CN1298425C - Aromatization catalyst, its preparation method and application - Google Patents

Aromatization catalyst, its preparation method and application Download PDF

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CN1298425C
CN1298425C CN 200410060301 CN200410060301A CN1298425C CN 1298425 C CN1298425 C CN 1298425C CN 200410060301 CN200410060301 CN 200410060301 CN 200410060301 A CN200410060301 A CN 200410060301A CN 1298425 C CN1298425 C CN 1298425C
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catalyst
zeolite
modified
aromatization
containing
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CN1651141A (en )
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郝代军
刘丹禾
魏小波
韩海波
龚旭辉
黄学政
俞安平
任潇航
沈方峡
王贵云
李昕
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中国石油化工集团公司
中国石化集团洛阳石油化工工程公司
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Abstract

本发明公开了一种芳构化催化剂,并且还公开了该催化剂的制备方法和应用。 The present invention discloses an aromatization catalyst, and also discloses a preparation method and application of the catalyst. 本发明催化剂由50~90重量%分子筛,0~32重量%载体和4~20重量%粘结剂组成,其中分子筛为改性HZSM-5分子筛和Y型分子筛,改性HZSM-5分子筛所用改性元素是锌、磷和稀土金属,改性元素在ZSM-5中的重量百分含量为0.01~20.0%。 The catalyst of the present invention consists of 50 to 90% by weight zeolite, 0 to 32 wt% carrier, and 4 to 20 wt% binder composition, wherein the modified molecular sieve is HZSM-5 zeolite and Y zeolite, modified HZSM-5 zeolite is modified with elements zinc, the weight percentage of phosphorus and rare earth, elements modified ZSM-5 is from 0.01 to 20.0%. 用本发明方法制备的催化剂具有较高的芳构化活性、强度、稳定性和流动性。 The catalyst prepared by the process of the present invention has higher aromatization activity, strength, stability and flowability. 本发明催化剂可用于改质劣质汽油生产高辛烷值汽油组分或者芳烃,用本发明方法生产的产品收率高,产品性能和产品分布稳定。 The catalyst of the present invention for upgrading low-quality production of high-octane gasoline component of gasoline or aromatics, produced by the method of the present invention, high product yield, product performance stability and product distribution.

Description

一种芳构化催化剂及其制备方法和应用 One kind aromatization catalyst and its preparation method and application

技术领域 FIELD

本发明属于石油炼制领域,涉及一种芳构化催化剂及其制备方法和应用。 The present invention belongs to the field of oil refining, to an aromatization catalyst and its preparation method and application.

背景技术 Background technique

我国汽油70%以上来自催化裂化装置,而我国催化裂化装置加工的原料有50%以上为石蜡基类(包括大庆原油、吉林原油、沈北原油等,统称为大庆类原油),由于其具有密度低、重金属含量低、硫含量低、氢含量高、饱和烃含量高等特点,无论是馏分油还是常压重油都是很好的催化裂化原料,然而其汽油辛烷值低是这类原料的不足之处,加工这类原料油的催化裂化装置汽油的研究法辛烷值总体水平约在87.5至89.5之间。 More than 70% of gasoline from a catalytic cracking unit, the cracking unit processing raw materials of 50% or more for paraffin type (including Daqing crude, Jilin crude oil, crude oil Shenbei, collectively referred to as category Daqing crude oil), since it has a density low, low heavy metal content, low sulfur content, hydrogen content was high, and high content of saturated hydrocarbons, either distillate or atmospheric residue are good catalytic cracking feedstock, however, is insufficient low octane gasoline feedstock such place, the overall level of research method octane number of FCC gasoline processing apparatus such feed oil between about 87.5 to 89.5. 随着环保要求的提高,禁止加铅。 With the improvement of environmental requirements, ban leaded. 因此,提高汽油的辛烷值已是当务之急。 Therefore, to improve the gasoline octane number is imperative.

众所周知,以晶型氧化铝为载体的含铂催化剂,或者含铂铼、铂锡等催化剂,以直馏汽油或石脑油为原料的催化重整,可以获得高辛烷值汽油组分,或者芳烃产品。 It is well known to the crystalline form supported on alumina reforming catalyst containing a platinum catalyst, or platinum-containing rhenium, platinum and tin catalyst, straight-run gasoline or naphtha as a raw material, a high octane gasoline component, or aromatic products. 但该工艺受到原料来源的限制。 However, this process is limited by the source of raw materials. 人们为了扩大原料来源,提出对二次加工汽油(如热裂化汽油、焦化汽油等)进行加氢精制,做为其原料的补充来源,但造成重整工艺的加工流程复杂和加工成本较大,企业经济效益受到很大的影响。 It order to expand the source of raw materials, gasoline presented to secondary processing (e.g., thermally cracked gasoline, coker gasoline, etc.) hydrorefining, added as its source of raw materials, but the resulting complex machining process to the reforming process and greater processing cost, economic efficiency of enterprises has been greatly affected. 芳构化工艺则无须对原料进行预处理,反应体系不需临氢,也不要求带压操作,可以得到与重整相似的液体产品组成,而芳构化油含有高支链成分及更多芳香族成分之烃类,如苯、芳香烃和异构烃等辛烷值高的组分,通过调合可以有效地提高汽油的辛烷值,完全可以作为汽油高辛烷值调和组分。 The aromatization process without pretreatment of the raw material, the reaction system without the presence of hydrogen and does not require pressurized operation, reforming can be obtained similar liquid product composition, the aromatization oil contains more highly branched aromatic component and high octane components of the hydrocarbon components, such as benzene, aromatic hydrocarbon isomers and the like can be effectively improved by blending octane gasoline, it can be used as a high octane gasoline blending component.

