CN103172081A - 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
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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 that a kind of polymer organic polymer template is synthetic has composite pore structural molecular sieve and preparation method thereof, belong to composite pore structural molecular sieve technical field.
Background technology
Zeolite molecular sieve has rule and uniform pore passage structure, the size and shape that comprises the duct, and it has higher specific surface and pore volume, higher hydrothermal stability make its be widely used in refining of petroleum with processing in the catalysis engineering, cracking, alkylation, hydrocracking, isomerization such as hydrocarbon polymer, secondly they also are widely used in adsorption separation process, as the drying of Sweet natural gas, splitting gas etc., take off CO
2, the field of purification such as desulfurization.Wherein the most representative is the synthetic work of ZSM-5 Series Molecules sieve.But because the aperture of zeolite molecular sieve is less, limited widely the velocity of diffusion of catalyzed reaction and the application [Corma, A. Chem. Rev. 97, (1997), 2373.] of the catalyzed reaction that participates at macromole.
Mobil company used the alkyl quaternary ammonium salts cats product to successfully synthesize mesopore molecular sieve MCM-41 series [Kresge, C. T., Leonowicz, M. E., Roth, W. J., Vartuli, J. C. ﹠amp as template first in 1992; Beck, J. S. Nature 352, (1992), 710.], the molecular screen material that this class has regular mesopore orbit is conducive to macromolecular absorption and diffusion, has bright prospects at aspects such as catalysis, membrane separation technique and molecular engineerings.Mesoporous material demonstrates excellent especially catalytic performance in the existing application widely of catalytic field in the catalyzed reaction that nowadays in the conversion of petroleum refining process, fine chemicals, has particularly had macromole to participate in.In refining of petroleum, the 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 exhaustion day by day and crude oil, traditional micro porous molecular sieve catalytic material is because the aperture is less, and heavy oil molecules can not enter the duct, thereby has limited the carrying out of catalyzed reaction.Ordered mesoporous material provides mesoporous pore passage structure, and this catalyzed conversion for heavy oil molecules provides a good opportunity.But mesoporous material is compared with the micro-pore zeolite material, lower hydrothermal stability, weak strength of acid with and the reason such as preparation cost height limited it in the application aspect catalysis.Demand in view of petrochemical complex and fine chemistry industry, a lot of researchs are devoted to seek a kind of in conjunction with micro-pore zeolite material and mesoporous material novel material of advantage both, not only had high hydrothermal stability and higher strength of acid but also included larger aperture, can obtain larger application at catalytic field.
Mould plate technique is widely used in the nanoassemble material preparation, and this technology can be by shape and the big or small control that realizes the shape to assembled material, structure and size that changes corresponding template.Utilizing the standby nano zeolite of restricted clearance legal system is growth limitation [Schmidt I. Inorg. Chem., 2000, (39): 2279-2283] in the small duct of inert media carbon black with zeolite grain.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, within zeolite can be grown in zeolite grain with the charcoal particle parcel of inertia, can stay mesopore orbit in zeolite crystal after removing the carbon black template by roasting, form the ZSM-5 with composite pore structural.Yousheng Tao [Tao, Y. J. Am. Chem. Soc. 2003,125,6044.] have a carbonization superpolymer aerosol template of high mesoporous porosity by utilization, successfully the carbon template is loaded in ZSM-5 molecular sieve, roasting obtains having the comparatively ZSM-5 zeolite material of homogeneous mesopore orbit except after the carbon elimination