CN104973608A - SAPO-34 molecular sieve of larger specific surface area and hollow alumina-rich hierarchical pore structures and application thereof - Google Patents
SAPO-34 molecular sieve of larger specific surface area and hollow alumina-rich hierarchical pore structures and application thereof Download PDFInfo
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Abstract
A SAPO-34 molecular sieve of a larger specific surface area and a hollow alumina-rich hierarchical pore structures and application thereof in a reaction that uses methanol to prepare low carbon olefin, belongs to the technical field of molecular sieves. The product by the invention is obtained by taking triethylamine as a template agent, adopting a traditional hydrothermal or solvothermal synthetic method, taking water or alcohol as a solvent, and introducing polyethylene glycol polymer in a high pressure reactor under an autogenous pressure through an in-situ alumina-rich method. A synthetic SAPO-34 molecular sieve sample is in a hollow and hierarchical pore structures cubic shape, the average crystal size is 5-10 [mu]m, and the mesoporou size is 2-15 nm. According to the invention, the yield of the synthetic SAPO-34 molecular sieve sample is extremely high, and can reach over 90%. The invention has extremely high selectivity of low carbon olefin in a reaction that uses methanol to prepare olefin (MTO), particularly the total yield of ethylene and propylene can reach over 85%, and the SAPO-34 molecular sieve is extremely suitable for industrial amplification application.
Description
Technical field
The invention belongs to technical field of molecular sieve, be specifically related to a kind ofly to have compared with bigger serface, the SAPO-34 molecular sieve of the rich aluminium hierarchical porous structure of hollow and the application in preparing low-carbon olefin by using methanol reaction thereof, may be used for the various hydrocarbon conversion, gas adsorption separation etc. in addition.
Background technology
The low-carbon alkene such as ethene, propylene, as one of the starting material of chemical industry, occupies vital effect in modern chemical industry system.Current petroleum cracking is the main path obtaining low-carbon alkene.But along with minimizing day by day that is cheap, the petroleum resources that are easy to get, the supply of low-carbon alkene is subject to tremendous influence, but domestic and international market is to the sustainable growth year by year of the demand of low-carbon alkene.Also the in short supply of petroleum resources more forces people to step up to find the low-carbon alkene fabricating technology not relying on petroleum resources just.A kind of desirable alternative techniques (M.Stocker.Microporous Mesoporous Mater.1999,29,3-48.) is considered to by the route of preparing light olefins from methanol (MTO).The feature such as, methyl alcohol production capacity surplus abundant in conjunction with coal resources in China deposit simultaneously, the transformation routes of MTO has great development advantage.By the end of the year 2013, China put into operation 6 cover coal (methyl alcohol) olefin hydrocarbon apparatus processed, aggregated capacity reaches annual 2660000 tons.These all greatly alleviate the demand of China for low-carbon alkene.
SAPO-34 molecular sieve is the poromerics that an eka-silicon replaces aluminum phosphate, developed (USP4440871) by American Association Carbide UCC for 1984, there is CHA topological framework, the molecular screen material of 8 membered ring channels (0.38 × 0.38 nanometer), belong to trigonal system, R3m spacer, it has good performance in gas adsorption separation, ion-exchange, the hydrocarbon conversion, especially in reaction (MTO) process of methanol-to-olefins, have high selectivity to ethene, propylene, cause scientists interest widely.
Between twenty or thirty year in the past, the large quantifier elimination that scientist both domestic and external carries out for the synthesis of SAPO-34, has also carried out constantly exploring to its synthesising law, has achieved a series of progress.The synthetic method of SAPO-34 molecular sieve is a lot, but conventional synthetic method comprises hydro-thermal reaction, solvent thermal reaction and Microwave Assisted Process.Template conventional in existing preparation method comprises one or more the mixture such as tetraethyl ammonium hydroxide, morpholine, triethylamine, diethylamine, piperidines, Isopropylamine.
But the MTO reaction process that current use SAPO-34 is catalyzer is still faced with catalyzer and is easy to produce serious carbon distribution, blocking duct, thus causes the problems such as fast deactivation.Therefore people are attempting adopting different methods to carry out modification to SAPO-34 molecular sieve, to the life-span of extending catalyst always.Wherein, in the SAPO-34 molecular sieve of micropore, introduce multi-stage porous is a kind of more common means, because multi-stage porous can improve the rate of diffusion of reactant and resultant effectively, and then reduce the formation of carbon distribution, improve catalytic life and catalytic activity (CN103011195, CN10299233).
