon source is tetraethoxy, water glass, white carbon black, water glass or silicon sol.
Aluminium source is aluminum isopropylate, KAlO
2(potassium metaaluminate), NaAlO
2(sodium metaaluminate), pseudo-boehmite, aluminum oxide and Al
2(SO
4)
3(Tai-Ace S 150) etc.;
Phosphorus source is the strong phosphoric acid of 85% massfraction;
Organic amine or organic quaternary ammonium salt are TPABr(4-propyl bromide), TPAOH(TPAOH), triethylamine, morpholine, diethylamine, di-n-propylamine;
Macromolecule organic amine polymkeric substance is polymine (PEI), and the molecular weight of polymine can regulate from 600 ~ 700000.
Method of the present invention is compared with background technology, utilize macromolecule organic amine polymkeric substance as mesoporous template, generate and there is the molecular sieve of certain composite pore structural, and the macromolecule organic amine polymer raw material used cheap, be easy to get, there is certain IP prospecting.
Accompanying drawing explanation
Fig. 1: traditional Z SM-5 (A) and the wide-angle XRD spectra of ZSM-5 (B) adding polymine;
Fig. 2: the Small angle XRD spectra adding the ZSM-5 of polymine;
Fig. 3: the nitrogen adsorption desorption curve adding the ZSM-5 of polymine;
Fig. 4: the BJH pore size distribution adding the ZSM-5 of polymine.
Embodiment
Embodiment 1: with macromolecule organic amine polymkeric substance and TPABr(4-propyl bromide) be composite template synthesis composite pore structural ZSM-5
Synthesis material: polymine, TPABr, tetraethoxy, Al
2(SO
4)
3(Tai-Ace S 150), NaOH(sodium hydroxide)
Concrete synthesis step: first 3gTPABr is dissolved in 72g water, 0.75gAl under certain stirring intensity
2(SO
4)
3and 0.72gNaOH adds, after the clarification of this solution, add 23.5g tetraethoxy continue to stir, NaOH is used to regulate pH to 12, at room temperature ageing adds 1g polymine after 6 hours again, continues to be stirred to after mixing and is reacted 1 day at 200 DEG C by the gel obtained loading teflon-lined stainless steel cauldron.After final sample washing, after 110 DEG C of dryings, 800 DEG C of calcinings 5 hours, obtain the ZSM-5 molecular sieve with composite pore structural.
The high molecular sieve of degree of crystallinity can be synthesized under polymer organic polymer template (polymine).Shown in XRD data (as Fig. 1), it is typical MFI mechanism.Fig. 2 display goes out peak by the ZSM-5 molecular sieve that polyethyleneimine: amine structure synthesizes at Small angle and shows that the ZSM-5 molecular sieve synthesized has higher orderly pore structure.Use the nitrogen adsorption desorption curve (Fig. 3) of the ZSM-5 molecular sieve of polymine templated synthesis and traditional ZSM-5 slightly to distinguish, low be typical micro-porous adsorption than nip, have certain absorption to show to contain part meso-hole structure in high specific pressure district.BJH pore size distribution (Fig. 4) shows the meso-hole structure that there is a certain amount of about 1.5 ~ 3nm, is due to the duct by staying after calcining ZSM-5 molecular sieve removing polymine.
Embodiment 2: with macromolecule organic amine polymkeric substance and TPABr(4-propyl bromide) be composite template synthesis composite pore structural ZSM-5
Synthesis material: polymine, TPABr, tetraethoxy, Al
2(SO
4)
3(Tai-Ace S 150), NaOH(sodium hydroxide)
Concrete synthesis step: first 8.43gTPABr is dissolved in 72g water, 0.75gAl under certain stirring intensity
2(SO
4)
3and 0.72gNaOH adds, after the clarification of this solution, add 23.5g tetraethoxy continue to stir, NaOH is used to regulate pH to 13, at room temperature ageing adds 5g polymine after 6 hours again, continues to be stirred to after mixing and is reacted 3 days at 180 DEG C by the gel obtained loading teflon-lined stainless steel cauldron.After final sample washing, after 110 DEG C of dryings, 300 DEG C of calcinings 18 hours, obtain the ZSM-5 molecular sieve with composite pore structural.