template.Liu Zhicheng [Liu Zhicheng, Xie Zaiku. petroleum journal (refining of petroleum) .2008,24:124.] etc. the people by starch being joined in the ZSM-5 molecular sieve gel, obtain having at last the ZSM-5 molecular sieve of composite pore structural by calcining, and can regulate mesoporous quantity by the ratio of regulating starch.The people such as Xie Zaiku [Zhu H B, Xie Z K. Chem Mater, 2008,20:1134.] are by using nano-calcium carbonate also successfully to prepare the Silicate-1 molecular sieve with meso-hole structure 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, can synthesize the Mesoporous Zeolite Materials with composite holes pore passage structure.Xiao [Xiao F S. Angew. Chem. Int. Ed., 2006,45 (19): 3090-3093] etc. the people uses the multipolymer (PDD2AM) of TPAOH (TPAOH) and Poly Dimethyl Diallyl Ammonium Chloride and acrylamide to synthesize the ZSM-5 molecular sieve with meso-hole structure under existing.Korea S scientist [Choi M, Cho H S, Srivastava R, et al. Nat. Mater., 2006,5 (9): 718-723] has designed 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 be at the end group of the methoxy silane of zeolite synthesis Water Under solution, the other end is the end group of organic ammonium, this tensio-active agent is added in synthetic system of zeolite to the zeolitic material that can single sintering has high mesoporous content.Ryong Ryoo[M. Choi, R. Srivastava and R. Ryoo, Chem. Commun., 2006,4380.] close both sexes the organosilane [(CH of use
3O)
3SiC
3H
6N (CH
3)
2C
16H
33] Cl synthesized multiple phosphate aluminium molecular sieve with composite pore structural.Xie Zaiku [Zhu H B, Xie Z K. J Phys Chem C, 2008,112 (44): 17257.] by using the PVB(polyvinyl butyral acetal) as mesoporous directed agents, successfully synthesized 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 the PEI(polymine) organic high molecular polymer of silicon modification is as template, successfully synthesized the ZSM-5 with meso-hole structure, and its mesoporous pore size can be by adjusting PEI(polymine) molecular weight control.But wherein much relate to the method for high molecular polymer due to the price of its template and the complexity of synthesis condition, be difficult to apply to industrial circle, therefore synthesizing high-stability, the high and low cost of acid intensity, 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, uses the macromolecule organic amine polymkeric substance as the meso-hole structure directed agents, and preparation has certain compound pore passage structure, and than high-ratio surface, the molecular sieve of high catalytic activity is to be fit to industrial production and application.
Zeolite molecular sieve involved in the present invention is primary be applied in various structures in refining of petroleum and chemical engineering industry field molecular sieve not only for Si-Al molecular sieve (as MFI type molecular sieve, the L-type molecular sieve, Y zeolite), wherein also comprise silica zeolite (as the Silicalite-1 molecular sieve), HTS (as the TS-1 molecular sieve), phosphate aluminium molecular sieve (as AFI type molecular sieve), aluminium silicophosphate molecular sieve (as SAPO Series Molecules sieve).
The Si-Al molecular sieve material preparation method with composite pore structural that the present invention relates to: silicon source and aluminium source are added to the water stir, and add with polymine and organic amine or organic quaternary ammonium salt as composite shuttering, and by NaOH(sodium hydroxide), KOH(potassium hydroxide) come the pH of Molecular regulator sieve mixing solutions to be in 12 ~ 14, prepare the molecular sieve that contains composite pore structural; The polymine add-on is 1% ~ 30% of mixing solutions total mass; The temperature of hydrothermal treatment consists is 100 ~ 200 ℃, and crystallization time is 1 ~ 7 day; Again thereby molecular screen material 300 ~ 800 ℃ of calcinings in air were obtained having the molecular sieve in open duct in 5 ~ 24 hours.
The Si-Al molecular sieve synthetic ratio: wherein the silicon source accounts for 25% ~ 50% of molecular sieve mixing solutions total mass, the 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.
