CN101479035A - 用于在烃类流化催化裂化期间除去对催化剂有毒的金属的添加剂 - Google Patents
用于在烃类流化催化裂化期间除去对催化剂有毒的金属的添加剂 Download PDFInfo
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Abstract
本发明提供了适于从烃类中除去有毒金属的组合物和方法。该组合物包括水滑石,所述水滑石具有分散在其外表面上的一种或多种捕集金属。
Description
背景技术
现代炼油工业的一个主要操作是催化裂化工艺。在该工艺中,使用流化的含沸石催化剂将在分馏全原油中所产生的一些重油(常称为“瓦斯油”)分解或“裂化”。
因为在过去数年里轻质的低硫原油已经逐渐减少,催化裂化在维持适用于各种燃料如汽油的烃类供应中显得日益重要。由于增加使用重质、酸性更大的原油所带来的问题是重质原油含有明显更多的有机金属化合物,例如钒和镍的卟啉化合物。这些金属在重油裂化中产生了许多不希望的反应,原因在于这些金属(具体地为镍和钒)对所使用的流化裂化催化剂十分有害。存在于高沸点馏分中的这些金属沉积在裂化催化剂上并且随时间积累。它们作为有毒物质起作用,具有增加不希望的氢和焦炭的产率、在制备液体产品时降低催化剂选择性的效果。还确定钒也攻击沸石本身、催化裂化催化剂的高活性组分。
炼油/炼油催化剂工业中的技术人员已经付出了许多了努力,试图处理在流化催化裂化(FCC)期间钒和其他金属对含沸石催化剂有毒的问题。美国专利6,610,255描述了已经建议的许多技术。这些技术中的大部分涉及添加所谓的“捕集剂(trapping agent)”,其与催化剂或烃原料一起添加;这些捕集剂如钡、钙和锶已经显示了减小有毒金属对含沸石的FCC催化剂的不利效应。
虽然最近FCC催化剂技术有了发展,但仍然需要用于将钒和其他有毒金属从烃类中有效除去的捕集剂在FCC过程中引入的工业可行方法。
发明内容
本发明通过提供适用于从烃类中除去一种或多种有毒金属的组合物和方法满足了当前的需要。本发明的组合物包括水滑石(HTC),该水滑石具有分散在其外表面上的一种或多种捕集金属。用于在FCC单元中从烃类中除去一种或多种有毒金属的本发明方法包括将水滑石加入到FCC单元中,该水滑石具有分散在其外表面上的一种或多种捕集金属。在本发明的一些实施方式中,本发明的组合物基本上由或全部由具有分散在其外表面上的至少一种捕集金属的水滑石组成。使用HTC作为在其上分散有一种或多种捕集金属的载体提供了有毒金属与捕集剂之间的良好接触。
虽然以下用具体实施方式来说明本发明,但应当理解的是,本发明不限于这些具体实施方式中的任何一个实施方式。
具体实施方式
水滑石
在本发明中可以采用任何水滑石。该水滑石可以包括(a)天然存在的水滑石、(b)合成的水滑石、(c)类水滑石材料、或者(d)上述(a)-(c)中的任何两种或更多种的混合物。适合的水滑石载体在美国专利4,347,353和4,284,762中有描述。适合的水滑石载体包括例如CaO、MgO和Al2O3的混合金属氧化物。一种适合的水滑石的化学式为Mg4.5Al2(OH)13·3.5H2O。适合的水滑石材料由日本大阪的协和化学工业株式会社(Kyowa Chemical Industry Company,Ltd.)制造,以产品名“DHT-4”和“DHT-4A”由日本大阪的三井化学株式会社(Mitsui andCompany,Ltd.)和德克萨斯州休斯顿的三井化学株式会社(Mitsui and Company(USA))销售。
类水滑石材料及其制备方法
