CN100421795C - Catalytic cracking catalyst containing faujasite and preparation method thereof - Google Patents

Catalytic cracking catalyst containing faujasite and preparation method thereof Download PDF

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CN100421795C
CN100421795C CN 200510047507 CN200510047507A CN100421795C CN 100421795 C CN100421795 C CN 100421795C CN 200510047507 CN200510047507 CN 200510047507 CN 200510047507 A CN200510047507 A CN 200510047507A CN 100421795 C CN100421795 C CN 100421795C
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faujasite
zeolite
catalyst
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CN1951566A (en )
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方向晨
松 陈
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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
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本发明涉及一种含八面沸石的催化裂化催化剂,以重量计含有高硅铝比八面沸石5%-95%,耐熔氧化物5%-95%,其中八面沸石的SiO<sub>2</sub>/Al<sub>2</sub>O<sub>3</sub>摩尔比为6~20,属于八面沸石中的Y型沸石,并具有片状形貌。 The present invention relates to catalytic cracking catalysts containing faujasite, by weight faujasite containing a high silica to alumina ratio of 5% to 95%, refractory oxide 5 to 95%, wherein the faujasite SiO <sub> 2 </ sub> / Al <sub> </ sub> <sub> </ sub> 3 2 O molar ratio of from 6 to 20, belonging to the faujasite Y zeolite, and having a platelet morphology. 本发明催化剂可以采用各种常规方法制备,其中的沸石采用模板剂法,在水热条件下直接合成。 The catalyst of the present invention can be prepared using various conventional methods, wherein the zeolite using template method, direct synthesis under hydrothermal conditions. 本发明加氢催化剂使用了新型分子筛,对反应的活性和选择性均有所提高,主要用于催化裂化等过程。 The present invention uses a hydrogenation catalyst, the molecular sieve on activity and selectivity of the reaction was improved, and the like is mainly used in catalytic cracking processes.

Description

一种含八面沸石的催化裂化催化剂及其制备方法技术领域本发明涉及一种用于催化裂化过程的烃裂化催化剂及其制备方法,特别是含有八面沸石的催化裂化催化剂及其制备方法。 Containing faujasite cracking catalyst and its preparation Technical Field The present invention relates to a method for preparing a hydrocarbon cracking catalyst and a process for catalytic cracking, in particular catalytic cracking catalyst containing a faujasite zeolite and its preparation method. 背景技术随着原料越来越重以及市场对重质燃料的需求日益减少,催化裂化工艺已成为最主要的重油加工手段,在重油转化中发挥着越来越重要的作用。 BACKGROUND As more and more raw materials as well as heavy demand for heavy fuel dwindling, catalytic cracking technology has become the most important means of processing heavy oil, it is playing an increasingly important role in the transformation of heavy oil. 催化剂对催化裂化过程起着关键作用,新材料的发现新催化剂的开发推动了催化裂化工艺的发展, 一种良好的重油催化裂化催化剂应具备以下性能:良好的重油裂解性能;抗重金属污染性能强;焦炭选择性好;良好的汽提性能; 水热稳定性高等。 The catalyst for the catalytic cracking process plays a key role in the discovery of new materials to develop new catalysts to promote the development of the catalytic cracking process, a kind of good heavy oil catalytic cracking catalysts should have the following properties: good heavy oil cracking performance; strong resistance to heavy metals pollution performance ; coke selectivity; good stripping performance; higher hydrothermal stability. 上述这些要求都对催化剂裂解组分—沸石提出了很高要求,其中最重要就是酸度和孔结构。 These requirements are cracking catalyst component - zeolite enormous demands, the most important is the pore structure and acidity. Y沸石经各种改性后,具有很强的酸性裂解功能,同时Y沸石属于八面沸石,具有较大空腔的超笼结构,使得其对大分子具有很好的扩散性能,特别适合大分子重油的催化裂解,因而在石油化工技术领域中的重油催化裂化过程得到广泛应用。 After various modified Y zeolite having a very acidic cracking function, while the Y zeolite belonging to the faujasite, having larger cavities super cage structures, such that it has good diffusion properties of the macromolecules, especially for macromolecular catalytic cracking of heavy oil, heavy oil catalytic cracking process and therefore in the field of petroleum technology is widely used in the chemical industry. 基于重油催化裂解的要求,为了改善催化剂性能,人们对Y沸石进行各种改性处理。 Based on the requirements of heavy oil catalytic cracking, in order to improve catalyst performance, various people Y zeolite reforming process. 随着催化裂化原料的不断重质化、劣质化,以及环保系统对无铅高辛烷值汽油需求量的日益增加,催化剂趋向高分子筛含量的超稳Y分子筛裂化催化剂发展,同时由于原料的变重,对催化裂化催化剂裂化大分子的能力也提出了新的要求。 With the increasing catalytic cracking raw material continues to heaviness, of poor quality, and environmental systems for high-octane lead-free gasoline demand, the catalyst tends to high levels of ultra-stable Y zeolite molecular sieve cracking catalyst development, but due to the change of raw materials weight, the ability of FCC catalyst cracking macromolecules also put forward new demands. 随着晶胞小、酸性中心数目少、氢转移活性低的高硅铝比分子筛的采用,催化剂中分子筛的加入量明显增加,因此不仅仅局限于Y沸石的改性,而是从沸石合成的初始就加以改进,也是沸石合成方法研究的一个重要领域。 With the small cell, the small number of acidic sites, low hydrogen transfer activity high silica to alumina ratio of the molecular sieve employed, the amount of catalyst added molecular sieves significantly increased, and therefore is not limited to modified Y zeolite, but the synthetic zeolite to improve on the original, but also an important area of ​​research zeolite synthesis method. US6160191公开了一种使用沸石催化剂的烃转化过程,其中催化剂涉及使用的沸石制备方法包括:将三价金属氧化物(如氧化铝)、氧化硅、碱金属阳离子和0—10w。 US6160191 discloses a hydrocarbon conversion process using a zeolite catalyst, wherein the zeolite catalyst preparation relates to a method for use comprising: a trivalent metal oxides (such as alumina), silicon oxide, an alkali metal cation and 0-10w. /。 /. 的沸石晶种和/或模板剂混合后在静态下合成大晶粒沸石。 The zeolite seeds and / or after mixing in a static template synthesized zeolite large grains. 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 6 - with a high silica to alumina ratio of 15, but that does not mean its products, 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"VSi02 =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并不高,该专利只是提供了一种方法,没有提供产品性质数据,而按其方法制备的沸石硅铝比只有5左右(投料硅铝比12时)。