New! View global litigation for patent families

CN100390059C - High silica/ aluminum ratio octagonal zeolite synthesizing method - Google Patents

High silica/ aluminum ratio octagonal zeolite synthesizing method Download PDF

Info

Publication number
CN100390059C
CN100390059C CN 200510047510 CN200510047510A CN100390059C CN 100390059 C CN100390059 C CN 100390059C CN 200510047510 CN200510047510 CN 200510047510 CN 200510047510 A CN200510047510 A CN 200510047510A CN 100390059 C CN100390059 C CN 100390059C
Authority
CN
Grant status
Grant
Patent type
Prior art keywords
zeolite
silica
method
aluminum
ratio
Prior art date
Application number
CN 200510047510
Other languages
Chinese (zh)
Other versions
CN1951812A (en )
Inventor
刘利军
张晓萍
谷明镝
松 陈
Original Assignee
中国石油化工股份有限公司;中国石油化工股份有限公司抚顺石油化工研究院
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Grant date

Links

Abstract

本发明涉及一种高硅铝比八面沸石的合成方法,特别是采用模板法合成的具有八面沸石特征沸石的方法。 The present invention relates to a method for the synthesis of high silica to alumina ratio of the faujasite zeolite, in particular zeolite having characteristics method faujasite template for the synthesis method. 本发明方法采用适宜的模板剂,在钠用量较少的条件下,采用水热晶化法直接合成出高硅铝比的八面沸石。 The method of the present invention using a suitable template, under conditions with less amount of sodium, using faujasite hydrothermally Direct Synthesis of high silica to alumina ratio. 与现有技术相比,本发明方法过程简单,晶化时间短,碱用量少,更适于在工业上应用。 Compared with the prior art, the process of the present invention, the method is simple, short crystallization time, with less alkaline, more suitable for industrial application.

Description

一种寓硅铝比八面沸石的合成方法 A synthetic method of blending silica to alumina ratio of the faujasite

技术领域 FIELD

本发明涉及一种八面沸石的合成方法,特别是在水热条件下合成高硅铝比八面沸石的方法。 The present invention relates to a method for the synthesis of faujasite, in particular in a method hydrothermal synthesis of high silica to alumina ratio of the faujasite.

背景技术 Background technique

沸石分子筛是具有独特孔结构的规整晶体结构,主要是结晶硅铝酸盐。 Zeolite is a crystalline structure having a regular pore structure is unique, mainly crystalline aluminosilicates. 沸石分子筛有很多种类,每一种都有特定尺寸和形状的孔道。 There are many types of zeolitic molecular sieves, each channel has specific size and shape. 沸石分子筛由硅氧四面体或铝氧四面体通过氧桥形成环状结构,然后进一步联结成各种笼 A zeolite molecular sieve or aluminum oxide silica tetrahedron tetrahedra form a ring structure through an oxygen bridge, and then is further coupled to a variety of cage

结构。 structure. 八面沸石(FAU型沸石)就是由e笼和六角柱笼构成,通过它们围成八面沸石笼得名。 Faujasite (FAU-type zeolite) is composed of a hexagonal prism e cages and cages, surrounded by their name faujasite cage. 八面沸石包括X型和Y型,两者的差别在于铝含量不同,也就是硅铝比(Si02/Al203)不同, 一般X型大约在2 — 3,而Y型在3 —5,它们通常都采用水热晶化法合成。 Faujasite-type zeolites include X and Y, difference is that a different aluminum content, i.e. silica to alumina ratio (Si02 / Al203) different from X type generally about 2 - 3 in the Y-3-5, they are typically We are hydrothermal crystallization synthesis.

由于八面沸石笼可以进一步形成具有较大空腔的超笼结构,使得八面沸石在多相催化过程中,尤其是需要良好扩散性的大分子多相催化过程中得到了广泛应用,例如石油化工技术领域中的重油催化裂化过程和加氢裂化过程等。 Since the faujasite super cage cage structure may further be formed having a larger cavity, so that the faujasite heterogeneous catalytic process, especially a heterogeneous catalytic macromolecule requiring good diffusion of process has been widely used, for example, petrochemicals RFCC art hydrocracking process and the like. 虽然同属于八面沸石,X沸石由于硅铝比低,不仅结构不稳定,而且其酸性质也达不到催化反应要求,因此多用作吸附剂或干燥剂,而Y沸石具有相对较好的结构稳定性而广泛用作各种裂化催化剂的组分。 Although belong faujasite, X zeolite is a low silica to alumina ratio since, not only the structure is unstable, and its properties can not be achieved the acid catalyzed reaction requires, so much as an adsorbent or desiccant, the Y zeolite having a relatively good structure stability of various widely used as components of the cracking catalyst.

在碱性介质下合成出的Y沸石是通过碱金属如钠离子来平衡骨架电荷,八 The synthesized zeolite Y in an alkaline medium is an alkali metal such as sodium ions to balance the framework charge by eight

面沸石骨架中钠和铝的分子个数是等量的,合成的Y沸石原粉是钠型的,其氧化钠含量大约10w9&左右。 Number of molecular surface of the zeolite framework is the same amount of sodium and aluminum, synthetic, sodium Y zeolite powder is the original type, the sodium oxide content of about 10w9 & about. 由于大量钠离子的存在,钠型Y沸石的酸度很低,因此在Y沸石的实际应用中,要将其转化成氢型产物,通常采用铵盐交换等方法。 Due to a large amount of sodium ion, Na-Y zeolite acidity is low, so in practice Y zeolite, to convert it to the hydrogen form product, usually an ammonium salt exchange method.

