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CN107206305A - 使用亚烷基桥接的可再生大孔吸附剂在填充移动床中利用微波再生将c2+链烷烃与甲烷分离 - Google Patents

使用亚烷基桥接的可再生大孔吸附剂在填充移动床中利用微波再生将c2+链烷烃与甲烷分离 Download PDF

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CN107206305A
CN107206305A CN201680006890.4A CN201680006890A CN107206305A CN 107206305 A CN107206305 A CN 107206305A CN 201680006890 A CN201680006890 A CN 201680006890A CN 107206305 A CN107206305 A CN 107206305A
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adsorbent
ngl
gas mixture
methane
hydrocarbon gas
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M·L·罗杰斯
B·J·克恩
S·T·麦特斯
H·R·戈尔茨
D·J·吉斯克
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Dow Global Technologies LLC
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Abstract

一种用于从含有天然气液和甲烷的烃气体混合物中分离天然气液(NGL)的方法，所述方法包含以下步骤：i)提供对NGL的选择性优于甲烷的吸附剂床；ii)使含有甲烷和NGL的烃气体混合物穿过所述吸附剂床，以从所述气体混合物中至少部分地去除NGL，以产生：(a)负载NGL的吸附剂和(b)NGL被消耗的烃气体混合物；ⅲ)回收所述NGL被消耗的烃气体混合物；iv)通过从所述吸附剂中至少部分地去除NGL使所述负载NGL的吸附剂再生；以及v)使用来自步骤(iv)的再生吸附剂依序重复步骤(ii)和(iii)。

Description

使用亚烷基桥接的可再生大孔吸附剂在填充移动床中利用微 波再生将C2+链烷烃与甲烷分离
技术领域
本发明涉及使用可再生聚合物吸附剂来分离烃(例如，来自C3和更高碳数的烷烃的C1或C2烷烃)。
背景技术
许多烃(如天然气)源包括链烷烃(例如，甲烷、乙烷、丙烷、丁烷等)以及各种更高碳数的烃和其它气体的混合物。随着水力压裂的激增，从这类混合物中经济地分离所选择烃(例如，甲烷、乙烷)变得日益重要。相比于传统的天然气源，这些新的天然气源中的许多者拥有含量高得多的天然气液(NGL)(例如，BTU值相比于接近1028的传统值大于1058)。其结果是使用这类气体作为燃料源的装置(例如，气体压缩机)在其设计参数以外操作，产生更高的操作温度，增加的污染水平以及更多的维护。对于与油共产生的烃气，存在类似的问题。因更高的BTU含量所致，对这类气体的储存和输送也成为了一个挑战。
已在气体分离中使用各种吸附剂，包括：氧化铝、水滑石、硅酸盐、硅胶以及clinoptilotics(US5993516)。含碳吸附剂，有时称作“碳分子筛”，也已被描述用于氢气纯化和从各种流体混合物中去除水、甲烷、硫、二氧化碳、氮氧化物以及卤烃。参见例如：US5059578、US5217505、US5972834以及US2013/0220935。也参见Cavenati等人,通过PSA从天然气源中纯化甲烷(Methane Purification by PSA from Natural Gas Sources),第2届化学工程南方共同市场大会(2nd Mercosur Congress on Chemical Engineering)。含碳吸附剂是碳化合物的碳化形式，所述碳化合物如煤炭、焦炭、泥炭、木炭、坚果壳炭、果仁炭(fruit nut char)、椰子壳炭、骨炭、酚树脂、呋喃树脂以及偏二氯乙烯共聚物，参见例如US5300468和US5972834。