Embodiment 3: with macromolecule organic amine Macroscopic single crystal composite pore structural L-type molecular sieve
Synthesis material: polymine, silicon sol (30% massfraction), NaAlO
2(sodium metaaluminate), NaOH(sodium hydroxide), KOH(potassium hydroxide)
Concrete synthesis step:
First take 3.2gNaOH, 5.2gKOH and, 1.4gNaAlO
2to be dissolved in 40.8g water and to stir, add after the clarification of this solution after the silicon sol 49.4g of 30% massfraction and continue to stir, and add 2g polymine be stirred to mix after the gel obtained loaded teflon-lined stainless steel cauldron react 80 hours at 150 DEG C.After final sample washing, after 110 DEG C of dryings, in 300 DEG C of calcinings 12 hours, obtain the L-type molecular sieve with composite pore structural.
Embodiment 4: with macromolecule organic amine Macroscopic single crystal composite pore structural Y zeolite
Synthesis material: polymine, NaOH(sodium hydroxide), silicon sol (30% massfraction), NaAlO
2(sodium metaaluminate)
Concrete synthesis step: first take 6.87gNaOH, 3.89gNaAlO
2be dissolved in 41.67g water, then drip the silicon sol 47.56g that massfraction is 30%, be stirred to and after 6.3g polymine evenly continues to stir, put into stainless steel autoclave crystallization 10 hours at 100 DEG C.Finally by suction filtration, wash to about pH=7, drying 10 hours at 120 DEG C, and calcining obtain the Y zeolite with composite pore structural in 6 hours at 550 DEG C.
Embodiment 5: with macromolecule organic amine Macroscopic single crystal composite pore structural pure silicon molecular sieve
Synthesis material: polymine, white carbon black, TPAOH(TPAOH)
Concrete synthesis step: 6g white carbon black and 6gTPAOH are dissolved in 36g water, is stirred to evenly and adds 4.8gPEI(polymine again) after continue to stir and put into teflon-lined stainless steel autoclave, crystallization 5 hours at 150 DEG C.Finally by filtration, wash to about pH=7, and within 24 hours, obtain the pure silicon molecular sieve with composite pore structural in 300 DEG C of calcinings after dry 4 hours at 110 DEG C.
Embodiment 6: with macromolecule organic amine Macroscopic single crystal composite pore structural pure silicon molecular sieve
Synthesis material: polymine, white carbon black, TPAOH(TPAOH)
Concrete synthesis step: 1.2g white carbon black and 1.2gTPAOH are dissolved in 3.6g water, be stirred to evenly and add 1.8gPEI(polymine again) after continue to stir and put into teflon-lined stainless steel autoclave, crystallization 2 hours at 200 DEG C.Finally by filtration, wash to about pH=7, and within 5 hours, obtain the pure silicon molecular sieve with composite pore structural in 500 DEG C of calcinings after dry 4 hours at 110 DEG C.
Embodiment 7: with macromolecule organic amine Macroscopic single crystal composite pore structural HTS
Synthesis material: polymine, TiO
2(titanium dioxide), white carbon black, TPAOH(TPAOH)
Concrete synthesis step: by 0.5g white carbon black, 0.1g titanium dioxide and 0.5gTPAOH are stirred to after being dissolved in 8.9g water evenly and add 0.1gPEI(polymine again) continue afterwards to stir after put into teflon-lined stainless steel autoclave, crystallization 3 days at 150 DEG C.Finally by filtration, wash to about pH=7, and at 110 DEG C after dry 6 hours at 300 DEG C calcining within 12 hours, obtain the HTS with composite pore structural.
Embodiment 8: with macromolecule organic amine Macroscopic single crystal composite pore structural HTS
Synthesis material: polymine, TiO
2(titanium dioxide), white carbon black, TPAOH(TPAOH)
Concrete synthesis step: by 3g white carbon black, 1g titanium dioxide and 3gTPAOH are stirred to after being dissolved in 13g water evenly and add 6gPEI(polymine again) continue afterwards to stir after put into teflon-lined stainless steel autoclave, crystallization 2 days at 170 DEG C.Finally by filtration, wash to about pH=7, and at 110 DEG C after dry 6 hours at 800 DEG C calcining within 5 hours, obtain the HTS with composite pore structural.