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,但它特别要求添加室温下长时间老化的硅铝酸钠晶种。专利涉及使用的晶种是在高碱性条件下制备的,特别要求在室温下晶化时间长达6 — 16天。该方法单纯使用模板剂而不用晶种辅助,晶化时间会很长,生产效率很低,但这种方法由于采用了晶种,应该归类于导向剂法,电镜下 The method of this patent a large amount of base, such as the feed material M "VSi02 = 0.2-1.0 (molar ratio), M + is an alkali metal, in terms of molar amount of the base ratio of Na2O / SiO2 is 0.4~2.0, the amount of base is too high While beneficial from the Y zeolite is formed, but too high will result in a sharp decline silica to alumina ratio of the product, not the actual high silica to alumina ratio zeolite product skeleton obtained by this method, this patent only provides a method does not provide product property data, and aluminosilicate zeolites and their methods of preparation is only about 5 ratio (feed alumina ratio 12) .US5549881 discloses a method for preparing faujasite zeolites, the patent also synthesized using organic templating agent having some type faujasite structural features of the composite zeolitic molecular sieve, it is particularly required to add sodium aluminosilicate seeds of long-term aging at room temperature. patent is directed to the use of seed crystals are prepared under highly alkaline conditions, in particular the crystallization time required at room temperature up to 6 - 16 days of the simple method without using a template by seed, crystallization time will be very long, low productivity, but this method due to the use of seed, should be classified in law directing agent, electron microscopy under 石形貌为多棱状颗粒。US5273945公开了一种催化裂化催化剂,其含有l一99w。/。的具有八面沸石特征的沸石和活性金属,其中所涉及的沸石硅铝比3 — 30,具有六方对称结构,该沸石合成过程使用剧毒且昂贵的冠醚做模板剂。针对现有技术的不足,本发明提供一种催化裂化催化剂,采用一种新型分本发明催化裂化催化剂以重量计含有高硅铝比八面沸石5-95〜%,耐熔氧化物5-95w。/。。其中八面沸石的SiCVAl203摩尔比为6〜20,优选为6〜12, XRD光谱分析属于八面沸石中的Y型沸石,晶体颗粒形貌(扫描电镜)具有片状形貌,Na20 含量低于lw。/。,优选低于0.2w。/。。八面沸石也可以用稀土元素改性,如采用镧和/或铈等稀土元素改性的八面沸石,稀土元素在八面沸石中的重量含一般为1%〜15%。本发明催化裂化催化剂中的耐熔氧化物选自氧化铝、氧化硅、氧化钛、 Stone morphology of polygonal shaped particles .US5273945 discloses a catalytic cracking catalyst which comprises a 99w./ l zeolite faujasite and having an active metal features, which aluminosilicate zeolite is involved than 3--30, having a hexagonal symmetry structure of the zeolite synthesis process uses highly toxic and expensive crown ethers as template. for deficiencies of the prior art, the present invention provides a catalytic cracking catalyst, using a new catalytic cracking catalysts of the present invention is divided by weight SiCVAl203 containing a high molar ratio of silica to alumina ratio 5-95~% faujasite, wherein the refractory oxide 5-95w./ .. faujasite zeolite 6~20, preferably 6~12, XRD spectroscopy belonging faujasite the zeolite Y-type zeolite, crystalline particle morphology (SEM) having a sheet-like morphology, Na20 content less than lw./., preferably less than 0.2w./ .. faujasite rare earth elements may be modified, the use of lanthanum and other rare earth elements modifying and / or cerium faujasite zeolites, faujasite weight rare earth element-containing typically at 1% ~ 15% of FCC catalyst of the present invention, refractory oxide selected from alumina , silicon oxide, titanium oxide, 氧化锆、白土、高岭土、膨润土、海泡石、其它类型沸石等一种或多种的物质。本发明催化裂化催化剂的制备过程可以采用本领域常规的方法,如将所需物料混合,加入粘结剂,成型、干燥、焙烧得到最终催化裂化催化剂。其中涉及的八面沸石采用如下过程制备:(1)将铝源、硅源、钠源和模板剂按照一定比例混合;(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;(3)将混合凝胶移入反应釜并密闭:(4)在90-13(TC条件下于反应釜自生压力下水热晶化24-240小时;(5)将晶化产物过滤并干燥得到沸石原粉;(6)将沸石原粉用铵盐交换1〜5次到得到低钠氢型沸石;低钠氢型沸石可以进一步用稀土离子交换得到稀土改性的八面沸石。 Zirconium oxide, clay, kaolin, bentonite, sepiolite, zeolite or more other types of substances. FCC catalyst preparation process of the present invention may be employed conventional methods in the art, such as mixing the desired material, viscous added caking agent, molding, drying and calcining to obtain a final catalytic cracking catalyst prepared by the process which involves the use of faujasite: (1) an aluminum source, silicon source, templating agent and sodium source according to a certain mixing ratio; (2) does not. under stirring over 7 (TC conditions and aged for 1 to 100 hours to form a uniform gel; (3) mixing the gel and transferred to a closed reaction vessel: (4) under the TC conditions 90-13 (autogenous pressure in the reactor hydrothermal crystallization of 24-240 hours; (5) the crystallized product was filtered and dried to give the original zeolite powder; (6) with the ammonium exchanged zeolite raw powder 1 ~ 5 times to obtain a low sodium zeolite hydrogen; hydrogen-type zeolite may hyponatremia further rare earth modified faujasite exchanged with rare earth ions. 混合物中各种原料的投料摩尔比为:5〜50 Si02 : 1.5〜15Na20 : A1203 : 0.05〜5.0模板齐[J : 60〜420 H20。 Feed mixture a molar ratio of raw materials: 5~50 Si02: 1.5~15Na20: A1203: 0.05~5.0 template Qi [J: 60~420 H20. 其中Na20/Si02摩尔比为0.05〜0.8,优选为0.1〜0.4, H20/Si02摩尔比为6〜40,优选为10〜22。 Wherein Na20 / Si02 molar ratio of 0.05~0.8, preferably 0.1~0.4, H20 / Si02 molar ratio of 6~40, preferably 10~22. 发明内容模板剂为有机碱类化合物和/或有机高分子化合物。 SUMMARY bases are organic template compound and / or an organic polymer compound. 其中,有机碱类化合物主要选自烷基氢氧化铵类化合物,如四甲基氢氧化铵、四乙基氢氧化铵、四丙基氢氧化铵、四丁基氢氧化铵等中的一种或几种。 Wherein the organic alkali compound is selected from primary alkyl ammonium hydroxide compounds such as tetramethylammonium hydroxide A tetraethyl ammonium hydroxide, tetrapropyl ammonium hydroxide, tetrabutyl ammonium hydroxide or several species. 所述的有机高分子化合物选自聚醇类化合物,如分子量为200〜10000聚乙二醇中的一种或几种。 The organic polymer compound selected from poly alcohols, such as one or more 200~10000 molecular weight polyethylene glycol. 两种模板剂可以单独使用,也可以混合使用,混合使用时比例可以不限。 Both templates may be used alone or in combination, the mixing ratio may be used is not limited. 混合物在室温〜7(TC条件下搅拌并老化1-100小时形成均匀凝胶,在90-130 。C条件下于反应釜自生压力下水热晶化24-240小时,优选24〜120小时。本发明加氢催化剂采用了一种新型八面沸石,该八面沸石具有高硅铝比和片状形貌。