The Measures compare producing hierarchical porous structure is many.Common comprises soft template method, hard template method, and the method for aftertreatment.Korea S inorganic chemist RYONG RYOO uses long chain organic silanes 3-trimethylsilylpropyl hexadecyldimethyl benzyl ammonium ammonium chloride (TPHAC), and for soft template successfully synthesizes, a series of SAPO Series Molecules with multi-stage porous sieves material, and has good catalytic performance (M.Choi; K.Na; J.Kim; Y.Sakamoto; Osamu, T.; Ryoo, R., Nature 2009,461,246; K.Na; C.Jo; J.Kim; K.Cho; J.Jung; Y.Seo; R.J.Messinger; Chmelka, B.F.; R.Ryoo, Science 2011,333,328.).Simultaneously, Zhu Kake etc. (CN 102992339 A) also add organosilane by original position and utilize dry gel method successfully to prepare and have hierarchical porous structure SAPO-34 molecular sieve, but organosilane fancy price but limits its practical application industrially.
The people such as Franz Schmidt use carbon ball and carbon nanotube also to prepare the SAPO-34 molecular sieve with hierarchical porous structure for hard template, find that obvious hysteresis loop appears in nitrogen adsorption, demonstrate mesoporous existence (F.Schmidt et al.Microporous and Mesoporous Materials 164 (2012) 214 – 221).But mesoporous not penetrating in the multi-stage porous SAPO-34 molecular sieve using carbon material to synthesize as hard template, and be not connected with micropore, only can play the carbon distribution deposited and produce in catalyzed reaction, the rate of diffusion of reactant and resultant can not be promoted, also will consume more energy when calcining template simultaneously.
Liu Zhongmin etc. use oxalic acid to carry out aftertreatment as treatment solution for synthesized SAPO-34 molecular sieve, have finally prepared multi-stage porous SAPO-34 molecular sieve (Journal of Natural Gas Chemistry 21 (2012) 431 – 434).This molecular sieve has the MTO catalytic performance of lower silicone content and lifting, but will produce more pollution while that post-treating method being cumbersome, also limit its application in the industrial production.
Thus seek a kind of simple, efficient and the preparation of the method for cheapness has high-performance hierarchical porous structure SAPO-34 molecular sieve has great practical application in industry meaning and prospect.
Summary of the invention
The object of the present invention is to provide a kind of prepare simple efficient, compared with bigger serface, the rich aluminium hierarchical porous structure of hollow SAPO-34 molecular sieve and be separated in the various hydrocarbon conversion, gas adsorption, the application especially in preparing low-carbon olefin by using methanol reaction.
Molecular sieve prepared by the present invention has hollow hierarchical porous structure, there is larger specific surface area simultaneously, outer surface area and microporous mesoporous volume, as the catalyzer of methanol to olefins reaction, greatly can improve reactant and product rate of diffusion in the catalyst, effectively reduce the generating rate of carbon distribution, the catalytic life of significant prolongation catalyzer, greatly improve the selectivity of low-carbon alkene, the especially productive rate of ethene and propylene simultaneously.
The present invention adopts traditional hydro-thermal or solvent process for thermosynthesizing, using water or alcohols as solvent, by the method for the rich aluminium of original position, add cheap polyoxyethylene glycol (PEG) polymkeric substance, modulation gel composition and concentration, in autoclave, obtain having comparatively bigger serface by autogenous pressure, the SAPO-34 molecular sieve of the rich aluminium hierarchical porous structure of hollow.
SAPO-34 sieve sample synthesized in the present invention is the cubes pattern of hollow, hierarchical porous structure, and its average mean crystal size is of a size of 5 ~ 10 μm, mesopore size 2 ~ 15nm.Described average mean crystal size is measured by scanning electron photomicrograph (SEM) and transmission electron micrograph (TEM) and is determined.SAPO-34 sieve sample synthesized in the present invention simultaneously all has larger specific surface area and pore volume, and is determined by the test of nitrogen adsorption desorption.