另一方面,为了提高Y沸石的热稳定性尤其是水热稳定性,通常要进一步提高Y沸石原粉的硅铝比,硅铝比的提高也会提高单个酸性中心的酸强度而带来更好的催化裂解性能。 On the other hand, to improve the thermal stability of zeolite Y, especially hydrothermal stability, usually to further enhance the silica to alumina ratio, Y zeolite to improve the original powder alumina ratio will also increase the acid strength of the acid sites and the individual lead to more catalytic cracking good performance. 要把Y沸石原粉的硅铝比提高,方法主要有化学脱铝和物理脱铝,前者如气相四氯化硅脱铝补硅、氟硅酸铵脱铝补硅、酸脱铝等, 后者如水热处理等,但无论什么方法都是这一系列的后处理过程在实际生产中都是很繁琐的。 Original powder should Y zeolite to alumina ratio improved, methods include physical and chemical dealumination dealumination, silicon tetrachloride vapor such as former dealuminated silicon element, ammonium fluorosilicate dealuminated silicon element, like acid dealumination, after by heat treatment, such as water, but no matter what method is the series of post-processing in the actual production it is very complicated.

归属于八面沸石的NaY,通常采用在碱性水热环境下的导向剂法(晶种导向剂)制备。 Attributable to the faujasite NaY, directing agent commonly used method in an alkaline hydrothermal environment (seed directing agent) was prepared. 对于NaY的合成,具体地说就是先在高碱度环境下制备出Y沸石晶种,然后加入到NaY合成的混合凝胶体系中。 For the synthesis of NaY, in particular Y zeolite is to first prepare seed crystals higher alkalinity, and then added to a mixed gel system NaY synthesis. 我们知道,晶种胶是指含有尚未完全结晶的晶核前体的胶体,晶种胶的老化可以增加晶核前体的数量,这些晶核前体在凝胶溶胶体系中充当了成核中心。 We know, refers to a colloidal seed gum containing nuclei before not yet fully crystalline body, seed gum aging can increase the number of precursor nuclei, these nuclei precursors act as nucleation centers in the sol-gel system . 这种方法通常很难合成出较高硅铝比的八面型沸石,而如果能直接合成出具有高硅铝比的八面型沸石将省去很多的后处理过程。 This method is usually difficult to synthesize a faujasite type zeolite of high silica to alumina ratio, whereas if directly synthesized faujasite type zeolite having a high silica to alumina ratio will save a lot of post-processing. 因此,是否可以像--些非八面型沸石那样,采用模板方法合成高硅铝比的FAU沸石,逐渐引起关注。 Therefore, if you can like - some non-octahedral type zeolite as a template method using synthetic high silica to alumina ratio of zeolite FAU, gradually causing concern.

US5716593公开了一种先挤出成型再晶化合成的沸石催化剂制备方法,涉及FAU沸石的制备,方法是将有机模板剂、硅源、铝源和水混合后再干燥直到形成一种可挤出成型的膏状物,然后将其装入小瓶中放入底部有水的高压釜中晶化合成。 US5716593 discloses a method for preparing synthetic zeolite catalyst re-crystallized prior extrusion, FAU zeolite prepared relates, is the organic templating agent, a silicon source, an aluminum source and water are mixed and then extruded and dried until the formation of an forming a paste, which was then placed in vials of water at the bottom of the autoclave crystallization synthesis. 虽然该专利的投料硅铝比在6—15,但这并不意味着其产物具有高的硅铝比,虽然专利没有公开其产物的硅铝比,但专利指出了一系列清除分子筛中没有进入分子筛骨架的氧化硅的后处理过程,因此可以推定其产品分子筛的硅铝比应低于投料的硅铝比。 Although the patent of feeding alumina ratio in the 6-15, but that does not mean that the product has a high silica to alumina ratio, although it does not disclose silica to alumina ratio of its products, but pointed out that the patent did not enter a series of clear molecular sieves post-processing the silica molecular sieve framework, so that their products can be estimated silicoaluminophosphate molecular sieve to alumina ratio should be less than than the feed material. 该专利合成的水/氧化硅比很低,要求不超过6,因此不能很好地使原料中的无定形硅结合到分子筛骨架中并保证良好的结晶度。 This patent synthetic water / silica ratio is very low, requiring no more than 6, and therefore not a good raw material of the amorphous silicon incorporated into the molecular sieve framework and to ensure good crystallinity. 该专利方法中碱的用量较大,如投料中M"7Si02 =0.2-1.0 (摩尔比),M"为碱金属,碱的用量换算为Na2O/SiO2的摩尔比为0.4〜2.0,碱量过高虽然由利于Y型沸石的形成,但过高会导致产品硅铝比的急剧下降,该方法得到的沸石产品的实际骨架硅铝比一般不高。 The amount of the base is large patent process, as the feed material M "7Si02 = 0.2-1.0 (molar ratio), M" is a molar ratio of alkali metal base is used in an amount in terms of Na2O / SiO2 is 0.4~2.0, the amount of base is too Although the formation of high favor Y zeolite, but too high will result in a sharp decline in product silica to alumina ratio, the actual aluminosilicate zeolite product skeleton obtained by this method is not higher than the average. 'US5549881公开了一种八面沸石制备方法,该专利也采用有机模板剂合成某种具有八面型沸石结构特征的分子筛复合物,但它仍然使用了需要添加某种硅铝酸钠晶种,而且晶化时间长达8 — 14天。 'US5549881 discloses a method for preparing faujasite zeolites, this patent also uses organic templating agent complexes synthesized molecular sieve having certain structural characteristics of the faujasite type zeolite, but it still requires the use of sodium aluminosilicate to add some seed crystals, Further crystallization time up to 8--14 days. 硅铝酸钠晶种是在高碱性条件下制备的,如其实施例中,硅铝酸钠晶种制备物料中Na20/Ab03的摩尔比为13.33,晶种制备过程中不使用模板剂,并且需要很长时间的老化。 Sodium aluminosilicate seeds are prepared under highly alkaline conditions, such as its embodiments, the molar ratio of sodium aluminosilicate material in the preparation of seed Na20 / Ab03 was 13.33, the preparation of the seed is not used templating agent, and aging need a long time. 使用晶种合成出的八面沸石晶粒形貌通常为多棱的颗粒,不利于反应过程分子的扩散, 不利于提高反应的选择性。 Synthesized using a seed grain morphology faujasite generally polygonal particles, the reaction process is not conducive to the diffusion of molecules, is not conducive to improve the selectivity of the reaction.

