CN103420391A - Small grain SAPO-34 molecular sieve preparation method - Google Patents
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Abstract
The invention relates to a small grain SAPO-34 molecular sieve preparation method, wherein the problem of large SAPO-34 molecular sieve grains obtained through the existing synthesis method in the prior art is mainly solved with the present invention. According to the technical scheme, the preparation method comprises: a) preparing a phosphorus source, an aluminum source, a silicon source, a template agent and water into a crystallization solution; b) carrying out stirring aging on the crystallization solution for 1-24 h at a temperature T1 of 20-100 DEG C; c) carrying out hydrothermal crystallization on the aged crystallization solution for 1-20 h at a temperature T2 of 180-250 DEG C; d) carrying out programmed cooling until a temperature T3 is room temperature-160 DEG C, and maintaining the temperature for at least 0.1 h; and e) carrying out programmed heating until a temperature T4 is 180-250 DEG C, and carrying out hydrothermal crystallization for 2-24 h to obtain the molecular sieve product. With the technical scheme, the problem is well solved, and the preparation method can be used for industrial production of small grain SAPO-34 molecular sieve preparation.
Description
Technical field
The present invention relates to a kind of preparation method of fine grain SAPO-34 molecular sieve.
Background technology
Ethene and propylene are the important basic organic chemical industry raw materials of chemical industry, in modern oil and chemical industry, play a part very important.In recent years, along with day by day shortage and crude oil price constantly high of Global Oil resource, produce by traditional petroleum path the disparities between supply and demand that ethene and propylene bring and be tending towards anxiety, each state all is devoted to develop the operational path that new non-oil is produced alkene.Wherein, coal or Sweet natural gas are by synthetic gas (CO+H
2) via the technique of preparing light olefins from methanol, be the technological line of the tool application prospect of generally acknowledging at present.Rich coal resources in China, once the relatively deficient energy structure of petroleum resources has also determined that the operational path of olefin hydrocarbon making by coal is got through, will, to expanding China's tradition Developing Coal Chemical Industry space, guarantee that national energy security has important and far-reaching meaning.At present, gasification in the olefin hydrocarbon making by coal technical process, synthesising gas systeming carbinol have developed into ripe coal chemical technology, and the industrialization technology exploitation of methanol-to-olefins (Methanol to Olefin is called for short MTO) is the key link that this operational path is realized.
The core of methanol-to-olefins technology is the exploitation of molecular sieve catalyst, and the catalyzer that early stage methanol-to-olefins is used mostly is the Si-Al zeolite molecular sieve, and as ZSM-5, but its aperture is relatively large, and acidity is too strong, and yield of light olefins is not high.Nineteen eighty-two, U.S. associating carbon compound company (UCC) synthesizes SAPO series silicoaluminophosphamolecular molecular sieves first, wherein the most noticeable is the SAPO-34 molecular sieve, it has the class chabazite structure, there is less aperture, moderate acid and stronger hydrothermal stability simultaneously, show excellent selectivity of light olefin in the catalysis methanol reaction for preparing light olefins, thereby cause the investigator's of China and foreign countries extensive concern.
There are some researches show, in the MTO reaction, the SAPO-34 molecular sieve of small particle size is because shorten in duct, be conducive to the diffusion of reactant and product, can improve apparent activity and diene (ethene+propylene) selectivity of molecular sieve catalyst, and effective inhibited reaction degree of depth, so carbon deposition quantity is low.Many investigators to how preparing fine grain SAPO-34 molecular sieve are studied, for example: Liu's red magnitude [Liu Hongxing, etc., catalysis journal, 2004,25 (9): 702-706; Liu Hongxing, etc., the catalysis journal, 2003,24 (4): 279-283] by using HF-TEA or TEAOH-C4H9NO double template, the SAPO-34 molecular sieve that to have obtained median size be 1.7 μ m, it is template that this result obviously is better than adopting single TEA or C4H9NO; [the Hendri van H. such as Hendri, Svetlana M. Thomas B. Chem. Mater., 2008,20:2956-2963] employing TEAOH is template, control the speed that adds of phosphoric acid, and prepared by the microwave hydrothermal synthesis method SAPO-34 molecular sieve that particle diameter is less than 300 nm; [the Norikazu N. such as Norikazu, Masumi K., Yuichiro H., et al. Applied Catalysis A:General, 2009,362:193-199] to adopt respectively the mixture of TEAOH, Mor, TEEDA, TEAOH and Mor be template, the SAPO-34 molecular sieve that to synthesize particle diameter be 800 nm; [CN 101462742 for Yuan Zhongyong etc., 2009] research finds that using triethylamine is template, by adding fluorochemical (as Sodium Fluoride, Neutral ammonium fluoride or hydrogen fluoride), particularly Neutral ammonium fluoride, can significantly reduce the grain-size of product, optimum can obtain the SAPO-34 molecular sieve of 1.4 μ m; Li Wei etc. [CN 101214974,2008] are on the basis of conventional hydrothermal synthesis method, and by introduce ultrasonic dispersion in the initial gel mixture whipping process, the SAPO-34 zeolite crystal size obtained is than conventional synthetic 50 % that reduce; [hole dawn such as hole dawn, Liu Xiaoqin, Liu Dinghua, Institutes Of Technology Of Nanjing's journal, research 2007,31(4): 528-532] has also proved the ultrasonic effect of fine grain SAPO-34 molecular sieve in synthetic that be dispersed in, and they take triethylamine as template, to static crystallization again after initial gel supersound process 0.5 h, the crystal grain mean size can be decreased to 1.2 μ m by 2.9 μ m.