近年来,人们对硅铝酸盐,特别是以高硅铝比分子筛为催化剂的芳构化过程进行了大量的研究,尤其以ZSM-5、ZSM-11分子筛为催化剂的过程进行了大量的研究。 In recent years, people aluminosilicates, particularly in a high silica alumina ratio of the molecular sieve is carried aromatization process a large amount of catalyst research, especially ZSM-5, ZSM-11 zeolite is a lot of research process of Catalyst . 如USP4288645公开了用载锌硅铝酸盐催化剂,以至少含50%的丙烷的轻烃制取芳烃混合物和氢气的过程。 As disclosed in USP4288645 zinc aluminosilicate catalyst carrier, made to light hydrocarbon containing at least 50% of the propane to take a mixture of aromatic hydrocarbons and hydrogen processes. 它要求丙烷最好大于60%,甲烷、乙烷小于20%。 It requires greater than 60% preferably propane, methane, ethane, less than 20%. CN1063121A公开的催化剂是以Zn、Al和稀土三种金属元素中的二种或三种对氢型ZSM-5分子筛进行改性制得催化剂,用于劣质汽油的催化改质及C2~C4烃分子的芳构化。 CN1063121A discloses a catalyst based on two or three Zn, Al and rare earth elements in the three metal hydrogen type ZSM-5 zeolite was modified to prepare a catalyst for the catalytic upgrading of low-grade gasoline and C2 ~ C4 hydrocarbon molecules aromatization. 所采用的催化剂组成为5.0~94.5%的氢型分子筛,用0.3~15%的锌、铝和稀土元素中选取二种或三种进行复合改性,余量为选自氧化铝、氧化硅或氧化铝和氧化硅的混合物、黏土的一种作为粘结剂。 The composition of the catalyst employed is 5.0 to 94.5% of the hydrogen form zeolite with 0.3 to 15% of zinc, aluminum and rare earth elements selected two or three modification composite, the balance being selected from alumina, silica, or a mixture of aluminum oxide and silicon oxide is a clay as a binder.

在已有的技术中,采用固定床反应形式,含镓或含锌分子筛催化剂活性稳定性较高,但存在价格昂贵或在芳构化过程中锌易流失,催化剂生焦快,造成催化剂迅速减活,解决这些问题通常是采用同时载有两种金属的方法,而另一种金属大多为贵金属;同时在反应过程中采用阶梯升温的方式并根据催化剂的失活情况对反应器进行频繁切换再生。 In the prior art, in the form of a fixed bed reactor, containing gallium or zinc high stability zeolite catalyst activity, but there are very expensive or zinc easily lost in the aromatization process, the fast coke catalyst, resulting in the rapid reduction of the catalyst live, to solve these problems is typically a method of simultaneously carrying two metals, most of the other metal is a noble metal; while using a stepped manner during the reaction warmed and frequent switching of the regeneration reactor in accordance with the deactivation of the catalyst . CN1063121A公开的催化剂具有较强的酸性,因此在固定床反应器中芳构化催化剂很容易因生焦而失活快,需要采用多个反应器串联和变温操作,同时造成装置的频繁的切换再生或停工组织再生,操作繁琐、催化剂的投资较大、存在产品分布质量不稳定,特别是到后期产品中干气产率增加较大,芳构化生产的氢气产率不稳定,而对后续的联合装置的操作产生影响。 CN1063121A discloses a catalyst having a strong acidity, thus easily aromatization catalyst deactivation due to coke and fast in a fixed bed reactor, the need to use a plurality of reactors in series and a variable temperature operation, also causing frequent switching of the reproducing apparatus suspension or tissue regeneration, complicated operation, a large investment in the catalyst, the presence of unstable quality product distribution, especially in the late-stage increase in the yield of dry gas is large, aromatization yield of hydrogen produced is unstable, and the subsequent joint operation of the impact device.

发明内容 SUMMARY

本发明是针对现有技术中芳构化催化剂容易生焦而失活的缺点而提出一种新的芳构化催化剂,该催化剂具有较高的芳构化活性、强度、稳定性和流动性。 The present invention is directed to drawbacks of the prior art aromatization catalyst is easily inactivated coke proposed a new aromatization catalyst, the aromatization catalyst has high activity, strength, stability and flowability.

另外,本发明还对该芳构化催化剂的制备方法和在移动床劣质汽油催化改质工艺上的应用进行了详细的描述。 Further, the present invention is also the preparation of the catalyst aromatization and applied on a moving bed catalytic upgrading inferior gasoline process of a detailed description.

本发明提出的芳构化催化剂由50~90重量%分子筛,0~32重量%载体和4~20重量%粘结剂组成。 Aromatization molecular sieve catalyst made by the present invention is 50 to 90 wt%, 0 to 32 wt% carrier, and 4 to 20 wt% binder composition. 其中分子筛为改性HZSM-5分子筛和Y型分子筛,改性HZSM-5分子筛所用改性元素是锌、磷和稀土金属,其中改性元素在ZSM-5中的重量百分含量为0.01~20.0%,最好为0.1~10.0%;Y型分子筛可以是经稀土金属离子交换后得到的稀土含量为0.01~25.0%,最好为0.1~20.0%的REY分子筛,也可以是经各种化学和/或物理方法,如水热法、酸处理法、抽铝补硅法或四氯化硅法等处理后得到的硅铝比较高、稳定化了的高硅Y型分子筛(简称为REUSY分子筛),其占催化剂总重量的0.1~20%,最好是0.5~15%。 Wherein the molecular sieve is HZSM-5 zeolite and a modified Y zeolite, modified HZSM-5 zeolite modified with element used is zinc, phosphorus and rare earth metals, wherein the weight percentage of the modifying element in the ZSM-5 is from 0.01 to 20.0 %, preferably 0.1 ~ 10.0%; Y-type zeolite may be exchanged by rare earth content of the rare earth metal ion obtained is 0.01 to 25.0%, preferably 0.1 to 20.0% REY molecular sieve, or may be by various chemical and after / or physical methods, hot water, acid treatment method, extraction method, or process of aluminum silicon element method, silicon tetrachloride obtained relatively high silica-alumina, a stabilized high silica Y type zeolite (referred to as REUSY molecular sieves), which comprises from 0.1 to 20% by weight of the total catalyst, preferably 0.5 to 15%. 载体为选自Al2O3、ZrO2、高岭土、ZnO和铝镁尖晶石中两种或两种以上,其在催化剂中的重量百分含量最好为5~20%,粘结剂是羟基氯化铝溶胶、硅溶胶、磷酸铝溶胶或它们的混合物,其在催化剂中的重量百分含量最好是5~15%。 Carrier is selected from Al2O3, ZrO2, kaolin, ZnO, and magnesium aluminate spinel in two or more, the weight percentages in the catalyst is preferably 5 to 20%, the binder is aluminum hydroxychloride sol, silica sol, aluminum phosphate sol or mixtures thereof, the weight percentages in the catalyst is preferably 5 to 15%.