高硅铝比有利于提高催化剂的稳定性和活性,片状形貌不仅具有更多的反应表面,而且有利于反应物分子的扩散,可以减少二次反应,提高选择性。现有技术中合成高硅八面沸石主要采用导向剂法(以晶种胶为导向剂),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。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。并 The mixture was stirred at room temperature for ~7 (TC conditions and aged for 1 to 100 hours to form a uniform gel, 90-130 .C conditions under autogenous pressure in the autoclave hydrothermal crystallization 24-240 hours, preferably 24~120 hours. This hydrogenation catalyst invention employs a novel faujasite, the zeolite having a high silica to alumina ratio faujasite platelet morphology and high silica to alumina ratio increases the stability and activity of the catalyst, not only a sheet-like morphology with more the reaction surface, and facilitate the diffusion of the reactant molecules, can reduce secondary reactions, to improve the selectivity in the prior art synthesis of high silica faujasite method mainly directing agent (seed crystal oriented adhesive agent), i.e. preparation faujasite zeolite seeds under conditions of high sodium, this seed crystal director faujasite synthesis of the final product; or synthetic faujasite directly in the conditions of the present invention employs high sodium template method directly under hydrothermal conditions. synthesis of high silica to alumina ratio of the faujasite zeolite, by using a suitable template, at a relatively low amount of sodium case, no first obtained zeolite seed, can obtain a high silica to alumina ratio of the faujasite under conditions of high sodium zeolite. and 本发明方法合成时间短,特别是采用聚醇类化合物时,合成时间更短,可以大大提高合成效率。本发明的八面沸石具有更高硅铝比,更好的结晶度,较低的钠含量和更大的酸性。使用晶种合成出的八面沸石晶粒形貌与用本发明模板纯法合成出的八面沸石由明显不同,前者通常为多棱的颗粒,而后者为具有更多平整表面的碎片状的片状形貌,类似于同样具有超笼结构的采用昂贵剧毒冠醚做模板剂合成的EMT分子筛。附图说明图1是实施例1八面沸石样品的XRD图,横座标为2 e角。图2是实施例1八面沸石样品的扫描电镜图。图3是比较例1方法合成八面沸石样品的扫描电镜图。具体实施方式本发明催化裂化催化剂最好由下列组分中可以含有中大孔氧化铝、无定型硅铝、本发明方法合成的八面沸石、粘结剂、粘土、高岭土等,以及其它类型的分子筛。其它类型分了 The method of the present invention is the synthesis of short time, especially when using polyethylene alcohols, shorter synthesis time, the synthesis can greatly improve the efficiency. Faujasite zeolite of the invention has a higher silica to alumina ratio, the better the degree of crystallinity, low sodium acid content and greater. the use of seed synthesize faujasite grain morphology and synthesized by the template method of the present invention is pure faujasite zeolite is distinctly different, the former generally polygonal particles, the latter having a more multi-planar surface topography of the sheet-shaped pieces, similar to the use of expensive equally toxic crown ether template synthesis do supercages EMT structure. BRIEF DESCRIPTION oF dRAWINGS FIG. 1 is a XRD pattern of faujasite zeolite sample Example 1 abscissa is the angle E 2. FIG. 2 is a scanning electron micrograph of the faujasite zeolite sample in Example 1. FIG. 3 is a scanning electron micrograph of a sample of synthetic zeolite faujasite Comparative Example 1 method. DETAILED DESCRIPTION catalytic cracking catalysts of the present invention is preferably faujasite, binder, clay, kaolin and the like, as well as other types of molecular sieves may contain the following components macroporous alumina, amorphous silica alumina, synthetic methods of the invention. other types of points 筛主要包括各种改性Y型分子筛(如超稳Y、稀土Y等)、 ZSM-5分子筛、(3分子筛等。粘结剂是各种可以胶溶并具有粘结性能的氧化铝或经过特殊改性的粘性硅溶胶、铝溶胶、硅铝复合溶胶、磷酸铝溶胶、磷酸铝凝胶或者它们的复合物等。 本发明催化剂一种具体制备方法可以参考以下过程:将粘土等材料与脱离子水混合打浆加入无机酸如盐酸酸化,再加入拟薄水铝石、铝溶胶、沸石分子筛打桨,经成型、干燥、焙烧等步骤即得本发明催化剂。详细的制备步骤包括: (1)按照催化剂的组成比例,将粘土与去离子水混合打浆20—40分钟,加入盐酸酸化O. 5—20小时,加入拟薄水铝石搅拌打浆20 — 40分钟;(2)在50 — 80。C老化0.5—2小时,再加入铝溶胶搅拌10—30分钟;(3)加入研磨好的沸石分子筛, 继续打浆20—40分钟;(4)干燥成型,如喷雾干燥;(6)在500 — 70( Screen include a variety of modified Y zeolite (e.g., ultra-stable Y, rare earth Y, etc.), ZSM-5 zeolite, (3 molecular sieves, etc. The adhesive can be a variety of peptization of alumina and having adhesive properties after or particular viscosity modified silica sol, alumina sol, silica-alumina composite sol, aluminum phosphate sol, aluminum phosphate gel, etc., or a composite catalyst for the present invention can be prepared specifically with reference to the following procedure: the material from clay, etc. sub-water mixing pulping acidified by adding a mineral acid such as hydrochloric acid, was added quasi boehmite, alumina sol, zeolite molecular sieve playing paddle, by molding, drying, roasting step to obtain the catalyst of the present invention in detail the preparation step comprises: (1) the composition of the catalyst according to the proportion of the clay slurried with deionized water for 20-40 minutes, hydrochloric acid was added O. 5-20 hours, stirred quasi boehmite beating 20--40 min; (2) at 50--80. C for 0.5-2 hours aging, alumina sol was added with stirring 10-30 min; (3) was added lapped zeolitic molecular sieves and continue beating 20-40 min; (4) drying and pressing, such as spray drying; (6) at 500-- 70 ( TC焙烧1 — 4小时得到产品。 TC firing 1--4 hours to obtain the product. 本发明加氢催化剂涉及的高硅铝比八面沸石的合成具体过程可以包括如下步骤:(1) 将铝源、硅源、钠源和模板剂按照一定比例混合;(2) 在不超过7(TC条件下搅拌并老化1-IOO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--13(TC条件下于反应釜自生压力下水热晶化24-240小时;(5) 将晶化产物过滤并干燥后得到沸石原粉。 在水热晶化过程中,在按照合成沸石所需要的配比将铝源、硅源、钠源和模板剂按照一定比例混合后,还需要一定时间的老化过程,目的是使混合体系形成均匀的凝胶,有利于后续晶化过程,譬如减少晶化诱导期,提高结晶度等。按照本发明,所涉及的沸石在90-13(TC条件下于反应釜自生压力下水热晶化24-240小吋。铝源、硅源、钠源可以采用本领域常规的各种原料。铝源如硫酸铝、氯化铝、硝酸铝的一种或几种。