Synthetic method of the present invention is simple, and crystallization time is short, and solvent-oil ratio is little, synthesizes with low cost simultaneously, does not need follow-up acid-alkali treatment, considerably reduces synthesis cost and generated time, the waste liquor contamination produced when also effectively reducing synthesis.The productive rate of the multi-stage porous SAPO-34 sample simultaneously synthesized by the present invention is high, more than 90% (calculating with the phosphorus source quality added) can be reached, in Methanol is for alkene (MTO) reaction, there is high selectivity of light olefin, especially the total recovery of ethene and propylene can reach more than 85%, is very suitable for industry and amplifies application.
Of the present invention have comparatively bigger serface, and hollow rich aluminium hierarchical porous structure SAPO-34 molecular sieve, adopts triethylamine (TEA) to be template, conventional hydrothermal or solvent process for thermosynthesizing synthesis, and its preparation process is as follows:
1) by aluminium source, triethylamine, solvent and polyethylene glycol polymer mixing, stir 5 ~ 10 hours under 30 ~ 50 DEG C of conditions, obtain uniform mixture solution;
2) silicon source, phosphorus source are joined in said mixture solution successively, stir 2 ~ 5 hours under 30 ~ 50 DEG C of conditions, obtain SAPO-34 molecular sieve initial gel mixture; Afterwards, obtained SAPO-34 molecular sieve initial gel mixture is stirred 2 ~ 8 hours again in the water-bath of 50 ~ 80 DEG C, obtains gel mixture;
3) by step 2) gel mixture that obtains carries out thermostatic crystallization, after crystallization is complete, centrifugation goes out solid product, then by solid matter with deionized water repetitive scrubbing to neutral, then dry under 60 ~ 85 DEG C of conditions, obtain SAPO-34 molecular screen primary powder;
4) high-temperature calcination of SAPO-34 molecular screen primary powder to be removed in former powder contained template and solvent, thus obtain having the SAPO-34 molecular sieve of cubes pattern of hollow, hierarchical porous structure.
In above-mentioned steps, in initial gel mixture, the mol ratio of each component oxide, template, solvent and polyethylene glycol polymer is SiO
2: P
2o
5=0.1 ~ 0.8:1, Al
2o
3: P
2o
5=4 ~ 8:1, TEA:P
2o
5=5 ~ 10:1, solvent: P
2o
5=20 ~ 200:1, PEG:P
2o
5=0.05 ~ 0.5:1.
Described solvent is one or more mixtures in water, methyl alcohol, ethanol, propyl alcohol.
Described silicon source is the one of white carbon black, active silica, water glass or tetraethyl silicate.
Described aluminium source is the one of aluminum isopropylate, aluminium sesquioxide, aluminium hydroxide or pseudo-boehmite.
Described phosphorus source is massfraction 85% phosphoric acid solution.
Described polyethylene glycol polymer is PEG-400, PEG-1000, PEG-2000, PEG-10000 etc.
Step c) in gel mixture carry out thermostatic crystallization, gel mixture is loaded have in teflon-lined stainless steel cauldron, again reactor is placed in baking oven and carries out thermostatic crystallization at autogenous pressures, the temperature of thermostatic crystallization is 180 ~ 230 DEG C, the time of thermostatic crystallization is 6 ~ 20 hours, naturally cools to room temperature after crystallization completes;
Steps d) in calcining temperature be 500 ~ 650 DEG C, calcination time is 5 ~ 12 hours.
Described SAPO-34 molecular sieve, can be used as crystal seed or precursor material in production molecular sieve.The molecular sieve prepared by the inventive method also can be used for the aluminium silicophosphate molecular sieve prepared and have identical topological framework type or different topology structure type that leads.
Described SAPO-34 molecular sieve also can make molecular screen membrane, is applied to the conversion of various hydro carbons, gas delivery, absorption, and the infiltration evaporation of mixing solutions is separated, and also can carry out other particles of load, carry out catalyzed reaction as matrix material.Described SAPO-34 molecular sieve shows selectivity and the productive rate of high catalytic life and low-carbon alkene in Methanol is for alkene (MTO) reaction simultaneously.
Accompanying drawing explanation
Fig. 1 is the X-ray diffraction spectrogram of embodiment 1 to embodiment 4 product.As can be seen from the figure, four embodiment samples are the SAPO-34 sample with CHA topological framework.
Fig. 2 is the electron scanning micrograph (SEM) of four embodiment samples.