Visible, existing document and patent report are mainly by the kind of change template and consumption, in synthetic system, add the SAPO-34 molecular sieves that auxiliary agent or introducing ultrasonic wave field etc. can obtain less crystal grain.The preparation method of fine grain SAPO-34 molecular sieve has been enriched in these researchs to a certain extent, yet the use due to specific template agent, auxiliary agent or medium field, limiting in varying degrees industrial applications, the fine grain SAPO-34 molecular sieve preparation method that development procedure is simple, suitability is strong can better address this problem.
Summary of the invention
Technical problem to be solved by this invention is the synthetic larger problem of SAPO-34 zeolite crystal of prior art, the invention provides a kind of new fine grain SAPO-34 molecular sieve preparation method.The method has advantages of that synthesis of molecular sieve crystal grain is less.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of preparation method of fine grain SAPO-34 molecular sieve comprises the following steps:
A) ,Gui source, ,Lv source, phosphorus source, template and water are made to crystallization liquid, mole proportioning of crystallization liquid is as follows: template: SiO
2: Al
2O
3: P
2O
5: H
2O=0.5 ~ 10:0.05 ~ 10:0.2 ~ 3:0.2 ~ 3:20 ~ 200;
B) crystallization liquid is at T
1Temperature is 20 ~ 100 ℃ and stirs aging 1 ~ 24 h;
C) by the crystallization liquid after aging at T
2Temperature is 180 ~ 250 ℃ of lower hydrothermal crystallizing 1 ~ 20 h;
D) programmed cooling is to T
3Temperature is room temperature ~ 160 ℃, and at least keeps 0.1 h in this temperature;
E) temperature programming is to T
4Temperature is 180 ~ 250 ℃, and hydrothermal crystallizing 2 ~ 24 h, obtain zeolite product.
In technique scheme, aluminium source preferred version is selected from least one in aluminum isopropylate, pseudo-boehmite or aluminum oxide; Phosphorus source preferred version is selected from least one in phosphoric acid, phosphoric acid salt or phosphorous acid; Silicon source preferred version is selected from least one in TEOS, white carbon black or silicon sol; The template preferred version is selected from least one in TEAOH, TPA, triethylamine, diethylamine or morpholine; Hydrothermal crystallizing temperature T in step c)
2Preferable range is 190 ~ 240 ℃; In step c), hydrothermal crystallizing time preferable range is 2 ~ 14 h, and more preferably scope is 2 ~ 8 h; The described programmed cooling of step d) is preferably water cooling, naturally cooling or oil cooling, more preferably oil cooling; The described programmed cooling of step d) is to T
3The temperature preferable range is 40 ~ 150 ℃, and keeps at least 0.1 h, wherein T
3Temperature at least will be lower than T
230 ~ 80 ℃ of temperature, more preferably scope is 40 ~ 60 ℃.The rate of temperature fall preferable range of the described programmed cooling of step d) is 0.1 ~ 10 ℃/min.The described temperature rise rate preferable range of step e) is 0.5 ~ 4 ℃/min; Step e) hydrothermal crystallizing temperature T
4Preferable range is 190 ~ 240 ℃, and the crystallization time preferable range is 4 ~ 24 h, and more preferably scope is 8-24 h; Gained SAPO-34 molecular sieve has at least a crystal grain to be not more than 1 micron, and preferred technical scheme gained zeolite product has at least a crystal grain to be not more than 0.5 micron.The median size of product is 0.2 ~ 3.0 micron, and preferable range is 0.5 ~ 1.5 micron, and more preferably scope is 0.8 ~ 1.2 micron.
