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CN110062653A - 用于脱蜡的催化剂系统 - Google Patents

用于脱蜡的催化剂系统 Download PDF

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Publication number
CN110062653A
CN110062653A CN201780076490.5A CN201780076490A CN110062653A CN 110062653 A CN110062653 A CN 110062653A CN 201780076490 A CN201780076490 A CN 201780076490A CN 110062653 A CN110062653 A CN 110062653A
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CN
China
Prior art keywords
catalyst
zsm
weight
zeolite
dewaxing
Prior art date
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Pending
Application number
CN201780076490.5A
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English (en)
Inventor
H·琼凯恩德
M·S·里古托
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Shell Internationale Research Maatschappij BV
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Shell Internationale Research Maatschappij BV
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Publication of CN110062653A publication Critical patent/CN110062653A/zh
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7034—MTW-type, e.g. ZSM-12, NU-13, TPZ-12 or Theta-3
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    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
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    • B01J29/703—MRE-type, e.g. ZSM-48
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Abstract

一种用于使烃原料脱蜡的催化剂系统，其包含至少两个催化部分，第一部分包含第一脱蜡催化剂，并且后续部分包含第二脱蜡催化剂，其中所述第一脱蜡催化剂为基于ZSM‑12沸石的催化剂，并且所述第二脱蜡催化剂为基于EU‑2和/或ZSM‑48沸石的催化剂。与仅含有基于ZSM‑12的催化剂或仅含有基于EU‑2/ZSM‑48的催化剂的系统相比时，所述催化剂系统显示出增强的性能。

Description

用于脱蜡的催化剂系统
技术领域
本发明涉及用于使烃原料脱蜡的催化剂系统，其包含基于ZSM-12沸石的催化剂和基于EU-2和/或ZSM-48沸石的催化剂，以及一种使用所述催化剂系统转化烃原料的方法。
背景技术
