CN103180044B - 烃类转化催化剂组合物 - Google Patents

烃类转化催化剂组合物 Download PDF

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CN103180044B
CN103180044B CN201180051446.1A CN201180051446A CN103180044B CN 103180044 B CN103180044 B CN 103180044B CN 201180051446 A CN201180051446 A CN 201180051446A CN 103180044 B CN103180044 B CN 103180044B
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zeolite
zsm
composition
raw material
coversion catalysts
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CN103180044A (zh
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L·多莫科斯
L·G·雨夫
H·琼金德
A·H·克拉金加
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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    • B01J29/7446—EUO-type, e.g. EU-1, TPZ-3 or ZSM-50
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    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
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Abstract

烃类转化催化剂组合物，其包含ZSM-48和/或EU-2沸石颗粒和基本不含氧化铝的耐高温氧化物粘合剂，其中所述ZSM-48和/或EU-2沸石颗粒的平均铝浓度是所述颗粒表面的铝浓度的至少1.3倍，制备这类催化剂组合物的方法，和在这类组合物的帮助下转化烃类原料的方法。

Description

烃类转化催化剂组合物
本发明涉及包含ZSM-48和/或EU-2沸石的烃类转化催化剂组合物，这类催化剂组合物的制备方法，和在这类组合物帮助下转化烃类原料的方法。
从US-A-4,741,891和US-A-5,075,269已知ZSM-48和/或EU-2沸石特别适合用于烃类转化催化剂中。如2000年出版的CatalogofDisorderinZeoliteFrameworks所述，ZSM-48和EU-2沸石二者都属于ZSM-48沸石家族。
现在已经意外发现，特定种类的ZSM-48和/或EU-2沸石赋予催化剂改善的烃类转化性能。这些催化剂组合物还可以利用常规的ZSM-48和/或EU-2沸石作为起始材料，以简单有效的方式制备。这类沸石可以包含杂质和/或具有比较高的二氧化硅与氧化铝摩尔比。这使得它不需要使用如WO-A-2005/092792中所述的纯沸石或者如WO-A-2007/070521所述的具有降低的二氧化硅与氧化铝的摩尔比的沸石。
本发明涉及烃类转化催化剂组合物，其包含ZSM-48和/或EU-2沸石和基本上不含氧化铝的耐高温氧化物粘合剂，其中所述ZSM-48和/或EU-2沸石颗粒的平均铝浓度是所述颗粒表面的铝浓度的至少1.3倍。
2010年10月25日提交的欧洲申请10306165.1描述了ZSM-48和/或EU-2沸石的通用脱铝。