本发明所述的稀土金属是指镧或铈或含有镧和/或铈的混合稀土金属,具体地说该稀土金属中必须含有镧或铈,其它稀土金属元素任意选择。 Rare earth metal according to the present invention means containing lanthanum or lanthanum and cerium or mischmetal / or cerium, particularly the rare earth metals comprising lanthanum or cerium must, other rare earth elements arbitrarily selected.

本发明使用的HZSM~5分子筛,为市售的HZSM-5分子筛,其SiO2/Al2O3比为20~500,最好为25~200,约束指数为1~2。 The present invention is used HZSM ~ 5 zeolite, a commercially available zeolite HZSM-5, which SiO2 / Al2O3 ratio of 20 to 500, preferably 25 to 200, a constraint index of 1 to 2.

本发明芳构化催化剂的制备方法是,将分子筛和载体粉碎后充分混合,球磨到400~1000目,加入滚动成型釜,将粘结剂与水按1∶5~1∶10的比例稀释,通过雾化设备间歇地喷入分子筛和载体的混合物中,连续滚动成型,直至成型为直径为1.4~2.0毫米的小球,然后在80~120℃下干燥2~10小时,在500~600℃温度下焙烧1~6小时,得本发明催化剂。 The catalyst preparation process of the present invention, textured aryl is pulverized after the molecular sieve and a carrier mixed, the ball 400 to 1000 mesh, rolling molding kettle was added, the binder diluted with water in proportion 1/5 to 1:10, mixture into a molecular sieve and a carrier intermittently through the atomizing device, the continuous rolling molding, until the molding having a diameter of 1.4 to 2.0 mm pellet, and then at 80 ~ 120 ℃ dried for 2 to 10 hours, at 500 ~ 600 ℃ calcination at a temperature of 1 to 6 hours to obtain the catalyst of the present invention.

本发明提供的芳构化催化剂可用于劣质汽油的芳构化改质和生产芳烃、液化气生产芳烃等工艺,也可部分替代重整工艺生产芳烃。 Aryl aromatization catalyst may be used in the present invention provides a configuration of inferior gasoline and producing aromatic hydrocarbons reforming, aromatics production processes liquefied gas, may replace part of the reforming process for producing aromatic hydrocarbons.

本发明芳构化催化剂在改质劣质汽油生产高辛烷值汽油组分或者芳烃中的应用方法,在非临氢状态下进行移动床芳构化反应的条件是:反应温度为350~550℃,反应压力为0.1~0.5Mpa,空速为0.5~5h-1,最好为1.0~3.0h-1,生产高辛烷值汽油调和组分时,反应温度最好为350~450℃,生产芳烃时最好为460~550℃,催化剂再生时的再生条件为:再生温度为400~550℃,在再生器中的停留时间为1~600分钟,采用空气再生。 The present invention is structured aromatic modified inferior catalysts produce high octane gasoline components of gasoline or aromatics in the application, moving bed aromatization reaction in the presence of hydrogen under non-state conditions are: a reaction temperature of 350 ~ 550 ℃ The reaction pressure is 0.1 ~ 0.5Mpa, a space velocity of 0.5 ~ 5h-1, preferably 1.0 ~ 3.0h-1, the production of high octane gasoline blending components, the reaction temperature is preferably 350 ~ 450 ℃, production when the aromatic hydrocarbon is preferably 460 ~ 550 ℃, regeneration conditions during regeneration of the catalyst: regeneration temperature 400 ~ 550 ℃, the residence time in the regenerator is from 1 to 600 minutes, using air fresheners.

与现有技术相比,本发明催化剂中的HZSM-5分子筛是一种高硅、具有三维交叉直通道的新型分子筛,具有亲油、疏水、热稳定性高等特点,采用铝溶胶或硅溶胶作为粘结剂、采用改性分子筛和滚动成型技术,使得本发明催化剂按照本发明制备方法可方便的制成具有直径为1.4~2.0毫米的小球形状和具有良好的芳构化反应再生性能,因此本发明催化剂具有较高的芳构化活性、强度、稳定性和流动性。 Compared with the prior art, the catalyst of the present invention HZSM-5 is a high silica zeolite, the molecular sieve having a three-dimensional intersection of a straight channel having oleophilic, hydrophobic, high thermal stability, as aluminum or silica sol binder, and rolling using the modified molecular sieve molding technology, so that the present invention is a catalyst prepared according to the method of the present invention can be easily made to have a pellet shape having a diameter of 1.4 to 2.0 mm and with good reproduction performance aromatization reaction, the catalyst of the present invention has higher aromatization activity, strength, stability and flowability.

本发明提供的芳构化催化剂应用在移动床上,因而避免了固定床芳构化工艺中催化剂很容易生焦而失活,且需要采用多个反应器串联和变温操作等缺点和不足,该应用方法可以在保持固定床芳构化工艺优点的基础上,进一步改进催化剂的反应和再生状态,实现反应再生连续化,使芳构化反应始终在接近新鲜催化剂的最佳条件下进行操作,反应温度可维持恒定,产品分布更优化(芳构化油和氢的产率较高)、收率更稳定,装置有较高的运转率,即实现长周期运转,而且对原料有更大的适应性。 Aromatization catalyst provided by the invention in a mobile bed, thus avoiding the fixed bed catalyst aromatization process readily inactivated coke, and a plurality of drawbacks and disadvantages need reactors in series and variable temperature operation, the application the method may be a fixed bed while maintaining the advantages of the aromatization process, to further improve the reaction and the regeneration state of the catalyst, the reaction to achieve continuous regeneration, so that the aromatization reaction is always operated under optimum conditions close to the fresh catalyst, the reaction temperature can be maintained constant, more optimized product distribution (high oil yield aromatization and hydrogen), the yield is more stable, has a higher rate of operation of the device, i.e. to achieve a long-term operation, and greater flexibility of raw materials . 当装置采用单反应器和单再生器构成时,投资也不大。 When the device employs a single reactor configuration and a single regenerator, investment is not large. 此外,装置所需的催化剂也较固定床节省二分之一。 Further, the catalyst bed are more desired devices save one-half.