发明内容 SUMMARY

针对现有技术的不足,本发明提供一种高硅铝比的八面沸石的合成方法, 本发明方法碱用量少,晶化时间短。 For the deficiencies of the prior art, the present invention provides a method of synthesizing faujasite a higher silica to alumina ratio, the method of the present invention with less base, a short crystallization time.

本发明高硅铝比八面沸石的合成方法包括以下过程: The method of the present invention is the synthesis of high silica-alumina ratio of the faujasite comprises the following procedures:

(1) 将铝源、硅源、钠源和有机碱模板剂按照一定比例混合; (1) an aluminum source, a silicon source, a sodium source and organic bases templating agent combined in a certain ratio;

(2) 在不超过7(TC条件下搅拌并老化1-100小时形成均匀凝胶; (2) was stirred at not more than 7 (TC conditions and aged for 1 to 100 hours to form a uniform gel;

(3) 将混合凝胶移入反应釜并密闭: (3) mixing the gel and transferred to a sealed reactor:

(4) 在90-13(TC条件下于反应釜自生压力下水热晶化24-240,优选24~120小时; (4) at 90-13 (TC conditions at autogenous pressure reactor hydrothermal crystallization 24-240, preferably 24 to 120 hours;

(5) 将晶化产物过滤并千燥后得到沸石原粉。 (5) The crystallized product was filtered and the obtained zeolite raw powder was dry. 其中各种原料投料摩尔比为:5〜50 S"0 : 1.5〜15Na20 : A1203 : 0. 3〜 Wherein the feed raw materials molar ratio: 5~50 S "0: 1.5~15Na20: A1203: 0. 3~

3.5有机碱模板剂:60〜420H20。 Organic bases template 3.5: 60~420H20. 其中混合物氧化硅/氧化铝摩尔比最好6〜 15,水/氧化铝摩尔比最好100〜180,模板剂四乙基氢氧化铵/氧化铝摩尔比最好0.8〜2. 5。 Wherein a mixture of silicon oxide / aluminum oxide molar ratio of preferably 6 ~ 15, preferably water / alumina molar ratio of 100~180, tetraethyl ammonium hydroxide template / alumina molar ratio is preferably 0.8~2. 5. 其中Na20/Si02摩尔比为0.05〜0.8,优选为0.1~0.4; HA/Si02摩尔比为6~40,优选为10〜22; S:U0/Ah03摩尔比6〜30,最好6〜15。 Wherein Na20 / Si02 molar ratio of 0.05~0.8, preferably 0.1 ~ 0.4; HA / Si02 molar ratio of from 6 to 40, preferably 10~22; S: U0 / Ah03 molar ratio of 6~30, preferably 6~15.

有机碱模板剂是垸基氢氧化铵,具体可以选自四乙基氢氧化铵、四丙基氢氧化铵和四丁基氢氧化铵中的一种或几种。 The organic templating agent is an alkyl with an alkali hydroxide, particularly may be selected from tetraethyl ammonium hydroxide, tetrapropyl ammonium hydroxide and tetrabutyl ammonium hydroxide in one or more.

硅源选自水玻璃、硅胶和硅溶胶的一种或混合物,铝源选自铝酸钠、硫酸铝、氯化铝和硝酸铝的一种或混合物,钠源来源于铝酸钠和/或氢氧化钠。 The silicon source is selected from one or a mixture of water glass, silica sol and silica gel, sodium aluminate source is selected from aluminum, aluminum sulfate, aluminum chloride, aluminum nitrate, and one or a mixture, from sodium aluminate and sodium source / or sodium hydroxide.

本发明涉及的沸石原粉具有八面沸石特征,因而在XRD光谱分析中表现出八面沸石XRD衍射特征,进一步说就是表现出同样属于八面沸石类的Y型沸石的XRD衍射特征。 The present invention relates to a zeolite raw powder having a characteristic faujasite zeolite, thereby showing the XRD XRD spectral features in the faujasite, that is to further exhibit the XRD features also belong to the type Y zeolite of the faujasite type. 产品沸石具有较高的硅铝摩尔比,并与现有方法合成的产品具有不同的形貌特征。 Zeolite product having a higher silica to alumina molar ratio, and the conventional method of synthesis of products with different topography.

