CN102333744A - 烷基化催化剂和相关方法 - Google Patents
烷基化催化剂和相关方法 Download PDFInfo
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- CN102333744A CN102333744A CN2010800072226A CN201080007222A CN102333744A CN 102333744 A CN102333744 A CN 102333744A CN 2010800072226 A CN2010800072226 A CN 2010800072226A CN 201080007222 A CN201080007222 A CN 201080007222A CN 102333744 A CN102333744 A CN 102333744A
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- solid acid
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Abstract
一种固体烷基化催化剂,具有氢化金属和稀土元素交换的分子筛形式的固体酸,其中所述催化剂的至少特征在于在直径小于100nm的孔中孔隙率小于0.20ml/g,并且总孔隙率大于0.30ml/g。还描述了使用所述催化剂的烷基化方法。
Description
背景技术
如本文中所使用的,术语烷基化是指可烷基化的化合物例如饱和烃和烷基化剂例如烯烃的反应。所述反应是引入注意的,例如因为其使得通过异丁烷和含有2-6个碳原子的烯烃的烷基化,可以获得具有高的辛烷数量并且沸点在汽油范围内的烷化物。和通过分馏重质石油馏分例如真空瓦斯油和常压渣油而获得的汽油不同,通过烷基化获得的汽油基本上不含杂质例如硫和氮,并且因此具有清洁燃烧特性。由高的辛烷数量表示的其较高抗爆性能降低了下列需要:增加环境上有害的抗爆化合物,例如芳族化合物或铅。此外,和通过改造石脑油或通过分馏重质石油馏分而获得的汽油不同,烷化物含有较少芳族化合物或烯烃(如果有的话),这进一步提供环境上的优势。
和竞争性液态酸烷基化方法相比,历史上看固体酸烷基化催化剂的活性和稳定性仍然留有很多期望改进之处。固体酸烷基化的近期发展包括:使用含有沸石的固体酸性催化剂的容易再生的烷基化方法,如WO/9823560(US 5986158)中公开;根据US专利申请公开2007/0293390的改善的固体酸性催化剂制备方法;根据WO 2005/075387的烷基化催化剂水合方法;根据US 7176340、US 2002/198422和EP 1485334的连续或半连续烷基化和再生方法、以及U.S.专利申请公开2008/0183025中教导的稀土元素(RE)交换的固体酸性催化剂。
然而,吃惊地,已经发现在这种固体酸烷基化催化剂中使用稀土元素交换的分子筛(例如Y-沸石类)赋予独特的孔隙率分布,当和没有本文中所述的特殊孔隙率特性的类似催化剂相比时,可提供更高的活性和稳定性。这是特别吃惊的,因为过去(US 6855856)发现没有RE的分子筛要求完全不同的孔隙率分布。
发明内容
因此,在本发明的一个实施方案中提供一种固体催化剂,包含氢化金属和稀土元素交换的分子筛形式的固体酸,其中所述催化剂的至少特征在于在直径小于100nm的孔中孔隙率小于0.20ml/g,并且总孔隙率大于0.30ml/g。
本发明的另一实施方案提供一种烷基化烃的方法,包括在烷基化处理条件下使饱和烃原料和一种或多种烯烃接触本发明的催化剂。
通过阅读下列详细描述,包括附图和权利要求书,本发明的这些和甚至其他实施方案、特征和优势将甚至更加明显。
附图简述
图1是对于根据本公开的试验部分制备的本发明的特定催化剂实施方案和不是本发明的比较催化剂的孔隙率分布对于孔径的图。
图2是对于根据本公开的试验部分制备的本发明的特定催化剂实施方案和不是本发明的比较催化剂的以烯烃转化(下面进一步定义)表示的催化剂活性随时间变化的图。
发明详述