结晶的阴离子粘土,包括羟镁铝石、水镁铁石、鳞镁铁矿、铬鳞铁矿、陨菱铁镍矿、镍锌水滑石(eardleyite)、水镁铝石(manassite)和水镁铬矿,是根据本发明的水滑石类材料。对于大多数工业应用,将结晶阴离子粘土成形为成形体例如球体。在成形体经受严格加工条件和环境的应用如炼油应用、分离、提纯和吸收工艺中,重要的是将含结晶阴离子粘土的成形体保持完好和防止磨损。由包括铝源和镁源的来源制备含结晶阴离子粘土的成形体的方法包括下列步骤:a)制备前体混合物,b)将前体混合物成形以获得成形体,c)可选择地处理该成形体,以及d)老化,以获得含结晶阴离子粘土的成形体。该成形体可以按许多方式制备。在一个实施方式中,铝源和硅源在浆料中结合为前体混合物。随后,将所述前体混合物成形。将所得到的成形体在液体中老化,可选地在热处理之后,以获得含结晶阴离子粘土的成形体。
还可以由仅仅一种来源如铝源或镁源来制备前体混合物,将其成形,然后在任何随后工艺步骤中将一种或多种其他源加入到该成形体中。在老化步骤期间,让各种源反应,以获得含结晶阴离子粘土的成形体。当然,还可以使用上述两种制备途径的结合,例如,添加铝源和镁源以形成前体混合物,成形为成形体,然后将该成形体在含有另外镁源的液体中老化,以形成含阴离子粘土的成形体,在该成形体的外部具有较高的镁含量。
适合的铝源包括:铝的氧化物和氢氧化物,例如过渡型氧化铝、三水合铝(水铝矿、三羟铝石)及其热处理形式(包括快速煅烧的氧化铝)、溶胶、无定形氧化铝、(假)勃姆石;含铝的粘土,例如高岭土、海泡石、水滑石和膨润土;改性的粘土,例如偏高岭土;铝盐,例如硝酸铝、氯化铝、氢氯酸铝、铝酸钠。用本文中所述的制备方法,还可以使用更粗等级的三水铝,例如BOC(Bauxite Oregon Concentrate)或者铝土矿。当使用粘土作为铝源时,可能需要通过酸或碱处理来活化粘土中的氧化铝,例如酸处理的膨润土、(水)热处理或它们的组合。酸处理包括用硝酸、醋酸、磷酸、硫酸、盐酸等处理。热处理通常在30-1000℃,有时在200-800℃的温度下进行几分钟到24小时,有时1-10小时。此外,可以使用上述铝源的混合物,所述不同铝源可以在前体混合物中按任意顺序结合。还可以在成形步骤之后添加铝源。在该情况下,该前体混合物可以含有或不含铝源。在一个实施方式中,如果在成形步骤之后添加铝源,则在与成形体接触时它是在液体中。这可以通过分散或溶解铝源以及将它加入到成形体中来完成。或者,铝源可以加入到成形体在其中老化的液体中。
此外,除了粘土以外的其他铝源,例如三水铝,可以在添加到前体混合物中之前或者在将它与成形体接触之前进行预处理。所述预处理可以包括用酸处理、碱处理、热和/或水热处理,所有处理可选择地在存在籽晶或其组合的情况下进行。不需要将所有铝源转化为结晶阴离子粘土。任何过量的铝在老化步骤期间被转化为二氧化硅-氧化铝、氧化铝(通常以γ-氧化铝或(结晶)勃姆石的形式)和/或氧化铝-氧化镁。这些化合物改善了成形体的结合性能,并且还可以提供成形体不同类型的所需官能团。例如,二氧化硅-氧化铝和氧化铝提供了用于催化裂化的酸位点,氧化铝(结晶)勃姆石还改善了成形体的镍包囊能力。例如,通过在前体混合物中、在铝源中或在老化期间添加籽晶可以促进(结晶)勃姆石的形成。
适合的镁源包括:镁的氧化物或氢氧化物,例如MgO、Mg(OH)2、水菱镁矿;镁盐如醋酸镁、甲酸镁、羟基醋酸镁、碳酸镁、碳酸羟镁、碳酸氢镁、硝酸镁、氯化镁;含镁的粘土,例如白云岩、皂石、海泡石。此外,可以使用上述镁源的混合物,所述不同镁源可以在前体混合物中按任何顺序和/或在成形步骤之后的任何工艺步骤中合并。在一个实施方式中,如果镁源在成形步骤之后添加,则在与成形体接触时它是在液体中。这可以通过分散或添加镁源和将它加入到成形体中来完成。或者,镁源可以加入到老化成形体的液体中。