硅源如水玻璃 Synthesis of high silica alumina hydrogenation catalyst specific process of the present invention may include more than faujasite following steps: (1) an aluminum source, silicon source, templating agent and sodium source according to a certain mixing ratio; (2) no more than 7 under stirring (TC conditions and aged for 1-IOO hour to form a uniform gel; (3) mixing the gel and transferred to a closed reaction vessel: (4) at 90--13 (TC conditions under autogenous pressure in the reactor of the hydrothermal crystallization 24-240 hours; (5) the crystallized product was filtered and dried to obtain a powder raw zeolite hydrothermal crystallization process, according to the proportion required will synthetic zeolite aluminum source, silicon source, templating agent and a sodium source. after mixing according to a certain proportion, the aging process also needs a certain time, the purpose is to make a mixed system forms a uniform gel, facilitates the subsequent crystallization process, for example, to reduce the crystallization induction period, enhance the crystallinity, etc. according to the present invention, relates TC zeolite under conditions of 90-13 (at autogenous pressure reactor hydrothermal crystallization 24-240 small inch aluminum source, a silicon source, sodium source raw materials conventional in the art may be employed. aluminum source such as aluminum sulfate, chloride aluminum, aluminum nitrate one or more silicon source such as water glass 硅胶和硅溶胶中的一种或几种,优选硅溶胶。钠源可以是铝酸钠〔同时也是铝源之一)、氢氧化钠的一种或几种。本发明所涉及的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。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。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的方式,采用动态和静态结合方式时,两者时间比例可以为l: 0.1~10。采用动态和静态结合时,先在静态下合成,然后在动态下合成,这样操作有利于提高晶化速度,并得到均匀的产品。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。铵盐交换制备低钠氢型八面沸石时,可以采用本领域常 One or more of silica sol and silica gel, preferably silica sol. Sodium [sodium aluminum source may be also one aluminum source), one or more of sodium hydroxide. Hydrothermal crystallization according to the present invention dynamic process may be a process accompanied by stirring, agitation or no static process. preferably, the process according to hydrothermal process of the present invention is then stirred without stirring to static and dynamic binding hydrothermal crystallization process. facilitate nucleation static, dynamic crystallization process to promote heat and mass transfer and facilitate to obtain a homogeneous product, a combination of dynamic and static may be employed using static binding and dynamic way, both the time ratio may be l: 0.1 ~ 10. a combination of static and dynamic, static first synthesized, and then synthesized under dynamic, this operation will help improve the crystallization rate, and to obtain a homogeneous product. taking whatever manner, the scope of the present invention are, and DETAILED what way, to determine the actual situation in the synthesis scale or production scale, and the size of the device. when preparing low sodium ammonium exchanged faujasite zeolite in the hydrogen form, normally in the art may be employed 规的操作方法。一般步骤如下:将晶化完全的沸石浆液用0.5〜5.0M的铵盐溶液交换到Na2O含量不大于3.0w。/。的Y沸石产物;铵盐交换后的沸石经过滤、水洗、干燥至干基^80w。/c) 后进行焙烧脱铵处理;将产物按上述离子交换方法与铵盐溶液再交换多次得到Na2O含量低于lw。/。或低于0.2w。/。的沸石产物。焙烧脱铵条件一般为300〜60(TC焙烧1〜20小时。由于本发明的合成沸石的特点,其制备成为氢型产品的复杂程度要比现有技术NaY要大为降低,突出表现在其铵盐交换次数减少,通常NaY要交换五次以上,而本发明沸石一般两到三次就可以达到要求。铵盐交换固液比为l: 8~1: 15,浓度为0.1〜10.0M,最好是0.5〜5.0M的铵盐溶液交换,所用的铵盐可为硝酸盐、氯化盐、硫酸盐等。 Method of operation gauge general steps are: the product is completely crystallized zeolite Y zeolite exchanged with an ammonium salt solution slurry to 0.5~5.0M Na2O content of not more than 3.0w./; filtered zeolite was ammonium exchanged. . washed with water and dried to dryness yl ^ 80w / c) after calcining ammonium removal process; the product of the above-described ion exchange with an ammonium salt solution was then exchanged many times Na2O content of less than or less than lw./ 0.2w./. . the zeolite product. calcining ammonium removal conditions in general. Because of the characteristics of the present invention, synthetic zeolite, which hydrogen form prepared as the complexity of the product is 300~60 (TC than prior art firing 1~20 hours to be greatly reduced NaY , highlighted in the ammonium exchange reduces the number of times, typically more than five times to be exchanged NaY, the zeolite of the invention is generally two to three times a salt exchange can achieve the requirements of the solid-liquid ratio l:. 8 ~ 1: 15, at a concentration of 0.1 ~10.0M, preferably the ammonium salt solution 0.5~5.0M exchange, the ammonium salt may be used a nitrate, chloride, sulfate and the like. 交换时进行充分搅拌,并维持温度在室温至10(TC 范围内,时间0.5〜5小时,最好是1.0〜3.0小时。制备稀土改性的八面沸石时采用本领域常规的稀土交换法。如用稀土盐溶液在室温〜10(TC交换1〜5次。最好是铵盐交换后再进行稀土交换。以下通过实施例进一步说明本发明催化剂的制备方法、性质和效果,实施例中的方案是在本发明范围权利要求范围内,具体实施方案并不构成对本发明的限制。(其中的百分比,w。/。均表示重量百分比)实施例l以水玻璃为硅源,铝酸钠为铝源,聚乙二醇6000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(Na20) : n(AlA): n(H20)=6 : 0.16 : 2 . 0: 1: 130。合成方法:按反应物配料摩尔比,把氢氧化钠和铝酸钠溶解于水中,搅拌30分钟后加入聚乙二醇6000,继续搅拌至溶解后再加入硅溶胶。将上述混合物在3(T Exchange performed sufficiently stirred, and maintained at a temperature of room temperature to 10 (within the range of TC, time 0.5~5 hours, preferably 1.0~3.0 hours using conventional in the art rare earth exchanged faujasite method when preparing a rare earth-modified. the rare earth salt solution at room temperature for ~10 (TC switching 1 ~ 5 times preferably rare earth exchanged and then ammonium exchanged. the following further illustrate the preparation of the catalyst of the present invention, the nature and effect of the embodiment, the embodiment of scheme is within the scope of the scope of the claimed invention, particular embodiments do not limit the present invention. (wherein the percentage, w. /. percentages are expressed by weight) in Example l sodium silicate as silica source, sodium aluminate is aluminum source, polyethylene glycol 6000 as a template, the cost of the zeolite by hydrothermal invention compound reactant molar ratio of ingredients:. n (Si02): n (template): n (Na20): n (AlA): n ( H20) = 6: 0.16: 2 0:. 