WO2014/160624描述了微孔碳分子筛用于将烯烃与烷烃分离的用途。材料包含非熔融粘合剂和在500到1000℃的温度下热解的无孔凝胶型磺化离子交换树脂。热解的凝胶型磺化离子交换树脂的类似用途也论述在以下中：Liu,J.等人“用于诸多气体分离的一种碳分子筛的高通量开发(High throughput development of one carbonmolecular sieve for many gas separations)”《微孔与间孔材料(Microporous andMesoporous Materials)》(2014)；Miura,K.,“负载金属纳米颗粒的新颖多孔碳的制备和其针对能量和环境相关问题的应用(Preparation of novel porous carbons supportingmetal nanoparticles and their applications to energy and environmentalrelated issues)”《工业与工程化学杂志(J.Ind.Eng.Chem.)》,11,第6期,(2005)797-817，以及Miura,K.等人“通过利用柱效应控制碳化离子交换树脂中微孔的形成(Control ofmicropore formation in the carbonized ion exchange resin by utilizing pillareffect),”《碳(Carbon)》37(1999)1455-1461。热解的磺化大孔离子交换树脂也描述在文献中。参见例如：Neely,J.对衍生自多孔磺化聚苯乙烯的聚合物碳的表征(Characterizationof Polymer Carbons Derived from Porous Sulfonated Polystyrene),《碳》19(1980)27-36、US4040990以及US4839331。在以下中提供对各种吸附剂和其于气体分离中的用途的概述：Tagliabue等人,通过选择性吸附的天然气处理：材料科学与化学工程相互作用,《化学工程杂志(Chemical Engineering Journal)》155(2009)553-566。
期望的是具有一种能够以经济方式从天然气中去除C2+链烷烃(例如，丙烷、丁烷)或NGL的可再生聚合物吸附剂和相关方法。理想地，可以单独地回收NGL。系统如分批、半分批或连续操作微波再生吸附方法是已知的。再生涉及将吸附剂暴露到更高温度或更低压力。用于将吸附剂暴露到更高温度的可应用技术包括用电加热器或气体加热器加热床，使热气体穿过床，以及用微波辐射照射吸附剂(参见例如US5509956、US594681以及JP2005/194132)。用微波照射是一种优选的方法。然而，这类系统的一个限制是其需要具有包括在解吸附室内的屏蔽件，因为传统的聚合物吸附剂不完全地吸收微波。此外，这些损失的微波经过设计来加热吸附剂，并且穿过吸附剂的任何微波构成废能量并且降低了系统的生产率。
发明内容
在一个实施例中，本发明包括一种用于从烃气体混合物中分离甲烷或乙烷的方法，所述烃气体混合物包含甲烷或乙烷或甲烷与乙烷的组合以及C2+链烷烃，其中所述方法包含以下步骤：
i)提供对C2+链烷烃的选择性优于甲烷和乙烷的吸附剂床；
ii)使烃气体混合物穿过吸附剂床，以从气体混合物中至少部分地去除C2+链烷烃，以产生：(a)负载C2+链烷烃的吸附剂和(b)C2+链烷烃被消耗的烃气体混合物；
iii)回收C2+链烷烃被消耗的烃气体混合物；
iv)通过从吸附剂中至少部分地去除C2+链烷烃使负载C2+链烷烃的吸附剂再生；以及
v)使用来自步骤(iv)的再生吸附剂依序重复步骤(ii)和(iii)。
在一个优选实施例中，使负载NGL的吸附剂再生的步骤包括用微波照射吸附剂。在另一个优选实施例中，吸附剂包括优选经过官能化(例如，具有含胺或硫的官能团)的亚烷基桥接的大孔吸附剂。
附图说明
图1是根据本发明的一个实施例的天然气吸附和再生系统的示意图。
图2包括根据实例1的测试方案使用DOWEXTMOPTIPORETMV493的甲烷、乙烷、丙烷、丁烷以及戊烷的吸附等温线。
