CN108368005A - 离子液体催化剂处理*** - Google Patents

离子液体催化剂处理*** Download PDF

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CN108368005A
CN108368005A CN201680073570.0A CN201680073570A CN108368005A CN 108368005 A CN108368005 A CN 108368005A CN 201680073570 A CN201680073570 A CN 201680073570A CN 108368005 A CN108368005 A CN 108368005A
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ionic liquid
process stream
stream
separator
method described
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M·利普曼
D·S·拉弗亚迪斯
D·A·纳菲斯
K·德特里克
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Honeywell UOP LLC
Universal Oil Products Co
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Universal Oil Products Co
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Abstract

描述了从工艺料流中除去离子液体的方法。将工艺料流引入聚结器以形成离子液体料流和具有比工艺料流更少离子液体的第一处理工艺料流。将第一处理工艺料流引入分离器以形成第二次处理工艺料流。第二处理工艺料流具有比第一处理工艺料流少的离子液体。分离器选自包含砂或碳的过滤区、吸附区、洗涤区、静电分离区或其组合。

Description

离子液体催化剂处理***
优先权声明
本申请要求2015年12月17日提交的美国申请62/268,865号的优先权,其内容通过引用整体并入本文。
背景技术
各种烃转化方法可以使用离子液体催化剂。烷基化通常用于将轻质烯烃(例如烯烃如丙烯和丁烯的混合物)与异丁烷结合以产生相对高辛烷值的支链烷烃燃料,包括异庚烷和异辛烷。类似地,烷基化反应可以使用芳族化合物如苯代替异丁烷来进行。当使用苯时,由烷基化反应得到的产物是烷基苯(如乙苯,枯烯,十二烷基苯等)。
用于轻质烯烃(例如乙烯,丙烯和丁烯)低聚以生产更高碳数烯烃产物(例如C6+烯烃)的方法是众所周知的。采用低聚方法生产高质量的发动机燃料组分以及来自乙烯,丙烯和丁烯的石化产品。这些低聚方法也被称为催化缩合和聚合,其中所得的发动机燃料通常被称为聚合物汽油。
链烷烃(例如异戊烷(iC5))的歧化反应涉及使两摩尔烃反应以形成一摩尔两种不同产物中的每一种,一种具有大于原料的碳数,另一种具有小于原料的碳数。整个过程中***中的总摩尔数保持不变,但是产物具有与反应物不同的碳计数。
线性烷烃异构化为它们的支化异构体增加了它们的辛烷值,并因此增加了其对精炼厂的价值。异构化方法包括使1摩尔烃(例如正戊烷)反应形成1摩尔该特定烃的异构体(例如异戊烷)。整个方法中总摩尔数保持不变,产物与反应物具有相同数量的碳。
酸性离子液体可用作烃转化方法中常用的强酸催化剂的替代物。离子液体是可用于各种催化反应的催化剂,包括烷烃与烯烃的烷基化。离子液体是由阳离子和阴离子组成的盐,通常在100℃以下熔化。
离子液体基本上是液态的盐,并且描述于美国专利4,764,440、5,104,840和5,824,832中。不同离子液体的性质差异很大,离子液体的使用取决于给定离子液体的性质。取决于离子液体的有机阳离子和阴离子,离子液体可以具有非常不同的性质。