Wherein Fig. 2 a is the SEM photo of embodiment 1, can find out that the SAPO-34 material obtained is hollow (it is of a size of about 2 μm), multi-stage porous (had both existed microvoid structure about 0.4nm at crystals, there is mesoporous 2 ~ 15nm and macroporous structure about 100nm simultaneously) structure cubic pattern, its average mean crystal size is of a size of 5 ~ 10 μm.
Wherein Fig. 2 b is the SEM photo of embodiment 2, can find out that the SAPO-34 material obtained is hollow (it is of a size of about 2 μm), multi-stage porous (had both existed microvoid structure about 0.4nm at crystals, there is mesoporous 2 ~ 15nm and macroporous structure about 100nm simultaneously) structure cubic pattern, its average mean crystal size is of a size of 5 ~ 10 μm.
Wherein Fig. 2 c is the SEM photo of embodiment 3, can find out that the SAPO-34 material obtained is hollow (it is of a size of about 2 μm), multi-stage porous (had both existed microvoid structure about 0.4nm at crystals, there is mesoporous 2 ~ 15nm and macroporous structure about 100nm simultaneously) structure cubic pattern, its average mean crystal size is of a size of 5 ~ 10 μm.
Wherein Fig. 2 d is the SEM photo of embodiment 4, can find out that the SAPO-34 material obtained is hollow (it is of a size of about 2 μm), multi-stage porous (had both existed microvoid structure about 0.4nm at crystals, there is mesoporous 2 ~ 15nm and macroporous structure about 100nm simultaneously) structure cubic pattern, its average mean crystal size is of a size of 5 ~ 10 μm.
Fig. 3 is the transmission electron microscope photo (TEM) of four embodiment samples.
Wherein Fig. 3 a is the TEM photo of embodiment 1, can find out that the SAPO-34 material obtained has 2 ~ 15nm mesopore orbit, and the micropore canals of 0.4nm.
Wherein Fig. 3 b is the TEM photo of embodiment 2, can find out that the SAPO-34 material obtained has 2 ~ 15nm mesopore orbit, and the micropore canals of 0.4nm.
Wherein Fig. 3 c is the TEM photo of embodiment 3, can find out that the SAPO-34 material obtained has 2 ~ 15nm mesopore orbit, and the micropore canals of 0.4nm.
Wherein Fig. 3 d is the TEM photo of embodiment 4, can find out that the SAPO-34 material obtained has 2 ~ 15nm mesopore orbit, and the micropore canals of 0.4nm.
Embodiment
Below by specific embodiment in detail the present invention is described in detail, but the present invention is not limited to these embodiments.
Embodiment 1:
Within 5 hours, mixture is obtained by stirring at 30 DEG C after aluminum isopropylate, water, triethylamine and poly(oxyethylene glycol) 400 (PEG 400) fully mix and blend; White carbon black, phosphoric acid are joined in said mixture successively, Keep agitation process 2 hours, obtain SAPO-34 molecular sieve initial gel mixture; Afterwards, obtained SAPO-34 molecular sieve initial gel mixture is stirred 3 hours again in 50 DEG C of water-baths, and in reaction system, in initial gel mixture, the mol ratio of each component is 5TEA: 0.3SiO
2: 1.0P
2o
5: 8Al
2o
3: 58.4H
2o:0.05PEG 400; Initial gel mixture is loaded and has in teflon-lined stainless steel cauldron, then reactor is placed in baking oven, be warming up to 180 DEG C, at autogenous pressures, carry out constant temperature (180 DEG C) crystallization under hydrothermal condition 18 hours.Then, solid product is through centrifugation, repeatedly extremely neutral with deionized water wash, at 60 DEG C after air drying, obtain SAPO-34 molecular screen primary powder, namely former powder obtains hollow, rich aluminium multi-stage porous SAPO-34 molecular sieve (numbering S1) after removing organic ammonium template in 10 hours through 550 DEG C of roastings.As shown in Figure 1, as shown in Figure 2 a, transmission electron microscope (TEM) photo as shown in Figure 3 a for scanning electron microscope (SEM) photo for the XRD spectra of former powder sample.Can prove that the sample obtained is the SAPO-34 molecular sieve with CHA topological framework, molecular sieve is hollow, hierarchical porous structure cubes pattern, has 2 ~ 15nm mesopore orbit simultaneously.In sample skeleton, contained aluminium content is greater than silicone content and phosphorus content summation simultaneously, and the sample synthesized by proving is rich aluminum molecular screen.(as shown in table 1)