图3包括根据实例1的测试方案的使用DOWEXTMOPTIPORETMV503的甲烷、乙烷、丙烷、丁烷以及戊烷的吸附等温线。
图4是温度(℉)随时间(min)而变的图并且对应于实例2。
图5是温度变化率(℉/min)随时间(分钟)而变的图并且对应于实例2。
具体实施方式
本发明包括一种用于分离烃(例如，NGL与甲烷分离；C2+链烷烃与甲烷或乙烷或甲烷与乙烷的组合分离)的方法和系统。在一个实施例中，待处理的源气体是包括链烷烃(甲烷、乙烷、丙烷以及丁烷)的组合的天然气。天然气最常见地获自油井、气井和凝液井。还可以存在各种成分气体。举例来说，未精制的天然气经常含有大量的杂质，如水或酸性气体，例如二氧化碳(CO2)、硫化氢(H2S)、二氧化硫(SO2)、二硫化碳(CS2)、氰化氢(HCN)、硫化羰(COS)以及硫醇。术语“天然气液”(NGL)广泛地指具有两个或更多个碳(如乙烷、丙烷、丁烷)和可能少量的戊烷或更高碳数的烃的烃。术语“C2+链烷烃”是指不为乙烷的NGL链烷烃。
在一个实施例中，本发明方法包括以下步骤：使加压的烃气体混合物穿过吸附剂床，以从烃气体混合物中至少部分地去除NGL，以产生：(a)负载NGL的吸附剂和(b)NGL被消耗的烃气体混合物。对床的配置不受特定限制并且可以使用填充床和流化床，但优选是填充移动床。可应用的床包括可加压容器或可加压室，其包括一个或多个气体入口和出口以及开口，所述开口用于转移吸附剂，例如转出负载NGL的吸附剂并且转入新鲜或再生的吸附剂。优选的操作条件包括：400到1200psi的压力；0.5到1800秒、更优选5到480秒的滞留时间；以及0.5英尺/秒到0.001英尺/秒的通过床的空间速度。可应用的烃气体混合物包括甲烷和NGL，例如含有甲烷和一种或多种更高碳数的烷烃(包括乙烷、丙烷以及丁烷)的气体混合物。
一旦吸附剂至少部分地负载有NGL，可以从床中移出吸附剂并且丢弃。或者，可以使负载NGL的吸附剂再生。再生涉及从吸附剂中至少部分地解吸附NGL。可以回收(储存、输送等)或丢弃经过解吸附的NGL。可以在发生吸附的同一床中发生再生过程，或可以将吸附剂转移到单独的床(容器)。再生涉及将吸附剂暴露到以下各项中的至少一项：相比于在NGL吸附步骤期间存在的条件，a)更高温度和b)更高压力。用于将吸附剂暴露到更高温度的可应用技术包括用电加热器或气体加热器加热床，使热气体穿过床，以及用微波辐射照射吸附剂(参见例如US5509956、US5946816以及JP2005/194132)。用微波照射是一种优选的方法。用于降低压力的技术包括将床通风到外部槽或大气。再生步骤可以按分批、半分批或连续操作进行并且可以包括TSA、PSA以及VSA的组合。
在一个优选实施例中，本发明方法涉及以下步骤：
i)提供对NGL的选择性优于甲烷的吸附剂床；
ii)使含有甲烷和NGL的烃气体混合物穿过吸附剂床，以从气体混合物中至少部分地去除NGL，以产生：(a)负载NGL的吸附剂和(b)NGL被消耗的烃气体混合物；
iii)回收NGL被消耗的烃气体混合物；
iv)通过从吸附剂中至少部分地去除NGL使负载NGL的吸附剂再生；以及
v)使用来自步骤(iv)的再生吸附剂依序重复步骤(ii)和(iii)。
在一个优选实施例中，步骤(i)发生在吸附室中，并且步骤(iv)发生在解吸附室中，并且负载NGL的吸附剂从吸附室连续地转移到解吸附室，并且再生吸附剂从解吸附室连续地转移吸附室。再生优选地通过用微波照射吸附剂来进行。虽然可以组合使用不同类型的吸附剂，但其优选形成随机或均匀的混合物，所述混合物形成单个填充移动床。在一个优选实施例中，使用单种类型的吸附剂。
本吸附剂展现通过微波高度再生的未预期特性，特定来说功能化的那些特性。其结果是，使用本吸附剂的微波再生的方法和系统能够获得新的效率水平并且在一些情况下对微波屏蔽件的需求降低。
在图1中说明用于实践本发明的代表性系统，其包括NGL吸附单元(10)、包括吸附剂床(2)的吸附槽(1)。天然气通过在吸附槽(1)下部的管线(3)进入吸附单元(10)并且(4)穿过吸附剂床(2)。吸附床(2)包含从天然气中选择性吸附C2、C3、C4、C5以及更高碳数的烃的吸附剂。吸附单元(10)的入口温度可以在5到100℃、优选15到80℃并且更优选20到70℃的范围内。可以使用14至1400psia、优选600至1200psia并且更优选地800至1000psia的压力。与天然气相比，极大地减少重烃含量的富甲烷天然气产物流从吸附槽(1)的顶部经由管线(5)离开吸附剂床(2)。可以回收或燃烧富甲烷天然气流。