The silicon source is tetraethoxy, water glass, white carbon black, water glass or silicon sol etc.;
The 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 the TPABr(4-propyl bromide), the TPAOH(TPAOH), triethylamine, quadrol, n-Butyl Amine 99;
The macromolecule organic amine polymkeric substance is polymine (PEI), and the molecular weight of polymine can be regulated from 600 ~ 700000;
The silica zeolite material preparation method with composite pore structural that the present invention relates to: the silicon source is added to the water, be stirred to evenly, in water-heat process, with polymine and organic amine or organic quaternary ammonium salt as composite shuttering, prepare the molecular sieve that contains composite pore structural, the hydrothermal treatment consists temperature is 150 ℃ ~ 200 ℃, and crystallization time is 2 ~ 5 hours.Finally by filtering, wash to the pH=7 left and right, and obtained having the pure silicon molecular sieve of composite pore structural in 5 ~ 24 hours in 300 ℃ ~ 500 ℃ calcinings after under 110 ℃ dry 4 hours.
The silica zeolite synthetic ratio: wherein the silicon source accounts for 10% ~ 20% of molecular sieve mixing solutions total mass, and 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 the silicon source is tetraethoxy, water glass, white carbon black, water glass or silicon sol;
Organic amine or organic quaternary ammonium salt are the TPABr(4-propyl bromide), the TPAOH(TPAOH), quadrol, n-Butyl Amine 99;
The macromolecule organic amine polymkeric substance is polymine (PEI), and the molecular weight of polymine can be regulated from 600 ~ 700000.
The preparation method of the titanium-silicon molecular screen material with composite pore structural that the present invention relates to: silicon source and titanium source are added to the water add after stirring with polymine and organic amine or organic quaternary ammonium salt as composite shuttering, obtain containing the molecular sieve of composite pore structural after hydrothermal crystallizing, hydrothermal temperature is 150 ℃ ~ 170 ℃, and crystallization time is 2 days ~ 3 days.Finally by filtering, wash to the pH=7 left and right, and calcined the HTS that obtained having composite pore structural in 5 ~ 12 hours under 300 ℃ ~ 800 ℃ after under 110 ℃ dry 6 hours.
The HTS synthetic ratio: wherein the silicon source accounts for 5% ~ 15% of molecular sieve mixing solutions total mass, the 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 the silicon source is tetraethoxy, water glass, white carbon black, water glass or silicon sol;
Organic amine or organic quaternary ammonium salt are the TPABr(4-propyl bromide), the TPAOH(TPAOH), quadrol, n-Butyl Amine 99;
The titanium source is TiO
2(titanium dioxide), isopropyl titanate, tetrabutyl titanate;
The macromolecule organic amine polymkeric substance is polymine (PEI), and the molecular weight of polymine can be regulated from 600 ~ 700000.
The phosphate aluminium molecular sieve material preparation method with composite pore structural that the present invention relates to: aluminium source and phosphorus source are added to the water stir and add with polymine and organic amine or organic quaternary ammonium salt as composite shuttering, obtain containing the molecular sieve of composite pore structural after hydrothermal crystallizing, hydrothermal temperature is 150 ℃ ~ 170 ℃, and crystallization time is 1 day ~ 2 days.Finally by filtering, wash to the pH=7 left and right, and calcined the phosphate aluminium molecular sieve that obtained having composite pore structural in 5 ~ 12 hours under 300 ℃ ~ 800 ℃ after under 110 ℃ dry 6 hours.
The phosphate aluminium molecular sieve synthetic ratio: the aluminium source accounts for 5% ~ 10% of molecular sieve mixing solutions total mass, the 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 the silicon source is tetraethoxy, water glass, white carbon black, water glass or silicon sol;
The 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;
The phosphorus source is the strong phosphoric acid of 85% massfraction;
The macromolecule organic amine polymkeric substance is polymine (PEI), and the molecular weight of polymine can be regulated from 600 ~ 700000.
The aluminium silicophosphate molecular sieve material preparation method with composite pore structural that the present invention relates to: phosphorus source, silicon source and aluminium source are added to the water stir, as composite shuttering, prepare the molecular sieve that contains composite pore structural with polymine and organic amine or organic quaternary ammonium salt; The polymine add-on is 1% ~ 30% of mixing solutions total mass; , then 150 ℃ ~ 200 ℃ lower crystallization 18 ~ 48 hours.Calcined the SAPO-34 molecular sieve that obtained having composite pore structural in 5 ~ 12 hours under 300 ~ 600 ℃ after the product washing after under 100 ℃ dry 6 hours.