Increasing nucleus quantity in synthetic system is to prepare one of effective method of small crystal grain molecular sieve, and method provided by the invention is in fact for system provides a large amount of tiny nucleus, specifically by temperature programmed control, crystallization is divided into to two sections and realizes.Proposition of the present invention is based on the research that prepared by traditional hydrothermal synthesis method to the crystallization process of SAPO-34 molecular sieve, result shows, the nucleus comparatively small amt generated by the system homogeneous nucleation, the crystallization initial stage, synthesis material generates the more macrobead molecular sieve crystal of defect rapidly centered by less nucleus, in the crystallization later stage, the more crystal of defect generates comparatively perfectly crystal of crystal grain under the effect of dissolving recrystallize, thereby the product grains size that Traditional Method obtains is larger.The macrocrystal generation phase that the present invention is more in the some amount defect, break system crystallization balance by programmed cooling, stop the crystallization process, again in Temperature Programmed Processes, the more newborn macrobead crystal of defect is under the effect of dissolution equilibrium, dissolve with the form of a large amount of fine debris, and, as the nucleus of subordinate phase crystallization, make the median size of final product greatly reduce.This method is equally applicable to adopt the preparation system of other template, thereby has suitability comparatively widely.
The SAPO-34 molecular sieve preparation method that the purpose of this invention is to provide the little crystal grain that a kind of step is simple, suitability is strong, characteristics are to increase by the temperature-rise period of lowering the temperature again by temperature programmed control in crystallization process to realize reducing the purpose of product grains size.The present invention is according to the different crystallization of the SAPO-34 molecular sieve Action of Crystal Growth in period, do not changing synthesis material and proportioning, do not introduce under the prerequisite of extra media field, crystallization process is carried out to temperature programmed control, increase by the temperature-rise period of lowering the temperature again with respect to prior synthesizing method and reach effective increase system nucleus, thereby obtain the purpose of the SAPO-34 zeolite product of less grain-size.The method is simple to operate, applied widely, adopts the synthetic system of different templates agent or raw material all can further effectively reduce the product grains size by synthetic method provided by the invention, thereby has stronger suitability for industrialized production application prospect.The synthetic system that the employing triethylamine of take is template is example, the median size of product that Traditional Method obtains is of a size of 3.5 μ m left and right, adopt the grain-size of product that present method obtains can be decreased to 1.3 μ m, after optimum condition, can further be down to 0.8 μ m left and right, crystal grain is decreased to full-sized 20 ~ 40 %, the SAPO-34 zeolite product of little crystal grain has good catalytic performance in MTO catalysis examination, the diene yield can reach 82.5%, the anti-coking performance also has obvious lifting, has obtained technique effect preferably.
The accompanying drawing explanation
Fig. 1 is the scanning electron microscope picture of the synthetic SAPO-34 molecular sieve of Comparative Examples 1.
Fig. 2 is the scanning electron microscope picture of the synthetic SAPO-34 molecular sieve of embodiment 1.
Fig. 3 is the scanning electron microscope picture of the synthetic SAPO-34 molecular sieve of embodiment 9.
Below by embodiment, the invention will be further elaborated, but be not limited only to the present embodiment.
Embodiment
[Comparative Examples 1]
12.1 gram γ Al
2O
3Mix and form solution a with 35.0 gram deionized waters; 23.3 mixing, gram ortho-phosphoric acid (85% weight), 37.5 gram deionized waters form solution b; A and b at room temperature stir and within 2 hours, form uniform solution c after mixing; Keep stirring, in c, add successively 31 gram triethylamines, 4.5 gram silicon sol and 27.0 gram deionized waters, obtain the crystallization liquid of synthetic SAPO-34 molecular sieve after fully stirring; The crystallization liquid prepared is at room temperature stirred to ageing 24 h, and the crystallization liquid that ageing is good was packed into in the teflon-lined crystallizing kettle, in 200 ℃ of lower crystallization 24 hours; Products therefrom through washing, centrifugal, 110 ℃ dry to obtain solid sample, the XRD result shows, products obtained therefrom is the SAPO-34 molecular sieve, average grain size 3.5 μ m, Fig. 1 is shown in by the scanning electron microscope picture.