一直在努力提供用于使烃原料催化脱蜡的改进催化剂。这些改进可包括具有增强活性的脱蜡催化剂或在处理某些烃原料时提供改进的润滑油原料产率。已经为此目的开发了几种类型的沸石。举例来说，在WO 2012/055755 A和WO 2012/055759 A中描述了某些特定的基于ZSM-48和/或EU-2沸石的催化剂，其显示出改进的烃转化性能。如2000年公布的沸石框架中的无序目录中所述，ZSM-48和EU-2沸石两者都属于ZSM-48沸石族。因此，在本文中，提到ZSM-48的地方，也可以读取EU-2，反之亦然。另一种沸石，命名为ZSM-12的结晶沸石，描述于US 3832449 A中。ZSM-12沸石在'449专利中指出，其具有可用于石油精炼方法的催化特征，所述方法包括降低链烷烃电荷原料的倾点和正链烷烃和环烷烃的异构化的方法。
一直需要更有活性和/或选择性的催化剂用于烃原料的催化脱蜡。为了增加活性，增加催化剂的沸石含量并不罕见。然而，这伴随着催化剂材料的较高成本。
还考虑了其它解决方案。举例来说，US 4599162 A描述了用于使烃原料脱蜡的双催化剂级联方法，其中蜡质原料通过具有在2与12之间的约束指数的结晶硅酸盐沸石催化剂，并且接着通过具有不小于2的约束指数的不同结晶硅酸盐沸石催化剂。
具体地，所述专利涉及级联催化加氢脱蜡方法，其包含(a)使含有选自正链烷烃和轻支链链烷烃群组的蜡质组分的烃原料通过加氢异构化催化剂，所述加氢异构化催化剂包含具有结构ZSM-12的结晶硅酸盐沸石与具有ZSM-23结构的结晶硅酸盐沸石的混合物，所述混合物具有氢化/脱氢活性以使原料加氢异构化；和(b)使至少大部分从步骤(a)回收的正常液态烃通过脱蜡催化剂，所述脱蜡催化剂包含具有ZSM-5结构的结晶硅酸盐沸石，所述步骤(b)的沸石具有氢化/脱氢活性以使回收的烃脱蜡。
在US 4599162 A的实例中使用双催化剂操作，其中在第一反应器区域中，使用混合物中包含0.44％Pt/ZSM-12和ZSM-23的催化剂，而在第二反应器区域中，使用包含基于Ni/ZSM-5的催化剂的催化剂。然而，US 4599162 A的表2中报告的结果表明显著的气体产量(C1-C5产率范围为7.4至9.8重量％)，其对基础油是不利的。
此外，在US 7261805 B2中描述了一种用于升级含有蜡质组分并且最终沸点超过650℉(343℃)的烃原料的方法，其包括使超大气压氢分压下的原料与包括ZSM-48的异构化脱蜡催化剂接触，并且然后使脱蜡产物与加氢裂化催化剂接触以生产具有降低的蜡含量的升级产物。'805专利的方法的产物为具有约330℉(166℃)至730℉(387℃)的沸腾范围的馏出物。
尽管已经在催化剂脱蜡方面取得了所有进步，但仍需要新的开发来提高催化剂的性能，优选对某些产物范围还具有更好的基础油产率和选择性，同时仍具有经济吸引力。本发明的一个目的是解决现有技术的缺陷。
发明内容
现已发现，在增强的选择性和/或较高的催化剂活性方面的改进的催化剂性能与现有技术中推荐的相比可以以另一种方式来实现。
令人惊讶的是，现在已经发现，当与仅含有基于ZSM-12或EU-2(ZSM-48)的催化剂的催化剂系统相比时，在堆叠顶部中具有基于ZSM-12的催化剂和在堆叠底部中具有基于EU-2(ZSM-48)的催化剂的堆叠催化剂系统分别表现出增强的性能和改进的基础油产率。
因此，本发明提供了一种用于使烃原料脱蜡的催化剂系统，其包含至少两个催化部分，第一部分包含第一脱蜡催化剂，并且后续部分包含第二脱蜡催化剂，其中第一脱蜡催化剂为基于ZSM-12沸石的催化剂，并且第二脱蜡催化剂为基于EU-2和/或ZSM-48沸石的催化剂。
具体实施方式
本发明的催化剂系统特别适用于生产基础油。因此，本发明还涉及用于脱蜡的方法，其包含使烃原料与根据本发明的催化剂系统接触。
用于本发明催化剂系统的基于ZSM-12沸石的催化剂可以，例如，根据WO 2013/090534 A中对于比较催化剂组合物A所述的程序制造。
在本发明的一个优选实施例中，本文中基于ZSM-12沸石的催化剂不含任何另外的沸石。
ZSM-12沸石组分的一个重要特征是二氧化硅与氧化铝的比率足够高，以提供最终的脱蜡催化剂，所述催化剂表现高活性的所需催化特性，同时提供高产率。为此，ZSM-12沸石组分优选具有至少50:1的二氧化硅与氧化铝的比率(在本文中有时也称为“SAR”；单位为mol:mol)。这里使用的术语二氧化硅与氧化铝的比率是指沸石框架中所含的二氧化硅和氧化铝的摩尔比。优选地，SAR大于60:1，或大于70:1，或大于75:1。ZSM-12沸石组分的SAR的上限优选为至多250:1，更具体地，上限为200:1，并且更优选为小于150:1，特别是小于110:1。如果如所合成的ZSM-12沸石的SAR太低，则可以使用本领域已知的方法进一步脱铝以提供具有所需二氧化硅与氧化铝的比率的脱铝ZSM-12沸石，其可用作本发明的催化剂系统的组分。