The aluminium silicophosphate molecular sieve synthetic ratio: the silicon source accounts for 2% ~ 5% of molecular sieve mixing solutions total mass, the aluminium source accounts for 5% ~ 10% of molecular sieve mixing solutions total mass, the 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 the silicon source is tetraethoxy, water glass, white carbon black, water glass or silicon sol.
The 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.;
The phosphorus source is the strong phosphoric acid of 85% massfraction;
Organic amine or organic quaternary ammonium salt are the TPABr(4-propyl bromide), the TPAOH(TPAOH), triethylamine, morpholine, diethylamine, di-n-propylamine;
The macromolecule organic amine polymkeric substance is polymine (PEI), and the molecular weight of polymine can be regulated from 600 ~ 700000.
Method of the present invention is compared with background technology, utilize the macromolecule organic amine polymkeric substance as mesoporous template, generation has the molecular sieve of certain composite pore structural, and the macromolecule organic amine polymer raw material that uses cheap, be easy to get, have certain IP prospecting.
Description of drawings
Fig. 1: traditional Z SM-5 (A) and the wide-angle XRD spectra that adds the ZSM-5 (B) of polymine;
Fig. 2: the Small angle XRD spectra that adds the ZSM-5 of polymine;
Fig. 3: the nitrogen adsorption desorption curve that adds the ZSM-5 of polymine;
Fig. 4: the BJH pore size distribution that adds the ZSM-5 of polymine.
Embodiment
Embodiment 1: take macromolecule organic amine polymkeric substance and TPABr(4-propyl bromide) be that composite shuttering synthesizes 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: at first 3gTPABr is dissolved in 72g water, under certain stirring intensity 0.75gAl
2(SO
4)
3And 0.72gNaOH adds, add the 23.5g tetraethoxy to continue to stir after this solution clarification, use NaOH to regulate pH to 12, at room temperature ageing adds the 1g polymine again after 6 hours, continue to be stirred to and the gel that the obtains teflon-lined stainless steel cauldron of packing into was reacted 1 day under 200 ℃ after mixing.After the final sample washing, after 110 ℃ of dryings, 800 ℃ of calcinings 5 hours, obtain having the ZSM-5 molecular sieve of composite pore structural.
Can synthesize the high molecular sieve of degree of crystallinity under polymer organic polymer template (polymine).As shown in XRD data (as Fig. 1), be typical MFI mechanism.Fig. 2 shows that going out the peak by the synthetic ZSM-5 molecular sieve of polyethyleneimine: amine structure at Small angle shows that synthetic ZSM-5 molecular sieve has higher orderly pore structure.The nitrogen adsorption desorption curve (Fig. 3) that uses the synthetic ZSM-5 molecular sieve of polymine template is slightly had any different with traditional ZSM-5, low be typical micro-porous adsorption than nip, have certain absorption to show in the high specific pressure district and may contain the part meso-hole structure.BJH pore size distribution (Fig. 4) shows the meso-hole structure that has a certain amount of 1.5 ~ 3nm left and right, is owing to removing by the calcining ZSM-5 molecular sieve duct that stays after polymine.
Embodiment 2: take macromolecule organic amine polymkeric substance and TPABr(4-propyl bromide) be that composite shuttering synthesizes 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: at first 8.43gTPABr is dissolved in 72g water, under certain stirring intensity 0.75gAl
2(SO
4)
3And 0.72gNaOH adds, add the 23.5g tetraethoxy to continue to stir after this solution clarification, use NaOH to regulate pH to 13, at room temperature ageing adds the 5g polymine again after 6 hours, continue to be stirred to and the gel that the obtains teflon-lined stainless steel cauldron of packing into was reacted 3 days under 180 ℃ after mixing.After the final sample washing, after 110 ℃ of dryings, 300 ℃ of calcinings 18 hours, obtain having the ZSM-5 molecular sieve of composite pore structural.