Embodiment 9: with macromolecule organic amine Macroscopic single crystal composite pore structural phosphate aluminium molecular sieve
Synthesis material: polymine, pseudo-boehmite, phosphoric acid (85% massfraction), TEA(triethylamine)
Concrete synthesis step: by 5g pseudo-boehmite, 10g strong phosphoric acid (85% massfraction), 10g triethylamine is dissolved in 75g water, add 1gPEI(polymine again), to be stirred to evenly at room temperature aging 2 hours, put into teflon-lined stainless steel autoclave, crystallization 1 day at 170 DEG C.Finally by filtration, wash to about pH=7, and at 110 DEG C after dry 6 hours at 300 DEG C calcining within 12 hours, obtain the AFI type phosphate aluminium molecular sieve with composite pore structural.
Embodiment 10: with macromolecule organic amine Macroscopic single crystal composite pore structural phosphate aluminium molecular sieve
Synthesis material: polymine, pseudo-boehmite, phosphoric acid (85% massfraction), TEA(triethylamine)
Concrete synthesis step: by 2g pseudo-boehmite, 3g strong phosphoric acid (85% massfraction), 3g triethylamine is dissolved in 12g water, add 6gPEI(polymine again), to be stirred to evenly at room temperature aging 2 hours, put into teflon-lined stainless steel autoclave, crystallization 2 days at 150 DEG C.Finally by filtration, wash to about pH=7, and at 110 DEG C after dry 6 hours at 800 DEG C calcining within 5 hours, obtain the AFI type phosphate aluminium molecular sieve with composite pore structural.
Embodiment 11: with macromolecule organic amine Macroscopic single crystal composite pore structural aluminium silicophosphate molecular sieve
Synthesis material: polymine, strong phosphoric acid (85% massfraction), pseudo-boehmite, silicon sol (30% massfraction), TEA(triethylamine)
Concrete synthesis step: 0.8g strong phosphoric acid (85% massfraction), 0.5g pseudo-boehmite, 0.2g silicon sol and 1.5g triethylamine are dissolved in 7g water, after fully stirring for some time, then add 3gPEI(polymine) continue again to stir.Said mixture is inserted in teflon-lined stainless steel cauldron, crystallization 18 hours at 200 DEG C.After product washing drying, at 300 DEG C, calcining obtains the SAPO-34 molecular sieve with composite pore structural for 12 hours.
Embodiment 12: with macromolecule organic amine Macroscopic single crystal composite pore structural aluminium silicophosphate molecular sieve
Synthesis material: polymine, strong phosphoric acid (85% massfraction), pseudo-boehmite, silicon sol (30% massfraction), TEA(triethylamine)
Concrete synthesis step: 3g strong phosphoric acid (85% massfraction), 2g pseudo-boehmite, 1g silicon sol and 4g triethylamine are dissolved in 10g water, after fully stirring for some time, then add 0.2gPEI(polymine) continue again to stir.Said mixture is inserted in teflon-lined stainless steel cauldron, crystallization 48 hours at 150 DEG C.After product washing drying, at 600 DEG C, calcining obtains the SAPO-34 molecular sieve with composite pore structural for 5 hours.