本发明最终组合物的ZSM-12沸石含量应为组合物总干重的至少10重量％且至多70重量％。用于本发明催化剂系统的第一催化剂的最终组合物的粘合剂含量可以在组合物总干重的至少30重量％且不超过90重量％范围内。优选地，组合物的ZSM-12沸石含量为至多60重量％，更优选，至多50重量％，且更特别是至多40重量％。进一步优选地，组合物的ZSM-12沸石含量为至少15重量％，且更优选至少20重量％。
用于本发明催化剂系统的基于EU-2/ZSM-48沸石的催化剂可以，例如，根据WO2012/055755 A中描述的用于脱铝包含基本上不含氧化铝的耐火氧化物粘合剂的基于ZSM-48和/或EU-2沸石的催化剂的方法制备。EU-2和/或ZSM-48沸石的SAR优选为至少60，更优选至少70，更具体地至少80，最优选至少90。EU-2和/或ZSM-48沸石的SAR优选为至多300，更具体地至多250，更具体地至多200，最具体地至多150。
当在本发明的上下文中使用粘合剂和沸石的含量时，是指以干物质计的含量。本发明的基于EU-2/ZSM-48沸石的催化剂组合物优选包含至多70重量％(重量％)的EU-2/ZSM-48沸石，更具体地至多65重量％，更具体地至多60重量％，最优选至多55重量％。此外，优选地，沸石的量为至少15重量％，更具体地至少20重量％，更具体地至少25重量％，最具体地至少30重量％。
任选地，除EU-2/ZSM-48沸石外，基于EU-2/ZSM-48沸石的催化剂中可存在另外的沸石；如果是这种情况，以存在的EU-2/ZSM-48沸石的量计，这种沸石优选以至多50重量％的量存在。用于本发明催化剂系统的第二催化剂的最终组合物的粘合剂含量可在组合物总干重的至少30重量％且不超过85重量％范围内。
在本文中提及粘合剂时，是指耐火氧化物粘合剂。耐火氧化物粘合剂材料的实例是氧化铝、二氧化硅、氧化锆、二氧化钛、二氧化锗、氧化硼和这些中的两种或更多种的混合物，例如二氧化硅-氧化锆和二氧化硅-二氧化钛。优选的粘合剂是二氧化钛、氧化锆和/或二氧化硅。二氧化硅是用于本发明催化剂系统的基于ZSM-12沸石的催化剂和基于EU-2/ZSM-48沸石的催化剂中特别优选的粘合剂。
用于本发明催化剂系统的基于ZSM-12沸石的催化剂和基于EU-2/ZSM-48沸石的催化剂，进一步优选各自包含贵金属组分，其优选选自以下群组：由钯和铂组成的贵金属。然而，优选的贵金属是基于ZSM-12沸石的催化剂和基于EU-2/ZSM-48沸石的催化剂的铂。贵金属组分优选在其处理或脱铝后并入混合物或颗粒中。然而，贵金属组分也可在处理或脱铝之前并入混合物或颗粒中。可以使用任何已知的合适的手段或方法将贵金属组分并入混合物或颗粒中。
理想的是，用于本发明催化剂系统的基于ZSM-12沸石的催化剂和基于EU-2/ZSM-48沸石的催化剂的贵金属含量以贵金属作为元素，无论其实际形式如何，以及催化剂组合物的总干重计，在向上至约3重量％范围内。优选地，贵金属组分以0.1重量％至3重量％范围内的浓度存在于催化剂组合物中。更优选地，贵金属组分在组合物中的存在量在0.2重量％至2重量％范围内，并且最优选地，其在0.3重量％至1重量％的范围内。
基于ZSM-12和EU-2/ZSM-48的沸石催化剂材料根据本领域已知的方法进一步挤出、干燥和煅烧。
根据本发明的催化剂系统包含任何系统，其中基于ZSM-12和EU-2/ZSM-48的沸石催化剂以第一个为基于ZSM-12的催化剂随后为基于EU-2/ZSM-48的催化剂的任何后续顺序放置。在本文中，需要脱蜡的原料首先通过基于ZSM-12的催化剂，然后通过基于EU-2/ZSM-48的催化剂。催化剂可以以层状构形堆叠，其可以在同一床中提供但仍然在单独的层中，在分开的区域/部分中或在单独的床中提供，或者每种催化剂可以在多个床中提供，并且催化剂可以在相同的反应器中，在单独的反应器中或各自在多个反应器中提供，任选地通过例如过滤部分或清洁部分分开。应当理解，在所有这些构形中，将要在任何这些催化剂构形上脱蜡的加氢处理的进料首先需要通过基于ZSM-12的催化剂，然后通过基于EU-2/ZSM-48的催化剂。