Embodiment 3: with the synthetic composite pore structural L-type molecular sieve of macromolecule organic amine polymkeric substance
Synthesis material: polymine, silicon sol (30% massfraction), NaAlO
2(sodium metaaluminate), NaOH(sodium hydroxide), KOH(potassium hydroxide)
Concrete synthesis step:
At first take 3.2gNaOH, 5.2gKOH reaches, 1.4gNaAlO
2Be dissolved in 40.8g water and stir, continue to stir after the silicon sol 49.4g that adds 30% massfraction after the clarification of this solution, and the teflon-lined stainless steel cauldron of after adding the 2g polymine to be stirred to mix, the gel that obtains being packed into reacted 80 hours under 150 ℃.After the final sample washing, after 110 ℃ of dryings, in 300 ℃ of calcinings 12 hours, obtain having the L-type molecular sieve of composite pore structural.
Embodiment 4: with the synthetic composite pore structural Y zeolite of macromolecule organic amine polymkeric substance
Synthesis material: polymine, NaOH(sodium hydroxide), silicon sol (30% massfraction), NaAlO
2(sodium metaaluminate)
Concrete synthesis step: at first take 6.87gNaOH, 3.89gNaAlO
2Be dissolved in 41.67g water, then drip massfraction and be 30% silicon sol 47.56g, be stirred to evenly after the 6.3g polymine put into stainless steel autoclave after continuing to stir 100 ℃ of lower crystallization 10 hours.Finally by suction filtration, wash to about pH=7 under 120 ℃ dry 10 hours, and calcining obtained having the Y zeolite of composite pore structural in 6 hours under 550 ℃.
Embodiment 5: with the synthetic composite pore structural pure silicon molecular sieve of macromolecule organic amine polymkeric substance
Synthesis material: polymine, white carbon black, TPAOH(TPAOH)
Concrete synthesis step: 6g white carbon black and 6gTPAOH are dissolved in 36g water, be stirred to add again the 4.8gPEI(polymine after even) after continue to stir and put into the teflon-lined stainless steel autoclave, got final product in 5 hours 150 ℃ of lower crystallization.Finally by filtering, wash to the pH=7 left and right, and obtained having the pure silicon molecular sieve of composite pore structural in 24 hours in 300 ℃ of calcinings after under 110 ℃ dry 4 hours.
Embodiment 6: with the synthetic composite pore structural pure silicon molecular sieve of macromolecule organic amine polymkeric substance
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, add again the 1.8gPEI(polymine after being stirred to evenly) after continue to stir and put into the teflon-lined stainless steel autoclave, got final product in 2 hours 200 ℃ of lower crystallization.Finally by filtering, wash to the pH=7 left and right, and obtained having the pure silicon molecular sieve of composite pore structural in 5 hours in 500 ℃ of calcinings after under 110 ℃ dry 4 hours.
Embodiment 7: with the synthetic composite pore structural HTS of macromolecule organic amine polymkeric substance
Synthesis material: polymine, TiO
2(titanium dioxide), white carbon black, TPAOH(TPAOH)
Concrete synthesis step: with the 0.5g white carbon black, 0.1g titanium dioxide and 0.5gTPAOH add the 0.1gPEI(polymine after being dissolved in and being stirred to after 8.9g water evenly again) after put into the teflon-lined stainless steel autoclave after continuing to stir, got final product in 3 days 150 ℃ of lower crystallization.Finally by filtering, wash to the pH=7 left and right, and after under 110 ℃ dry 6 hours under 300 ℃ calcining obtained having the HTS of composite pore structural in 12 hours.