镁源可以在添加到前体混合物之前和/或添加到成形体中之前进行预处理。所述预处理可以包括热处理和/或水热处理、酸处理、碱处理,所有处理任选在存在籽晶和/或它们的组合下。
不需要将所有镁源转化为结晶阴离子粘土。任何过量的镁通常被转化为氢氧镁石、氧化镁或氧化铝-氧化镁。为了清楚,成形颗粒中的过量镁化合物在说明书中被称为氧化镁。氧化镁或氧化铝-氧化镁在成形体中的存在可以为成形体提供所需的官能团。氧化镁的存在提供了碱性位点,该碱性位点使得成形体适合于除去或中和气体或液体的强酸流。
下面详细说明各工艺步骤。
类水滑石材料及其制备方法-前体混合物的制备
在该步骤中,在液体中由铝源和/或镁源制备前体混合物。事实上,所有液体是适合的,只要它们不有害地干扰各种源。适合的液体是水、乙醇、丙醇等。可以选择液体的量,使得获得乳状物质的混合物,而且具有较高粘度的混合物例如生面团状物质是适合的。如果前体混合物使用一种以上的源,则这些源可以作为固体物添加,但它们还可以在液体中添加。各种源可以按任何顺序添加。前体混合物的制备可以用或不用搅拌且在室温下或高温下进行。可选择地,前体混合物和/或独立的源例如通过研磨来均匀化。在结合各种源时可能发生一些向结晶阴离子粘土的转化。在某些情况下,已经形成了最终总量的至少大约5wt%的阴离子粘土,在某些情况下,转化也在成形步骤之后进行。在其它的情况下,在成形步骤之后形成了超过最终总量的大约25wt%,或者超过大约50wt%,或者超过大约75wt%,或者大约80~大约95wt%的成形体中的阴离子粘土。Mg:Al比率可以改变,例如大约1~大约10,大约1~大约6,或者大约2~大约4。
如果需要,可以将例如用于控制pH的有机或无机酸和碱加入到前体混合物中,或者在加入到前体混合物中之前加入到铝源和/或镁源的任何一种中。当使用铵碱改性剂时,在干燥时,没有有害的阳离子保留在阴离子粘土中。该前体混合物可以在成形步骤之前预老化。所述预老化温度可以为大约30℃~大约500℃,并且可以在大气压或增高的压力下进行,例如在超过大约100℃温度下自生压力下进行。老化时间可以为大约1分钟到几天,例如大约7天。通过将特定阴离子加入到该前体混合物和/或任何铝源和/或镁源中,可以控制所存在的层间电荷平衡阴离子。适合的阴离子的实例是碳酸根、碳酸氢根、硝酸根、氯、硫酸根、硫酸氢根、钒酸根、钨酸根、硼酸根、磷酸根、柱撑阴离子如V10O28-6、Mo7O24-6、PW12O40-3、B(OH)4-、B4O5(OH)4-2、HBO4-2、HGaO3-2、CrO4-2、甲酸阴离子、乙酸阴离子和它们的混合物。还认为的是,一部分的这些阴离子如碳酸根、碳酸氢根、硫酸根或硝酸根阴离子的存在影响了副产物如氢氧镁石的形成。例如,添加氢氧化铵促进了羟镁铝石形成,而添加碳酸铵促进了水滑石形成。
类水滑石材料及其制备方法-成形
适合的成形方法包括喷雾干燥、造粒、挤出(可选地与捏合结合)、珠粒形成或者催化剂和吸收剂领域中使用的任何其他常规成形方法或这些方法的组合。用于成形的前体混合物中所存在的液体量应该适用于即将实施的成形步骤。有时适宜的是,(部分)除去前体混合物中所使用的液体和/或添加另外或其他的液体,和/或改变前体混合物的pH值,使得该前体混合物可胶化,并且因此适合于成形。通常用于各种成形方法的各种添加剂例如挤出添加剂可以加入到用于成形的前体混合物中。
类水滑石样及其制备方法-热处理