Embodiment 2:
By pseudo-boehmite, water, methyl alcohol (MeOH), triethylamine, and after the abundant mix and blend of Macrogol 2000 at 50 DEG C stir within 8 hours, obtain mixture; Active silica, phosphoric acid are joined in said mixture successively, Keep agitation process 2 hours, obtain SAPO-34 molecular sieve initial gel mixture; Afterwards, obtained SAPO-34 molecular sieve initial gel mixture is stirred 2 hours again in 80 DEG C of water-baths, and in reaction system, in initial gel mixture, the mol ratio of each component is 10TEA: 0.8SiO
2: 1.0P
2o
5: 4Al
2o
3: 200H
2o: 40MeOH: 0.5PEG 2000; Initial gel mixture is loaded and has in teflon-lined stainless steel cauldron, then reactor is placed in baking oven, be warming up to 230 DEG C, at autogenous pressures, carry out constant temperature (230 DEG C) crystallization under hydrothermal condition 6 hours.Then, solid product is through centrifugation, repeatedly extremely neutral with deionized water wash, at 85 DEG C after air drying, obtain SAPO-34 molecular screen primary powder, namely former powder obtains rich aluminium multi-stage porous SAPO-34 molecular sieve (numbering S2) of hollow after removing organic ammonium template in 5 hours through 650 DEG C of roastings.As shown in Figure 1, as shown in Figure 2 b, transmission electron microscope (TEM) photo as shown in Figure 3 b for scanning electron microscope (SEM) photo for the XRD spectra of former powder sample.Can prove that the sample obtained is the SAPO-34 molecular sieve with CHA topological framework, molecular sieve is hollow, hierarchical porous structure cubes pattern, has 2 ~ 15nm mesopore orbit simultaneously.In sample skeleton, contained aluminium content is greater than silicone content and phosphorus content summation simultaneously, and the sample synthesized by proving is rich aluminum molecular screen.(as shown in table 1)
Embodiment 3:
Within 5 hours, mixture is obtained by stirring at 40 DEG C after aluminium sesquioxide, ethanol (EtOH), triethylamine and the abundant mix and blend of cetomacrogol 1000; Tetraethyl silicate, phosphoric acid are joined in said mixture successively, Keep agitation process 5 hours, obtain SAPO-34 molecular sieve initial gel mixture; Afterwards, obtained SAPO-34 molecular sieve initial gel mixture is stirred 8 hours again in 60 DEG C of water-baths, and in reaction system, in initial gel mixture, the mol ratio of each component oxide, triethylamine and solvent is 7TEA: 0.1SiO
2: 1.0P
2o
5: 8Al
2o
3: 20EtOH: 0.2PEG 1000; Initial gel mixture is loaded and has in teflon-lined stainless steel cauldron, then reactor is placed in baking oven, be warming up to 200 DEG C, at autogenous pressures, carry out constant temperature (200 DEG C) crystallization under hydrothermal condition 20 hours.Then, solid product is through centrifugation, repeatedly extremely neutral with deionized water wash, at 75 DEG C after air drying, obtain SAPO-34 molecular screen primary powder, namely former powder obtains rich aluminium multi-stage porous SAPO-34 molecular sieve (numbering S3) of hollow after removing organic ammonium template in 12 hours through 500 DEG C of roastings.As shown in Figure 1, as shown in Figure 2 c, transmission electron microscope (TEM) photo as shown in Figure 3 c for scanning electron microscope (SEM) photo for the XRD spectra of former powder sample.Can prove that the sample obtained is the SAPO-34 molecular sieve with CHA topological framework, molecular sieve is hollow, hierarchical porous structure cubes pattern, has 2 ~ 15nm mesopore orbit simultaneously.In sample skeleton, contained aluminium content is greater than silicone content and phosphorus content summation simultaneously, and the sample synthesized by proving is rich aluminum molecular screen.(as shown in table 1)
Embodiment 4:
Within 10 hours, mixture is obtained by stirring at 40 DEG C after aluminium hydroxide, propyl alcohol (PrOH), triethylamine and the abundant mix and blend of PEG20000; Water glass, phosphoric acid are joined in said mixture successively, Keep agitation process 4 hours, obtain SAPO-34 molecular sieve initial gel mixture; Afterwards, obtained SAPO-34 molecular sieve initial gel mixture is stirred 5 hours again in 70 DEG C of water-baths, and in reaction system, in initial gel mixture, the mol ratio of each component is 8TEA: 0.4SiO