Embodiment 8: with the synthetic composite pore structural HTS of macromolecule organic amine polymkeric substance
Synthesis material: polymine, TiO
2(titanium dioxide), white carbon black, TPAOH(TPAOH)
Concrete synthesis step: with the 3g white carbon black, 1g titanium dioxide and 3gTPAOH add the 6gPEI(polymine after being dissolved in and being stirred to after 13g water evenly again) after put into the teflon-lined stainless steel autoclave after continuing to stir, got final product in 2 days 170 ℃ of lower crystallization.Finally by filtering, wash to the pH=7 left and right, and after under 110 ℃ dry 6 hours under 800 ℃ calcining obtained having the HTS of composite pore structural in 5 hours.
Embodiment 9: with the synthetic composite pore structural phosphate aluminium molecular sieve of macromolecule organic amine polymkeric substance
Synthesis material: polymine, pseudo-boehmite, phosphoric acid (85% massfraction), TEA(triethylamine)
Concrete synthesis step: with the 5g pseudo-boehmite, 10g strong phosphoric acid (85% massfraction), the 10g triethylamine is dissolved in 75g water, add again the 1gPEI(polymine), after being stirred to evenly at room temperature aging 2 hours, put into the teflon-lined stainless steel autoclave, 170 ℃ of lower crystallization 1 day.Finally by filtering, wash to the pH=7 left and right, and after under 110 ℃ dry 6 hours under 300 ℃ calcining obtained having the AFI type phosphate aluminium molecular sieve of composite pore structural in 12 hours.
Embodiment 10: with the synthetic composite pore structural phosphate aluminium molecular sieve of macromolecule organic amine polymkeric substance
Synthesis material: polymine, pseudo-boehmite, phosphoric acid (85% massfraction), TEA(triethylamine)
Concrete synthesis step: with the 2g pseudo-boehmite, 3g strong phosphoric acid (85% massfraction), the 3g triethylamine is dissolved in 12g water, add again the 6gPEI(polymine), after being stirred to evenly at room temperature aging 2 hours, put into the teflon-lined stainless steel autoclave, 150 ℃ of lower crystallization 2 days.Finally by filtering, wash to the pH=7 left and right, and after under 110 ℃ dry 6 hours under 800 ℃ calcining obtained having the AFI type phosphate aluminium molecular sieve of composite pore structural in 5 hours.
Embodiment 11: with the synthetic composite pore structural aluminium silicophosphate molecular sieve of macromolecule organic amine polymkeric substance
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 the 3gPEI(polymine) continue again to stir.Said mixture is inserted in the teflon-lined stainless steel cauldron, 200 ℃ of lower crystallization 18 hours.Calcine under 300 ℃ after the product washing is dry and obtained having the SAPO-34 molecular sieve of composite pore structural in 12 hours.
Embodiment 12: with the synthetic composite pore structural aluminium silicophosphate molecular sieve of macromolecule organic amine polymkeric substance
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 the 0.2gPEI(polymine) continue again to stir.Said mixture is inserted in the teflon-lined stainless steel cauldron, 150 ℃ of lower crystallization 48 hours.Calcine under 600 ℃ after the product washing is dry and obtained having the SAPO-34 molecular sieve of composite pore structural in 5 hours.
Claims (10)
1. the synthetic composite pore structural molecular sieve of polymer organic polymer template, is characterized in that being specially Si-Al molecular sieve, silica zeolite, HTS, phosphate aluminium molecular sieve or aluminium silicophosphate molecular sieve.
2. polymer organic polymer template according to claim 1 is synthesized the preparation method of composite pore structural molecular sieve, it is characterized in that described Si-Al molecular sieve material preparation method: silicon source and aluminium source are added to the water stir, and add with polymine and organic amine or organic quaternary ammonium salt as composite mould plate agent, and come the pH of Molecular regulator sieve mixing solutions to be in 12 ~ 14 by NaOH or KOH, prepare the molecular sieve that contains composite pore structural; The polymine add-on is 1% ~ 30% of mixing solutions total mass; The temperature of hydrothermal treatment consists is 100 ~ 200 ℃, and crystallization time is 1 ~ 7 day; Again thereby molecular screen material 300 ~ 800 ℃ of calcinings in air were obtained having the molecular sieve in open duct in 5 ~ 24 hours.