Claims (8)
1. the preparation method of Si-Al molecular sieve, is characterized in that wherein using polymine and organic quaternary ammonium salt as composite shuttering; Silicon source and aluminium source are added to the water and stir, and add using polymine and organic quaternary ammonium salt as composite mould plate agent, and be in 12 ~ 14 by the pH that NaOH or KOH carrys out Molecular regulator sieve mixing solutions, prepare the molecular sieve containing composite pore structural; Polymine add-on is 1% ~ 30% of mixing solutions total mass; The temperature of hydrothermal treatment consists is 100 ~ 200 DEG C, and crystallization time is 1 ~ 7 day; Again by molecular screen material 300 ~ 800 DEG C of calcinings 5 ~ 24 hours thus obtain the molecular sieve with open duct in atmosphere; Wherein silicon source accounts for 25% ~ 50% of molecular sieve mixing solutions total mass, and aluminium source accounts for 0.75% ~ 4% of molecular sieve mixing solutions gross weight, and template accounts for 3% ~ 8% of molecular sieve mixing solutions total mass, and water accounts for 42% ~ 72% of molecular sieve mixing solutions total mass;
Silicon source is tetraethoxy, water glass, white carbon black, water glass or silicon sol;
Aluminium source is aluminum isopropylate, KAlO
2, NaAlO
2, pseudo-boehmite, aluminum oxide or Al
2(SO
4)
3;
Organic quaternary ammonium salt template is 4-propyl bromide, TPAOH;
The molecular weight of polymine regulates from 600 ~ 700000.
2. the preparation method of silica zeolite, silicon source is it is characterized in that to be added to the water, be stirred to evenly, in water-heat process, using polymine and organic quaternary ammonium salt as composite shuttering, prepare the molecular sieve containing composite pore structural, hydrothermal treatment consists temperature is 150 DEG C ~ 200 DEG C, and crystallization time is 2 ~ 5 hours; Finally by filtration, wash to pH=7, and within 5 ~ 24 hours, obtain the silica zeolite with composite pore structural in 300 DEG C ~ 500 DEG C calcinings after dry 4 hours at 110 DEG C.
3. the preparation method of silica zeolite according to claim 2, it is characterized in that silica zeolite synthetic ratio: wherein silicon source accounts for 10% ~ 20% of molecular sieve mixing solutions total mass, template accounts for 10% ~ 20% of molecular sieve mixing solutions total mass, and water accounts for 60% ~ 80% of molecular sieve mixing solutions total mass;
Wherein silicon source is tetraethoxy, water glass, white carbon black, water glass or silicon sol;
Organic quaternary ammonium salt is 4-propyl bromide, TPAOH;
The molecular weight of polymine regulates from 600 ~ 700000.
4. the preparation method of HTS, add using polymine and organic quaternary ammonium salt as composite shuttering after it is characterized in that silicon source and titanium source are added to the water stirring, obtain the molecular sieve containing composite pore structural after hydrothermal crystallizing, hydrothermal temperature is 150 DEG C ~ 170 DEG C, and crystallization time is 2 days ~ 3 days; Finally by filtration, wash to pH=7, and at 110 DEG C after dry 6 hours at 300 DEG C ~ 800 DEG C calcining within 5 ~ 12 hours, obtain the HTS with composite pore structural.
5. the preparation method of HTS according to claim 4, it is characterized in that HTS synthetic ratio: wherein silicon source accounts for 5% ~ 15% of molecular sieve mixing solutions total mass, titanium source accounts for 1% ~ 5% of molecular sieve mixing solutions total mass, template accounts for 5% ~ 15% of molecular sieve solution total mass, and water accounts for 65% ~ 89% of molecular sieve mixing solutions total mass;
Wherein silicon source is tetraethoxy, water glass, white carbon black, water glass or silicon sol;
Organic quaternary ammonium salt is 4-propyl bromide, TPAOH;
Titanium source is titanium dioxide, isopropyl titanate, tetrabutyl titanate;
The molecular weight of polymine regulates from 600 ~ 700000.
6. the preparation method of phosphate aluminium molecular sieve, it is characterized in that aluminium source and phosphorus source to be added to the water and carry out stirring and add using polymine and organic quaternary ammonium salt as composite shuttering, the molecular sieve containing composite pore structural is obtained after hydrothermal crystallizing, hydrothermal temperature is 150 DEG C ~ 170 DEG C, and crystallization time is 1 day ~ 2 days; Finally by filtration, wash to pH=7, and at 110 DEG C after dry 6 hours at 300 DEG C ~ 800 DEG C calcining within 5 ~ 12 hours, obtain the phosphate aluminium molecular sieve with composite pore structural.