随着吸附剂负载有NGL，其经由输送机构(9)穿过吸附槽(1)的底部，经由管线(11)进入具有再生槽(21)和微波加热系统(32)的微波再生单元(20)。微波加热系统(32)的操作温度可以在105到350℃、优选140到250℃并且更优选145到200℃的范围内。可以使用20到600psia、优选100到400psia并且更优选150到200psia的压力。微波电源(30)在微波加热系统(32)中加热吸附剂(2)，使得NGL蒸发(33)。微波加热系统(32)可以包括加热设备和加热或辐射系统(图中未示)以及任选地净化气体系统(24)。加热设备可以耦接到辐射系统并且与其连通以便接收由辐射系统产生的热能(如微波辐射或电磁能)，并且与净化气体系统(24)连通以便接收净化气体以有助于从吸附剂中去除挥发物。NGL是经由抽真空系统(40)通过抽吸口(28)从再生槽(21)中提取。再生槽(21)可以任选地装配有净化气体系统(24)，其中净化气体(例如氮气)经由管线(22)进入并且在再生槽(21)的底部分散(25)。允许再生吸附剂(23)从再生槽(21)的底部穿过管线(26)，随后返回到吸附槽(1)。一部分富甲烷天然气从槽(1)的顶部经由管线(6)循环通过鼓风机(7)，经由管线(8)输送再生吸附(23)以从天然气(3)中再次吸附NGL。
从再生槽(21)中真空提取的NGL穿过真空提取系统(40)，通过气体压缩系统(50)并且进入冷凝器(60)，在冷凝器中NGL冷凝，任选地分离，并且以NGL的混合物或乙烷、丙烷、丁烷、戊烷和/或更高碳数的烃的个别部分形式排放到一个或多个槽(72、73、74和/或75)中。所排放的NGL可以回收、输送、液化、再注入、排除、分流或燃烧。使得到达冷凝器的任何甲烷经由管线(61)再循环回到吸附槽(1)，并且可以经由管线(62)分离任何其它气体、净化气体、水和/或污染物。
在所说明的实施例中，NGL分离方法是使得吸附剂连续再生的连续方法。举例来说，在所说明的实施例中，在吸附剂槽(1)与再生槽(21)之间的管线(11)中存在阀(12)，并且在再生槽(21)与收集槽(17)之间的管线(26)中存在阀(27)。阀门(12)和(27)同步以允许保留来自吸附槽(1)的负载吸附，同时吸附在再生器单元(20)中再生。当吸附剂在再生器槽(21)中再生时，阀(27)允许再生吸附剂(23)离开再生器槽(21)并且输送回到吸附槽(1)。随后阀(12)允许负载的吸附剂进入再生器槽(21)以待再生。重复这一过程并且允许吸附介质连续再生。
在本发明的另一个实施例中，NGL分离方法是使得吸附剂分批再生的分批方法。举例来说，图1中，在吸附槽(1)与再生槽(21)之间存在储料槽(13)。当吸附剂(2)被负载时，其全部经由输送机构(9)和管线(11)从吸附槽(1)运送到储料槽(13)。随后储料槽(13)的内含物经由管线(15)输送到再生槽(21)，在再生槽中负载的吸附介质再生并且返回到吸附剂槽(1)，在吸附剂槽中使用其直到负载为止并且重复所述过程。
用于本发明的吸附剂处于熟知类别，即亚烷基桥接的大孔聚合物吸附剂，有时亦被称作“macronets”或“超高交联”吸附剂。本吸附剂可与含碳吸附剂区分，因为含碳吸附剂是热解的(即碳化的)。相比于含碳吸附剂，用于本发明的吸附剂也展现高得多的压碎强度(crush strength)(例如，高于500克/珠粒，并且优选高于750克/珠粒)。本吸附剂可通过具有0.1到0.9:1、优选0.4到0.8:1并且更优选0.6到0.8:1的亚烷基桥接与酚的比率而与传统的大孔离子交换树脂区分(参见US5079274)。本吸附剂进一步可通过具有相对高的表面积，例如500到2100m2/g、优选750到2000m2/g并且更优选1000到1500m2/g)而与大孔交换树脂区分。本吸附剂进一步可通过具有高得多的压碎强度而与传统的大孔离子交换树脂区分，例如DOWEX MARATHON MSC的抗压强度是375-475克/珠粒，而DOWEXTMOPTIPORETMV493的压碎在950-1150克/珠粒范围内。