离子液体比其他催化剂提供了优点,包括非挥发性。
离子液体也已经用于分离方法中,例如如US 7,749,377、8,574,426、8,574,427、8,580,107、8,608,943、8,608,949、8,608,950、8,608,951、8,709,236中所述从烃中除去各种污染物,和例如如US 8,754,254、9,000,214中所述从氧化产物中除去污染物。
然而,离子液体的使用呈现出独特和新的废物处理挑战,这是由于化学品和化合物对于单元正常操作的特殊性质。这些物质中的许多(包括但不限于离子液体本身)不适于被释放、排出或以其他方式排放到标准精炼厂释放***、废物处理***或旨在管理废物或单元非产物料流的其他类似***。
例如,US 8067656描述了使用聚结器从烃中分离离子液体的方法。该方法包括:(a)将包含烃和离子液体的混合物供至聚结器,烃具有分散于其中的离子液体滴,并且聚结器包含聚结剂材料;(b)将至少一部分离子液体滴粘附到聚结剂材料上以提供捕获的液滴;(c)将捕获的液滴聚结成聚结的液滴;和(d)使聚结的液滴从聚结剂材料中落下以将离子液体与烃分离并提供烃流出物,其中聚结剂材料比烃对离子液体具有更强的亲和力。液滴落到聚结器的底部并形成离子液体层,然后可以从聚结器中除去离子液体层。多级聚结剂材料可以串联、并联或两者。各级可以在聚结剂材料中具有不同尺寸的开口。据说烃流出物包含40ppm或更少的离子液体,或者20ppm或更少的离子液体,或者10ppm或更少的离子液体。
然而,已经发现在一些实施方案中,这些离子液体水平仍然太高。例如,已经发现10至40ppm的离子液体水平可能仍然对污水处理设施中的微生物有毒。来自各种方法的产物料流在送去储存或使用之前可能还需要去除离子液体。
因此,仍然需要一种处理含有离子液体催化剂的料流的***。
发明内容
本发明的一个方面是从工艺料流中除去离子液体的方法。在一个实施方案中,所述方法涉及将工艺料流引入聚结器以形成离子液体料流和第一处理工艺料流,所述第一处理工艺料流的离子液体水平低于所述工艺料流中离子液体的水平。将第一处理工艺料流引入分离器以形成第二处理工艺料流,所述第二处理工艺料流具有比所述第一处理工艺料流中的离子液体水平低的离子液体水平。分离器选自包含砂或碳的过滤区、吸附区、洗涤区、静电分离区或其组合。
附图说明
附图示出了用于从工艺料流中除去离子液体的方法的一个实施方案。
发明详述
附图阐示了用于从工艺料流中除去离子液体的方法100的一个实施方案。工艺料流可以是含有离子液体的任何类型的工艺料流,包括但不限于有机料流和无机料流。为了方便起见,将参照已经通过离子液体促进的烃转化方法来描述该图。
由于烃在离子液体中的低溶解度,因此使用离子液体的大多数烃转化反应或污染物去除是双相的且在液态界面发生。
尽管简单地通过使烃进料和离子液体催化剂接触来进行反应或去除,但单独接触的反应或去除速率可能太慢而无法在商业上可行。因此,烃进料和离子液体经常混合以提供更好的接触。混合产生离子液体滴在烃中的分散体。需要从烃料流中除去分散的离子液体滴。
含有分散的离子液体滴的烃进料流105被送至任选的重力沉降器110。由于离子液体和烃之间的密度差而发生分离。较轻的烃相位于较重的离子液体相上方。离子液体相可以作为第一离子液体料流115从重力沉降器去除。
较轻的烃相作为沉降器流出物料流120从重力沉降器110中去除,沉降器流出物料流120具有比进入的烃进料流105更低水平的离子液体。
沉降器流出物料流120被送到聚结器125。聚结器125是具有合适材料以促进不混溶液体分离的装置。聚结器125通常包含以下中的至少一个:一个或多个金属丝,一个或多个叶片,金属网或填料,一个或多个玻璃或聚合物纤维,玻璃珠,砂,无烟煤,和陶瓷膜。这些组分可以由表现出疏水-亲油特性的材料构成或涂覆。聚结器可以是静态的。或者,它可以是主动聚结器,例如2015年4月30日提交的名称为Active Coalescer to Remove FineParticles的美国申请14/700,919中所描述的,其通过引用并入本文。