1: 130. synthesis method: molar reactant ratio of ingredients, the sodium hydroxide and sodium aluminate dissolved in water, stirred for 30 minutes, polyethylene glycol 6000 was added, stirring was continued to dissolve and then adding the silica sol. the mixture in 3 (T C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,在搅拌状态下(100转/分)11(TC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样品A。 B的Si02/Al203摩尔比为10.6, XRD图见附图一,扫描电镜图见图二。实施例2以硅溶胶为硅源,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。反应物配料摩尔比:n(SiO》:n(模板剂):n(歸):n(AlA):n(H20)=8 : 0. 8 : 3 . 5: 1: 140。合成方法:按反应物配料比把氢氧化钠和铝酸钠加入20%的四乙基氢氧化铵溶液中,混合均匀后再加入硅溶胶。将上述混合物在4(TC下搅拌6小时后再在室温老化24小时,移入高压釜中,密闭,采用静态在110。C晶化120h。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样品B。 A的Si(VA:U0:靡尔比为7. After stirring for C 12 hours. After allowed to stand overnight at room temperature into the autoclave with polytetrafluoroethylene, sealed under stirring (100 r / min) 11 (TC crystallized after 120h. Complete crystallization, the product was filtered, after washing with water 11 (TC dried, then Al203 molar ratio of 55 (TC firing to obtain a sample template removal of A. B Si02 / to 10.6, XRD FIG see a reference, a scanning electron microscope is shown in Figure II. Example 2 silica sol as the silicon source, an aluminum source is sodium aluminate, tetraethyl ammonium hydroxide as templating agent compound cost zeolite by hydrothermal reaction was ingredients molar ratio invention:. n (SiO ": n (template): n (normalized): n (AlA): n (H20) = 8: 0. 8:. 3 5: 1: 140. synthesis method: charge ratio of the reactants to sodium hydroxide and sodium aluminate 20% of tetraethyl ammonium hydroxide solution, and then uniformly mixed silica sol was added. the mixture was stirred (at 4 TC 6 hours after aged at room temperature for 24 hours, transferred to an autoclave, sealed, in the static crystallization 120h 110.C after completion of crystallization, the product was filtered, washed with water at 11 (TC dried, and then obtain a sample B. a calcined at 550 .C removal of the templating agent Si (VA: U0: 7 Dalby extravagant. 2。实施例3以水玻璃为硅源,氯化铝为铝源,四乙基氢氧化铵为模板剂,水热晶化合成本发明沸石。反应物配料摩尔比:n(SiO》:n(模板剂):n(關):n(Am):n(H20)=15: 0.5: 6.0: 1: 170。合成方法:按反应物配料摩尔比,把氢氧化钠和铝酸钠加入到20%四丙基氢氧化铵溶液中,混合均匀后再加入硅溶胶。将上述混合物在4(TC下搅拌6小时后再在室温老化24小时,移入高压釜中,密闭,先在静态在于ll(TC晶化24h,然后在动态在于ll(TC晶化48h(搅拌速度200转/分)。 2. Example 3 water glass as a silicon source, an aluminum source is aluminum chloride, tetraethyl ammonium hydroxide as templating agent, the cost of the zeolite by hydrothermal invention compound reactant molar ratio of ingredients:. N (SiO ": n (template): n (off): n (Am): n (H20) = 15: 0.5: 6.0: 1: 170. synthesis method: molar reactant ratio of ingredients, the sodium hydroxide and sodium aluminate were added to 20% tetrapropyl ammonium hydroxide solution, and then uniformly mixed silica sol was added. the mixture was stirred (at 4 TC 6 hours after aged at room temperature for 24 hours, transferred to an autoclave, sealed, wherein the first static ll (TC crystallization 24h, then that dynamic LL (TC 48h crystallization (stirring speed 200 rev / min). 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样品C。 C的Si(VAlA摩尔比为9. 1。实施例4以固体硅胶为硅源,硝酸铝为铝源,四乙基氢氧化铵为模板剂,水热晶化合成本发明沸石。反应物配料摩尔比:n(SiO》:n(模板剂):n(歸):n(AlA): n(H20)=45 : 3 . 0: 15: 1: 32 0。合成方法:按反应物配料摩尔比,把氢氧化钠和铝酸钠加入到20%四乙基氢氧化铵溶液中,加入聚乙二醇2000,混合均匀后再加入硅溶胶,两种模板剂用量摩尔比为l: 1。将上述混合物在65r下搅拌12 小时后再在室温老化12小时,移入高压釜中,密闭,搅拌状态下(100转/分) 在12(TC晶化72h。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样品D。 D的Si02/AlA摩尔比为12. 6。实施例5以水玻璃为硅源,铝酸钠和氯化铝为铝源,聚乙二醇400为模板剂,水热晶 After completion of crystallization, the product was filtered, washed with water at 11 (TC dried, then Si 55 (TC firing to obtain a sample template Removal of C. C (VALA molar ratio of 4 to 9. Example 1 as a solid silica gel The silicon source, an aluminum source is aluminum nitrate, tetraethyl ammonium hydroxide as templating agent, the compound cost by hydrothermal reaction was ingredients invention zeolite molar ratio of:. n (SiO ": n (template): n (normalized): n (AlA): n (H20) = 45:. 3 0: 15: 1: 32 0. synthesis: molar reactant ratio of ingredients, the sodium hydroxide and sodium aluminate was added to a 20% tetraethylammonium hydroxide ammonium solution of polyethylene glycol 2000 was added, mixed well and then added to the silica sol, both templates dosage molar ratio l: 1. the mixture was stirred for 12 hours at 65R then aged at room temperature for 12 h, transferred to a high pressure after 12 (TC crystallization 72h. crystallization was complete, the autoclave product was filtered, sealed state under stirring (100 rev / min), washed with water at 11 (TC dried and then calcined to obtain the removal of the templating agent 550 .C samples of D. D Si02 / AlA molar ratio of 12. Example 5 6 water glass as a silicon source, aluminum chloride and sodium aluminate as the aluminum source, the template agent is polyethylene glycol 400, hydrothermal crystallization 化合成本发明沸石。反应物配料摩尔比:n(SiO》:n(模板剂):n(N&0) : n(Al203): n(H20)=24: 2.0: 2.0: 1: 230。合成方法:按反应物料摩尔比,把氢氧化钠、 铝酸钠加入到水中,搅拌30分钟后加入聚乙二醇400,再加入氯化铝(加入量为总Al20:,的30。/。),继续搅拌均匀后再加入水玻璃。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,在搅拌状态下(50转/分)11(TC晶化96h。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样品E。 E的Si(VAh03摩尔比为11. 3。比较例l按US5549881方法。首先制备晶种:配料比12.5(Si0》:13.33(歸): (A1A): 267 0W));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。其次,以硅溶胶为硅源 24 n (H20) =:: 2.0: 2.0: 1: 230. Synthesis method of compound Cost invention zeolite reactants Ingredients molar ratio of:. N (SiO ": n (template): n (N & 0): n (Al203) : molar ratio of the reaction mass, the sodium hydroxide, sodium aluminate was added to the water, stirring for 30 minutes after the addition of polyethylene glycol 400, then add aluminum chloride (total amount of Al20 :, 30./.) after continued stirring well and then added to water glass. the mixture was stirred (under TC 3 12 hours and left at room temperature overnight after the PTFE tape into an autoclave, sealed, under stirring (50 rev / min) 11 (TC crystallization after 96h. complete crystallization, the product was filtered, washed with water in. 11 (TC dried, then VAh03 molar ratio of 55 (TC firing to obtain a sample template removal E. E is Si (11. 