用于本发明的ZSM-48和/或EU-2可以通过从所述沸石颗粒的表面选择性除去铝的脱铝来制备。
对于所述铝浓度，铝本身和含铝化合物例如氧化铝均被计入。
脱铝方法可以在沸石本身上或沸石与粘合剂的混合物上进行。平均铝浓度是表面铝浓度的至少1.1倍，优选是表面铝浓度的至少1.2、更特别是至少1.3、更特别是至少1.4、更特别是至少1.5、更特别是至少1.6、更特别是至少1.7、更特别是至少1.8、最优选至少2倍。
平均铝浓度可以通过许多化学分析技术的任一种来测定。这类技术包括X-射线荧光、原子吸附和电感耦合等离子体-原子发射光谱法(ICP-AES)。对于本发明，平均铝浓度通过X-射线荧光测定。
表面的铝浓度可以通过本领域技术人员已知的任何方法测定，例如通过次级离子质谱法(SIMS)或通过X-射线光电子光谱法(XPS)。本发明使用XPS。
制备本发明所用的沸石的脱铝方法是本领域公知的。本发明优选的脱铝方法选自用不能进入沸石孔隙的酸例如大体积的有机酸处理沸石颗粒和用含氟盐处理沸石颗粒。
优选地，用于脱铝的酸是包含至少2个碳原子、更优选2至6个碳原子的有机酸。最优选地，所述有机酸包含2个羧基。最优选地，所述有机酸是草酸。优选在10至100℃温度下进行1至10小时时间的接触。所述有机酸优选是含有0.01至1摩尔有机酸/升的水溶液。沸石优选用这样的有机酸以沸石与有机酸溶液2∶1至1∶30的重量比进行处理。
最优选地，通过用沸石与含氟盐溶液接触的方法进行脱铝，所述含氟盐例如氟化铵，更特别是选自氟硅酸盐和氟钛酸盐的化合物。这些方法在US-A-4,753,910中有更详细的描述。最优选地，脱铝方法包括将沸石与氟硅酸盐溶液接触，其中所述氟硅酸盐由下式表示：
(A)2/bSiF6
其中′A′是除H+以外的′b′价金属或非金属阳离子。′b′价阳离子的例子是烷基铵、NH4+、Mg++、Li+、Na+、K+、Ba++、Cd++、Cu+、Ca++、Cs+、Fe++、Co++、Pb++、Mn++、Rb+、Ag+、Sr++、Tl+和Zn++。优选地，′A′是铵阳离子。
包含氟硅酸盐的溶液优选是水溶液。所述盐的浓度优选是至少0.005摩尔氟硅酸盐/1，更优选至少0.007、最优选至少0.01摩尔氟硅酸盐/1。所述浓度优选最大0.5摩尔氟硅酸盐/1，更优选最大0.3、最优选最大0.1氟硅酸盐/1。优选地，氟硅酸盐溶液与沸石的重量比是氟硅酸盐溶液比沸石为50∶1至1∶4。如果沸石与粘合剂一起存在，粘合剂不计入这些重量比。
含氟硅酸盐的水溶液的pH优选在2和8之间，更优选3和7之间。
沸石材料优选与所述氟硅酸盐溶液接触0.5至20小时，更特别是1至10小时。温度优选从10至120℃，更特别是从20至100℃。氟硅酸盐的量优选是至少0.002摩尔氟硅酸盐/100克ZSM-48和EU-2沸石总量，更特别是至少0.003、更特别是至少0.004、更特别是至少0.005摩尔氟硅酸盐/100克ZSM-48和EU-2沸石总量。所述量优选是最多0.5摩尔氟硅酸盐/100克ZSM-48和EU-2沸石总量，更优选最多0.3、更优选最多0.1摩尔氟硅酸盐/100克ZSM-48和EU-2沸石总量。如果沸石与粘合剂一起存在，粘合剂不计入这些重量比。
ZSM-48和EU-2沸石可以作为沸石粉末被脱铝。然而，优选ZSM-48和/或EU-2沸石在与耐高温氧化物粘合剂的混合物中、更特别是作为挤出物的一部分被脱铝。这使得所述沸石可以更容易被操作，同时粘合剂的存在不会引起任何不利的副作用。
在本发明中，对ZSM-48和EU-2沸石的指称是用来表明可以使用属于无序结构的ZSM-48家族的所有沸石，所述无序结构的ZSM-48家族还被称为*MRE家族，并描述在2000年以国际沸石协会结构委员会(StructureCommissionoftheInternationalzeoliteAssocation)名义出版的“theCatalogofDisorderinZeoliteFrameworks”中。即使EU-2被认为与ZSM-48不同，但ZSM-48和EU-2均可被用于本发明。沸石ZBM-30和EU-11非常类似ZSM-48，并且也被认为是结构属于ZSM-48家族的沸石的成员。在本申请中，对ZSM-48沸石的任何指称也是对ZBM-30和EU-11沸石的指称。