7. the preparation method of phosphate aluminium molecular sieve according to claim 6, it is characterized in that phosphate aluminium molecular sieve synthetic ratio: aluminium source accounts for 5% ~ 10% of molecular sieve mixing solutions total mass, phosphorus source accounts for 10% ~ 15% of molecular sieve mixing solutions total mass, template accounts for 10% ~ 15% of molecular sieve mixing solutions total mass, and water accounts for 60% ~ 75% of molecular sieve mixing solutions total mass;
Wherein silicon source is tetraethoxy, water glass, white carbon black, water glass or silicon sol;
Aluminium source is aluminum isopropylate, potassium metaaluminate, sodium metaaluminate, pseudo-boehmite, aluminum oxide or Al
2(SO
4)
3;
Organic quaternary ammonium salt is TPAOH;
Phosphorus source is the strong phosphoric acid of massfraction 85%;
The molecular weight of polymine regulates from 600 ~ 700000.
8. the preparation method of aluminium silicophosphate molecular sieve, is characterized in that phosphorus source, silicon source and aluminium source to be added to the water to stir, and using polymine and organic quaternary ammonium salt as composite shuttering, prepares the molecular sieve containing composite pore structural; Polymine add-on is 1% ~ 30% of mixing solutions total mass; Then crystallization 18 ~ 48 hours at 150 DEG C ~ 200 DEG C; Calcine at 300 ~ 600 DEG C after dry 6 hours at 100 DEG C after product washing and within 5 ~ 12 hours, obtain the SAPO-34 molecular sieve with composite pore structural;
Aluminium silicophosphate molecular sieve synthetic ratio: silicon source accounts for 2% ~ 5% of molecular sieve mixing solutions total mass, aluminium source accounts for 5% ~ 10% of molecular sieve mixing solutions total mass, phosphorus source accounts for 8% ~ 15% of molecular sieve mixing solutions total mass, template accounts for 15% ~ 20% of molecular sieve mixing solutions total mass, and water accounts for 50% ~ 70% of molecular sieve mixing solutions total mass;
Wherein silicon source is tetraethoxy, water glass, white carbon black, water glass or silicon sol;
Aluminium source is aluminum isopropylate, potassium metaaluminate, sodium metaaluminate, pseudo-boehmite, aluminum oxide or Tai-Ace S 150;
Phosphorus source is the strong phosphoric acid of massfraction 85%;
Organic quaternary ammonium salt is 4-propyl bromide, TPAOH;
The molecular weight of polymine regulates from 600 ~ 700000.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310114100.2A CN103172081B (en) | 2013-04-02 | 2013-04-02 | High-molecular organic polymer template synthesized compound pore structure molecular sieve and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310114100.2A CN103172081B (en) | 2013-04-02 | 2013-04-02 | High-molecular organic polymer template synthesized compound pore structure molecular sieve and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103172081A CN103172081A (en) | 2013-06-26 |
| CN103172081B true CN103172081B (en) | 2015-06-24 |
Family
ID=48632364
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310114100.2A Active CN103172081B (en) | 2013-04-02 | 2013-04-02 | High-molecular organic polymer template synthesized compound pore structure molecular sieve and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103172081B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104591205B (en) * | 2015-02-06 | 2016-08-17 | 厦门大学 | A kind of preparation method with compound duct catalysis material |
| CN106809858B (en) * | 2015-11-30 | 2019-07-02 | 中国科学院大连化学物理研究所 | A kind of synthetic method of nano-ZSM-5 molecular sieve |
| CN106423262B (en) * | 2016-09-06 | 2019-04-19 | 西北大学 | A kind of SAPO-34 molecular sieve catalyst and preparation method thereof with ordered mesoporous |
| CN107162388B (en) * | 2017-06-30 | 2020-03-13 | 西安交通大学 | Method for preparing macroporous bioactive glass nanocluster by using dendritic polyethyleneimine as template agent and catalyst |
| CN107551993A (en) * | 2017-08-31 | 2018-01-09 | 长沙埃比林环保科技有限公司 | A kind of method that heavy metals sorbing material is prepared using Organic Ingredients |