现有技术中合成高硅八面沸石主要采用导向剂法(以晶种为导向剂),即在高钠条件下制备八面沸石晶种,以此晶种为导向剂合成最终的八面沸石产品;或在高钠条件下直接合成八面沸石。 The prior art synthesis of high silica faujasite method mainly directing agent (agent-oriented seed crystal), i.e. faujasite zeolite seeds prepared under conditions of high sodium, this seed guiding agent for the final faujasite product; or synthetic faujasite directly in the high sodium conditions. 本发明采用模板剂法直接在水热条件下合成了高硅铝比的八面沸石,通过采用适宜的模板剂,在钠用量相对较低的情况下,不需要在高钠条件下先制得沸石晶种,可以得到高硅铝比的八面沸石。 The present invention employs template was directly synthesized high silica to alumina ratio of the faujasite zeolite under hydrothermal conditions by using a suitable template, at a relatively low amount of sodium case, no high-sodium under conditions to prepare a zeolite seed, can obtain a high silica to alumina ratio of the faujasite. 并且本发明方法合成时间短,可以大大提高合成效率。 The method of the present invention and the synthesis time is short, can greatly improve the efficiency of the synthesis. 本发明方法得到的八面沸石具有更高的硅铝比,更好的结晶度,较低的钠含量和更大的酸性。 The method of the present invention obtained faujasite having a higher silica to alumina ratio, the better crystallinity, low sodium content and greater acidity. 本发明方法合成的八面沸石具有片状晶体形貌,有利于反应分子的扩散,提高反应的选择性。 The method of the present invention, a sheet having synthetic faujasite crystal morphology is conducive to the diffusion of the reaction molecules, to improve the selectivity of the reaction.

具体实施方式 detailed description

本发明所涉及的物料混合温度一般为室温〜70'C,优选40^60'C。 The present invention relates to a material mixing temperature is generally room temperature ~70'C, preferably 40 ^ 60'C. 水热晶化过程可以是一种伴随搅拌的动态过程,或者是无搅拌的静态过程。 Hydrothermal crystallization process may be a process dynamically with stirring or without stirring to a static process. 最好, 按照本发明过程的水热晶化过程是先搅拌然后无搅拌的动态和静态结合水热晶化过程。 Preferably, according to the process of the hydrothermal crystallization process of the present invention is then stirred without stirring to static and dynamic binding hydrothermal crystallization process. 静态有利于成核,动态晶化过程促进传质传热而有利于得到均匀的产品,也可以采用动态和静态结合方式,两者时间比例可以为l: 0.1~10。 Facilitate nucleation static, dynamic crystallization process to promote heat and mass transfer and facilitate to obtain a uniform product, it can also be used in conjunction with dynamic and static manner, both the time ratio may be l: 0.1 ~ 10. 无论采取什么方式,都是本发明的范围,而具体采用什么方式,决定于合成规模或生产规模的大小以及设备的实际情况。 Whatever the way to take the scope of the present invention are, in what way and specifically, depending on the actual synthesis scale or production scale, and the size of the device.

以下通过实施例进一步说明本发明沸石的制备方法,实施例中的方案虽然是在本发明范围权利要求范围内的具体实施方案,但并不构成对本发明的限制。 The following further illustrate the preparation of the zeolite according to the present invention through examples, although the example programs are specific embodiments within the scope of the scope of the claimed invention, but not limit the present invention. (其中的百分比,d均表示重量百分比) (Where percentages, d represents a weight percentage)

实例l Examples l

以硅溶胶为硅源,铝酸钠为铝源,四丙基氢氧化铵为模板剂,水热晶化 Silica sol as the silicon source, an aluminum source is sodium aluminate, tetrapropyl ammonium hydroxide as templating agent hydrothermal

合成本发明沸石。 Synthetic zeolites of the present invention. 反应物配料摩尔比:n(Si02): n(Na20): n(模板剂):n(Al203): n(H20)=6: 1.8: 1.2: 1: 110。 Ingredients molar ratio of reactants: n (Si02): n (Na20): n (template): n (Al203): n (H20) = 6: 1.8: 1.2: 1: 110. 合成方法:按反应物配料比,把氢氧化钠和 Synthesis method: charge ratio of the reactants, and the sodium hydroxide

铝酸钠加入到25%四丙基氢氧化铵溶液中,混合均匀后再加入硅溶胶。 Sodium aluminate was added to a 25% tetrapropyl ammonium hydroxide solution, mixed well and then added to the silica sol. 将上述混合物在5(TC下搅拌24小时后,移入带聚四氟乙烯的高压釜中,密闭,在10(TC静态晶化120h。晶化完毕后,将产物过滤,水洗后在11(TC干燥,然后在55(TC焙烧脱除模板剂得到本发明样品。 After the mixture was stirred at 5 (the TC 24 hours into the autoclave with polytetrafluoroethylene, sealed, after 10 (TC static crystallization 120h. Complete crystallization, the product was filtered, washed with water at 11 (TC dried, and then the present invention is to obtain a sample 55 (TC firing template removal.