除了ZSM-48和/或EU-2沸石以外，所述催化剂组合物中还可以存在其它沸石，特别是如果期望改变它的催化性质的话。已经发现，存在沸石ZSM-12可以是有利的，这种沸石已经定义在2007/2008年以国际沸石协会结构委员会的名义出版的“DatabaseofZeoliteStructures”中。
ZSM-48和/或EU-2沸石的二氧化硅与氧化铝摩尔比可能影响来源于它的催化剂的性质。二氧化硅与氧化铝摩尔比(“SAR”)通过体积比确定。这种比率也被称为总比(overallratio)。这种比率与结晶骨架的SAR不同。所述体积比或总比可以通过许多化学分析技术的任何一种来测定。这类技术包括X-射线荧光、原子吸附和电感耦合等离子体-原子发射光谱法(ICP-AES)。它们都将提供基本上相同的体积比的值。用于本发明的二氧化硅与氧化铝摩尔比通过X-射线荧光测定。
所述ZSM-48和/或EU-2沸石的SAR优选至少50，更特别是至少70，更特别是至少100，最优选至少150。所述ZSM-48和/或EU-2沸石的SAR优选最多300，更特别是最多250，更特别是最多230，最特别是最多210。
所述ZSM-48和/或EU-2沸石可以用本领域技术人员已知的任何方式来制备。US-A-5,075,269和US-A-4741891描述了适用于SAR从100到250的沸石的制造方法。
当粘合剂和沸石的含量用在本发明的情况中时，所述含量是指干基含量。本发明的催化剂组合物优选包含最多70重量％(wt％)的沸石，更特别是最多65wt％，更特别是最多60wt％，优选最多58wt％，最优选最多55wt％。这些量优选适用于所述ZSM-48和/或EU-2沸石。此外，优选ZSM-48和/或EU-2沸石的量是至少15wt％，更特别是至少20wt％，更特别是至少25wt％，最特别是至少30wt％。如果除ZSM-48和/或EU-2沸石以外还存在其它沸石，基于ZSM-48和EU-2沸石的存在量，这类沸石的存在量优选最多50wt％。
基本不含氧化铝的耐高温氧化物粘合剂材料的例子是二氧化硅、氧化锆、二氧化钛、二氧化锗、氧化硼、和这些的两种或更多种的混合物如，举例来说，二氧化硅-氧化锆和二氧化硅-二氧化钛。所述粘合剂优选具有低酸度，因为低酸度耐高温氧化物粘合剂，优选二氧化钛、氧化锆和/或二氧化硅，倾向于不与所述沸石相互作用。因此，沸石可以与低酸度耐高温氧化物结合，而不会影响沸石的固有活性，像用酸性粘合剂例如氧化铝可能发生的那样。优选的低酸度耐高温氧化物粘合剂是二氧化硅和/或二氧化钛。虽然不希望存在大量氧化铝，但是存在一定量氧化铝不会立即产生不利影响。在本说明书中，基本不含氧化铝的表述表明存在最多有限量的氧化铝。基于粘合剂本身，粘合剂中存在的氧化铝的量按干重计优选为最多2wt％，更特别是最多1.1wt％，更特别是最多0.8wt％，更特别是最多0.5wt％，更特别是最多0.3wt％，最特别是最多0.2wt％。
本发明的催化剂组合物优选通过制备包含粘合剂和ZSM-48和/或EU-2沸石的可挤出料团而制造。这种可挤出的料团应该具有充分的粘度以便挤出成形。本领域的技术人员将知道如何获得这种糊状物样混合物。优选所述可挤出的料团的含水量不超过60％，并优选至少35重量％。
如果粘合剂是二氧化硅，优选在所述组合物的制备中使用二氧化硅溶胶和二氧化硅粉末二者作为二氧化硅来源。二氧化硅溶胶可以是酸性或碱性的。