在成形之后,可以任选地将成形体进行热处理。这种处理提高了颗粒的物理强度。该热处理可以在含氧气氛中、在惰性气氛中或者在蒸汽中且在大约30℃~大约900℃的温度下进行大约几分钟到大约24小时的时间。例如在喷雾干燥时,固有地包括热处理,进一步热处理是不必要的。
类水滑石材料及其制备方法-老化
在该步骤中,将成形体浸渍在质子液体或质子气体介质中。在老化步骤过程中,发生结晶为结晶阴离子粘土。适合的质子老化液体或气体介质是其中成形体不溶解的那些液体和气体介质,例如水、乙醇、甲醇、丙醇、蒸汽、气体水、气体乙醇等。增加液体的温度和/或压力可以减少老化时间。老化还可以在自生的条件下进行。老化温度可以是大约30℃~大约500℃。老化时间可以是大约1分钟到几天,例如大约7天。对于某些目的,可以有利地进行几个老化步骤,可选择地具有中间干燥步骤,可选择地接着是煅烧步骤。例如,温度低于大约100℃的老化步骤可以接着是高于大约100℃的温度和自生压力下的水热老化步骤,或者反之亦然。如以下所详细说明的,添加剂可以在任意老化步骤之前、之后或者期间添加。通过将特定的阴离子加入到老化介质中,可以控制所存在的层间电荷平衡阴离子。适合的阴离子的实例包括碳酸根、碳酸氢根、硝酸根、氯、硫酸根、硫酸氢根、钒酸根、钨酸根、硼酸根、磷酸根、柱撑阴离子如V10O28-6、Mo7O24-6、PW12O40-3、B(OH)4-、B4O5(OH)4-2、HBO4-2、HGaO3-2、CrO4-2、甲酸阴离子、乙酸阴离子和它们的混合物。还认为,一部分的这些阴离子如碳酸根、碳酸氢根、硫酸根或硝酸根阴离子的存在影响了副产物如氢氧镁石的形成。例如,添加氢氧化铵促进了类羟镁铝石粘土的形成,而添加碳酸铵促进了类水滑石粘土的形成。
对于某些应用,希望在本发明的成形体中和/或在本发明的成形体上存在添加剂,包括金属和非金属,例如稀土金属(尤其Ce和La)、Si、P、B、VI族金属、贵金属如Pt和Pd、碱土金属(例如Ca和Ba)和/或过渡金属(例如Mn、Fe、Ti、V、Zr、Cu、Ni、Zn、Mo、Sn)。所述金属和非金属可以单独或者作为混合物在本发明的任何制备步骤中添加。例如,它们可以容易地在老化之前、期间或之后沉积于成形体上,或者它们可以加入到前体混合物和/或任何铝源或镁源中。适合的金属源或非金属源是氧化物、卤化物或任何其它的盐,例如盐酸盐、硝酸盐、磷酸盐等。如上所述,金属和非金属可以在任何制备步骤中添加。这对于控制金属和非金属在成形体中的分布是特别有利的。甚至还可以将成形体煅烧,再水化和添加其它添加剂。
借助添加剂,可以提供成形体所需要的官能度,或者可以通过添加添加剂来提高所需要的官能度。含阴离子粘土的成形体用于除去FCC中的SOx和/或NOx化合物的适应性可以通过添加Ce和/或V来改进。V和Zn的存在改进了用于除去FCC的汽油和柴油馏分的S-化合物的适应性。如上所述,这些官能团还可以通过使用过量的铝源和/或镁源来形成。这些手段的组合提高了该效果。
还可以制备含有常规催化剂组分如基质或填料(例如,粘土如高岭土、二氧化钛、氧化锆、氧化铝、二氧化硅、二氧化硅-氧化铝、膨润土等)、分子筛材料(例如,沸石Y、ZSM5等)的含结晶阴离子粘土的成形体。所述常规催化剂组分可以在成形步骤之前添加。因为阴离子粘土原位形成,所得成形体将使阴离子粘土和催化剂组分均匀分散。用根据本发明的方法,可以制备可用作催化剂或催化剂添加的多功能体。
该制备方法可以间歇或连续地进行,可选择地为连续多步操作。该方法还可以部分间歇和部分连续地进行。
如果需要,用本发明的方法制备的含结晶阴离子粘土的成形体可以进行离子交换,其中用其他的阴离子置换该粘土的层间电荷平衡阴离子。所述其他的阴离子是通常存在于阴离子粘土中的那些阴离子,包括柱撑阴离子例如V10O28-6、Mo7O24-6、PW12O40-3、B(OH)4-、B4O5(OH)4-2、HBO4-2、HGaO3-2、CrO4-2。美国专利4,774,212给出了其他适合的柱撑阴离子的实例。一旦形成结晶阴离子,可以进行所述离子交换。