另外,在移动床反应器中,可以实现芳构化催化剂的连续再生,一方面依靠催化剂的自重,在再生器(及反应器)中,由上往下移动,另一方面,再生后移动到下部的催化剂(或反应底部待生催化剂)依靠气力输送技术,提升到反应器(或再生器)顶部,进行反应(再生),构成脉冲式近于连续化的过程。 Further, in a moving bed reactors, continuous regeneration may be achieved aromatization catalyst, on the one hand the own weight of the catalyst, in the regenerator (and reactor), moving from top to bottom, on the other hand, moves to the regeneration the lower portion of the catalyst (or the bottom of the reaction the spent catalyst) continuous process relies on near pneumatic conveying, lifting to the reactor (or regenerator) top, reaction (regeneration), constituting the pulse.

移动床反应再生过程,在石油化工领域有成熟的工业应用,如石脑油连续重整装置。 Moving bed reactor regeneration process, mature industrial applications, such as naphtha reforming unit in the petrochemical industry. 移动床反应器对催化剂的物理性质要求:堆积密度小于0.8g/cm3,粒度分布在φ1.4~2.0mm的应大于99%;压碎强度大于40N.粒-1及抗磨损性能较好。 Moving bed reactor requires the physical properties of the catalyst: a bulk density of less than 0.8g / cm3, φ1.4 ~ 2.0mm in particle size distribution should be greater than 99%; grain crush strength greater than 1 and preferably 40N abrasion resistance. 现有的用于固定床的芳构化催化剂,分子筛含量较高、同时使用硝酸作为粘结剂,粘结分子筛的能力有限,不能制成满足上述要求的球形颗粒催化剂。 Aryl conventional fixed bed catalyst configuration, higher sieve content, while nitric acid is used as the binder, the limited capacity of the molecular sieve binder, spherical particles of the catalyst can not be made to meet the above requirements. 而采用本发明催化剂的组成和制备方法,则可以方便地制成满足移动床再生工艺要求的球形颗粒催化剂,从而实现移动床芳构化反应。 The use of the catalyst of the present invention the composition and preparation methods, it can easily be made to meet the spherical particles moving bed catalyst regeneration process requirements, thereby realizing the moving bed aromatization reaction.

本发明移动床芳构化反应的原料为低辛烷值汽油或石脑油,对其芳烃潜含量无要求,也无须对原料进行预处理;反应-再生可连续进行,从而可维持恒定的反应温度,使产品收率高、产品性能和产品分布稳定。 Aromatic feedstock moving bed reactor of the present invention structured as low octane gasoline or naphtha, its potential aromatic content is not required, there is no need for the raw material pretreatment; reaction - regeneration can be carried out continuously, thereby maintaining a constant reaction temperature, high product yield, product performance stability and product distribution. 用本发明方法制备的芳构化催化剂性能好、活性和稳定性高,同时又能得到很好的产品分布。 Aromatic prepared by the process of the present invention structured good catalyst performance and high activity and stability, while the distribution of products well.

本说明书中所涉及的百分含量未具体标注的均为重量百分含量。 In this specification are weight percentages relate to the percentage of non-specific labeling.

具体实施方式 detailed description

下面用实施例对本发明的催化剂及其制备和应用作进一步的说明,但实施例并不限制本发明的范围。 Following Examples and the preparation and use of the catalyst of the present invention will be further illustrated, but not limit the scope of embodiments of the present invention.

实施例1取市售硅铝比为60的HZSM-5分子筛1500克,用含206克Zn(NO3)2的溶液1000ml和用含25克混合氯化稀土(其中含氧化镧21%、氧化铈11%)的溶液200ml进行交换。 EXAMPLE 1 Commercially available silica to alumina ratio of 60 to 1500 g HZSM-5 zeolite with a solution containing 1000ml 206 g of Zn (NO3) 2 and containing 25 g of a mixed rare earth chloride (wherein lanthanum oxide containing 21% cerium oxide 11%) was exchanged 200ml. 即在40℃下,快速搅拌交换2小时,然后过滤浆液,110℃下干燥滤饼2小时,滤饼经焙烧、粉碎后,再用含63.9克(NH4)2HPO4的溶液1000ML再交换2小时。 I.e., at 40 ℃, exchange with rapid stirring for 2 hours and then the slurry was filtered, the filter cake was dried at 110 deg.] C for 2 hours and the filter cake was calcined, pulverized, and then 1000ML solution containing 63.9 g (NH4) 2HPO4 exchange again for 2 hours. 经干燥、焙烧、粉碎后,得改性HZSM-5分子筛a,其中Zn含量为2.7%,稀土元素氧化物总量为0.5%(其中氧化镧0.3%、氧化铈0.2%),P含量为1%。 The dried, calcined, pulverized, to obtain a modified HZSM-5 zeolite a, wherein the Zn content is 2.7%, 0.5% of the total rare earth element oxide (0.3%, wherein lanthanum oxide, cerium oxide, 0.2%), P content is 1 %.

将714克铝溶胶溶液(pH值为3.0,含Al2O321%),加入100毫升去离子水。 The 714 g of alumina sol solution (pH value 3.0, containing Al2O321%), was added to 100 ml of deionized water. 把500克改性ZSM-5分子筛a,150克REY型分子筛和200克拟薄水铝石混合均匀,球磨到400~1000目,取少量加入滚球釜中,开动滚球机,间歇地喷入铝溶胶溶液,直至成型为直径为1.8~2.0毫米的小球催化剂,然后在80~120℃下干燥2~10小时,在500~600℃温度下焙烧1~6小时,得催化剂A。 The 500 grams of ZSM-5 modified a, 150 g of REY molecular sieve and 200 g of quasi boehmite mixed, milled to 400 mesh to 1000, was added a small amount bowls kettle start ball machine, intermittently spraying into alumina sol solution, until forming a diameter of 1.8 to 2.0 mm catalyst pellets, then at 80 ~ 120 ℃ dried for 2 to 10 hours, calcined at a temperature 500 ~ 600 ℃ 1 ~ 6 hours to obtain a catalyst A. 按干基计算,含50%改性ZSM-5分子筛,含15%REY,含氧化铝35%。 On a dry basis, containing 50% of modified ZSM-5 zeolite, containing 15% REY, containing 35% alumina.