离子液体滴接触聚结器125中的聚结剂材料并且在聚结剂材料上形成更大的液滴。如果液滴的密度大于烃的密度并且在聚结器125的底部形成离子液体层,则这些液滴然后落到聚结器125的底部。离子液体可以作为第二离子液体料流130除去。
来自聚结器125的聚结器流出物135仍含有分散的离子液体滴。聚结器流出物135中的离子液体水平低于沉降器流出物120中的水平。然而,发现该水平仍然太高而不能将聚结器流出物135释放到标准废水处理设施。聚结器流出物135中的离子液体对于用于各种产品来说也可能太高。例如,内燃机可能不允许汽油或柴油燃料中ppm水平的离子液体杂质。最终用作聚合物的化学品可能不耐受ppm数量的离子液体,其可能对聚合方法产生有害影响。由于监管限制,精细化学或制药应用可能不允许ppm数量的离子液体。
因此,聚结器流出物135必须在分离器140中进一步处理。第一分离器140可以是一个或多个包含砂或碳的过滤区,吸附区,洗涤区,静电分离区或其组合。分离器可以包括一个或多个一种类型的分离器,随后是一个或多个不同类型的分离器。例如,可能有两个过滤区,接着是三个吸附区,接着是一个洗涤区。
过滤区包括容器,该容器包含在容器顶部的砂或碳颗粒的固定床以及在容器底部的分离区。聚结器流出物料流135进入容器的顶部,并且随着液体传送通过砂或碳颗粒的固定床,一些小的离子液体滴聚结成较大的液滴。这些较大的液滴然后沉降到分离区的底部,以在容器的底部形成离子液体层,其可以作为第三离子液体料流145提取。烃从分离区的靠近容器底部的一侧作为料流150去除,或者其可以流到另外的过滤区,吸附区或洗涤区。砂或碳颗粒具有适当大小以聚结存在于聚结器流出物料流135中的一些剩余的小的离子液体滴。
吸附区包含含吸附剂的吸附床。在一些实施方案中,吸附剂包含氧化物和氧化物材料如二氧化硅,硅胶,玻璃,玻璃珠,砂和氧化铝中的至少一种可用作颗粒状,纤维状,丸状或其它形式的吸附剂。传统上用作干燥剂的盐如MgSO4和CaSO4可以用作吸附剂材料。其他盐由于电荷-偶极和偶极-偶极的相互作用也可以吸附离子液体。离子交换树脂如磺酸树脂也可是吸附剂,纤维材料如含杂原子的聚合物如尼龙-6和其他纤维如羊毛也可是吸附剂。相信活性炭和粘土也可以用作吸附剂。沸石也可用作吸附剂。
当吸附剂用完时,可以引入解吸剂以从吸附剂解吸离子液体。在另一个实施方案中,可以加热吸附床以除去解吸剂。或者,可以更换吸附剂,并且废吸附剂可以被丢弃。
吸附区可以包括多个容器,容器具有处于摆动构型或滞后构型的床。或者,吸附区可以是以交替的吸附和解吸模式操作的单个容器。床可以是流化床或固定床。
在一些实施方案中,洗涤区包含水和苛性碱中的至少一种。洗涤区可以包括含有一个或多个盘和/或分配板的容器。
合适的静电分离区的一个实例在2014年11月19日提交的名称为Ionic LiquidRecovery From a Hydrocarbon Stream Using Electrostatic Force的美国申请No.62/081702中描述,其通过引用并入本文。具有分散的离子液体滴的烃料流被供到静电分离器。静电分离器包含建立电场的电极,烃料流流入电场。电场可以是交流电(AC)场,其在离子液体滴上诱导极化,导致它们增加它们的碰撞频率并聚结。极化液滴和电极之间还有额外的静电力。较大的离子液体滴落到分离器的底部并被收集。电场也可以是导致离子液体滴电泳运动的直流电(DC)场,也导致碰撞频率增加并因此导致聚结。也可以使用脉冲AC或DC场。
在一些实施方案中,从分离器140中的聚结器流出物135去除的离子液体可以作为第三离子液体料流145从分离器140去除。在其他实施方案中,例如用吸附剂,可能不存在离子液体料流。