为了得到强催化剂组合物，优选将所用的二氧化硅溶胶的量相对于所用的二氧化硅粉末的量最大化，同时仍然得到充分粘度的所述可挤出料团。所用的二氧化硅粉末的最佳量将取决于沸石含量，其中在催化剂的沸石含量低的情况下，将不得不使用更多的二氧化硅粉末。鉴于上述教导，本领域技术人员可以容易地确定最佳组成。所述二氧化硅粉末可以是商业获得的二氧化硅粉末，例如Sipernat22或50(得自DegussaAG)、PPGIndustries的NasilcoUltrasilVN3SP或HiSil233EP。所述固体二氧化硅粉末颗粒优选平均直径在10μm和200μm之间。
任选地，优选在实际行挤出之前不久向所述可挤出料团添加增塑剂。增塑剂用来增加所述混合物的粘度，以便得到可挤出的料团。合适的增塑剂是例如右旋糖、明胶、葡萄糖、胶、树胶、盐、蜡、淀粉和纤维素醚。在本发明的实践中，甲基纤维素和/或甲基纤维素衍生物特别适合作为有机粘合剂，优选甲基纤维素、羟丙基甲基纤维素、或它们的组合。优选的纤维素醚来源是DowChemicalCo.的MethocelA4M、F4M、F240和K75M。
挤出可以通过任何公知的挤出法执行。这类方法的例子是通过螺杆挤出机、板式挤出机或柱塞式挤出机执行的挤出。挤出物可以具有广泛的各种形状和尺寸。
挤出之后，获得的挤出物优选在它们进行脱铝之前进行干燥和煅烧。干燥优选在60℃至250℃的温度下进行足够的时间例如至少1小时以干燥所述挤出物。煅烧优选在250℃至850℃的温度下在空气或其他惰性气体中进行例如1至48小时或更长的时间段。
这样得到的挤出物可以如上所述进行脱铝。脱铝之后，脱铝的挤出物和粘合剂优选在50至300℃、更特别是80至200℃的温度下干燥0.5至10小时的时间，然后在200至650℃、更特别是350至600℃的温度下煅烧0.2至5小时的时间。
对于大多数烃类转化应用而言，所述催化剂组合物中将掺入一种或多种催化金属以使其合适作为催化剂。可以用本领域技术人员已知的任何方式例如离子交换来掺入这些催化金属。典型的离子交换技术包括将催化剂组合物与预定替代离子的盐接触。这可以通过例如孔隙体积浸渍(porevolumeimpregnation)或连续溶液浸渍来进行。代表性的离子交换技术公开在许许多专利说明书，包括US-A-3140249、US-A-3140251和US-A-3140253中。优选地，所述催化金属通过孔隙体积浸渍而掺入。
优选地，所述催化金属选自如1983年第63版“HandbookofChemistryandPhysics”中所示的元素周期表的IIA、IIB和VIII族金属，更特别是铂、钯、钴、钼、铁、钨和镍。最优选地，所述一种或多种催化金属选自铂、钯和镍。
在与预定替代离子的溶液接触之后，然后优选用水洗涤催化剂组合物，并如上所述干燥和煅烧。
通过本发明的方法制备的催化剂可以在多种烃类转化方法例如加氢裂化、异构化、加氢、脱氢、聚合、重整、催化加氢裂化、甲苯岐化和乙苯转化中发挥效用。本发明的组合物可以在添加或者不添加活性金属组分下使用。通过本发明方法制备的催化剂可以有利地在公知的催化脱蜡条件下或在烷基芳族化合物异构化中用作脱蜡催化剂，用于制备二甲苯含量、更特别是对二甲苯含量增加的产物。所述催化剂还可以用作包括加氢处理然后加氢裂化的加氢裂化方法的部分，其中润滑油基础油被脱蜡。
所述催化剂尤其适合用于增加含有具有8个碳原子的芳烃的烃类馏分的二甲苯含量，更特别是对二甲苯含量。所述烃流优选含有最多60wt％的乙苯，更特别是最多50wt％。优选地，所述烃流包含至少5wt％，更特别是至少8wt％，优选至少10wt％，最优选至少15wt％的乙苯。所述烃流优选在300至450℃范围内、优选至少350℃并优选最高400℃的温度下，与所述催化剂接触。
最优选地，本发明的催化剂用于脱蜡。催化脱蜡通过选择性加氢异构化/加氢裂化正构链烷烃和轻度分支链烷烃，用来改善柴油燃料和润滑油的冷流性。所述脱蜡方法将所述原料的倾点降低了至少10℃，更优选至少20℃。当前的催化剂可以与高压加氢裂化或缓和加氢裂化催化剂包组合，在第一和第二级应用中用于常规柴油燃料脱蜡至深度脱蜡(产生Artie等级)，用于降低缓和加氢裂化器底部馏分的倾点以便储存和运输和/或制造质量优异的润滑油。