2: 1.0P
2o
5: 7.5Al
2o
3: 50PrOH: 0.3PEG 10000; Initial gel mixture is loaded and has in teflon-lined stainless steel cauldron, then reactor is placed in baking oven, be warming up to 200 DEG C, at autogenous pressures, carry out constant temperature (200 DEG C) crystallization under hydrothermal condition 20 hours.Then, solid product is through centrifugation, repeatedly extremely neutral with deionized water wash, at 65 DEG C after air drying, obtain SAPO-34 molecular screen primary powder, namely former powder obtains rich aluminium multi-stage porous SAPO-34 molecular sieve (numbering S4) of hollow after removing organic ammonium template in 10 hours through 580 DEG C of roastings.As shown in Figure 1, as shown in Figure 2 d, transmission electron microscope (TEM) photo as shown in Figure 3 d for scanning electron microscope (SEM) photo for the XRD spectra of former powder sample.Can prove that the sample obtained is the SAPO-34 molecular sieve with CHA topological framework, molecular sieve is hollow, hierarchical porous structure cubes pattern, has 2 ~ 15nm mesopore orbit simultaneously.In sample skeleton, contained aluminium content is greater than silicone content and phosphorus content summation simultaneously, and the sample synthesized by proving is rich aluminum molecular screen.(as shown in table 1)
Embodiment 5:
We carry out ultimate analysis and nitrogen adsorption test to embodiment 1 to 4 obtained 4 samples, and result is as shown in table 1.4 samples all have higher specific surface area and higher outer surface area as can be seen from Table 1, and the sample prepared by proving is multi-stage porous SAPO-34 molecular sieve.
Meanwhile, 4 samples embodiment 1 to 4 obtained carry out compressing tablet, are crushed to 20 ~ 40 orders.Take 0.3g sample and load fixed-bed reactor, carry out MTO evaluation.At 500 DEG C, logical nitrogen activation 1.5 hours, is then cooled to 450 DEG C.Methyl alcohol is carried by nitrogen, and nitrogen flow rate is 15ml/min, methanol weight air speed 4.0h
-1.The product obtained is analyzed by online gas-chromatography (Agilent7890), the results are shown in Table 2.As can be seen from Table 2,4 samples all have high catalytic life, and the total recovery of ethene and propylene has exceeded 85.0% simultaneously.
Table 1: elementary composition, specific surface area (BET) data of sample prepared by each embodiment
Table 2: sample preparing olefin by conversion of methanol reaction test result data
Claims (9)
1. comparatively bigger serface, a hollow rich aluminium hierarchical porous structure SAPO-34 molecular sieve, it is prepared by following steps:
1) aluminium source, triethylamine TEA, solvent and polyethylene glycol polymer PEG are mixed, stir 5 ~ 10 hours under 30 ~ 50 DEG C of conditions, obtain uniform mixture solution;
2) silicon source, phosphorus source are joined in said mixture solution successively, stir 2 ~ 5 hours under 30 ~ 50 DEG C of conditions, obtain SAPO-34 molecular sieve initial gel mixture; Afterwards, obtained SAPO-34 molecular sieve initial gel mixture is stirred 2 ~ 8 hours again in the water-bath of 50 ~ 80 DEG C, obtains gel mixture; In initial gel mixture, the consumption mol ratio of each component oxide, template, solvent, polyethylene glycol polymer is SiO
2: P
2o
5=0.1 ~ 0.8:1, Al
2o
3: P
2o
5=4 ~ 8:1, TEA:P
2o
5=5 ~ 10:1, solvent: P
2o
5=20 ~ 200:1, PEG:P
2o
5=0.05 ~ 0.5:1;
3) by step 2) gel mixture that obtains carries out thermostatic crystallization, after crystallization is complete, centrifugation goes out solid product, then by solid matter with deionized water repetitive scrubbing to neutral, then dry under 60 ~ 85 DEG C of conditions, obtain SAPO-34 molecular screen primary powder;
4) high-temperature calcination of SAPO-34 molecular screen primary powder to be removed in former powder contained template and solvent, thus obtain having the SAPO-34 molecular sieve of cubes pattern of hollow, hierarchical porous structure.