3. polymer organic polymer template according to claim 2 is synthesized the preparation method of composite pore structural molecular sieve, it is characterized in that the Si-Al molecular sieve synthetic ratio: wherein the silicon source accounts for 25% ~ 50% of molecular sieve mixing solutions total mass, the 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;
The silicon source is tetraethoxy, water glass, white carbon black, water glass or silicon sol etc.;
The aluminium source is aluminum isopropylate, KAlO
2, NaAlO
2, pseudo-boehmite, aluminum oxide or and Al
2(SO
4)
3
Organic amine or organic quaternary ammonium salt template are 4-propyl bromide, TPAOH, triethylamine, quadrol, n-Butyl Amine 99;
The molecular weight of polymine can be regulated from 600 ~ 700000.
4. polymer organic polymer template according to claim 1 is synthesized the preparation method of composite pore structural molecular sieve, it is characterized in that silica zeolite material preparation method: the silicon source is added to the water, be stirred to evenly, in water-heat process, with polymine and organic amine or organic quaternary ammonium salt as composite shuttering, prepare the molecular sieve that contains composite pore structural, the hydrothermal treatment consists temperature is 150 ℃ ~ 200 ℃, and crystallization time is 2 ~ 5 hours; Finally by filtering, wash to the pH=7 left and right, and obtained having the pure silicon molecular sieve of composite pore structural in 5 ~ 24 hours in 300 ℃ ~ 500 ℃ calcinings after under 110 ℃ dry 4 hours.
5. polymer organic polymer template according to claim 4 is synthesized the preparation method of composite pore structural molecular sieve, it is characterized in that the silica zeolite synthetic ratio: wherein the 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 the silicon source is tetraethoxy, water glass, white carbon black, water glass or silicon sol;
Organic amine or organic quaternary ammonium salt are 4-propyl bromide, TPAOH, quadrol, n-Butyl Amine 99;
The molecular weight of polymine can be regulated from 600 ~ 700000.
6. polymer organic polymer template according to claim 1 is synthesized the preparation method of composite pore structural molecular sieve, the preparation method who it is characterized in that titanium-silicon molecular screen material: silicon source and titanium source are added to the water add after stirring with polymine and organic amine or organic quaternary ammonium salt as composite shuttering, obtain containing the molecular sieve of composite pore structural after hydrothermal crystallizing, hydrothermal temperature is 150 ℃ ~ 170 ℃, and crystallization time is 2 days ~ 3 days; Finally by filtering, wash to the pH=7 left and right, and calcined the HTS that obtained having composite pore structural in 5 ~ 12 hours under 300 ℃ ~ 800 ℃ after under 110 ℃ dry 6 hours.
7. polymer organic polymer template according to claim 6 is synthesized the preparation method of composite pore structural molecular sieve, it is characterized in that the HTS synthetic ratio: wherein the silicon source accounts for 5% ~ 15% of molecular sieve mixing solutions total mass, the 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 the silicon source is tetraethoxy, water glass, white carbon black, water glass or silicon sol;
Organic amine or organic quaternary ammonium salt are 4-propyl bromide, TPAOH, quadrol, n-Butyl Amine 99;
The titanium source is titanium dioxide, isopropyl titanate, tetrabutyl titanate;
The molecular weight of polymine can be regulated from 600 ~ 700000.
8. polymer organic polymer template according to claim 1 is synthesized the preparation method of composite pore structural molecular sieve, it is characterized in that phosphate aluminium molecular sieve material preparation method: aluminium source and phosphorus source are added to the water stir and add with polymine and organic amine or organic quaternary ammonium salt as composite shuttering, obtain containing the molecular sieve of composite pore structural after hydrothermal crystallizing, hydrothermal temperature is 150 ℃ ~ 170 ℃, and crystallization time is 1 day ~ 2 days; Finally by filtering, wash to the pH=7 left and right, and calcined the phosphate aluminium molecular sieve that obtained having composite pore structural in 5 ~ 12 hours under 300 ℃ ~ 800 ℃ after under 110 ℃ dry 6 hours.