来自分离器的分离器流出物150可以具有小于40ppmw的离子液体,或者小于20ppmw,或者小于10ppmw,或者小于5ppmw,或者小于3ppmw,或者小于1ppmw。
在一些实施方案中,如果离子液体的水平足够低,则来自分离器140的分离器流出物150可以根据需要送到普通废物处理设施(未示出)。在其他实施方案中,例如,分离器流出物可被送至产品储存设施或用于另外的工艺中。
第一、第二和第三离子液体料流115,130,145中的一个或多个可被回收并再循环到处理区(未示出)中,一个或多个这些料流中的全部或一部分离子液体可根据需要再生和/或再活化。
已经开发了多种再生离子液体的方法。例如,US 7,651,970;US 7,825,055;US 7,956,002;US7,732,363中的每一个通过引用并入本文,描述了将含有混合聚合物的离子液体与还原金属(例如Al),惰性烃(例如己烷)和氢气接触并加热至100℃以将混合聚合物转移至烃相,将混合聚合物从离子液体相中除去。另一种方法涉及在惰性烃(例如己烷)存在下使含有混合聚合物的离子液体与还原金属(例如Al)接触并加热至100℃以将混合聚合物转移至烃相,将混合聚合物从离子液体相中除去。参见例如US7,674,739B2;其通过引用并入本文。再生离子液体的另一种方法包括使含有混合聚合物的离子液体与还原金属(例如Al),HCl和惰性烃(例如己烷)接触,并加热至100℃以将混合聚合物转移至烃相。参见例如US 7,727,925,其通过引用并入本文。离子液体可通过向含有混合聚合物和惰性烃(例如己烷)的离子液体中加入均相金属氢化催化剂(例如(PPh3)3RhCl)并引入氢气而再生。混合聚合物被还原并转移到烃层。参见例如US 7,678,727,其通过引用并入本文。再生离子液体的另一种方法包括将HCl,异丁烷和惰性烃加入到含有混合聚合物的离子液体中并加热至100℃。混合聚合物反应形成不带电荷的络合物,其转移到烃相中。参见例如US 7,674,740,其通过引用并入本文。离子液体还可以通过向含有混合聚合物和惰性烃(例如己烷)的离子液体中加入负载型金属氢化催化剂(例如Pd/C)而再生。引入氢气,并将混合聚合物还原并转移到烃层。参见例如US 7,691,771,其通过引用并入本文。另一种方法涉及向含有混合聚合物的离子液体中加入合适的基质(例如吡啶)。经过一段时间之后,加入惰性烃以冲洗释放的混合聚合物。将离子液体前体[丁基吡啶][Cl]加入到含有混合聚合物的离子液体(例如[丁基吡啶][Al2Cl7])中,然后加入惰性烃。混合后,分离烃层,产生再生的离子液体。参见例如US 7,737,067,其通过引用并入本文。另一种方法包括将含有混合聚合物的离子液体加入合适的基质(例如吡啶)和含有两个铝电极和惰性烃的电化学电池中。施加电压,并测量电流以测定还原程度。在给定的时间之后,分离惰性烃,产生再生的离子液体。参见例如US 8,524,623,其通过引用并入本文。离子液体还可以通过与硅烷化合物(美国专利9120092),硼烷化合物(美国公开No.2015/0314281),布朗斯台德酸,(美国专利9079176),或C1至C10链烷烃(美国专利9,079,175)接触而再生,其每一个通过引用并入本文。实施例
实施例1:
向720克去离子(DI)水中加入10.1克六氟磷酸1-丁基-3-甲基咪唑离子液体(BMIM),得到pH为3。然后用4.9克NaOH中和该溶液,形成主要是氢氧化铝的固体沉淀物,并使溶液的pH值达到6。过滤除去沉淀物后,测试该溶液(含有0.014mg离子液体/mg溶液)的毒性。然后测定该溶液的半最大效应浓度(EC-50)用于费氏弧菌细菌(Aliivibrio fischeribacteria)的发光以评估溶液的毒性。测定EC-50在5.7mg溶液/升水的稀释度下达到。因此,该离子液体的EC-50为80ppB,远低于仅通过将重力沉降与聚结器结合可实现的水平。
实施例2:
向770克去离子(DI)水中加入10.1克三丁基戊基离子液体(TBPP),得到pH值为3。然后用4.3克NaOH中和该溶液,形成主要是氢氧化铝固体沉淀物,并使溶液的pH值达到6。过滤除去沉淀物后,测定该溶液(含有0.013mg离子液体/mg溶液)的毒性。然后测定该溶液的EC-50用于费氏弧菌细菌的发光以评估溶液的毒性。测定EC-50在1.2mg溶液/升水的稀释度下达到。因此,该离子液体的EC-50为16ppB,远低于仅通过将重力沉降与聚结器结合可实现的水平。
具体实施方式
尽管结合具体实施方案描述了以下内容,但应理解的是,该描述旨在说明而不是限制前面的描述和所附权利要求的范围。
本发明的第一实施方案是用于从工艺料流中除去离子液体的方法,包括将工艺料流引入聚结器以形成离子液体料流和第一处理工艺料流,其中第一处理工艺料流的离子液体水平低于工艺料流中的离子液体水平;将第一处理工艺料流引入分离器中以形成第二处理工艺料流,第二处理工艺料流的离子液体水平低于第一处理工艺料流中离子液体的水平,分离器选自包含砂或碳的过滤区,吸附区,洗涤区,静电分离区或其组合。本发明的一个实施方案为从该段中第一实施方案开始的该段中先前实施方案中的一个、任何或全部,其中第二处理工艺料流中的离子液体水平低于40ppmw。本发明的一个实施方案为从该段中第一实施方案开始的该段中先前实施方案中的一个、任何或全部,其中第二处理工艺料流中的离子液体水平低于20ppmw。本发明的一个实施方案为从该段中第一实施方案开始的该段中先前实施方案中的一个、任何或全部,其中第二处理工艺料流中的离子液体水平低于5ppmw。本发明的一个实施方案为从该段中第一实施方案开始的该段中先前实施方案中的一个、任何或全部,其中分离器是吸附区,并且其中吸附区含有吸附剂,吸附剂包含氧化物、盐、离子交换树脂、聚合物、纤维材料、活性炭、粘土、分子筛、沸石或其组合中的至少一种。本发明的一个实施方案为从该段中第一实施方案开始的该段中先前实施方案中的一个、任何或全部,还包括用解吸剂或通过加热从吸附剂解吸离子液体。本发明的一个实施方案为从该段中第一实施方案开始的该段中先前实施方案中的一个、任何或全部,其中分离器是洗涤区,并且其中洗涤区包含水和苛性碱中的至少一种。本发明的一个实施方案为从该段中第一实施方案开始的该段中先前实施方案中的一个、任何或全部,其中洗涤区包括含有盘、分配板或其组合的容器。本发明的一个实施方案为从该段中第一实施方案开始的该段中先前实施方案中的一个、任何或全部,还包括在将工艺料流引入聚结器之前将工艺进料流引入重力沉降器以形成工艺料流和重力沉降器离子液体料流。本发明的一个实施方案为从该段中第一实施方案开始的该段中先前实施方案中的一个、任何或全部,还包括回收来自聚结器的离子液体料流和来自分离器的离子液体料流中的至少一种。本发明的一个实施方案为从该段中第一实施方案开始的该段中先前实施方案中的一个、任何或全部,还包括以下至少一项:将至少一部分所回收的离子液体再生;将至少一部分所回收的离子液体再循环至处理区。本发明的一个实施方案为从该段中第一实施方案开始的该段中先前实施方案中的一个、任何或全部,还包括将第二处理工艺料流传送至储存设施;将第二处理工艺料流作为进料流送至反应区;将第二处理工艺料流送至废物处理设施;并将第二处理工艺料流作为最终产品回收中的至少一项。
本发明的第二实施方案是用于从工艺料流中除去离子液体的方法,该方法包括将工艺进料流引入重力沉降器中以形成工艺料流和离子液体料流,该工艺料流的离子液体水平低于工艺进料流中的离子液体水平;将工艺料流引入聚结器以形成第二离子液体料流和第一处理工艺料流,第一处理工艺料流的离子液体水平低于工艺料流中离子液体的水平;将第一处理工艺料流引入分离器以形成第二处理工艺料流,第二处理工艺具有小于40ppmw的离子液体水平,所述分离器选自包含砂或碳的过滤区,吸附区,洗涤区,静电分离区或其组合。本发明的一个实施方案为从该段中第二实施方案开始的该段中先前实施方案中的一个、任何或全部,其中第二处理工艺料流中的离子液体水平低于20ppmw。