实例2 Example 2

以硅溶胶为硅源,铝酸钠为铝源,四丁基氢氧化铵为模板剂,水热晶化合成本发明沸石。 Silica sol as the silicon source, an aluminum source is sodium aluminate, tetrabutyl ammonium hydroxide as templating agent compound hydrothermal zeolite cost invention. 反应物配料摩尔比:n(Si02): n(歸):n (模板剂):n(Al203): Ingredients molar ratio of reactants: n (Si02): n (normalized): n (template): n (Al203):

n(H20)=12: 3.5: 0.8: 1: 180。 n (H20) = 12: 3.5: 0.8: 1: 180. 合成方法:按反应物配料比,把氢氧化钠和 Synthesis method: charge ratio of the reactants, and the sodium hydroxide

铝酸钠加入水中,再加入25%四丁基氢氧化铵溶液中,混合均匀后再加入硅溶胶。 Sodium aluminate was added to water, then add 25% tetrabutyl ammonium hydroxide solution, mixed well and then added to the silica sol. 将上述混合物在6(TC下搅拌6小时后再在室温老化24小时,移入带聚四氟乙烯的高压釜中,密闭,在ll(TC静态晶化180h。晶化完毕后,将产物过滤, 水洗后在11(TC干燥,然后在55(TC焙烧脱除模板剂得到本发明样品。 The mixture was stirred at (TC 6 6 hours after the aging at room temperature for 24 hours and transferred to an autoclave with polytetrafluoroethylene, sealed after ll (TC static crystallization 180h. Complete crystallization, the product was filtered, after washing with water 11 (TC dried, and then the present invention is to obtain a sample 55 (TC firing template removal.

实例3 Example 3

以水玻璃和硅溶胶为混合硅源,铝酸钠为铝源,四乙基氢氧化铵为模板剂,水热晶化合成本发明沸石。 Mixing water glass and silica sol as the silicon source, an aluminum source is sodium aluminate, tetraethyl ammonium hydroxide as templating agent compound hydrothermal zeolite cost invention. 反应物配料摩尔比:n(Si02): n(歸)- n(模 Ingredients molar ratio of reactants: n (Si02): n (normalized) - n (mold

板剂):n歸,):n(H20)=16: 4.0: 2.5: 1: 320。 Agent plate): n normalization,): n (H20) = 16: 4.0: 2.5: 1: 320. 合成方法:按反应物配料 Synthesis method: Reaction was Ingredients

比,把铝酸钠加入到的35%四乙基氢氧化铵溶液中,混合均匀后再加入硅溶胶和水玻璃(两者提供的硅源为2: 1)。 Ratio, the sodium aluminate was added to a 35% tetraethylammonium hydroxide solution, mixed well and then added to a silica sol and water glass (silicon source is provided in both the 2: 1). 将上述混合物在3(TC下搅拌3小时后, 在室温下放置48小时后移入带聚四氟乙烯的高压釜中,密闭,在120。C静态晶化18小时,动态(搅拌速度200转/分)晶化54h。晶化完毕后,将产物过滤, 水洗后在11(TC干燥,然后在550'C焙烧脱除模板剂得到本发明样品。 Moved with polytetrafluoroethylene after the mixture was stirred at 3 (TC 3 hours and allowed to stand at room temperature for 48 hours in an autoclave, sealed, in the static crystallization 120.C for 18 hours dynamic (stirring speed 200 revolutions / min) crystallization 54h. after completion of the crystallization, the product was filtered, washed with water at 11 (TC dried to obtain a sample of the present invention and then calcined at 550'C template removal.

实例4 Example 4

以硅溶胶为硅源,硫酸铝和铝酸钠为铝源(两者提供的铝源为l: 2),四乙基氢氧化铵为模板剂,水热晶化合成本发明沸石。 Silica sol as the silicon source, aluminum sulfate and sodium aluminate as the aluminum source (aluminum source to provide both l: 2), tetraethyl ammonium hydroxide as templating agent, the compound cost zeolite by hydrothermal invention. 反应物配料摩尔比-n(SiO》:n(Na20): n(模板剂):n(Al203): n(H20)=25: 8.0: 2.0: 1: 190。 The reaction molar ratio of the ingredients was -n (SiO ": n (Na20): n (template): n (Al203): n (H20) = 25: 8.0: 2.0: 1: 190.

合成方法:按反应物料配比,把铝酸钠和硫酸铝加入到35%四乙基氢氧化铵 Synthesis Methods: reactant ratio, the sodium aluminate and aluminum sulfate was added to a 35% tetraethylammonium hydroxide

溶液中,混合均匀后再加入硅溶胶。 Solution, mixed well and then added to the silica sol. 将上述混合物在5(TC下搅拌3小时后,在室温下放置24小时后移入带聚四氟乙烯的高压釜中,密闭,在110。C动态(搅拌速度200转/分)晶化72h。晶化完毕后,将产物过滤,水洗后在11(TC干燥, 然后在55(TC焙烧脱除模板剂得到本发明样品。 After autoclave the mixture was stirred at 5 (the TC 3 hours, allowed to stand at room temperature for 24 hours into the strip of polytetrafluoroethylene, sealed in a dynamic 110.C (stirring speed 200 rev / min) Crystallization 72h. after completion of crystallization, the product was filtered, washed with water at 11 (TC dried, then 55 (TC template removal calcined sample was obtained according to the present invention.