捕集剂
适合的捕集剂可以包括以下任何元素、它们的离子或这些元素和/或它们的离子的混合物:钡、钙、锰、镧、铁、锡、锌、铈或如使用新IUPAC格式的元素周期表(即目前的IUPAC格式)的2族中的任何元素。
所述捕集剂可以包括钡和钡的化合物中的至少一种。目前认为,大多数钡的形式是有效的。钛酸钡和氧化钡是适合用作捕集剂的钡化合物。适用于本发明的钡化合物可以是有机或无机的。油溶性和水溶性钡化合物是适合的。适合的无机钡化合物包括无机酸的钡盐和碱性钡化合物。氧化钡是适合的捕集剂。适合的钡盐的实例是硝酸钡、硫酸钡、卤化钡如氯化钡以及卤氧化钡,如Ba(ClO3)2。含卤素的无机化合物是不优选的,因为它们对工艺设备具有腐蚀效应。适合使用的代表性碱性钡化合物是氢氧化钡、硫氢化钡和碳酸钡。适合的有机钡化合物包括羧酸的钡盐和钡螯合剂络合物。钡羧酸盐可以含有大约1~大约40个碳原子/分子,并且酸部分可以是脂族或者芳族性质的。代表性化合物是醋酸钡、丁酸钡、柠檬酸钡、甲酸钡和硬脂酸钡。适合的钡络合物包括其中钡通过螯合剂如1,3-二酮、乙二胺四乙酸和次氨基三乙酸来引入的络合物。戊二酸钡是适合的捕集剂。
将捕集剂分散到水滑石的外表面上
捕集剂可以加入到水滑石中,而水滑石根据本文所述的程序或根据目前已知或者后来开发的其他程序来制备。或者,捕集剂例如可以加入到现有的水滑石中,例如通过孔体积浸渍或者通过使用适合的钡源,这是本领域技术人员所熟悉的。使用任何这些方法,至少一部分的捕集剂将分散在水滑石的外表面上。
尽管本发明不限于任何特定量的在水滑石外表面上的捕集剂,但是在根据本发明的一种组合物中,以捕集剂和水滑石的总重量为基准,分散于外表面的捕集剂为大约5~大约35wt%或者大约10~大约20wt%的水滑石是有用的。
本发明的添加剂在FCC中的添加
根据本发明的组合物可以与烃原料,同时与一种或多种催化剂一起,或者在添加了烃原料和一种或多种催化剂之后加入到FCC单元中。在一个实施方式中,本发明的组合物可以与一种或多种FCC催化剂组合,使得本发明的组合物基于该组合物加FCC催化剂的总重量的重量百分率为大约1wt%~大约30wt%,或者大约2wt%~大约20wt%,或者大约5wt%~大约10wt%。
实施例
实施例1
根据本发明的Me-HTC(其中Me表示Ba、Sr、Ca、Fe、Mn、Ce、La或Zn)通过将作为盐的Me组分加入到已经研磨和老化的4:1摩尔比MgO:Al2O3浆料(20wt%固体)中来制备。然后将含有Me、Mg和Al的混合物喷雾干燥,以保持大约75微米的平均粒径。然后将该干燥的材料在550℃下煅烧1小时,并且在水浆料中于30℃下再水化30分钟。然后将所得的混合物干燥。以10wt%的水平与工业FCC催化剂共混合。然后在金属化失活后使用残油原料在流化床微反应器单元中评价该共混物。该共混物使用米切尔浸渍方法(Mitchellimpregnation route)失活,随后在3000ppm的Ni和3000ppm的V下蒸汽处理。表1示出了本发明的优点。与使用工业FCC催化剂但没有本发明的Me-HTC所产生的数据相比,焦炭产率显著降低,而转化率和汽油收率得到改善。
表1
催化剂 | 基础FCC催化剂 | 基础FCC催化剂+Ba-HTC | 基础FCC催化剂+Sr-HTC | 基础FCC催化剂+Ca-HTC | 基础FCC催化剂+Fe-HTC | 基础FCC催化剂+Mn-HTC | 基础FCC催化剂+Ce-HTC | 基础FCC催化剂+La-HTC | 基础FCC催化剂+HTC | 基础FCC催化剂+Zn-HTC |