可购自陶氏化学公司(The Dow Chemical Company)的DOWEXTMOPTIPORETMV493是用于本发明的合适吸附剂的一实例。这种吸附剂是非官能化的亚烷基桥接的大孔聚合物吸附剂，其包含苯乙烯-二乙烯基苯交联共聚物基质。来自陶氏化学公司的另一种合适的吸附剂是DOWEXTMOPTIPORETMV503，一种类似于OPTIPORETMV493的吸附剂，然而存在于基质中的残余氯甲基与二乙基苯反应，使得吸附剂具有增加的疏水性。(参见US5504163)。在一个优选实施例中，本吸附剂是官能化的并且干重容量(dry weightcapacity)是0.5到2.0毫当量/克(meq/g)。可购自陶氏化学公司的代表性吸附剂包括DOWEXTMOPTIPORETMSD-2，一种包含用弱碱基团(二甲胺)官能化的苯乙烯-二乙烯基苯交联共聚物基质的亚烷基桥接的大孔聚合物吸附剂。(参见US4950332)。
本吸附剂优选在35℃和66.6kPa(500mm Hg)丙烷下每克吸附(并且在脱气后再吸附)大于60cm3(STP)的丙烷。在另一个实施例中，在暴露于暴露到在2.45GHz下操作的微波时45秒后，本吸附剂优选达到至少100℉的温度。(在测试之前，在95℃下吸附剂干燥至少15小时)。对于暴露于在2.45GHz下操作的微波的第一次3分钟暴露，吸附剂也优选具有至少25℉的温度增加速率。
用于制备并且表征本吸附剂的方法有广泛记载。参见例如：以引用的方式并入本文中的US3729457、US4263407、US4950332、US4965083、US5460725、US5616622、US5683600以及US5893947。也参见：V.A.Davankov等人,《反应聚合物(Reaction Polymers)》,第13卷,27(1990)和V.A.Davankov等人,“超高交联的聚苯乙烯吸附剂的结构和吸附剂特性(Structure and Adsorbent Properties of Hypercrosslinked PolystyreneSorbents)”,《离子交换开发和应用(Ion Exchange Developments and Applications)》,JA.Greig编(1996)。这类吸附剂(包括非官能化型式)的传统用途包括脱色(US4950332)、脱矿化(US5893947)、去苦味(US4965083)、酸去除(EP0481603)、脱咖啡因(US5021253)以及烃去除(US5079274、US5288307、US5509956)。吸附剂可以使用通常与离子交换树脂结合使用的标准技术官能化(磺化、胺化等)。代表性技术描述于US4950332(胺化)、US5616622(磺化)以及US5893947中。本吸附剂可以按各种形式(例如球粒、颗粒等)提供，然而，珠粒形式是优选的，其中中数直径是10到2000微米，并且更优选300到1500微米，并且甚至更优选500到1000微米。珠粒可以具有高斯(Gaussian)粒度分布或可以具有相对均一的粒度分布，即“单分散的”，也就是说，至少90体积百分比的珠粒的粒径是体积平均粒径的约0.8到约1.2倍，并且更优选0.9到1.1倍。
本吸附剂是大孔的。如本领域中常用的，术语“大孔型”意指聚合物同时具有大孔和中孔。中孔的直径是到约并且大孔的直径大于约虽然本吸附剂还包括微孔(直径小于)，但大孔的存在将本吸附剂与凝胶型或微孔离子交换树脂区分开来。本吸附剂的孔隙度是0.1到0.7立方厘米孔隙体积/立方厘米树脂(cc/cc)。孔隙度、平均孔隙大小以及表面积通过氮吸附方法确定，在氮吸附方法中在自动体积吸附分析仪上分析干燥并脱气的样品。仪器基于在既定氮气分压下测量样品所吸附的气态氮的体积的原理来工作。在B.E.T.型号中使用各种压力下吸附的气体体积以计算样品的表面积。由样品的表面积与孔隙体积之间的关系计算平均孔隙半径。