3. comparison of Example l was first prepared by the method of seed US5549881: compounding ratio 12.5 (Si0 ": 13.33 (normalized): (A1A): 267 0W)); the process is added to the aluminum hydroxide dissolved in water to aluminum hydroxide sodium sol, sodium silicate and then slowly added, with vigorous stirring after bringing water uniformly, placed at room temperature for 16 days use. then, silica sol as the silicon source 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(SiO》:n(模板剂):n(Na20) : 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%硫酸铝浓度)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110。 Tetrabutyl ammonium hydroxide as templating agent, hydrothermal compound cost invention the zeolite, the reaction was Ingredients molar ratio: n (SiO ": n (template): n (Na20): n (AlA): n (H20) = 18: 3.6: 1.2: 1: 275. 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 sol (silica content 40%), 11.9g 16 days aging at room temperature the above seed, 63. 7g tetrabutyl ammonium hydroxide and sodium aluminate solution obtained above 5. 17g, 7.44g aluminum sulfate solution (50% aluminum sulfate concentration) and 135 g of the replenishment; after the mixture was stirred at (the TC 3 12 hours and left at room temperature overnight after the PTFE tape into an autoclave, sealed under static 110. C晶化分别120h、 240h。 C 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11(TC干燥,然后在55(TC焙烧脱除模板剂得到样品F。 F的Si02/Ah03摩尔比为6.5。电镜图见图3,可以看出其晶体颗粒的形貌为不规则多棱体颗粒,颗粒粒径较大。比较例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(投料Si(^/A:U03摩尔比为12),然后依次加入11.3g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50X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。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对比样品G, G的Si(VAlA摩尔比为5.2。实例6为样品A经过铵盐交换得到的氢型沸石F。取实例l合成的Si02/Al203 10.6, Na2 120h crystallized product is amorphous, 240h to give the product crystallized, the product was filtered, washed with water at 11 (TC dried, then 55 (TC firing removed to obtain a sample template F. F of Si02 / Ah03 molar ratio of 6.5. SEM is shown in Figure 3, it can be seen that the crystal morphology of particles of irregular polygonal particles, particle size is large. Comparative Example 2 a method according to US5716593, was added to the sodium aluminum 51. 6g 150. 2g silica mixed for 10 minutes (feed Si (^ / A: U03 molar ratio of 12), followed by addition of sodium hydroxide and 11.3g 349.6g tetraethyl ammonium hydroxide and stirring was continued mixing for 4 hours and then 60g of water into a paste which was then heated at 66 degrees so that the mixture of volatiles weight loss reduces the total weight of 230g 50X i.e., overnight at room temperature into a closed crucible, the crucible and then placed in 12ml water with a bottom of the autoclave, the crystallization 160H respectively 110 degrees. after the completion of the crystallization, the product was filtered, washed with water at 11 (TC dried, and then in example 55 (TC firing removal template comparative sample of G, Si VAlA G molar ratio of (5.2. 6 a sample of zeolite is the hydrogen form obtained after salt exchange from example F. synthesis of l Si02 / Al203 10.6, Na2 0 6.2w。/。的样品B50g,用净水将固液比稀释到l: 10,然后按照2.0M的浓度加入硝酸铵,搅拌、升温至90。C,恒温搅拌2小时,然后降温至5(TC过滤,经两次铵盐交换的沸石样品,洗涤至pH达到5〜6,然后放入干燥箱中,110〜12(TC干燥6小时然后在焙烧炉中升温到54(TC,恒温10小时。将高温焙烧脱铵的产物经粉碎后按上述方法再铵交换一次,即得到本发明模板合成法制备的氢型沸石F。 样品F Si02/AL03摩尔比为11. 2, Na02含量0. 15%。实例7为样品B经过铵盐交换并酸处理脱铝得到的氢型沸石G。取实例2合成的Si02/Al2037.2, Na2O8.3w。/。的样品A50g,用净水将固液比稀释到l: 10,然后按照2.0M的浓度加入硝酸铵,搅拌、升温至90〜95'C,恒温搅拌2小时,然后降温至50〜6(TC过滤,经两次铵盐交换的沸石样品,洗涤至pH达到5〜6,然后放入干燥箱中,11(TC干燥6小时然后在焙烧炉中升温 . 0 6.2w./ B50G sample, was diluted with water to a solid-liquid ratio of l: 10, and that the concentration of 2.0M ammonium nitrate was added, with stirring, was heated to 90.C, constant stirring for 2 hours, then cooled to 5 (TC was filtered, the zeolite samples were ammonium exchanged twice, washed until a pH of 5 to 6, and then into the dry box, 110~12 (TC dried for 6 hours and then allowed to warm to 54 is (TC, a thermostat 10 in a firing furnace h. the de-temperature calcination product was pulverized ammonium as described above and then ammonium exchanged once, i.e., to obtain the synthesis AL03 templates of the invention the molar ratio of hydrogen-type zeolite prepared by F. sample F Si02 / is 11. 2, Na02 content 0. 15%. example 7 a sample B after salt exchange and acid treatment in the hydrogen form dealuminated zeolite obtained in synthesis example 2 G. taken Si02 / Al2037.2, Na2O8.3w./. samples A50g, the solid with water ratio was diluted to l: 10, and that the concentration of 2.0M ammonium nitrate was added, stirred, warmed to 90~95'C, constant stirring for 2 hours, then cooled to 50~6 (TC was filtered, dried ammonium exchanged twice sample of zeolite washed to a pH of 5 to 6, and then into the dry box, 11 (TC dried for 6 hours and then heated in a firing furnace lj54(TC,恒温10小时。将高温焙烧脱铵的产物经粉碎后按上述方法再铵交换一次。交换后的产物12(TC干燥6小时后,再用净水将固液比稀释到l: 10,然后按照0.6M的浓度加入盐酸,搅拌升温至90。C,恒温搅拌2小时,降温至5(TC过滤后放入干燥箱中,11(TC干燥6小时。 .. Lj54 (TC, temperature 10 hours off temperature calcination product was pulverized ammonium as described above and then ammonium exchanged product was exchanged again 12 (after drying TC 6 hours, then diluted with clean water to solid-liquid ratio of l: 10, and that the concentration of 0.6M hydrochloric acid was added, stirring was heated to 90.C, constant stirring for 2 hours, cooled down to 5 (TC after filtration into the dry box,. 