2. one as claimed in claim 1 comparatively bigger serface, hollow rich aluminium hierarchical porous structure SAPO-34 molecular sieve, is characterized in that: solvent is the mixture of one or more in water, methyl alcohol, ethanol, propyl alcohol.
3. one as claimed in claim 1 comparatively bigger serface, hollow rich aluminium hierarchical porous structure SAPO-34 molecular sieve, is characterized in that: silicon source is the one of white carbon black, active silica, water glass or tetraethyl silicate.
4. one as claimed in claim 1 comparatively bigger serface, hollow rich aluminium hierarchical porous structure SAPO-34 molecular sieve, is characterized in that: aluminium source is the one of aluminum isopropylate, aluminium sesquioxide, aluminium hydroxide or pseudo-boehmite.
5. one as claimed in claim 1 comparatively bigger serface, hollow rich aluminium hierarchical porous structure SAPO-34 molecular sieve, is characterized in that: phosphorus source is massfraction 85% phosphoric acid solution.
6. one as claimed in claim 1 comparatively bigger serface, hollow rich aluminium hierarchical porous structure SAPO-34 molecular sieve, is characterized in that: polyethylene glycol polymer is PEG-400, PEG-1000, PEG-2000 or PEG-10000.
7. one as claimed in claim 1 comparatively bigger serface, hollow rich aluminium hierarchical porous structure SAPO-34 molecular sieve, it is characterized in that: step c) in gel mixture carry out thermostatic crystallization, gel mixture is loaded have in teflon-lined stainless steel cauldron, again reactor is placed in baking oven and carries out thermostatic crystallization at autogenous pressures, the temperature of thermostatic crystallization is 180 ~ 230 DEG C, the time of thermostatic crystallization is 6 ~ 20 hours, naturally cools to room temperature after crystallization completes.
8. one as claimed in claim 1 comparatively bigger serface, hollow rich aluminium hierarchical porous structure SAPO-34 molecular sieve, is characterized in that: steps d) in calcining temperature be 500 ~ 650 DEG C, calcination time is 5 ~ 12 hours.
9. according to claim 1 a kind of compared with bigger serface, the application of hollow rich aluminium hierarchical porous structure SAPO-34 molecular sieve in preparing low-carbon olefin by using methanol reaction, the various hydrocarbon conversion or gas adsorption are separated.
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| CN108602684A (en) * | 2016-03-16 | 2018-09-28 | 沙特基础工业全球技术公司 | The synthesis of SAPO-34 and the application in chloromethanes olefine reaction |
| 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 |
| CN110255579A (en) * | 2019-06-19 | 2019-09-20 | 正大能源材料(大连)有限公司 | Metal-modified hollow SAPO-34 molecular sieve of one kind and its preparation method and application |
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| CN111686797A (en) * | 2020-07-09 | 2020-09-22 | 常州工程职业技术学院 | Fe-SAPO-34 molecular sieve catalyst, preparation method and application |
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| CN114797497A (en) * | 2022-05-30 | 2022-07-29 | 江西师范大学 | Method for preparing AlPO-18 molecular sieve membrane by alcohol acceleration and application |
| CN114890435A (en) * | 2022-06-22 | 2022-08-12 | 中国石油大学(华东) | Hollow-structure SAPO-34 molecular sieve prepared by MTO waste catalyst and preparation method and application thereof |
| CN115417426A (en) * | 2022-09-19 | 2022-12-02 | 常州大学 | Preparation method and application of small-grain and multi-stage-pore SAPO-34 molecular sieve |
| CN115520877A (en) * | 2021-06-25 | 2022-12-27 | 中国石油化工股份有限公司 | SAPO-34 molecular sieve, and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102219237A (en) * | 2010-04-15 | 2011-10-19 | 中国石油化工股份有限公司 | Method for preparing SAPO (Silico-Aluminophosphate) molecular sieve material with multi-level-hole structure |