实施例2取市售硅铝比为35的HZSM-5分子筛1500克,用含420克Zn(NO3)2的溶液1000ml和用含50克硝酸镧(其中镧含量为13.1%)的溶液200ml进行交换。 EXAMPLE 2 Commercially available silica to alumina ratio of 35 to 1500 g HZSM-5 zeolite, containing 420 g Zn (NO3) 2 and a solution of 1000ml 200ml solution containing 50 g of lanthanum nitrate (wherein the lanthanum content of 13.1%) were exchange. 即在40℃下,快速搅拌交换2小时,然后过滤浆液,110℃下干燥2小时,经焙烧、粉碎后,再用含63.9克(NH4)2HPO4的溶液1000ML再交换2小时。 I.e., at 40 ℃, exchange with rapid stirring for 2 hours and then the slurry was filtered, dried for 2 hours at 110 deg.] C, calcined, pulverized, and then with 63.9 g (NH4) 1000ML 2HPO4 was again exchanged for 2 hours. 经干燥、焙烧、粉碎后得改性HZSM-5分子筛b,其中Zn含量为5.6%,稀土元素镧含量为0.398%,P含量为1%。 The dried, calcined, pulverized to obtain a modified HZSM-5 zeolite b, where the Zn content is 5.6%, the concentration of La was 0.398%, P content is 1%.

取476克铝溶胶溶液(pH值为3.0,含Al2O321%),加入100毫升去离子水。 Take 476 g of alumina sol solution (pH value 3.0, containing Al2O321%), was added to 100 ml of deionized water. 把600克改性ZSM-5分子筛b,80克REUSY型分子筛和220克拟薄水铝石混合均匀,球磨到400~1000目,取少量加入滚球釜中,开动滚球机,间歇地喷入铝溶胶溶液,直至成型为直径为1.8~2.0毫米的小球催化剂,然后在80~120℃下干燥2~10小时,在500~600℃温度下焙烧1~6小时,得催化剂B。 The 600 grams of ZSM-5 modified b, 80 g of zeolite and 220 grams REUSY quasi boehmite mixed, milled to 400 mesh to 1000, was added a small amount bowls kettle start ball machine, intermittently spraying into alumina sol solution, until forming a diameter of 1.8 to 2.0 mm catalyst pellets, then at 80 ~ 120 ℃ dried for 2 to 10 hours, calcined at a temperature 500 ~ 600 ℃ 1 ~ 6 hours to obtain catalyst B. 按干基计算,含60%改性ZSM-5分子筛,含8%REUSY,含氧化铝32%。 Dry basis, 60% modified ZSM-5 zeolite containing 8% REUSY, containing 32% alumina.

实施例3取市售硅铝比为100的HZSM-5分子筛1500克,用含420克Zn(NO3)2的溶液1000ml和用含100克硝酸镧(其中镧含量为13.1%)(的溶液200ml进行交换。即在40℃下,快速搅拌交换2小时,然后过滤浆液,110℃下干燥2小时,经焙烧、粉碎后,再用含63.9克(NH4)2HPO4的溶液1000ML再交换2小时。经干燥、焙烧、粉碎后得改性HZSM-5分子筛c,其中Zn含量为5.6%,稀土元素镧含量为0.8%,,P含量为1%。 Example 3 taken as a commercially available silica to alumina ratio of zeolite HZSM-5 100 1500g 1000ml 420 g of a solution containing Zn (NO3) 2 and containing 100 g of lanthanum nitrate (wherein the lanthanum content of 13.1%) (200ml of a solution of exchanged words at 40 ℃, exchange with rapid stirring for 2 hours and then the slurry was filtered, dried at 110 deg.] C for 2 hours and calcined, pulverized, and then with 63.9 g (NH4) 1000ML 2HPO4 was again exchanged for 2 hours. warp dried, calcined, pulverized to obtain a modified HZSM-5 zeolite c, where the Zn content is 5.6%, the concentration of La was 0.8% ,, P content of 1%.

取476克铝溶胶溶液(pH值为3.0,含Al2O321%),加入100毫升去离子水。 Take 476 g of alumina sol solution (pH value 3.0, containing Al2O321%), was added to 100 ml of deionized water. 把600克改性ZSM-5分子筛c,80克REY型分子筛和220克拟薄水铝石混合均匀,球磨到400~1000目,取少量加入滚球釜中,开动滚球机,间歇地喷入铝溶胶溶液。 The 600 grams of ZSM-5 modified c, 80 g of zeolite and 220 grams REY quasi boehmite mixed, milled to 400 mesh to 1000, was added a small amount bowls kettle start ball machine, intermittently spraying into alumina sol solution. 直至成型为直径为1.8~2.0毫米的小球催化剂,然后在80~120℃下干燥2~10小时,在500~600℃温度下焙烧1~6小时,得催化剂C。 Until molding having a diameter of 1.8 to 2.0 mm catalyst pellets, and then dried for 2 to 10 hours at 80 ~ 120 ℃, at a baking temperature of 500 ~ 600 ℃ 1 to 6 hours, to obtain a catalyst C. 按干基计算,含60%改性ZSM-5分子筛,含8%REY,含氧化铝32%。 Dry basis, 60% modified ZSM-5 zeolite containing 8% REY, containing 32% alumina.