Will sample be checked and rated at 550 ℃ of lower roasting 5 h, obtain the SAPO-34 molecular sieve powder, through compressing tablet, be ground into 20-40 order particle, for the MTO catalytic performance, check and rate.The fixed-bed reactor that the stainless steel tube that evaluation device employing Φ 12 mm wall thickness are 1 mm is made, apparatus with catalyst inside 2.0 g, product is analyzed gas-phase product with Agilent 6890N chromatograph and is formed after gas-liquid separation.
Comparative sample S0 shows the catalysis appraisal result of MTO reaction, and when reaction proceeds to 30 min, its diene (ethene+propylene) selectivity reaches high point, is 80.2 %.
[embodiment 1]
The initial crystallization liquid of preparation identical with Comparative Examples 1, this crystallization liquid in 200 ℃ of lower crystallization after 4 hours, stops heating in crystallizing kettle, is cooled to 120 ℃, after keeping 0.5 h, with the speed of 2 ℃/min, again is warming up to 200 ℃, continues crystallization 20 h; Products therefrom through washing, centrifugal, 110 ℃ dry to obtain solid sample, the XRD result shows, products obtained therefrom is the SAPO-34 molecular sieve, average grain size 1.3 μ m, Fig. 2 is shown in by the scanning electron microscope picture.The catalysis appraisal result of MTO reaction shows, when reaction proceeds to 45 min, its diene (ethene+propylene) selectivity reaches high point, is 81.9 %.
[embodiment 2～5]
Identical with operation steps and the experiment condition of embodiment 1, first stage 200 ℃ of lower crystallization 8 hours, be cooled to 120 ℃, after keeping 0.5 h, speed with 2 ℃/min is warming up to 200 ℃ again, continues crystallization 20 h, and gained sample average particle diameter and MTO catalytic result are in Table 1.
Table 1
[embodiment 6～8]
Identical with operation steps and the experiment condition of embodiment 1, first stage 200 ℃ of lower crystallization 4 hours, be cooled to 150 ℃, after keeping 0.5 h, speed with 2 ℃/min is warming up to 200 ℃ again, continues crystallization n hour, and gained sample average particle diameter and MTO catalytic result are in Table 2.
Table 2
[embodiment 9]
Identical with operation steps and the experiment condition of embodiment 1, but template used dose of triethylamine is replaced by TEAOH by stoichiometric ratio.The particle diameter of gained molecular sieve at least is less than 250 nm on a dimension, and Fig. 3 is shown in by the scanning electron microscope picture.
[embodiment 10～12]
Identical with operation steps and the experiment condition of embodiment 1, selected ,Gui source, phosphorus source difference only, gained sample average particle diameter and MTO catalytic result are in Table 3.
Table 3
[embodiment 13～15]
Identical with operation steps and the experiment condition of embodiment 1, raw materials used mol ratio difference only, gained sample average particle diameter and MTO catalytic result are in Table 4.
Table 4
Claims (10)
1. the preparation method of a fine grain SAPO-34 molecular sieve comprises the following steps:
A) ,Gui source, ,Lv source, phosphorus source, template and water are made to crystallization liquid, mole proportioning of crystallization liquid is as follows: template: SiO
2: Al
2O
3: P
2O
5: H
2O=0.5 ~ 10:0.05 ~ 10:0.2 ~ 3:0.2 ~ 3:20 ~ 200;
B) crystallization liquid is at T
1Temperature is to stir aging 1 ~ 24 h under 20 ~ 100 ℃;
C) by the crystallization liquid after aging at T
2Temperature is 180 ~ 250 ℃ of lower hydrothermal crystallizing 1 ~ 20 h;
D) programmed cooling is to T
3Temperature is room temperature ~ 160 ℃, and at least keeps 0.1 h in this temperature;
E) temperature programming is to T
4Temperature is 180 ~ 250 ℃, and hydrothermal crystallizing 2 ~ 24 h, obtain zeolite product.
2. the preparation method of fine grain SAPO-34 molecular sieve according to claim 1, is characterized in that the aluminium source is selected from least one in aluminum isopropylate, pseudo-boehmite or aluminum oxide; The phosphorus source is selected from least one in phosphoric acid, phosphoric acid salt or phosphorous acid; The silicon source is selected from least one in TEOS, white carbon black or silicon sol; Template is selected from least one in TEAOH, TPA, triethylamine, diethylamine or morpholine.