| CN102219236A (en) * | 2010-04-15 | 2011-10-19 | 中国石油化工股份有限公司 | Multi-stage porous structure SAPO (silicoaluminophosphate) molecular sieve monolith material and preparation method thereof |
| CN102992339A (en) * | 2011-09-15 | 2013-03-27 | 华东理工大学 | Solvent volatilization self-assembly method used for preparing multistage-channel SAPO-34 and SAPO-18 molecular sieves |
| CN103130241A (en) * | 2013-03-21 | 2013-06-05 | 上海绿强新材料有限公司 | Synthesis method of low-silicon nano SAPO-34 molecular sieve |
| CN103641131A (en) * | 2013-12-10 | 2014-03-19 | 吉林大学 | Slice-shaped nanometer SAPO-34 molecular sieve with relatively low silicon content, preparation method and application thereof |
| CN104556092A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Hierarchical porous structure SAPO molecular sieve material and preparation method thereof |
-
2015
- 2015-06-16 CN CN201510334437.3A patent/CN104973608B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102219237A (en) * | 2010-04-15 | 2011-10-19 | 中国石油化工股份有限公司 | Method for preparing SAPO (Silico-Aluminophosphate) molecular sieve material with multi-level-hole structure |
| CN102219236A (en) * | 2010-04-15 | 2011-10-19 | 中国石油化工股份有限公司 | Multi-stage porous structure SAPO (silicoaluminophosphate) molecular sieve monolith material and preparation method thereof |
| CN102992339A (en) * | 2011-09-15 | 2013-03-27 | 华东理工大学 | Solvent volatilization self-assembly method used for preparing multistage-channel SAPO-34 and SAPO-18 molecular sieves |
| CN103130241A (en) * | 2013-03-21 | 2013-06-05 | 上海绿强新材料有限公司 | Synthesis method of low-silicon nano SAPO-34 molecular sieve |
| CN104556092A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Hierarchical porous structure SAPO molecular sieve material and preparation method thereof |
| CN103641131A (en) * | 2013-12-10 | 2014-03-19 | 吉林大学 | Slice-shaped nanometer SAPO-34 molecular sieve with relatively low silicon content, preparation method and application thereof |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108602684A (en) * | 2016-03-16 | 2018-09-28 | 沙特基础工业全球技术公司 | The synthesis of SAPO-34 and the application in chloromethanes olefine reaction |
| CN108262068A (en) * | 2017-01-04 | 2018-07-10 | 中国石油化工股份有限公司 | The method of oxygenate producing light olefins |
| 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 |
| CN110255579A (en) * | 2019-06-19 | 2019-09-20 | 正大能源材料(大连)有限公司 | Metal-modified hollow SAPO-34 molecular sieve of one kind and its preparation method and application |
| CN110407220B (en) * | 2019-08-27 | 2022-08-12 | 中化泉州能源科技有限责任公司 | Rapid preparation method of SAPO-34 molecular sieve with large specific surface area |
| CN110407220A (en) * | 2019-08-27 | 2019-11-05 | 中化泉州能源科技有限责任公司 | A kind of fast preparation method of bigger serface SAPO-34 molecular sieve |
| CN111686797A (en) * | 2020-07-09 | 2020-09-22 | 常州工程职业技术学院 | Fe-SAPO-34 molecular sieve catalyst, preparation method and application |
| CN112225226A (en) * | 2020-10-22 | 2021-01-15 | 郑州大学 | Preparation method of hierarchical pore SAPO-34 molecular sieve |
| CN115520877A (en) * | 2021-06-25 | 2022-12-27 | 中国石油化工股份有限公司 | SAPO-34 molecular sieve, and preparation method and application thereof |
| CN114797497A (en) * | 2022-05-30 | 2022-07-29 | 江西师范大学 | Method for preparing AlPO-18 molecular sieve membrane by alcohol acceleration and application |
| CN114890435A (en) * | 2022-06-22 | 2022-08-12 | 中国石油大学(华东) | Hollow-structure SAPO-34 molecular sieve prepared by MTO waste catalyst and preparation method and application thereof |
| CN114890435B (en) * | 2022-06-22 | 2023-08-25 | 中国石油大学(华东) | Hollow-structure SAPO-34 molecular sieve prepared by MTO spent catalyst, and preparation method and application thereof |
| CN115417426A (en) * | 2022-09-19 | 2022-12-02 | 常州大学 | Preparation method and application of small-grain and multi-stage-pore SAPO-34 molecular sieve |
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