本发明的催化剂包含氢化金属和稀土元素交换的分子筛形式的固体酸。合适的氢化金属的例子是过渡金属,例如元素周期表的VIII族金属及其混合物。其中,元素周期表的VIII族贵金属是优选的。铂是特别优选的。氢化金属的量将取决于其性质。当氢化金属是元素周期表的VIII族贵金属时,以金属计算,催化剂通常将含有约0.01至约2重量%的金属。在另一实施方案中,金属的量为约0.1至约1重量%。除非本文中另有说明,本公开中提供的重量%基于干燥催化剂的总重量,其可使用在使催化剂在600℃下加热1小时时的重量损失(灼烧失量,或LOI 600,1小时)来计算。
分子筛的例子是沸石类,例如沸石β、MCM-22、MCM-36、发光沸石、八面沸石例如X-沸石类和Y-沸石类(包括HY-沸石类和USY-沸石类)。优选固体酸是沸石类,包括沸石β、八面沸石例如X-沸石类和Y-沸石类(包括HY-沸石类和USY-沸石类)。还可使用固体酸的混合物。在一个实施方案中,固体酸是单晶胞尺寸(a0)为24.72至约25.00埃的八面沸石,在另一实施方案中,固体酸是单晶胞尺寸为24.34-24.72埃的Y-沸石。在又一实施方案中,固体酸是单晶胞尺寸为24.56-24.72埃的Y-沸石。
催化剂的固体酸组分包含稀土元素(RE),即选自镧系的一种或多种元素。在一个实施方案中,稀土元素的量为约0.5重量%至约32重量%。在另一实施方案中,稀土元素的量为约2重量%至约9重量%。在又一实施方案中,稀土元素的量为约3重量%至约6重量%。本文中所有涉及稀土元素的重量%都是以稀土元素氧化物折干计算(600℃,1小时)。镧或富镧RE混合物可特别适用于用作稀土元素。富镧RE混合物是指镧是使用的稀土元素的总量的约70至80重量%或更高。
稀土元素可通过下面更充分描述的常规方式交换到固体酸组分中。在固体酸组分的交换过程中,钠(Na+)从催化剂中除去。在一个实施方案中,固体酸组分含有不超过约1.5重量%的Na2O;在另一实施方案中,固体酸组分含有不超过约1.0重量%的Na2O;并且在又一实施方案中,固体酸组分含有少于或等于约0.8重量%的Na2O。在甚至另外实施方案中,其含有少于或等于约0.6重量%的Na2O,所有都是折干计算(600℃,1小时)。
本发明的某些催化剂可另外含有基质材料。合适的基质材料的例子为氧化铝、氧化硅、氧化钛、氧化锆、粘土及其混合物。通常优选包含氧化铝的基质材料。在一个实施方案中,基于催化剂中含有的固体酸和基质材料的总重量,催化剂包含约10重量%至约40重量%的基质材料,并且余量为固体酸。
催化剂优选不含卤素组分。
优选地,除了氢化金属组分,本发明的催化剂包含约65至约85重量%的固体酸和约15至约35重量%的基质材料。更优选地,催化剂包含约70至约80重量%的固体酸和约20至约30重量%的基质材料。
根据本发明的方法中使用的催化剂通过调节含水量来制备。例如,固体酸成分可混合基质材料以形成载体颗粒,然后煅烧颗粒。氢化功能可例如通过使用氢化金属组分溶液浸渍载体颗粒而引入催化剂组成中。在浸渍后催化剂可煅烧。
在一个实施方案中,催化剂在约200至约500℃的温度下在还原气体例如氢气中还原。在另一实施方案中,催化剂在约250至约350℃的温度下还原。还原可在调节含水量之前、将水加入催化剂中之后、和/或通过使用还原作为调节含水量的方式来进行。在一个实施方案中,还原在调节含水量之前进行。在另一实施方案中,还原在将催化剂在干燥非还原气体(例如氮气、氦气、空气等)中干燥之后进行。
催化剂应该含有的含水量为约1.5至约6重量%,而在另一实施方案中含水量为约1.8至约4重量%,在另一实施方案中其为约2至约4重量%。含水量定义为在烷基化过程中使用的含水量,并且通过测定将催化剂在600加热2小时时的重量损失(LOI)来测量。催化剂的含水量可通过各种方法来调节,如PCT/EP2005/000929中所述,其通过引用的方式全部并入。这些方法下面列举为方法1、2和3。