3. the preparation method of fine grain SAPO-34 molecular sieve according to claim 1, is characterized in that T in step c)
2Temperature is 190 ~ 240 ℃, and the hydrothermal crystallizing time is 2 ~ 8 hours.
4. the preparation method of fine grain SAPO-34 molecular sieve according to claim 1, is characterized in that the described programmed cooling of step d) is water cooling or oil cooling.
5. according to the preparation method of claim 1 or 4 described fine grain SAPO-34 molecular sieve, the rate of temperature fall that it is characterized in that the described programmed cooling of step d) is 0.1 ~ 10 ℃/min, T
3Temperature at least will be lower than T
230 ~ 80 ℃ of temperature.
6. the preparation method of fine grain SAPO-34 molecular sieve according to claim 1, is characterized in that the described programmed cooling of step d) is to T
3Temperature is 40 ~ 150 ℃, and keeps at least 0.1 h, T
3Temperature at least will be lower than T
240 ~ 60 ℃ of temperature.
7. the preparation method of fine grain SAPO-34 molecular sieve according to claim 1, is characterized in that the described temperature programming speed of step e) is 0.5 ~ 4 ℃/min.
8. the preparation method of fine grain SAPO-34 molecular sieve according to claim 1, is characterized in that T in step e)
4Temperature is 190 ~ 240 ℃, hydrothermal crystallizing 8 ~ 24 h.
9. the preparation method of fine grain SAPO-34 molecular sieve according to claim 1, is characterized in that the gained zeolite product has at least a crystal grain to be not more than 1 micron, and the median size of product is 0.2 ~ 3.0 micron.
10. the preparation method of fine grain SAPO-34 molecular sieve according to claim 9, is characterized in that the gained zeolite product has at least a crystal grain to be not more than 0.5 micron, and the median size of product is 0.5 ~ 1.5 micron.
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| CN104355316A (en) * | 2014-09-03 | 2015-02-18 | 中国科学院上海高等研究院 | Preparation method for SAPO-34 molecular sieve membrane |
| CN105399109A (en) * | 2015-12-18 | 2016-03-16 | 西安元创化工科技股份有限公司 | Preparation method and applications of small crystalline grain silicoaluminophosphate molecular sieve |
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| CN107902672A (en) * | 2017-12-08 | 2018-04-13 | 东北石油大学 | A kind of 34 molecular sieves of multistep crystallization synthesizing small-grain SAPO and its synthetic method |
| CN112279262A (en) * | 2020-11-16 | 2021-01-29 | 四川奥力奋催化材料有限公司 | Silicoaluminophosphate molecular sieve, catalyst for preparing olefin from methanol, preparation method and application thereof |
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| CN104058426A (en) * | 2014-06-30 | 2014-09-24 | 中国科学院上海高等研究院 | Method for preparing SAPO-34 zeolite membrane in temperature changing mode |
| CN104058426B (en) * | 2014-06-30 | 2017-09-29 | 中国科学院上海高等研究院 | The method that temperature-switching method prepares the molecular screen membranes of SAPO 34 |
| CN104355316A (en) * | 2014-09-03 | 2015-02-18 | 中国科学院上海高等研究院 | Preparation method for SAPO-34 molecular sieve membrane |
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| CN105417551A (en) * | 2014-09-09 | 2016-03-23 | 中国石油化工股份有限公司 | SAPO-34 molecular sieve preparation method |
| CN105399109A (en) * | 2015-12-18 | 2016-03-16 | 西安元创化工科技股份有限公司 | Preparation method and applications of small crystalline grain silicoaluminophosphate molecular sieve |
| CN105399109B (en) * | 2015-12-18 | 2018-06-12 | 西安元创化工科技股份有限公司 | A kind of preparation method and application of little crystal grain silicoaluminophosphamolecular molecular sieves |
| CN107902672A (en) * | 2017-12-08 | 2018-04-13 | 东北石油大学 | A kind of 34 molecular sieves of multistep crystallization synthesizing small-grain SAPO and its synthetic method |
| CN112279262A (en) * | 2020-11-16 | 2021-01-29 | 四川奥力奋催化材料有限公司 | Silicoaluminophosphate molecular sieve, catalyst for preparing olefin from methanol, preparation method and application thereof |
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