在本发明的催化剂系统中，第一脱蜡催化剂与第二脱蜡催化剂的催化剂体积比优选在10:90至90:10范围内。更优选地，所述比率为20:80至90:10，甚至更优选40:60至85:15。第一脱蜡催化剂与第二脱蜡催化剂的高度优选的催化剂体积比为75:25。
使用常规方法和常规手段制备本发明的催化剂系统。可以以这样的方式装载任何类型的反应器，使得进料首先通过基于ZSM-12的催化剂，然后通过基于EU-2/ZSM-48的催化剂。当例如工业反应器以自上而下的流动操作时，催化剂系统的制备通常将包含用基于ZSM-12和EU-2/ZSM-48的催化剂以这样的方式装载反应器，使得基于EU-2/ZSM-48的催化剂位于反应器的下部(当操作自上而下流动时)并且将基于ZSM-12的催化剂装载到其上方。为了完整起见，必须提到的是，在基于EU-2/ZSM-48的催化剂下面，可以存在另外的催化剂用于例如加氢精制目的。
对于商业单位，可以使用各种装载技术，这些技术通常由专业公司(如荷兰公司“Mourik”)执行。
本发明的催化剂系统非常适用于使烃原料脱蜡。所述系统可以作为任何常规系列中的脱蜡部分(包含用于使烃原料脱蜡的部分)放置。
在本发明的一个优选实施例中，烃原料可以在催化剂系统的上游预处理，例如，在单独的防护件或催化剂床中，以减少或去除任何含氮和硫的化合物和/或其中存在芳香族的化合物。替代地，可以在同一反应器床中在本发明的催化剂系统的上游使用另外的催化剂，以便在与所述催化剂系统接触之前预处理原料。
催化脱蜡用于通过正和轻支链链烷烃的选择性加氢异构化/加氢裂化来改进柴油燃料和润滑油的冷流特性。在馏出物脱蜡中，脱蜡方法优选将原料的倾点降低至少10℃，更优选降低至少20℃。目前的催化剂系统可用于常规柴油燃料脱蜡至一级和二级应用中的深度脱蜡(Artic级生产)，与高压加氢裂化或温和加氢裂化催化剂包组合，在温和的加氢裂化器底部降低倾点用于储存和运输和/或生产质量优异的润滑油。本发明的催化剂系统特别适用于生产基础油。
因此，本发明进一步涉及一种用于使烃原料脱蜡的方法，其包含使烃原料与本发明的催化剂系统在升高的温度，优选200℃至450℃和5×105至200×105Pa的压力下接触。更具体地，温度为250至400℃，优选为275至375℃。总压力更具体地为15×105至170×105Pa，优选为25×105至150×105Pa。液时空速优选在0.1至10h-1范围内。
根据本发明待在脱蜡方法中使用的合适的烃油进料为高沸烃的混合物，如，例如，重油馏分。已经发现特别适合使用衍生自常压残余物的真空馏出物馏分，即通过真空蒸馏残余馏分而得到的馏出物馏分，其通过常压蒸馏原油获得，作为进料。这种真空馏出物馏分的沸腾范围通常在300与620℃之间，合适地在350与580℃之间。然而，也可以施加脱沥青残油馏分，其包括脱沥青常压残余物和脱沥青真空残余物。待进行脱蜡的原料优选是瓦斯油或润滑油基础原料。
因此，在一个实施例中，原料是含蜡进料，其通常在130与450℃之间，合适地在150与390℃之间的范围内沸腾。这些是柴油、煤油和喷气燃料的沸腾范围。
在优选的实施例中，原料是润滑油基础原料。这种原料优选是含蜡进料，其在200℃或更高，朝向600℃下在通常具有10％蒸馏点的润滑油范围内沸腾，如通过ASTM D-2887-93所测量。具有相对高量蜡质化合物的进料的实例是合成蜡质提余液(费-托(Fischer-Tropsch)蜡质提余液)、加氢裂化器底部馏分(加氢蜡)，即最终沸点为至少320℃，优选至少360℃的那些馏分和由加氢处理或溶剂精制的蜡质馏出物的脱蜡得到的疏松蜡。这些进料的蜡含量为至少50重量％，优选至少80重量％，并且更优选至少90重量％。蜡含量是在环境温度下为塑料并且在45℃以上熔化以得到低粘度液体的化合物的含量。蜡的量可通过ASTM方法D3235测定。
如果原料含有大量含硫和/或含氮污染物，例如硫含量高达3重量％，并且氮含量高达1重量％，则在使用本发明的催化系统的催化脱蜡方法之前将原料进料到加氢脱硫和加氢脱氮步骤的对象可能是有利的。
本发明的方法可用于制备粘度指数(VI)高于120，且特别是高于135的润滑基础油。