实施例4取市售硅铝比为200的HZSM-5分子筛1500克,用含420克Zn(NO3)2的溶液1000ml和用含150克混合氯化稀土(其中含氧化镧21%、氧化铈11%)的溶液200ml进行交换。 EXAMPLE 4 Commercially available silica to alumina ratio of the zeolite HZSM-5 200 1500g 1000ml 420 g of a solution containing Zn (NO3) 2 and containing 150 grams of rare earth chloride mixture (wherein the lanthanum oxide containing 21% cerium oxide 11%) was exchanged 200ml. 即在40℃下,快速搅拌交换2小时,然后过滤浆液,110℃下干燥2小时,经焙烧、粉碎后,再用含63.9克(NH4)2HPO4的溶液1000ML再交换2小时。 I.e., at 40 ℃, exchange with rapid stirring for 2 hours and then the slurry was filtered, dried for 2 hours at 110 deg.] C, calcined, pulverized, and then with 63.9 g (NH4) 1000ML 2HPO4 was again exchanged for 2 hours. 经干燥、焙烧、粉碎后得改性HZSM-5分子筛d,其中Zn含量为5.6%,稀土元素含量为1.5%(其中镧1%、铈0.5%),P含量为1%。 The dried, calcined, pulverized to obtain a modified HZSM-5 zeolite d, wherein the Zn content 5.6%, rare earth element content of 1.5% (of which 1% of lanthanum, cerium 0.5%), P content is 1%.

将476克铝溶胶溶液(pH值为3.0,含Al2O321%),加入100毫升去离子水。 The 476 g of alumina sol solution (pH value 3.0, containing Al2O321%), was added to 100 ml of deionized water. 把600克改性ZSM-5分子筛d,80克REY型分子筛和220克拟薄水铝石混合均匀,球磨到400~1000目,取少量加入滚球釜中,开动滚球机,间歇地喷入铝溶胶溶液。 The 600 g modified ZSM-5 zeolite d, 80 g of zeolite and 220 grams REY quasi boehmite mixed, milled to 400 mesh to 1000, was added a small amount bowls kettle start ball machine, intermittently spraying into alumina sol solution. 直至成型为直径为1.8~2.0毫米的小球催化剂,然后在80~120℃下干燥2~10小时,在500~600℃温度下焙烧1~6小时,得催化剂D。 Until molding having a diameter of 1.8 to 2.0 mm catalyst pellets, and then dried for 2 to 10 hours at 80 ~ 120 ℃, at a baking temperature of 500 ~ 600 ℃ 1 to 6 hours to obtain catalyst D. 按干基计算,含60%改性ZSM-5分子筛,含8%REY,含氧化铝32%。 Dry basis, 60% modified ZSM-5 zeolite containing 8% REY, containing 32% alumina.

实施例5取市售硅铝比为500的HZSM-5分子筛1500克,用含420克Zn(NO3O2的溶液1000ml和用含100克硝酸铈(其中铈13.38%)的溶液200ml进行交换。即在40℃下,快速搅拌交换2小时,然后过滤浆液,110℃下干燥2小时,经焙烧、粉碎后,再用含63.9克(NH4)2HPO4的溶液1000ML再交换2小时。经干燥、焙烧、粉碎后得改性HZSM-5分子筛e,其中Zn含量为5.6%,稀土元素铈含量为0.78%,P含量为1%。 Example 5 To a commercially available silica to alumina ratio of zeolite HZSM-5 500, 1500 g, containing 420 g Zn (1000ml solution and with a solution containing 100 g of cerium nitrate 200ml (wherein cerium 13.38%) of NO3O2 be exchanged. I.e. at 40 ℃, exchange with rapid stirring for 2 hours and then the slurry was filtered, dried for 2 hours at 110 deg.] C, calcined, pulverized, and then with 63.9 g (NH4) 1000ML 2HPO4 was again exchanged for 2 hours. the dried, calcined, pulverized after the modified HZSM-5 zeolite have e, where the Zn content 5.6%, rare earth element cerium content 0.78%, P content is 1%.

将476克铝溶胶溶液(pH值为3.0,含Al2O321%),加入100毫升去离子水。 The 476 g of alumina sol solution (pH value 3.0, containing Al2O321%), was added to 100 ml of deionized water. 把600克改性ZSM-5分子筛e,80克REY型分子筛和220克拟薄水铝石混合均匀,球磨到400~1000目,取少量加入滚球釜中,开动滚球机,间歇地喷入铝溶胶溶液。 The 600 g modified ZSM-5 zeolite e, 80 g of zeolite and 220 grams REY quasi boehmite mixed, milled to 400 mesh to 1000, was added a small amount bowls kettle start ball machine, intermittently spraying into alumina sol solution. 直至成型为直径为1.8~2.0毫米的小球催化剂,然后在80~120℃下干燥2~10小时,在500~600℃温度下焙烧1~6小时,得催化剂E。 Until molding having a diameter of 1.8 to 2.0 mm catalyst pellets, and then dried for 2 to 10 hours at 80 ~ 120 ℃, at a baking temperature of 500 ~ 600 ℃ 1 to 6 hours, to obtain a catalyst E. 按干基计算,含60%改性ZSM-5分子筛,含8%REY,含氧化铝32%。 Dry basis, 60% modified ZSM-5 zeolite containing 8% REY, containing 32% alumina.

实施例6按照实施例二的方法制备催化剂,只是将铝溶胶溶液调整为381克(pH值为3.0,含Al2O321%),加入去离子水调整为150毫升。 Example 6 A catalyst was prepared according to Example II, except that the alumina sol solution was adjusted to 381 g (pH value 3.0, containing Al2O321%), deionized water was added was adjusted to 150 ml. REY型分子筛调整为10克和拟薄水铝石为320克,制得催化剂F。 REY zeolite was adjusted to 10 g and pseudo-boehmite to 320 g, to obtain Catalyst F. 按干基计算,含60%改性ZSM-5分子筛b,含1%REY,含氧化铝39%。 On a dry basis, 60% modified ZSM-5 zeolite B, containing 1% REY, containing 39% alumina.

实施例7按照实施例二的方法制备催化剂,只是将改性ZSM-5分子筛b的含量调整为650克,铝溶胶溶液调整为571克(pH值为3.0,含Al2O321%),加入去离子水调整为150毫升。 Example 7 A catalyst was prepared according to Example II, except that the content of the modified ZSM-5 zeolite b is adjusted to 650 g, alumina sol solution was adjusted to 571 g (pH value 3.0, containing Al2O321%), deionized water adjusted to 150 ml. REY型分子筛调整为50克和拟薄水铝石为257克,制得催化剂G。 REY zeolite was adjusted to 50 g and pseudo-boehmite to 257 g, to obtain Catalyst G. 按干基计算,含65%改性ZSM-5分子筛b,含5%REY,含氧化铝30%。 On a dry basis, 65% B modified ZSM-5 zeolite containing 5% REY, containing 30% alumina.