在恒定转化率73%下的收率 | ||||||||||
催化剂/油,wt/wt | 5.9 | 2.8 | 3.4 | 3.6 | 3.1 | 3.4 | 3.5 | 4.4 | 4.6 | 4.9 |
δ焦炭,wt% | 2.1 | 2.0 | 2.2 | 1.9 | 2.9 | 2.3 | 2.4 | 2.0 | 2.4 | 1.9 |
焦炭 | 12.5 | 5.7 | 7.6 | 6.9 | 8.9 | 7.6 | 8.3 | 8.8 | 11.0 | 9.4 |
干燥气体 | 5.8 | 4.7 | 5.0 | 5.3 | 5.2 | 5.1 | 5.3 | 5.3 | 5.5 | 5.4 |
汽油 | 41.7 | 46.1 | 45.1 | 44.6 | 43.8 | 44.5 | 44.1 | 43.9 | 42.3 | 43.7 |
底部产物 | 9.7 | 10.2 | 10.4 | 10.5 | 10.3 | 10.9 | 10.4 | 10.6 | 11.2 | 10.3 |
净底部产物转化率 | 77.7 | 84.1 | 82.0 | 82.6 | 80.8 | 81.5 | 81.3 | 80.5 | 77.8 | 80.2 |
在恒定CTO=5下的收率 | ||||||||||
转化率,wt% | 70.5 | 80.8 | 77.7 | 77.1 | 77.8 | 78.3 | 77.0 | 74.7 | 74.3 | 73.3 |
δ焦炭,wt% | 2.2 | 1.8 | 2.1 | 1.8 | 2.2 | 2.0 | 2.1 | 1.9 | 2.4 | 1.9 |
焦炭 | 11.0 | 9.0 | 10.6 | 9.2 | 11.2 | 9.9 | 10.4 | 9.5 | 11.8 | 9.6 |
汽油 | 42.0 | 43.3 | 43.5 | 43.9 | 43.2 | 43.7 | 43.1 | 43.8 | 42.1 | 43.7 |
底部产物 | 11.6 | 6.4 | 7.8 | 8.1 | 7.8 | 7.8 | 8.2 | 9.5 | 10.3 | 10.2 |
在恒定焦炭10%下的收率 | ||||||||||
转化率,wt% | 68.7 | 82.2 | 76.9 | 78.3 | 75.4 | 78.5 | 76.3 | 75.9 | 70.8 | 73.9 |
汽油 | 42.0 | 42.0 | 44.0 | 43.4 | 43.7 | 43.7 | 43.4 | 43.6 | 42.4 | 43.5 |
底部产物 | 13.0 | 5.7 | 8.3 | 7.4 | 9.0 | 7.7 | 8.6 | 8.7 | 12.6 | 9.8 |
实施例2
现有喷雾干燥的水滑石的用钡进行孔体积浸渍。颗粒及其断面的SEM图与Ba、Mg和Al的元素分析图一起显示出Ba在水滑石颗粒的外表面上。
实施例3
现有喷雾干燥的水滑石在存在钡的情况下于50℃下再水化30分钟至30wt%固体物,过滤并且在110℃下干燥过夜。颗粒及其断面的SEM图与Ba、Mg和Al的元素分析图一起显示出Ba在水滑石颗粒的外表面上。
实施例4
将MgO/CATAPAL浆料研磨至2.5的孔径,在50℃下老化2小时。添加硝酸钡,然后将该混合物喷雾干燥,煅烧,在水中再水化。颗粒及其断面的SEM图与Ba、Mg和Al的元素分析图一起显示出Ba的分布比实施例2和3差。
预计使用本发明的添加剂获得了具有改进的耐金属性(这对于残油单元非常有价值)的催化剂。