此外，原料可能在进行脱蜡之前已经过加氢处理和/或加氢裂化。加氢处理通常包括使原料与加氢处理催化剂在高达500℃，更具体地250至500℃的温度，以及10×105至200×105Pa，更具体地30×105至130×105Pa的氢分压下接触。加氢裂化通常涉及使原料与加氢裂化催化剂在氢分压(在反应器入口处)接触，所述氢分压在3×106至2.9×107Pa，更优选8×106至1.75×107Pa范围内并且氢气与原料的比率(总气体速率)在100至5000Nl/kg范围内，但优选在200至3000Nl/kg范围内。
附图说明
图1显示了与分别仅使用ZSM-12和仅使用EU-2的催化剂相比，使用基于ZSM-12和EU-2的催化剂的催化剂堆叠的性能数据。还显示了ZSM-12/EU-2催化剂混合物的性能数据。
图例：“wof％”为进料中的重量％。“C1-C4”表示含有1、2、3或4个碳原子的产物的量。“C5-150℃”表示碳数为5的产物直至沸点为150℃的产物的量。“150-370℃”表示沸点在150与370℃之间的范围内的产物的量。“>370℃”表示用ASTM D2887-93测量的沸点为370℃或更高的产物的量。“Treq.dPP 75℃”代表所需的反应器温度，以获得75℃的倾点(PP)改进。
现将通过以下非限制性实例说明本发明的方法。
实例
实例1.ZSM-12组成
通过将来自Zeolyst国际(Zeolyst International)的SAR为90的ZSM-12沸石与无定形二氧化硅、氨和水组合来制备可挤出物料。挤出物料以得到具有圆筒形状且平均直径为1.6mm的挤出物。将这些挤出物干燥并煅烧以得到白色挤出物。
挤出物在90℃的温度下用六氟硅酸铵(AHS)水性溶液未搅拌处理5小时。溶液与挤出物的重量比为5:1。随后，将挤出物与溶液分离，用去离子水洗涤，并干燥和煅烧。
此后，通过孔体积浸渍将0.7％wt./wt.铂与含有四胺硝酸铂(Pt(NH3)4(NO3)2)(3.37％wt./wt.Pt)的水性溶液在约10分钟期间并入组合物中。
浸渍的组合物未洗涤，但在轧制床上平衡1.5小时，干燥并煅烧。然后，将催化剂冷却至室温。
实例2.EU-2(ZSM-48)组成
如在US 4741891 A中所述制备SAR为110的沸石EU-2(ZSM-48)。通过将EU-2与无定形二氧化硅、氨和水组合来制备可挤出物料。挤出物料以得到具有圆筒形状且平均直径为1.6mm的挤出物。将这些挤出物干燥并煅烧以得到白色挤出物。
挤出物在90℃的温度下用六氟硅酸铵(AHS)水性溶液未搅拌处理5小时。溶液与挤出物的重量比为5:1。随后，将挤出物与溶液分离，用去离子水洗涤，并干燥和煅烧。
此后，通过孔体积浸渍将0.7％wt./wt.铂与含有四胺硝酸铂(Pt(NH3)4(NO3)2)(3.3％wt./wt.Pt)的水性溶液在约10分钟期间并入组合物中。
浸渍的组合物未洗涤，但在轧制床上平衡1.5小时，干燥并煅烧。然后，将催化剂冷却至室温。
实例3.堆叠催化剂的性能测试
实例1和2的催化剂在250℃下干燥3小时。随后，将每种催化剂与足够的惰性材料(例如SiC)混合以确保适当的活塞流动条件并装入下行流模式的单管测试反应器(比较实例)中。为了制备堆叠的实例，将与足够的惰性材料混合的催化剂彼此叠加到下行流模式的单管测试反应器中。
总共制备了4个堆叠的实例：
(a)50％“EU-2”/50％“ZSM-12”；
(b)25％“ZSM-12”/75％“EU-2”；
(c)50％“ZSM-12”/50％“EU-2”；和
(d)75％“ZSM-12”/25％“EU-2”，
其中“EU-2”是指实例2的催化剂，且“ZSM-12”是指实例1的催化剂。
因此，例如25％“ZSM-12”/75％“EU-2”是指：25％总的脱蜡催化剂体积被催化剂占据，其中ZSM-12位于堆叠顶部，以及75％总的脱蜡催化剂体积被催化剂占据，其中EU-2位于堆叠的底部。
随后，施加140巴的氢分压，并且然后以20℃/h的速率将温度从室温升至125℃，并保持2小时。以50℃/h的速度将温度进一步升高至300℃，并保持8小时以确保金属相的适当还原。将反应器冷却至200℃，并且然后引入表1的进料。在进料中断后，在4小时内将温度升至250℃，并保持过夜。
以1.2kg l-1h-1的重时空速添加表1的进料。
表1
在330℃与350℃之间的范围内的温度下评价催化剂或催化剂堆叠的性能。