实施例8按照实施例二的方法制备催化剂,只是将改性ZSM-5分子筛b的含量调整为690克,铝溶胶溶液调整为571克(pH值为3.0,含Al2O321%),加入去离子水调整为150毫升。 Example 8 A catalyst was prepared according to Example II, except that the content of the modified ZSM-5 zeolite b is adjusted to 690 g, alumina sol solution was adjusted to 571 g (pH value 3.0, containing Al2O321%), deionized water adjusted to 150 ml. REY型分子筛调整为10克和拟薄水铝石为257克,制得催化剂H。 REY zeolite was adjusted to 10 g and pseudo-boehmite to 257 g, to obtain Catalyst H. 按干基计算,含69%改性ZSM-5分子筛b,含1%REY,含氧化铝30%。 On a dry basis, containing 69% of modified ZSM-5 zeolite B, containing 1% REY, containing 30% alumina.

实施例9按照实施例二的方法制备催化剂,只是将改性ZSM-5分子筛b的含量调整为700克,铝溶胶溶液调整为619克(pH值为3.0,含Al2O321%),加入去离子水调整为150毫升。 Example 9 A catalyst was prepared according to Example II, except that the content of the modified ZSM-5 zeolite b is adjusted to 700 g, alumina sol solution was adjusted to 619 g (pH value 3.0, containing Al2O321%), deionized water adjusted to 150 ml. REY型分子筛调整为100克和拟薄水铝石为100克,制得催化剂I。 REY zeolite adjusted 100 g boehmite and pseudoboehmite 100 g, to obtain Catalyst I. 按干基计算,含70%改性ZSM-5分子筛b,含10%REY,含氧化铝20%。 On a dry basis, containing 70% of modified ZSM-5 zeolite B, containing 10% REY, containing 20% ​​alumina.

实施例10按照实施例二的方法制备催化剂,只是将改性ZSM-5分子筛b的含量调整为750克,铝溶胶溶液调整为476克(pH值为3.0,含Al2O321%),加入去离子水调整为150毫升。 Example 10 A catalyst was prepared according to Example II, except that the content of the modified ZSM-5 zeolite b is adjusted to 750 g, alumina sol solution was adjusted to 476 g (pH value 3.0, containing Al2O321%), deionized water adjusted to 150 ml. REY型分子筛调整为30克和拟薄水铝石为171克,制得催化剂J。 REY molecular sieve 30 g and adjusted quasi boehmite is 171 g, to prepare a catalyst J. 按干基计算,含75%改性ZSM-5分子筛b,含3%REY,含氧化铝22%。 On a dry basis, containing 75% of modified ZSM-5 zeolite B, containing 3% REY, containing 22% alumina.

实施例11按照实施例二的方法制备催化剂,只是将改性ZSM-5分子筛b的含量调整为800克,铝溶胶溶液调整为714克(pH值为3.0,含Al2O321%),加入去离子水调整为170毫升。 Example 11 A catalyst was prepared according to Example II, except that the content of the modified ZSM-5 zeolite b is adjusted to 800 g, alumina sol solution was adjusted to 714 g (pH value 3.0, containing Al2O321%), deionized water adjusted to 170 ml. REY型分子筛调整为50克,制得催化剂K。 REY zeolite was adjusted to 50 g, to obtain Catalyst K. 按干基计算,含80%改性ZSM-5分子筛b,含5%REY,含氧化铝15%。 On a dry basis, containing 80% of modified ZSM-5 zeolite B, containing 5% REY, containing 15% alumina.

实施例12在移动床反应器上,以胜利原油的石脑油为原料,以制得的催化剂B为催化剂,非临氢状态下,在反应压力0.1Mpa(表压),空速为1.0h-1,考察催化剂在不同反应温度下的芳构化性能,结果见表1和表2。 Example 12 in the moving bed reactor to naphtha feedstock of Shengli crude oil, the catalyst B is a catalyst prepared, the non-presence of hydrogen state, at a reaction pressure 0.1Mpa (gauge pressure), a space velocity of 1.0h aromatization performance -1 investigated catalyst at different reaction temperatures, the results in table 1 and table 2.

表1催化剂在不同反应温度时的芳构化反应性能 Table 1 aromatization reaction performance of the catalyst at different reaction temperatures

表2裂化气组成,% Table 2 Composition of cracked gas,%

实施例13在移动床反应器上,以胜利原油的石脑油为原料,非临氢状态下,在反应压力0.1Mpa(表压),体积空速为1.0h-1,反应温度为410℃,对实施例1,2,6~11制备的催化剂的芳构化性能进行评价,结果见表3。 Example 13 in the moving bed reactor to Shengli crude oil as the raw naphtha, the state of the non-presence of hydrogen, at a reaction pressure 0.1Mpa (gauge pressure), LHSV of 1.0h-1, the reaction temperature is 410 ℃ , Aromatization of the catalyst prepared in Example 2, 6 to 11 were evaluated, the results shown in Table 3.

表3不同分子筛含量的催化剂芳构化反应性能 Table 3 Catalyst aryl sieve content of different reactivity textured

实施例14以胜利原油的石脑油为原料,非临氢状态下,利用催化剂B分别在固定床和移动床反应器进行芳构化试验,考察两种工艺对产品性能和分布的影响,两种情况下反应压力为0.1Mpa(表压),体积空速为1.0h-1,结果见表4。 Example 14 Shengli crude oil feedstock is naphtha, non Hydrogen state, the catalyst B were aromatization tests in a fixed bed and moving bed reactors, both processes investigate the influence on product performance and distribution of two case the reaction pressure was 0.1Mpa (gauge pressure), LHSV of 1.0h-1, the results shown in table 4.