9. polymer organic polymer template according to claim 8 is synthesized the preparation method of composite pore structural molecular sieve, it is characterized in that the phosphate aluminium molecular sieve synthetic ratio: the aluminium source accounts for 5% ~ 10% of molecular sieve mixing solutions total mass, the 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 the silicon source is tetraethoxy, water glass, white carbon black, water glass or silicon sol;
The aluminium source is aluminum isopropylate, potassium metaaluminate, sodium metaaluminate, pseudo-boehmite, aluminum oxide or Al
2(SO
4)
3
Organic amine or organic quaternary ammonium salt are triethylamine, diethylamine, di-n-propylamine or TPAOH;
The phosphorus source is the strong phosphoric acid of massfraction 85%;
The molecular weight of polymine can be regulated from 600 ~ 700000.
10. polymer organic polymer template according to claim 1 is synthesized the preparation method of composite pore structural molecular sieve, it is characterized in that aluminium silicophosphate molecular sieve material preparation method: phosphorus source, silicon source and aluminium source are added to the water stir, as composite shuttering, prepare the molecular sieve that contains composite pore structural with polymine and organic amine or organic quaternary ammonium salt; The polymine add-on is 1% ~ 30% of mixing solutions total mass; , then 150 ℃ ~ 200 ℃ lower crystallization 18 ~ 48 hours; Calcined the SAPO-34 molecular sieve that obtained having composite pore structural in 5 ~ 12 hours under 300 ~ 600 ℃ after the product washing after under 100 ℃ dry 6 hours;
The aluminium silicophosphate molecular sieve synthetic ratio: the silicon source accounts for 2% ~ 5% of molecular sieve mixing solutions total mass, the aluminium source accounts for 5% ~ 10% of molecular sieve mixing solutions total mass, the 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 the silicon source is tetraethoxy, water glass, white carbon black, water glass or silicon sol;
The aluminium source is aluminum isopropylate, potassium metaaluminate, sodium metaaluminate, pseudo-boehmite, aluminum oxide or Tai-Ace S 150;
The phosphorus source is the strong phosphoric acid of massfraction 85%;
Organic amine or organic quaternary ammonium salt are 4-propyl bromide, TPAOH, triethylamine, morpholine, diethylamine or di-n-propylamine;
The molecular weight of polymine can be regulated from 600 ~ 700000.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104591205A (en) * | 2015-02-06 | 2015-05-06 | 厦门大学 | Preparation method of catalyst material with composite pores |
| CN106423262A (en) * | 2016-09-06 | 2017-02-22 | 西北大学 | SAPO-34 molecular sieve based catalyst with ordered middle holes and preparation method thereof |
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| 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 |
| CN108993610A (en) * | 2018-07-10 | 2018-12-14 | 大连理工大学 | The preparation method and its usage of the amorphous mesoporous titanium-silicon material of hybrid inorganic-organic |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102745708A (en) * | 2011-04-22 | 2012-10-24 | 中国石油天然气股份有限公司 | Synthetic method of mesoporous-microporous molecular sieve with improved hydrothermal stability |
-
2013
- 2013-04-02 CN CN201310114100.2A patent/CN103172081B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102745708A (en) * | 2011-04-22 | 2012-10-24 | 中国石油天然气股份有限公司 | Synthetic method of mesoporous-microporous molecular sieve with improved hydrothermal stability |
Non-Patent Citations (2)
| Title |
|---|
| WANG H: "MFI zeolite with small and uniform intracrystal mesopores", 《ANGEWANDTE CHEMIE INTERNATIONAL EDITION》 * |
| 刘志成等: "淀粉模板法合成介孔ZSM-5分子筛", 《石油学报》 * |
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