方法1包括通过使催化剂暴露于水而增加催化剂的LOI。这可通过下列方式实现:使催化剂暴露于含水气氛,例如周围条件下的空气。本方法的实施方案包括使还原的催化剂暴露于水,直到达到期望的LOI,从而使未还原的催化剂暴露于水,直到达到高于期望水平的LOI,接着还原催化剂,从而使LOI降低至期望水平,进而使还原的催化剂暴露于水,直到达到高于期望水平的LOI,接着在惰性或还原气氛中处理催化剂,从而使LOI降低至期望水平,并且将催化剂在氢气和含水气氛中还原。
方法2包括通过使用LOI高于期望水平的未还原的催化剂还原而使现有催化剂的LOI降低至期望水平。
方法3包括通过下列方式的原位水加成:使用LOI低于期望水平的催化剂开始烷基化方法,并且将水加入烷基化直到在处理过程中,例如通过将水加入烃的进料,通过将催化剂在含水气氛和/或使再生的催化剂暴露于含水气氛。
还可使用两种或多种上述方法的联合。
优选地,所述催化剂基本上由氢化金属、稀土元素交换的分子筛、和任选的基质材料构成。更优选地,所述催化剂基本上由一种或多种稀土元素交换的八面沸石、一种或多种VIII族贵金属和一种或多种基质材料构成。甚至更优选地,本发明的催化剂基本上由一种或多种VIII族贵金属化合物、一种或多种稀土元素交换的Y-沸石类和包含氧化铝的一种或多种基质构成。
所述催化剂可通过本领域已知的方法来制备,改善以实现本发明的特定孔的特性。典型的方法包括下列连续步骤:
(i)任选地在使其混合基质材料后成型例如使固体酸成分挤出,以形成颗粒;
(ii)煅烧所得颗粒,以及
(iii)通过例如使用氢化金属组分溶液浸渍所述颗粒和/或(竞争性)离子交换,将氢化金属引入煅烧颗粒。
可选择地,催化剂可例如通过包括下列连续步骤的方法来制备:
(i)将氢化金属引入固体酸成分或引入固体酸成分和基质材料的混合物,
(ii)成型例如挤出所得材料以形成颗粒,以及
(iii)煅烧所得颗粒。
对于催化剂的制备,还可以遵守US 2008183025中所述的方法,为了获得本发明的特定孔隙率特性,特别有用仔细地实施挤出步骤。因此,特别有用如下实施挤出:
1)混合基质材料(例如析出的氧化铝粉末)、稀土元素交换的分子筛(例如沸石)、水、硝酸和数百分率的挤出助剂(例如甲基纤维素)以形成混合物,
2)将该混合物进料至挤出机中,以及
3)取决于所得挤出产物的肉眼检查,在挤出过程中加入一些额外的水。
在实施该试验过程以获得本发明的催化剂中,观察到最终挤出混合物的含水量(LOI 600℃,1小时)在40至45重量%的级别。加入0.15至0.25当量级别的(相对于氧化铝粉末)硝酸。折干计算(600℃,1小时),挤出物的沸石含量在65至85重量%的级别,并且余量为基质和氢化金属(0.05至0.5重量%的Pt)。本领域技术人员目前可意识到额外的LOI和酸加成要求赋予挤出物期望的性能(包括物理强度,例如侧面耐压强度和散装耐压强度),这取决于使用的分子筛含量和基质材料的特定性能。这通常通过下列方式来测定:在测量初始组分材料后进行试验和误差实验。平均颗粒长度为约2至约6mm,颗粒直径为约0.5至约3mm,并且侧面耐压强度为约1.5至约10lbs/mm。
所述催化剂特别适用于饱和烃的烷基化。因此本发明还涉及在这些原料的烷基化中使用本发明的催化剂。如上所述,这包括在本发明的催化剂的存在下使饱和烃和烯烃或烯烃前体反应,以得到具有更高分子量的高度支化的饱和烃。
优选地,烃是支化的饱和烃,例如具有约4-10个碳原子的异烷烃。合适的异烷烃的例子是异丁烷、异戊烷、异己烷或其混合物,最优选异丁烷。烷基化方法中使用的烯烃通常具有约2-10个碳原子,优选具有2-6个碳原子,甚至更优选具有约3-5个碳原子,并且最优选具有约4个碳原子。最优选地,烷基化过程由异丁烷和丁烯的烷基化构成。
如本领域技术人员明显知道的,烷基化方法可以以任何合适的形式来施用,包括流化床方法、浆料方法和固定床方法。所述方法可在多个床和/或反应器中实施,其中均单独加入烯烃。在这样的情况下,本发明的方法可在各单独床或反应器中实施。
合适的烷基化处理条件是本领域技术人员已知的。优选地,施加WO9823560中公开的烷基化方法,但是使用本文中所述的催化剂。在该方法中施加的处理条件概述于下表:
温度范围(℃) | 压力范围(巴) | 饱和烃和烯烃的摩尔比 | |
优选 | -40-250 | 1-100 | 5∶1-5000∶1 |
更优选 | 20-150 | 5-40 | 50∶1-1000∶1 |
最优选 | 65-95 | 15-30 | 150∶1-750∶1 |
优选地,在烷基化过程中施用WO 9823560中所述的再生技术。更特别地,在烷基化过程中催化剂优选地通过下列方式间歇地经历再生步骤:接触含有脂肪族化合物和氢气的进料,所述再生优选在约90%或更低、更优选约60%或更低、甚至更优选约20%或更低、并且最优选约10%或更低的催化剂的有效周期下实施。催化剂的有效周期定义为从开始进料烷基化剂至下列时刻的时间:当和进入含有催化剂的反应器部分中比较时,约20%的烷基化剂离开含有催化剂的反应器部分而未转化,未计算分子内的异构化。
任选地,在该方法中,催化剂可周期性经历高温再生,其中气相中为氢气。该高温再生优选在至少约150℃、更优选约175-600℃、最优选约200-400℃的温度下实施。对于该再生过程的细节,参照WO 9823560,特别是第4页第5-19列、和第9页第13列至第13页第2列。本发明的催化剂可在分批、半连续和连续烷基化过程中使用,并且可进行再生。因此例如WO/9823560(US 5986158)、US专利申请公开2007/0293390、WO2005/075387、US 7176340、US 2002/198422和EP 1485334与U.S.专利申请公开2008/0183025中教导的烷基化方法可使用本发明的催化剂在本文中教导的条件下实施。
在上述烷基化过程中使用本发明的催化剂导致较高烯烃转化率(在反应中转化的进料中的烯烃的量)、较高C5+烷化物收率(产生的C5+烷化物的重量除以消耗的烯烃的总重量)和较高辛烷数量,同时可限制不期望的C9+副产物的量,并且因此可改善催化剂的稳定性。对于这些参数的细节,参照WO 9823560。
下列实施例为了描述而展示,并且不旨在限制本发明的范围。
试验
试验中使用的挤出机是市售的双螺杆挤出机,得自Werner-PfleidererCorp.,型号ZSK-30。另外,基于Washburn等式通过汞(Hg)的侵入来测定制备的催化剂的在直径小于100nm的孔中孔体积以及总孔体积
其中D是孔直径,p是测量过程施加的压力,γ是表面张力,考虑为480达因/cm,并且θ是接触角,考虑为140°。在本测量中,压力在这样的范围内变化,其中测量覆盖直径为3.6-8000nm的孔。
在这些试验样品中,在制备各催化剂中使用约70至约83重量%的稀土元素交换的Y-沸石,在挤出之前在样品中余量为氧化铝基质。
具有稀土元素离子的Y-沸石通过US 2008183025中所述的常规路线来制备,即制备钠-Y-沸石(NaY)(氧化硅与氧化铝的摩尔比(SAR)为5.5,Na2O约13重量%),接着和稀土元素离子(优选富镧RE混合物)和NH4 +离子(剩余Na2O典型为约4.2重量%)离子交换,在约400至约500℃蒸气加工。在蒸气处理后,进行和NH4 +离子的交换,然后干燥沸石。然而,如果需要,可以使用多次蒸气加工和与NH4 +离子的交换步骤,以实现合适的SAR、a0和Na2O含量。
通过浸渍煅烧挤出物而含有约0.20重量%的铂的测试催化剂,沸石Na2O含量为约0.8重量%,沸石a0为约24.66,并且RE含量为约4重量%。样品中的沸石含量在70至75重量%之间变化。从此处展示的数据可见,具有最高活性的样品的活性高于(>20%)可从沸石含量差异小于10%(75%vs.70%沸石)来解释。通过改变基质和沸石的量,并且通过加入酸(例如HNO3)和水,可以控制通过成型技术例如挤出形成的催化剂颗粒的孔隙率。通过扫描电子显微法(SEM)测定的沸石颗粒的尺寸在100至1000nm的级别。
催化剂A-D依照下列方法来制备,使用如上制备的在催化剂C和D的情况下70%和在催化剂A和B的情况下75%的RE交换的沸石,余量为氧化铝基质和约0.20重量%的Pt(所有都是折干计算LOI 600℃1小时)。如上所述进行挤出。挤出物的平均长度为约4mm,并且平均直径为约1mm。因此,根据之前US 6855856中的方法计算的特定长度为约0.22mm。