实例5 Example 5

以水玻璃胶为硅源,氯化铝和铝酸钠为铝源(两者提供的铝源为2: 1), 四乙基氢氧化铵为模板剂,水热晶化合成本发明沸石。 Water glass gel as silica source, aluminum chloride and sodium aluminate as the aluminum source (aluminum source to provide both a 2: 1), tetraethyl ammonium hydroxide as templating agent compound hydrothermal zeolite cost invention. 反应物配料摩尔比: n(SiO》:n(歸):n(模板剂):n(Al203): n(H20)=32: 10.0: 3.0: 1: 300。 Ingredients molar ratio of reactants: n (SiO ": n (normalized): n (template): n (Al203): n (H20) = 32: 10.0: 3.0: 1: 300.

合成方法:按物料配比要求,把铝酸钠加入到35%四乙基氢氧化铵溶液中, Synthesis Methods: material ratio required, the sodium aluminate was added to a 35% tetraethylammonium hydroxide solution,

混合均匀后再依次加入硅溶胶和氯化铝。 Uniformly mixed silica sol were successively added and then aluminum chloride. 将上述混合物在50。 The mixture was 50. C下搅拌3小时后,在室温下放置24小时后移入带聚四氟乙烯的高压釜中,密闭,在115。 After stirring at C 3 hours, allowed to stand at room temperature for 24 hours into the autoclave with polytetrafluoroethylene, sealed at 115. C晶化72h。 C crystallization 72h. 晶化完毕后,将产物过滤,水洗后在11(TC干燥,然后在55(TC焙烧脱除模板剂得到本发明样品。 After completion of crystallization, the product was filtered, washed with water at 11 (TC dried, then 55 (TC template removal calcined sample was obtained according to the present invention.

实例6 Example 6

以固体硅胶为硅源,铝酸钠为铝源,四乙基氢氧化铵为模板剂,水热晶化合成本发明沸石。 Solid silica as the silicon source, an aluminum source is sodium aluminate, tetraethyl ammonium hydroxide as templating agent compound hydrothermal zeolite cost invention. 反应物配料摩尔比:n(Si02): n(Na20): n(模板剂): n(Al203): n(H20)=45: 12.5: 3.2: 1: 400。 Ingredients molar ratio of reactants: n (Si02): n (Na20): n (template): n (Al203): n (H20) = 45: 12.5: 3.2: 1: 400. 合成方法:按反应物料配比,把铝酸钠加入到的35%四乙基氢氧化铵溶液中,然后加入硅胶,将上述混合物在50。 Synthesis Methods: reactant ratio, the sodium aluminate was added to a 35% tetraethylammonium hydroxide solution, and then silica gel was added, the mixture at 50. C下搅拌16小时后,在室温下放置24小时后移入带聚四氟乙烯的高压釜中,密闭,在115"C静态晶化36h,然后在动态(搅拌速度100转/分)晶化36h。 晶化完毕后,将产物过滤,水洗后在11(TC干燥,然后在55(TC焙烧脱除模板剂得到本发明样品。 After stirring for C 16 hours, allowed to stand at room temperature for 24 hours into the autoclave with polytetrafluoroethylene, sealed at 115 "C static crystallization 36h, then the dynamic (stirring speed of 100 rev / min) Crystallization 36h after. complete crystallization, the product was filtered, washed with water at 11 (TC dried, and then the present invention is to obtain a sample 55 (TC firing template removal.

比较例l Comparative Example l

按US5549881方法。 By US5549881 method. 首先制备晶种:配料比12.5(Si0》:13.33(歸): (A1203): 267(H20);过程为将氢氧化铝加入到溶解有氢氧化钠的水中的到铝酸钠溶胶,然后再缓慢加入硅酸钠,补足水后剧烈搅拌均匀后,室温下放置16 天使用。 First, the seed crystal prepared: Ingredients ratio of 12.5 (Si0 ": 13.33 (normalized): (A1203): 267 (H20); the process is added to the aluminum hydroxide is dissolved in water containing sodium hydroxide to sodium aluminate sol, then sodium silicate was added slowly, with vigorous stirring after bringing water uniformly, placed at room temperature for 16 days use.

其次,以硅溶胶为硅源,四丁基氢氧化铵为为模板剂,水热晶化合成本发明沸石,反应物配料摩尔比:n(Si02): n(模板剂):n(歸):n(AlA): n(H20)=18: 3.6: 1.2: 1: 275。 Next, the silica sol as the silicon source, tetrabutyl ammonium hydroxide as a template, the cost of the zeolite by hydrothermal compound of the invention, the molar ratio of the reactants Ingredients: n (Si02): n (template): n (normalized): n (AlA): n (H20) = 18: 3.6: 1.2: 1: 275. 方法:依次把59g氢氧化钠和75g氢氧化铝加入到100g水中,加热搅拌溶解后再补足水直到250g,得到铝酸钠溶液;另外, 将42.5g硅溶胶(氧化硅含量40%)、 11.9g上述室温老化16天的晶种、63.7g四丁基氢氧化铵和上述得到的铝酸钠溶液5. 17g、 7.44g硫酸铝溶液(50繊酸铝浓度)并补水到135g;将上述混合物在3(TC下搅拌12小时后,室温放置一夜后移入带聚四氟乙烯的高压釜中,密闭,在静态下ll(TC晶化分别120h、 240h。 Method: 59g of sodium hydroxide and 75g turn the aluminum hydroxide is added to 100g of water, and then make up the water heating and stirring until dissolved 250g, to obtain sodium aluminate solution; Separately, 42.5g of silica sol (silica content of 40%), 11.9 g above room temperature for 16 days aging seed, 63.7g of tetrabutyl ammonium hydroxide and sodium aluminate solution obtained above 5. 17g, 7.44g aluminum sulfate solution (concentration 50 Xian, aluminum) and 135 g of the replenishment; 3 the above mixture after stirring (the TC 12 hours and allowed to stand overnight at room temperature into the autoclave with polytetrafluoroethylene, sealed under static ll (TC crystallization are 120h, 240h.