11 (TC dried for 6 hours. 在即得到本发明模板合成法制备的氢性沸石G。 Template synthesis of the present invention obtained soon hydrogen zeolite prepared by G. 样品G Si(VAlA摩尔比为9.3, NaO2含量0. 12%。实例8为样品C经过铵盐和稀土交换得到的稀土沸石H。取实例3合成的SiCVAl203 9.1, Na20 6.2w。/。的样品B50g,用净水将固液比稀释到l: 10,然后按照2.0M的浓度加入硝酸铵,搅拌、升温至9(TC,恒温搅拌2小时,然后降温至5(TC过滤, 经一次铵盐交换的沸石样品,洗涤至pH达到5〜6,然后放入干燥箱中12(TC干燥6小时。干燥样品再用净水将固液比稀释到l: 10,然后按照3%的浓度加入氯化铈,搅拌升温至卯。C,恒温搅拌2小时,然后降温至50〜6(TC过滤,再放入干燥箱中120。C干燥6小时。然后在焙烧炉中升温到54(TC,恒温10小时。将高温焙烧脱铵的产物经粉碎后按上述方法再用上述方法处理一次,即得到本发明模板合成法制备的稀土改性沸石H。样品H Si02/Al20:;摩尔比为9. 8, Na02含量0. 15%, 稀土含量7w。/()。实例9为本发明催化裂化催 Sample G Si (VAlA molar ratio of 9.3, NaO2 content of 0.12%. Example 8 Samples of zeolite is a rare earth ammonium and rare earth exchanged through C obtained in Synthesis Example 3 H. taken SiCVAl203 9.1, Na20 6.2w./. Samples B50G, diluted with water to a solid-liquid ratio of l: 10, and that the concentration of 2.0M ammonium nitrate was added, stirred, warmed to 9 (TC, constant stirring for 2 hours, then cooled to 5 (TC was filtered through a salt exchanged zeolite samples were washed until the pH reaches 5 to 6, and then placed in a drying oven 12 (TC dried sample was dried for 6 hours and then diluted with clean water to solid-liquid ratio of l:. 10, then follow the chlorine concentration of 3% was added cerium, d .C warmed to stir, constant stirring for 2 hours, then cooled to 50~6 (TC was filtered, then placed 120.C oven dried for 6 hours and then allowed to warm to 54 (TC, the temperature in the calciner 10 hours to de-temperature calcination product was pulverized ammonium. Repeat the process once as described above, the present invention is to obtain synthesis template H. sample H of rare earth modified zeolite prepared by Si02 / Al20 :; 9 molar ratio. 8, Na02 content of 0.15%, the rare earth content 7w ./ (). example 9 of the present invention is a catalytic cracking catalyst 剂l、 2、 3。将高岭土浆液850Kg (固含量35%)、拟薄水铝石450Kg (固含量40%)、铝溶胶150Kg (铝含量15%)、 500Kg水制得均匀浆液,用盐酸调整PH值为3,在75'C温度下,老化处理15小时,制得基体组份浆液I ;再取实施例6、 7、 8本发明沸石分子筛F、 G、 H 300Kg、 600 Kg、 900 Kg 搅拌均匀,用氨水调整PH值为6.0,打浆处理15小时,制得改性活性组份浆液II; 将I、 II浆液混合,搅拌24小时,喷雾干燥制得催化剂;将制得的催化剂洗涤、 干燥后,即得催化剂产品l、 2、 3,其中含本发明高硅铝比八面沸石分别为35%, 55%, 65%。比较例3为参比催化剂。取一种工业生产的NaY(温州催化剂厂生产,Si02/Al2034.6, Na2O10.7w。/。的样品50g,用净水将固液比稀释到l: 10,然后按照2.0M的浓度加入硝酸铵,搅拌、升温至9(TC,恒温搅拌2小时,然后降温至5(TC过滤,反复三次交换后,放入干燥箱中12 Agents l, 2, 3. 850Kg kaolin slurry (35% solids), pseudoboehmite, boehmite 450Kg (solids content 40%), 150Kg alumina sol (Al content 15%), 500Kg water to prepare a uniform slurry, with hydrochloric acid adjusting the PH value 3, at a temperature of 75'C, the aging treatment for 15 hours to obtain parts of the base component slurry I; then take in Example 6, 7, 8 zeolite molecular sieve invention F, G, H 300Kg, 600 Kg, 900 stir Kg adjust PH value of 6.0 with aqueous ammonia, beating for 15 hours to prepare the modified parts of the active slurry II; the I, II slurry was mixed, stirred for 24 hours, spray-dried to prepare a catalyst; the resulting catalyst was washed after drying, the catalyst product l, 2, 3 have, according to the present invention which contain a high ratio of aluminosilicate faujasite zeolite were 35%, 55%, 65%. Comparative Example 3 is a reference catalyst. take an industrial production of NaY (Wenzhou catalyst factory, Si02 / Al2034.6, Na2O10.7w./ sample 50g, was diluted with water to the solid-liquid ratio l:. 10, and that the concentration of 2.0M ammonium nitrate was added, stirred, warmed to 9 (TC, the temperature stirred for 2 hours, then cooled to 5 (TC was filtered, repeatedly switching times, into the oven 12 (TC干燥6小时。干燥样品在焙烧炉中升温到54(TC, 恒温10小时。将高温焙烧脱铵的产物经粉碎后再按上述方法用硝酸铵反复交换三次,得到氢性沸石样品HY。样品HY Si(VAL0:,摩尔比为5. 3, Na(^含量0.08 %。进一步,按照上述实例9的组成和制备方法制备参比催化剂,唯一区别的就是所采用的沸石活性组分为上述制备的HY (组成含量与本发明催化裂化催化剂l相同)。 (TC dried for 6 hours. The sample was dried to 54 is heated in the baking furnace (TC, temperature 10 hours. The de-temperature calcination product was pulverized ammonium as described above and then repeatedly exchanged three times with ammonium nitrate to give the hydrogen HY zeolite samples. samples molar ratio of HY Si (VAL0 :, to 5. 3, Na (^ content of 0.08%. further, according to the composition and preparation method for preparing the reference catalyst of example 9, the active zeolite is employed the only difference in the above-described divided HY prepared (the content of the same FCC catalyst composition of the present invention, l). 实例io上述本发明催化剂l、 2、 3和参比催化剂经过800。 Io Examples of the catalyst of the present invention, l, 2, 3, and 800 through the reference catalyst. C、 20h、 100%水蒸气老化处理后,在45(TC、剂油比5的条件下进行重油(馏程35(K53(TC)微反评价。 表l的结果表明,本发明催化剂与参比催化剂相比,未转化重油分别减少6.7%、 8.2%和9.3%,轻质油收率分别高出4.2%、 5.3%和6.8%。表l重油微反评价结果<table>table see original document page 14</column></row> <table> C, 20h, after 100% steam-aging treatment at 45 (TC, heavy oil agent (distillation range 35 (K53 (TC) than the micro-reactor at 5 Evaluation of the results in Table l indicate that the catalyst of the present invention with reference compared ratio of the catalyst, unconverted heavy oil were reduced by 6.7%, 8.2% and 9.3%, 4.2% higher than the yield of light oil, 5.3% and 6.8%. table l heavy oil microreactor evaluation results <table> table see original document page 14 </ column> </ row> <table>

Claims (8)

  1. 1. 一种含八面沸石的催化裂化催化剂,以重量计含有高硅铝比八面沸石5%-95%,耐熔氧化物5%-95%,其特征在于其中八面沸石的SiO2/Al2O3摩尔比为6~20,沸石XRD光谱分析属于八面沸石中的Y型沸石,晶体颗粒形貌具有片状形貌,Na2O含量低于1w%。 A catalytic cracking catalyst comprising a zeolite of faujasite, by weight faujasite containing a high silica to alumina ratio of 5% to 95%, refractory oxide 5 to 95%, wherein wherein the faujasite SiO2 / Al2O3 molar ratio of 6 to 20, belonging to the zeolite XRD spectral faujasite Y-type zeolite crystal particles having platelet morphology morphology, Na2O content of less than 1w%.