| CN107551992A (en) * | 2017-08-31 | 2018-01-09 | 长沙埃比林环保科技有限公司 | A kind of method that heavy metals sorbing material is prepared using inorganic raw material |
| CN107519837A (en) * | 2017-08-31 | 2017-12-29 | 长沙埃比林环保科技有限公司 | A kind of method that microwave prepares heavy metals sorbing material |
| CN108993610B (en) * | 2018-07-10 | 2020-04-14 | 大连理工大学 | Preparation method and application of organic-inorganic hybrid amorphous mesoporous titanium-silicon material |
| CN112871204A (en) * | 2021-01-19 | 2021-06-01 | 中国科学院大连化学物理研究所 | High-activity propylene gas-phase epoxidation catalyst and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102745708B (en) * | 2011-04-22 | 2014-04-02 | 中国石油天然气股份有限公司 | Synthetic method of mesoporous-microporous molecular sieve by raising hydrothermal stability |
-
2013
- 2013-04-02 CN CN201310114100.2A patent/CN103172081B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN103172081A (en) | 2013-06-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103172081B (en) | High-molecular organic polymer template synthesized compound pore structure molecular sieve and preparation method thereof | |
| US10160656B2 (en) | Organotemplate-free solid-state synthetic method for zeolite molecular sieves | |
| CN106185977B (en) | A kind of method of green syt ZSM-5 molecular sieve | |
| TWI490167B (en) | Method of preparing zsm-5 zeolite using nanocrystalline zsm-5 seeds | |
| CN103848439B (en) | Synthetic method of ZSM-5 type molecular sieve | |
| Camblor et al. | Synthesis and Structure of ITQ‐3, the First Pure Silica Polymorph with a Two‐Dimensional System of Straight Eight‐Ring Channels | |
| WO2018227849A1 (en) | Molecular sieve scm-14, synthesis method therefor and use thereof | |
| KR102356362B1 (en) | SCM-15 molecular sieve, preparation method thereof and use thereof | |
| Zhang et al. | Facile fabrication of mesopore-containing ZSM-5 zeolite from spent zeolite catalyst for methanol to propylene reaction | |
| KR102035397B1 (en) | MFI zeolite with hierarchical structure having micropores and mesopores, a preparation method thereof, and catalytic use thereof | |
| CN101279750A (en) | Magadiite/ZSM-5 intergrowth material and synthetic method thereof | |
| CN104229826A (en) | ZSM-5 molecular sieve and preparation method thereof | |
| CN112794338B (en) | ZSM-5 molecular sieve and preparation method and application thereof | |
| CN108658087B (en) | Hierarchical pore TS-1 zeolite material and preparation method thereof | |
| CN103058208B (en) | Preparation method of SAPO-56 molecular sieve | |
| CN1749161A (en) | Hard template synthetic composite hole zeolite molecular sieve and its preparing method | |
| US11434140B2 (en) | Hierarchical zeolites and preparation method therefor | |
| CN103723741B (en) | A kind of method of synthesizing ZSM-5/MCM-41 composite molecular screen | |
| CN106946268A (en) | A kind of MOR/ZSM-35 composite molecular screens and its synthetic method | |
| CN102060310B (en) | Method for preparing ZSM-5 zeolite secondary structural unit-containing molecular sieve | |
| Zhou et al. | Sodium carbonate-assisted synthesis of hierarchically porous single-crystalline nanosized zeolites | |
| CN113135578B (en) | Preparation method of silicon-germanium ISV zeolite molecular sieve | |
| CN101417810A (en) | Mesoporous material and preparation method thereof | |
| CN111099613B (en) | Molecular sieves, methods of synthesis, and uses thereof | |
| CN101195490B (en) | Method for producing middle and fine diplopore molecular sieve with nano-minicrystal and ionic surface active agent in microwave radiation condition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20170214 Address after: 213023 Changzhou Economic Development Zone, Jiangsu bell tower Economic Development Zone, No. 213 ERON Road, Changzhou bell tower high tech service center building, No. 8812 Patentee after: Changzhou Yingzhong Nano Technology Co., Ltd. Address before: Gehu Lake Road Wujin District 213164 Jiangsu city of Changzhou province No. 1 Patentee before: Changzhou University |