本发明的一个实施方案为从该段中第二实施方案开始的该段中先前实施方案中的一个、任何或全部,其中第二处理工艺料流中的离子液体水平低于5ppmw。本发明的一个实施方案为从该段中第二实施方案开始的该段中先前实施方案中的一个、任何或全部,其中分离器是吸附区,并且其中吸附区包含吸附剂,吸附剂包含氧化物、盐、离子交换树脂、聚合物、纤维材料、活性炭、粘土、分子筛、沸石或其组合中的至少一种。本发明的一个实施方案为从该段中第二实施方案开始的该段中先前实施方案中的一个、任何或全部,其中分离器是洗涤区,并且其中洗涤区包含洗涤离子液体,水和苛性碱中的至少一种,并且其中洗涤区包含含有盘、分配板或其组合的容器。本发明的一个实施方案为从该段中第二实施方案开始的该段中先前实施方案中的一个、任何或全部,还包括回收来自重力沉降器的离子液体料流、来自聚结器的第二离子液体料流、和来自分离器的离子液体料流中的至少一种。本发明的一个实施方案为从该段中第二实施方案开始的该段中先前实施方案中的一个、任何或全部,还包括以下中的至少一项:将至少一部分所回收的离子液体再生;将至少一部分所回收的离子液体再循环至处理区。本发明的一个实施方案为从该段中第二实施方案开始的该段中先前实施方案中的一个、任何或全部,还包括将第二处理工艺料流送至储存设施;将第二处理工艺料流作为进料流送至反应区;将第二处理工艺料流送至废物处理设施;并第二处理工艺料流作为最终产品回收的至少一项。
没有进一步的阐述,相信使用先前的描述,本领域技术人员可以最大程度地利用本发明,并且在不脱离本发明的精神和范围的情况下容易地确定本发明的基本特征,对本发明进行各种改变和修改并使其适应各种用途和条件。因此,上述优选的具体实施方案应被解释为仅是说明性的,并且不以任何方式限制本公开的其余部分,并且其旨在覆盖包括在所附权利要求的范围内的各种修改和等同布置。
在前文中,除非另有说明,所有温度均以摄氏度列出,并且所有份数和百分数均以重量计。

Claims (10)

1.一种从工艺料流中除去离子液体的方法,包括:
将工艺料流引入聚结器以形成离子液体料流和第一处理工艺料流,第一处理工艺料流的离子液体水平低于工艺料流中的离子液体水平;和
将第一处理工艺料流引入分离器以形成第二处理工艺料流,第二处理工艺料流具有比第一处理工艺料流中的离子液体水平低的离子液体水平,所述分离器选自包含砂或碳的过滤区、吸附区、洗涤区、静电分离区或其组合。
2.根据权利要求1所述的方法,其中第二处理工艺料流中的离子液体水平小于40ppmw。
3.根据权利要求1-2中任一项所述的方法,其中分离器是吸附区,并且其中吸附区含有吸附剂,吸附剂包含氧化物、盐、离子交换树脂、聚合物、纤维材料、活性炭、粘土、分子筛、沸石或其组合中的至少一种。
4.根据权利要求3所述的方法,还包括:
用解吸剂或通过加热从吸附剂解吸离子液体。
5.根据权利要求1-2中任一项所述的方法,其中分离器是洗涤区,并且其中洗涤区含有水和苛性碱中的至少一种。
6.根据权利要求5所述的方法,其中洗涤区包括含有盘、分配板或其组合的容器。
7.根据权利要求1-2中任一项所述的方法,还包括:
在将工艺料流引入聚结器之前将工艺进料流引入重力沉降器以形成工艺料流和重力沉降器离子液体料流。
8.根据权利要求1-2中任一项所述的方法,还包括回收来自聚结器的离子液体料流和来自分离器的离子液体料流中的至少一种。
9.根据权利要求8所述的方法,还包括以下中的至少一项:
将至少一部分所回收的离子液体再生;和
将至少一部分所回收的离子液体再循环至处理区。
10.根据权利要求1-2中任一项所述的方法,还包括以下中的至少一项:
将第二处理工艺料流送至储存设施;
将第二处理工艺料流作为进料流送至反应区;
将第二处理工艺料流送至废物处理设施;和
将第二处理工艺料流作为最终产品回收。
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