  2. 2、 按照权利要求l所述的催化剂,其特征在于所述的八面沸石的^02/八1203 摩尔比为6〜12。 2. A catalyst as claimed in claim l, characterized in that 02/1203 eight molar ratio of the faujasite ^ is 6~12.
  3. 3、 按照权利要求l所述的催化剂,其特征在于所述的八面沸石Na20含量低于0.2w0/0。 3. A catalyst as claimed in claim l, wherein said faujasite Na20 content less than 0.2w0 / 0.
  4. 4、 按照权利要求l所述的催化剂,其特征在于所述的八面沸石为稀土改性八面沸石,稀土元素在八面沸石中的重量含量为1%~15%。 4. The catalyst as claimed in claim l, wherein the faujasite zeolite is a rare earth modified faujasite, the weight content of the rare earth element in the faujasite is from 1% to 15%.
  5. 5、 按照权利要求4所述的催化剂,其特征在于所述的稀土元素为铈和/或镧。 5. A catalyst as claimed in claim 4, wherein said rare earth element is cerium and / or lanthanum.
  6. 6、 一种权利要求l所述催化剂的制备方法,将所需物料混合,加入粘结剂, 成型、干燥、焙烧得到最终催化裂化催化剂,其特征在于其中涉及的八面沸石采用如下过程制备:(1)将铝源、硅源、钠源和模板剂按照一定比例混合;(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;(3)将均匀凝胶移入反应釜并密闭;(4)在90-130°C条件下于反应釜自生压力下水热晶化24-240小时;(5)将晶化产物过滤并干燥得到沸石原粉;(6)将沸石原粉用铵盐交换1〜5次到得到低钠氢型八面沸石。 Preparation 6 A catalyst as claimed in claim l, the desired materials are mixed, adding a binder, molding, drying and calcining to obtain a final catalytic cracking catalyst, wherein the zeolite prepared by the process which involves the use of faujasite: (1) the aluminum source, silicon source, templating agent and sodium source according to a certain mixing ratio; (2) was stirred and aged for 100 hours to form a homogeneous gel at temperatures not exceeding 7 (TC conditions; (3) the homogeneous gel and transferred to a closed reactor; (4) at 90-130 ° C in the reactor conditions autogenous pressure hydrothermal crystallization 24-240 hours; (5) the crystallized product was filtered and dried to give the original zeolite powder; (6) ammonium exchanged zeolite raw powder with ~ 5 times to obtain a low-sodium hydrogen faujasite type.
  7. 7、 按照权利要求6所述的方法,其特征在于所述的低钠氢型八面沸石用稀土离子交换得到稀土改性的八面沸石。 7. The method of claim 6, wherein said low sodium-hydrogen faujasite zeolite is a rare earth-modified faujasite exchanged with rare earth ions.
  8. 8、 按照权利要求6所述的方法,其特征在于所述的模板剂为有机碱类化合物和/或有机高分子化合物;其中,有机碱类化合物选自四甲基氢氧化铵、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;所述的有机高分子化合物选自分子量为200〜10000聚乙二醇中的一种或几种。 8. A method as claimed in claim 6, characterized in that said templating agent is an organic compound bases and / or organic polymer; wherein the compound is selected from organic bases tetramethylammonium hydroxide, tetraethylammonium ammonium hydroxide, tetrapropyl ammonium hydroxide and one or more of tetrabutyl ammonium hydroxide; said organic polymer compound is selected from one or more 200~10000 molecular weight polyethylene glycol.
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US5716593A (en) 1996-07-31 1998-02-10 Chevron U.S.A. Inc. Preparation of Y-type faujasite using an organic template
CN1382631A (en) 2001-04-28 2002-12-04 中国石油化工股份有限公司 Rare-earth Y-type zeolite
CN1415704A (en) 2001-10-30 2003-05-07 中国石油化工股份有限公司 Cracking catalyst with hydrogen being added for noble metal and its prepn. method
CN1676577A (en) 2004-03-31 2005-10-05 中国石油化工股份有限公司 Petroleum hydrocarbon cracking catalys containing rare earth superstable Y-type zeolite

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US5192520A (en) 1989-09-13 1993-03-09 Societe National Elf Aquitaine Synthesis of aluminosilicate zeolites of faujasite structure
US5716593A (en) 1996-07-31 1998-02-10 Chevron U.S.A. Inc. Preparation of Y-type faujasite using an organic template
CN1382631A (en) 2001-04-28 2002-12-04 中国石油化工股份有限公司 Rare-earth Y-type zeolite
CN1415704A (en) 2001-10-30 2003-05-07 中国石油化工股份有限公司 Cracking catalyst with hydrogen being added for noble metal and its prepn. method
CN1676577A (en) 2004-03-31 2005-10-05 中国石油化工股份有限公司 Petroleum hydrocarbon cracking catalys containing rare earth superstable Y-type zeolite

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