虽然参照一个或多个优选实施方式描述了本发明,但应该理解的是,在不偏离如由权利要求所阐明的本发明范围的情况下可以做出其他改变。
Claims (6)
1.一种适于从烃类中除去一种或多种有毒金属的组合物,所述组合物包括水滑石,该水滑石具有分散在其外表面上的一种或多种捕集金属。
2.如权利要求1所述的组合物,其中,所述水滑石包括天然存在的水滑石、合成水滑石或类水滑石材料。
3.如权利要求1所述的组合物,其中,所述一种或多种捕集金属包括钡、钙、锰、镧、铁、锡、锌、铈或者元素周期表中所述的任何2族元素。
4.一种适于从烃类中除去一种或多种有毒金属的组合物,所述组合物基本上由水滑石组成,该水滑石具有分散在其外表面上的一种或多种捕集金属。
5.一种用于在FCC单元中从烃类中除去一种或多种有毒金属的方法,该方法包括将水滑石加入到FCC单元中,该水滑石具有分散在其外表面上的一种或多种捕集金属。
6.一种用于在FCC单元中从烃类中除去一种或多种有毒金属的方法,该方法基本上由将水滑石加入到FCC单元中组成,该水滑石具有分散在其外表面上的一种或多种捕集金属。
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US20150096922A1 (en) | 2013-10-04 | 2015-04-09 | Johnson Matthey Process Technologies, Inc. | Process for reactivating an iron-contaminated fcc catalyst |
JP6915985B2 (ja) * | 2016-12-27 | 2021-08-11 | 日揮触媒化成株式会社 | 金属捕捉剤、金属捕捉剤の製造方法、及び流動接触分解触媒 |
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US4485184A (en) * | 1981-04-10 | 1984-11-27 | Ashland Oil, Inc. | Trapping of metals deposited on catalytic materials during carbometallic oil conversion |
US4774212A (en) | 1987-12-22 | 1988-09-27 | Amoco Corporation | Pillared hydrotalcites |
US4889615A (en) * | 1988-12-06 | 1989-12-26 | Mobil Oil Corporation | Additive for vanadium capture in catalytic cracking |
US6010619A (en) * | 1997-01-22 | 2000-01-04 | Greenvue Company, Llc | FCC process with zeolite and hydrotalcite |
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US20060060504A1 (en) * | 2004-09-08 | 2006-03-23 | Vierheilig Albert A | Additives for metal contaminant removal |
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