120h晶化产品为无定型,240h得到晶化产品,将产物过滤,水洗后在ll(TC干燥,然后在55(TC焙烧脱除模板剂得到样品F。 F的Si02/Al20應尔比为6.5。 120h crystallized product is amorphous, 240h to give the product crystallized, the product was filtered, washed with water at ll (TC dried, then 55 (TC firing removed to obtain a sample template F. F of Si02 / Al20 should Dalby 6.5 .

比较例2 Comparative Example 2

按US5716593方法,把51. 6g铝酸钠加入到150. 2g硅溶胶中混合搅拌10分钟,然后依次加入ll. 3g氢氧化钠和349. 6g四乙基氢氧化铵并继续混合搅拌4 小时,然后加入60g水成膏状物,再在66度下加热使得混合物中挥发物减重50 X即总重减少230g,室温下密闭一夜后放入坩锅中,再将坩锅放入底部有12ml 水的高压釜中,在110度分别晶化160h。 A method according to US5716593, the addition of aluminum to 51. 6g sodium stirred 150. 2g silica sol mixed for 10 minutes, followed by addition of ll. 3g 349. 6g of sodium hydroxide and tetraethylammonium hydroxide and mixing was continued for 4 hours, 60g of water was then added into a paste, and then was heated at 66 degrees so that the mixture 50 X volatiles weight loss reduces the total weight of 230g i.e., overnight at room temperature into a closed crucible, the crucible and then placed in the bottom 12ml autoclave water at 110 degrees, respectively crystallization 160h. 晶化完毕后,将产物过滤,水洗后在IIO'C干燥,然后在55(TC焙烧脱除模板剂得到对比样品G, G的Si02/Al20應尔比为5.2。 After completion of crystallization, the product was filtered, washed with water and dried in IIO'C, then 55 (TC firing removal template comparative sample of G, Si02 / Al20 should Dalby G was 5.2.

表l各实施例产品主要性质 The main properties of the product of Example l each of the embodiments in Table

<table>table see original document page 11</column></row> <table> <Table> table see original document page 11 </ column> </ row> <table>

Claims (9)

1、一种高硅铝比八面沸石的合成方法,包括以下过程: (1)将铝源、硅源、钠源和有机碱模板剂按照一定比例混合; (2)在不超过70℃条件下搅拌并老化1-100小时形成均匀凝胶; (3)将混合凝胶移入反应釜并密闭; (4)在90-130℃条件下于反应釜自生压力下水热晶化24-240h; (5)将晶化产物过滤并干燥后得到沸石原粉; 上述(1)各种原料投料摩尔比为:5~50 SiO2∶1.5~15Na2O∶Al2O3∶0.3~3.5有机碱模板剂∶60~420H2O;其中Na2O/SiO2摩尔比为0.05~0.8,H2O/SiO2摩尔比为6~40; 所述的有机碱模板剂选自四乙基氢氧化铵、四丙基氢氧化铵和四丁基氢氧化铵中的一种或几种。 1, a method for synthesizing high silica to alumina ratio of the faujasite zeolite, the process comprising: (1) an aluminum source, a silicon source, a sodium source and organic bases templating agent combined in a certain ratio; (2) does not exceed 70 ℃ conditions and aged for 100 hours with stirring to form a homogeneous gel; (3) mixing the gel and transferred to a closed reactor; (4) at 90-130 deg.] C at autogenous pressure reactor hydrothermal crystallization 24-240h; ( 5) the crystallized product was filtered and dried to obtain a powder raw zeolite; (1) above raw materials feed molar ratio: 5 ~ 50 SiO2:1.5 ~ 15Na2O:Al2O3:0.3 ~ 3.5 organic base template :60 ~ 420H2O; wherein Na2O / SiO2 molar ratio is 0.05 ~ 0.8, H2O / SiO2 molar ratio of from 6 to 40; is selected from tetraethyl ammonium hydroxide, organic bases of the template, tetrapropylammonium hydroxide and tetrabutylammonium hydroxide in one or several.
2、 按照权利要求l所述的方法,其特征在于所述的水热晶化时间为24〜120h。 2. The method as claimed in claim l, wherein the hydrothermal crystallization time 24~120h.
3、 按照权利要求l所述的方法,其特征在于所述的(1)中混合物料中氧化硅/氧化铝摩尔比为6〜15,水/氧化铝摩尔比为100〜180,有机碱模板剂/氧化铝摩尔比为0.8〜2.5。 3. The method according to claim l, wherein one of (1) the feed mixture silica / alumina molar ratio of 6~15, water / alumina molar ratio of 100~180, an organic base template agent / alumina molar ratio of 0.8~2.5.
4、 按照权利要求l所述的方法,其特征在于所述的Na20/Si02摩尔比为0.1〜0.4, &0/&02摩尔比为10〜22。 4. The method as claimed in claim l, wherein said Na20 / Si02 molar ratio of 0.1~0.4, & 0/02 & molar ratio of 10~22.
5、 按照权利要求l所述的方法,其特征在于所述的硅源选自水玻璃、硅胶和硅溶胶的一种或混合物,铝源选自铝酸钠、硫酸铝、氯化铝和硝酸铝的种或混合物,钠源来源于铝酸钠和/或氢氧化钠。 5. The method as claimed in claim l, wherein said silicon source is selected from one or a mixture of water glass, silica sol and silica gel, aluminum source is selected from sodium aluminate, aluminum sulfate, aluminum chloride and nitrate species or a mixture of aluminum, a source of sodium from sodium aluminate and / or sodium hydroxide.
6、 按照权利要求l所述的方法,其特征在于(2)中所述的搅拌老化温度为40。 6. The method according to claim l, wherein (2) said aging temperature is stirred for 40. C〜60。 C~60. C。 C.
7、 按照权利要求l所述的方法,其特征在于所述的水热晶化过程是一种伴随搅拌的动态过程,或者是无搅拌的静态过程。 7. A method according to claim according to claim l, wherein the hydrothermal crystallization process is accompanied by a process of dynamic stirring or without stirring static process.
8、 按照权利要求l所述的方法,其特征在于所述的水热晶化过程是先搅拌然后无搅拌的动态和静态结合水热晶化过程。 8. A method as claimed in claim l, characterized in that the hydrothermal crystallization process is then stirred without stirring to static and dynamic binding hydrothermal crystallization process.
9、 按照权利要求8所述的方法,其特征在于所述的动态和静态结合水热晶化过程的时间比例为l: 0.1〜10。 9. A method as claimed in claim 8, wherein said static and dynamic binding ratio of time during hydrothermal crystallization of l: 0.1~10.
CN 200510047510 2005-10-19 2005-10-19 High silica/ aluminum ratio octagonal zeolite synthesizing method CN100390059C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN 200510047510 CN100390059C (en) 2005-10-19 2005-10-19 High silica/ aluminum ratio octagonal zeolite synthesizing method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN 200510047510 CN100390059C (en) 2005-10-19 2005-10-19 High silica/ aluminum ratio octagonal zeolite synthesizing method