使用上述参照的Hg方法来分析各催化剂的孔体积。孔体积分布绘制在图1中,并且在直径小于100nm的孔中测定的孔体积和总孔体积列于下表1中。
表1
在表2中,对于催化剂A-D,展示US 6,855,856中定义的大孔隙率和大孔隙率与特定长度的比例。
表2
可以看到只有催化剂D(参照)具有根据US 6,855,856的优选性能。本发明的催化剂A、B和C显示出和早期发明的优选性能的明显差异,这示出本发明的催化剂的令人吃惊的行为。注意,相对于催化剂D,催化剂A-C的大孔隙率(孔>40nm)相对较高。
催化剂A的特定长度为0.22mm,并且从汞侵入测量(例如参见图1的图)估计的大孔体积为约0.36ml/g,使得大孔体积与特定长度的比例为0.36/0.22=1.6,远高于US 6,855,856中之前教导的最大比例。
各催化剂A-D用于如下进行的烷基化方法中:WO 9823560中所述的固定床循环反应器,其通过引用的方式全部并入本文,直径2cm,填充1∶1体积/体积的38.6克的催化剂挤出物(折干计算,即实际重量,校正用于含水量)和碳化硅颗粒(60目)的混合物。在反应器管的中心布置直径6mm的热电偶。反应器用干燥氮气冲洗30分钟(21Nl/小时)。然后,测试系统在高压下的泄露情况,此后将压力设定为21巴,并且将氮气气流设定为21Nl/小时。然后以1℃/min的速度将反应器温度升至275℃,在275℃将氮气用干燥氢气取代,并且将催化剂在275℃下还原。
可选择地,在相同催化剂样品在运行之间的高温再生的情况下,在用氢气排出和冲洗反应器以除去烃同时保持烷基化反应温度后,将氢气气流设定为21Nl/小时,并且然后以1℃/min的速度将反应器温度升至275℃,然后将催化剂在275℃再生。
在2小时后,将反应器温度降至约75℃的反应温度。在冷却过程中将水加入氢气气流中以获得催化剂的LOI为约2-4重量%(在该情况下催化剂的LOI定义为在600下加热2小时后催化剂的重量损失)。
在达到反应温度时停止氢气气流。含有约4重量%烷化物(添加以加速钝化率,加入的烷化物的组成类似于通过在所述条件下的方法制备的烷化物)和约1摩尔%的溶解的氢气的异丁烷以约4.0kg/小时的速度供应至反应器。将约95-98%的异丁烷/烷化物混合物返回至反应器。排出约2-5%用于分析。将这样量的异丁烷/烷化物混合物供应至反应器以确保系统中的液体的恒定的量。当系统稳定时,停止氢气加入,并且将一定量的0.16的顺-2-丁烯加入以得到顺-2-丁烯-WHSV。系统中液体的总流速保持为约4.0kg/h。在反应器入口处异丁烷与顺-2-丁烯的重量比为约500-650。反应器中的压力设定为约21巴。通过控制排出流以进行分析,在测试过程中烃循环流(从加入和产生的烷化物)的总烷化物浓度保持为约10重量%。
在反应1小时后的各次,将催化剂通过下列方式进行再生:用异丁烷/烷化物混合物洗涤5分钟,接着通过接触在异丁烷/烷化物混合物中的1摩尔%的Hb的溶液进行50分钟的再生,然后用异丁烷/烷化物混合物洗涤另外5分钟(总洗涤和再生时间为1小时)。在该洗涤步骤后,再次开始烷基化。
在洗涤步骤、再生步骤和反应步骤的过程中的温度相同。
如上所述进行该过程,并且测量作为时间函数的催化性能。性能表征为通过每个反应器的烯烃转化。通过每个反应器的烯烃转化是在催化剂床的入口和出口之间转化的烯烃的重量部分(作为百分率),未计算烯烃分子内的异构化。结果绘制在图2的图中。
如可从图2中催化剂A至D的催化活性的绘制结果所见,当比较催化剂D的性能时,直径小于100nm的孔中孔体积小于0.2ml/g并且总孔体积大于0.3ml/g的联合的催化剂(催化剂A、B和C)显示出吃惊地有益结果。图2中所示催化剂A-C的活性的有益增加不能通过下列方式在百分率基础上解释:催化剂A、B和C中沸石的量的增加百分率对催化剂D的情况。孔特性的该独特组合明显提供在烷基化活性中的未预料的有益改善。