用于本发明方法的合适的烃油原料是高沸点烃的混合物，例如重油馏分。已经发现，特别适合使用从常压渣油得到的减压馏出物馏分，即将原油常压蒸馏得到的残余馏分进行减压蒸馏而得到的馏出馏分，作为原料。这类减压馏出物馏分的沸腾范围通常在300和620℃之间，适合在350和580℃之间。然而，脱沥青的渣油馏分，包括脱沥青的常压渣油和脱沥青的减压渣油，也可以适用。如果所述减压馏出物馏分包含大量的含硫和氮的污染物，例如，具有高达3重量％的硫水平和高达1重量％的氮水平，将该原料在本发明的催化脱蜡过程之前进行加氢脱硫和加氢脱氮步骤处理，可能是有利的。
脱蜡通常包括在最高450℃、更特别是250至400℃、优选275至350℃的温度下和5～200x105Pa、更特别是15～170x105Pa、优选25～150x105Pa的总压力下，将原料与本发明的催化剂接触。液时空速优选在0.1至10hT-1的范围内。
待进行脱蜡的原料优选是汽油或润滑油基础油料。所述原料优选是润滑油基础油料。所述原料优选是在润滑油范围内沸腾的含蜡原料，通过ASTMD-2887测量，其10％馏出点通常在200℃或更高。具有比较大量蜡状化合物的原料的例子是合成蜡状萃余液(Fischer-Tropsch蜡状萃余液)，加氢裂化器底部馏分(蜡油)，即终馏点至少320℃、优选至少360℃的那些馏分，和从加氢处理或溶剂精制的含蜡馏分脱蜡得到的散腊。这些原料的蜡含量为至少50重量％，优选至少80重量％并更优选至少90重量％。蜡是在环境温度下是塑性的并在超过45℃时熔化产生低粘度液体的化合物。蜡的量可以通过ASTM方法D3235测定。
本发明的方法可用于制备粘度指数(VI)超过120并特别是超过135的润滑基础油。
此外，所述原料在进行脱蜡之前可以已经加氢处理和/或加氢裂化过。
加氢处理通常包括在最高500℃、更特别是250至500℃的温度下和10～200x105Pa、更特别是30～130x105Pa的氢分压下，将原料与加氢处理催化剂接触。
加氢裂化通常包括在(反应器入口处)的氢分压在3x106至2.9x107Pa、更优选8x106至1.75x107Pa和氢气与原料的比率(总气体速率)在100至5000Nl/kg、但是优选200至3000Nl/kg之下，将原料与加氢裂化催化剂接触。

Claims (6)

1.烃类转化催化剂组合物，其包含ZSM-48和/或EU-2沸石颗粒和基于干重计含有至多2wt％的氧化铝的耐高温氧化物粘合剂，其中所述ZSM-48和/或EU-2沸石颗粒的平均铝浓度是所述颗粒表面的铝浓度的至少2倍，并且其中所述ZSM-48和/或EU-2沸石具有的二氧化硅与氧化铝的摩尔比为至少150并且最大210，其中根据总的最终催化剂组合物计算，所述沸石含量以干基计是20至60wt％，并且其中所述耐高温氧化物粘合剂选自二氧化硅和/或二氧化钛。
2.权利要求1的烃类转化催化剂组合物，其中根据总的最终催化剂组合物计算，所述沸石含量以干基计是30至55wt％。
3.用于制备权利要求1或2所述的烃类转化催化剂组合物的方法，所述方法包括将所述ZSM-48和/或EU-2沸石与含氟盐的溶液接触。
4.用于制备含催化金属的烃类转化催化剂的方法，所述方法包括根据权利要求3制备烃类转化催化剂组合物，并在所述催化剂组合物中掺入一种或多种催化金属。
5.用于转化烃类原料的方法，所述方法包括在100至600℃的温度和1至100巴的绝对压力下，将所述原料与权利要求1或2所述的催化剂组合物接触。
6.权利要求5的方法，在所述方法中，通过ASTMD86测量，所述原料的10％馏出点大于343℃。
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