表4两种工艺对比 Table 4 Comparison of Two Process

Claims (7)

  1. 1.一种芳构化催化剂,其特征在于:该催化剂由50~90重量%分子筛,0~32重量%载体和4~20重量%粘结剂组成,其中分子筛为改性HZSM-5分子筛和Y型分子筛,改性HZSM-5分子筛所用改性元素是锌、磷和稀土金属,改性元素在ZSM-5中的重量百分含量为0.01~20.0%,Y型分子筛是经稀土金属离子交换后得到的稀土含量为0.01~25.0%的REY分子筛,或者是经各种化学和/或物理方法处理后得到的高硅Y型分子筛,占催化剂总重量的0.1~20%。 An aromatization catalyst, wherein: the catalyst consists of 50 to 90 wt% molecular sieve, 0 to 32 wt% carrier, and 4 to 20 wt% binder composition, wherein the modified molecular sieve is HZSM-5 zeolite and Y-type zeolite, modified HZSM-5 zeolite modified with element zinc is used, the weight percentage of phosphorus and rare earth, elements modified ZSM-5 is from 0.01 ~ 20.0%, Y zeolite is ion exchanged by rare earth metal after the obtained rare earth content of 0.01 to 25.0% of REY zeolite, high silica Y or zeolite by various chemical and / or physical methods to give after treatment, 0.1 to 20% of the total weight of the catalyst.
  2. 2.根据权利要求1所述的催化剂,其特征在于:所述Y型分子筛占催化剂总重量的0.5~15%,载体占催化剂总重量的5~20%,粘结剂占催化剂总重量的5~15%。 The catalyst according to claim 1, wherein: said Y zeolite comprises about 0.5 to 15% by total weight of the catalyst carrier comprises 5 to 20% by weight of the total catalyst, of the total weight of the binder comprises 5 catalyst to 15%.
  3. 3.根据权利要求1所述的催化剂,其特征在于:改性HZSM-5分子筛中改性元素在ZSM-5中的重量百分含量为0.1~10.0%。 3. The catalyst according to claim 1, wherein: the weight percentage content of the modified HZSM-5 zeolite of ZSM-5 in the modifier element in the range 0.1 to 10.0%.
  4. 4.根据权利要求1所述的催化剂,其特征在于:所述的稀土金属是镧或铈或含有镧和/或铈的混合稀土金属。 4. A catalyst according to claim 1, wherein: said rare earth metal is lanthanum or cerium or mischmetal containing lanthanum and / or cerium.
  5. 5.权利要求1所述芳构化催化剂的制备方法,其特征在于:该方法是将分子筛和载体粉碎后充分混合,球磨到400~1000目后加入到滚动成型釜中,将粘结剂与水按1∶5~1∶10的比例稀释,间歇地喷入分子筛和载体的混合物中,连续滚动成型,直至成型为直径为1.4~2.0毫米的小球,然后在80~120℃下干燥2~10小时,在500~600℃温度下焙烧1~6小时,得芳构化催化剂。 Aromatization method for preparing the catalyst according to claim 1, characterized in that: the method the molecular sieve is mixed well and pulverized carrier, milled to 400 mesh was added to 1000 to scroll autoclave molding, a binder and diluted with water in proportion 1/5 to 1:10, the mixture was intermittently sprayed into a molecular sieve and a carrier, forming a continuous rolling until molding having a diameter of 1.4 to 2.0 mm pellet, and then at 80 ~ 120 ℃ dried to 10 hours, and calcined for 1-6 hours at a temperature of 500 ~ 600 ℃, have aromatization catalyst.
  6. 6.权利要求1所述芳构化催化剂在改质劣质汽油生产高辛烷值汽油组分或者芳烃中的应用,其特征在于:在非临氢状态下进行移动床芳构化反应的条件是,反应温度为350~550℃,反应压力为0.1~0.5Mpa,空速为0.5~5h-1,催化剂再生时的再生温度为400~550℃,在再生器中的停留时间为1~600分钟,采用空气再生。 1 aromatization catalyst component of claim 1 or aromatics in the gasoline in a modified application produce high octane gasoline of poor quality, which is characterized in that: the moving bed conditional aromatization reaction in the presence of hydrogen under non-state the reaction temperature is 350 ~ 550 ℃, the reaction pressure is 0.1 ~ 0.5Mpa, a space velocity of 0.5 ~ 5h-1, regenerated catalyst regeneration temperature is 400 ~ 550 ℃, the residence time in the regenerator is from 1 to 600 minutes using air fresheners.
  7. 7.根据权利要求6所述芳构化催化剂的应用,其特征在于:当芳构化催化剂用于生产高辛烷值汽油组分时,反应温度为350~450℃;用于生产芳烃时,反应温度为460~550℃。 7. Application of the aromatization catalyst 6 according to claim, wherein: when the aromatization catalyst for producing a high octane gasoline component, the reaction temperature is 350 ~ 450 ℃; for the production of aromatic hydrocarbons, The reaction temperature is 460 ~ 550 ℃.
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CN101314731B (en) 2007-05-31 2012-01-25 中国石油化工股份有限公司 Aromatization method without hydrogen for light hydrocarbon
CN101733140B (en) 2008-11-18 2012-01-11 中国石油天然气股份有限公司 Preparation method of shape-selective molecular sieve combination
CN101440302B (en) 2008-12-22 2013-02-13 洛阳瑞泽石化工程有限公司 Method for lowering benzene content in gasoline and catalyst thereof
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CN102218341B (en) * 2010-04-13 2013-01-02 中国石油化工集团公司 Aromatization catalyst and applications thereof
CN103357430B (en) * 2012-03-30 2015-08-19 中国科学院大连化学物理研究所 One kind of co-crystallized with an aromatization molecular sieve catalyst preparation method and application
CN103657708A (en) * 2012-09-07 2014-03-26 中国石油天然气集团公司 Catalyst for aromatization and quality modification of catalytic gasoline
CN103394366B (en) * 2013-08-09 2015-01-21 清华大学 Catalyst for converting alcohol ether and C3-8 alkane into aromatic hydrocarbon, and preparation and application method thereof
CN103816936B (en) * 2014-02-27 2015-09-09 赵连堂 A modified aluminophosphate molecular sieve and preparation method
CN105195211B (en) * 2014-06-16 2018-06-19 中国石油化工股份有限公司 And c species methanol aromatization catalyst and hydrocarbon aromatization process
CN105435839B (en) * 2015-12-07 2018-02-16 中国海洋石油总公司 Aromatics containing methanol and a catalyst preparation method of two kinds of molecular sieves

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