应该理解,在该文件中任一处由化学名称或化学式表示的反应物和组分,无论以单数还是复数表示,都确定为如同在与用化学名称或化学类型提及的另一种物质(例如,另一种反应物、溶剂或等)接触之前它们所存在的那样。无论在所得混合物或溶液或反应介质中发生什么初级化学变化、转化和/或反应(如果有),这些变化、转化和/或反应是在按照本公开要求的条件下将特定的反应物和/或组分组合的正常结果。因而反应物和其他材料确定为与执行所希望的化学反应或形成用于实施要求的反应的混合物有关的待汇集的成分。此外,即使实施方案可能以现在时态(“包括”、“包含”、“是”等)提及物质、组分和/或成分,其涵义是物质、组分或成分按照本公开与一种或更多其他物质、组分和/或成分最初接触、掺合或混合之前存在的状态。
除非另外清楚地指明,如果以及如本文所用的冠词“a”或“an”不是打算并且也不应当被理解为将权利要求限制到该冠词涉及的单一要素。更合适地,除非文中另外清楚地表明,如果以及如本文所用的冠词“a”或“an”试图覆盖一种或更多这种要素。
本说明书任何部分提及的每个专利或其他出版物或公开的文献并入本公开作为参考,如同本文完全地阐述。通过参考引入本文的引用的文件和该公开的明确文本之间的任何不一致应该有利于本公开的明确文本而解决。
在所附权利要求书的精神和范围内本发明容易进行大量的改变。
Claims (18)
1.一种固体催化剂,包含氢化金属和稀土元素交换的分子筛形式的固体酸,其中所述催化剂的至少特征在于在直径小于100nm的孔中孔隙率小于0.20ml/g,并且总孔隙率大于0.30ml/g。
2.根据权利要求1所述的固体酸性催化剂,其中所述分子筛包括沸石。
3.根据权利要求2所述的固体酸性催化剂,其中所述沸石包括具有八面沸石结构的沸石。
4.根据权利要求3所述的固体酸性催化剂,其中所述沸石是Y-沸石。
5.根据权利要求4所述的固体酸性催化剂,其中所述Y-沸石的单晶胞尺寸为24.56-24.72埃。
6.根据权利要求5所述的固体酸性催化剂,其中所述单晶胞尺寸为24.62-24.70埃。
7.根据前述权利要求中任一项所述的固体酸性催化剂,其中折干计算(600℃,1小时),所述固体酸包含不超过约1重量%的Na2O。
8.根据权利要求7所述的固体酸性催化剂,其中折干计算(600℃,1小时),所述固体酸包含不超过约0.8的Na2O。
9.根据前述权利要求中任一项所述的固体催化剂,其中在直径小于100nm的孔中孔隙率小于0.18ml/g,并且所述总孔隙率大于0.30ml/g。
10.根据前述权利要求中任一项所述的固体催化剂,其中在直径小于100nm的孔中孔隙率小于0.18ml/g,并且所述总孔隙率大于0.34ml/g。
11.根据前述权利要求中任一项所述的固体催化剂,其中所述氢化金属基本上由VIII族贵金属构成。
12.根据权利要求11所述的固体酸性催化剂,其中所述VIII族贵金属是铂。
13.根据前述权利要求中任一项所述的固体酸性催化剂,其中所述催化剂另外包含基质材料。
14.根据权利要求13所述的固体酸性催化剂,其中所述基质材料包括氧化铝。
15.根据前述权利要求中任一项所述的固体酸性催化剂,其中所述稀土元素是镧或稀土元素的富镧混合物。
16.根据前述权利要求中任一项所述的固体酸性催化剂,其中所述催化剂还包含约1.5至约6重量%的量的水。
17.根据权利要求16所述的固体酸性催化剂,其中所述水的量为约2至约4重量%。
18.一种烷基化烃的方法,包括在烷基化处理条件下使饱和烃原料和烯烃接触催化剂,所述催化剂是依照权利要求1-17中任一项所述的催化剂。
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US11225614B2 (en) | 2017-03-01 | 2022-01-18 | Emanuel Hermanus Van Broekhoven | Alkylation process with improved octane number |
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