[方法：在330℃与350℃之间的范围内的温度下评价催化剂(堆叠)的性能。催化剂(堆叠)的性能在倾点改进为75℃下进行评价，其是指产物具有比原料的倾点低75℃的倾点。根据ASTM D97测量这些倾点。表1的进料以1.2kg l-1h-1的重时空速添加。]
催化剂/催化剂堆叠的性能示于图1中。在此图中，表达wof％代表进料中的重量％。C1-C4代表含有1、2、3或4个碳的产物的量。C5-150℃代表碳数为5的烃产物直至沸点为150℃的产物的量。150-370℃代表沸点落在150与370℃之间的范围内的产物的量。>370℃代表用ASTM D2887-93测量的沸点为370℃或更高的产物的量。“Treq.dPP 75℃”代表所需的反应器温度，以获得75℃的倾点(PP)改进。
在表2中，结果列出了其数值。
实例4
实例1和2的催化剂，在250℃下干燥3小时。随后，制备75％的基于ZSM-12的催化剂和25％的基于EU-2(ZSM-48)的催化剂的混合物。然后将ZSM-12/EU-2(ZSM-48)催化剂混合物与0.1mm SiC惰性材料以1:1的体积/体积比混合，以确保适当的活塞流动条件并小心地装入下行流模式的单管测试反应器中。这以与实例3中类似的方式发生，其中催化剂彼此叠加。总催化剂体积为20ml。随后，施加140巴的氢气部分，并且然后以20℃/h的速率将温度从室温升至125℃，并保持2小时。以50℃/h的速度将温度进一步升高至300℃，并保持8小时以确保金属相的适当还原。将反应器冷却至200℃，并且然后引入表1的进料。在进料中断后，将温度在4小时内升至250℃，并保持过夜。
根据实例3中描述的方法评价催化剂的性能。
催化剂混合物的性能示于图1，紧邻催化剂堆叠的性能。有关图中数字和缩写的说明，请参见实例3。
在表2中，结果列出了其数值。
表2
结论
从实例3和4的性能数据可以得出结论，不仅与仅含有基于EU-2的催化剂的催化剂系统相比时，而且与两种催化剂的比例混合物相比时，在堆叠顶部具有基于ZSM-12的催化剂并且在堆叠底部具有基于EU-2的催化剂的本发明的堆叠催化剂系统表现出增强的性能和改进的基础油产率。此外，与仅含有基于ZSM-12的催化剂的催化剂系统相比，本发明的堆叠系统表现出改进的基础油产率，而与仅含有基于ZSM-12的催化剂的催化剂系统相比，其性能非常相当或甚至更好。

Claims (9)

1.一种用于使烃原料脱蜡的催化剂系统，其包含至少两个催化部分，第一部分包含第一脱蜡催化剂，并且后续部分包含第二脱蜡催化剂，其中所述第一脱蜡催化剂为基于ZSM-12沸石的催化剂，并且所述第二脱蜡催化剂为基于EU-2和/或ZSM-48沸石的催化剂。
2.根据权利要求1所述的催化剂组合物，其中所述ZSM-12沸石在所述第一脱蜡催化剂组合物中的存在量为至少10重量％且至多70重量％，并且所述第一脱蜡催化剂组合物还包含至少30重量％且不超过90重量％的量的粘合剂，其中此类重量％是以所述组合物的干重计。
3.根据权利要求1或2所述的催化剂系统，其中所述EU-2和/或ZSM-48沸石在所述第二脱蜡催化剂组合物中的存在量为至少15重量％且至多70重量％，并且所述第二脱蜡催化剂组合物还包含至少30重量％且不超过85重量％的量的粘合剂，其中此类重量％是以所述组合物的干重计。
4.根据权利要求1至3中任一项所述的催化剂系统，其中所述第一脱蜡催化剂和所述第二脱蜡催化剂各自包含贵金属组分。
5.根据权利要求1至4中任一项所述的催化剂系统，其中所述ZSM-12沸石的二氧化硅与氧化铝的摩尔比为至少50:1且至多250:1。
6.根据权利要求1至5中任一项所述的催化剂系统，其中所述EU-2和/或ZSM-48沸石的二氧化硅与氧化铝的摩尔比为至少60:1且至多300:1。
7.根据权利要求1至6中任一项所述的催化剂系统，其中所述第一脱蜡催化剂与所述第二脱蜡催化剂的所述催化剂体积比在10:90至90:10范围内。
8.一种用于使烃原料脱蜡的方法，其包含使烃原料与根据权利要求1至7中任一项所述的催化剂系统在200℃至450℃的温度和5至200×105Pa的压力下接触。
9.根据权利要求8所述的方法，在所述方法中的所述原料为含蜡进料，其在200℃或更高下在具有10％蒸馏点的润滑油范围内沸腾，如通过ASTM D-2887-93所测量。
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