Publications (2)

Publication Number Publication Date
CN1951812A true CN1951812A (en) 2007-04-25
CN100390059C true CN100390059C (en) 2008-05-28

Family

ID=38058401

Family Applications (1)

Application Number Title Priority Date Filing Date
CN 200510047510 CN100390059C (en) 2005-10-19 2005-10-19 High silica/ aluminum ratio octagonal zeolite synthesizing method

Country Status (1)

Country Link
CN (1) CN100390059C (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105439168A (en) * 2014-08-28 2016-03-30 中国科学院大连化学物理研究所 Method for preparing Y type molecular sieve with high silica-alumina ratio
CN104528763A (en) * 2014-12-17 2015-04-22 上海大学 Preparation method of X-type zeolite molecular sieve

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5716593A (en) 1996-07-31 1998-02-10 Chevron U.S.A. Inc. Preparation of Y-type faujasite using an organic template
CN1388063A (en) 2001-05-30 2003-01-01 中国石油化工股份有限公司 Synthesis of Cr-Si molecular sieve in MFI crystal structure

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5716593A (en) 1996-07-31 1998-02-10 Chevron U.S.A. Inc. Preparation of Y-type faujasite using an organic template
CN1388063A (en) 2001-05-30 2003-01-01 中国石油化工股份有限公司 Synthesis of Cr-Si molecular sieve in MFI crystal structure

Also Published As

Publication number Publication date Type
CN1951812A (en) 2007-04-25 application

Similar Documents

Publication Publication Date Title
US4151189A (en) Synthesizing low sodium crystalline aluminosilicate zeolites with primary amines
US5460796A (en) Process for producing substantially binder-free zeolite
US4257885A (en) Novel zeolite compositions and processes for preparing and using same
US5558851A (en) Preparation of aluminosilicate zeolites
US4340573A (en) Preparation of zeolites
US5171556A (en) Beta type zeolite and its preparation process
US5554356A (en) Method of making essentially silicic zeolite beta
US4714601A (en) Process for preparing a high silica faujasite aluminosilicate, ECR-4
JPH05163015A (en) Production of zeolite x type molded product
CN1332114A (en) Optimized and oriented growth process of MFT-type zeolite crystal
US5393511A (en) Synthesis of zeolites of faujasite structure
EP0142347A2 (en) Process for preparing type L zeolites by nucleating technique
US4187283A (en) Method for improving organic cation-containing zeolites
CN1296913A (en) Process for preparing molecular sieve (MCM-22) with special crystal structure
WO1997033830A1 (en) Synthesis of zeolite and zeotypes isomorphous with zeolite beta
CN1208718A (en) Composite medium and micro porous molecular sieve and synthesis method therefor
CN1435374A (en) Composite molecular sieve and preparing process thereof
US5637287A (en) Synthesis process for faujasite family zeolites using mother liquor recycle
US20060140854A1 (en) Process for making a germanium-zeolite
US4879103A (en) Composition and process for preparing ECR-30
Jon et al. Hydrothermal conversion of FAU into∗ BEA zeolites
CN1785808A (en) Preparation method of high silicon aluminium ratio small crystal NaY molecular sieve
EP0213739A2 (en) A paulingite-like synthetic zeolite
CN102311124A (en) Method for preparing Silicalite-1/ZSM-5 composite molecular sieve
CN1749162A (en) High molecule polymer template synthetic composite hole zeolite molecular sieve and its preparing method

Legal Events

Date Code Title Description
C06 Publication
C10 Request of examination as to substance
C14 Granted