本发明的亚烷基桥接的大孔聚合物吸附剂是基于至少一种单乙烯基芳香族单体和聚乙烯基芳香族交联单体的致孔剂改性的交联共聚物基质。交联共聚物基质进一步通过后续亚烷基桥接来交联。单乙烯基芳香族单体包括苯乙烯、乙烯基甲苯、乙基乙烯基苯以及乙烯基萘并且还可以包括杂环单体，如乙烯基吡啶。优选的单乙烯基芳香族单体包括苯乙烯、乙烯基甲苯、乙基乙烯基苯以及其混合物。苯乙烯、乙基乙烯基苯以及其混合物是最优选的。单乙烯基芳香族单体占全部单体混合物的45到80重量百分比，优选占全部单体混合物的65到80重量百分比。
单乙烯基脂肪族单体包括丙烯酸和甲基丙烯酸以及丙烯腈的衍生物。优选的单乙烯基脂肪族单体包括甲基丙烯酸甲酯、丙烯腈、丙烯酸乙酯、甲基丙烯酸2-羟基乙基酯以及其混合物。单乙烯基脂肪族单体占全部单体混合物的0到20重量百分比。由于后续的亚烷基桥接发生在芳香族环之间，因此经常优选地，不采用任何单乙烯基脂肪族单体或将其量保持在最低。
聚乙烯基芳香族交联单体包括二乙烯基苯和三乙烯基苯，其中二乙烯基苯是最优选的。商业二乙烯基苯通常由具有20到45重量百分比乙基乙烯基苯的混杂物中的55到80重量百分比二乙烯基苯组成。实际的聚乙烯基芳香族交联单体占全部单体混合物的20到35重量百分比。在任何所给出实例中，单乙烯基芳香族和脂肪族单体与聚乙烯基芳香族交联单体的比率是1.8-4.0。
形成本发明基础的交联共聚物基质是致孔剂改性的，即，其在致孔溶剂(porogenic solvent)或两种或更多种这类致孔溶剂的混合物存在下通过悬浮聚合来制备。致孔溶剂是适用于形成孔隙和/或在聚合期间位移聚合物链的那些溶剂。在US4224415中描述了这类溶剂的特征和在形成大孔吸附剂中的用途。致孔溶剂是溶解共聚的单体混合物但不溶解共聚物的致孔溶剂。另外，致孔溶剂必须对聚合条件有惰性，即，既不干扰聚合也不进入聚合。对于由本发明的单乙烯基芳香族单体和聚乙烯基芳香族交联单体制备的交联共聚物，如甲苯、二甲苯和乙苯的芳香族烃，如庚烷和异辛烷的C6-C12饱和脂肪族烃以及如叔戊醇、仲丁醇和2-乙基己醇的C4-C10烷醇是尤其有效的。芳香族烃和C6-C12饱和脂肪族烃以及其混合物是优选的；单独的甲苯或甲苯与C6-C8饱和脂肪族烃的混合物是最优选的。需要足够浓度的致孔溶剂以实现相分离或聚合物链位移。通常，致孔溶剂占单体混合物和致孔溶剂的总重量的50到70重量百分比，并且优选55到65重量百分比。
术语悬浮聚合是本领域的技术人员所熟知的术语，并且在介质中包含皆不可溶的单体或单体混合物的悬浮液滴和致孔溶剂的悬浮液滴。这可以通过在任何添加剂下将单体或单体混合物和致孔溶剂添加到含有分散剂或悬浮剂的悬浮介质中来实现。对于本发明的烯系不饱和芳香族单体，悬浮介质通常是水并且悬浮剂一种悬浮稳定剂，例如明胶、聚乙烯醇或纤维素，如羟乙基纤维素、甲基纤维素或羧甲基甲基纤维素。当搅拌介质时，有机相(单体和致孔溶剂)分散成精细液滴。聚合通过在自由基引发剂存在下加热来实现。自由基引发剂可以是用于在烯系不饱和单体的聚合中产生自由基的常规引发剂中的任一种或组合。代表性引发剂是UV辐射引发剂和化学引发剂，如偶氮化合物，如偶氮二异丁腈；和过氧化合物，如过氧化苯甲酰、过苯甲酸叔丁酯以及过碳酸异丙酯。仅需要催化量的引发剂。根据单体混合物的重量，常见范围是约0.01％到约3％的引发剂。优选的范围是0.1％到1.5％。大部分通过所选择特定单体的性质、所存在杂质的性质以及所使用致孔剂的体积来确定引发剂的最优量。举例来说，当采用更高含量的聚乙烯基芳香族交联单体时，可能需要使用更大百分比、例如大于0.5重量百分比的自由基引发剂。
在典型的悬浮聚合中，含有单体、致孔溶剂以及引发剂的有机相悬浮在搅拌的水性介质内。一般来说，按有机相和悬浮介质的总重量计，悬浮介质以30到70重量百分比、优选35到50重量百分比的量采用。聚合是在30℃与130℃之间、优选70℃在与110℃之间的温度下进行。
或者，共聚物珠粒可以通过如描述于例如US4419245、US4564644以及US5231115(它们以引用的方式并入本文中)中的连续添加的接种方法来制备。在这类方法中，交联共聚物的种子颗粒悬浮于水相中并且用如上文所描述的有机相-即单体混合物、致孔溶剂以及引发剂-溶胀。在聚合40％到95％后，连续地添加第二有机相，同时继续聚合。第二有机相可以与第一有机相相同或不同，其限制条件为单乙烯基芳香族单体、聚乙烯基芳香族交联单体以及致孔溶剂的比率在本发明的限制内。优选地，第二有机相不含引发剂。
本发明的吸附剂可以通过聚合后个别聚合物链的额外亚烷基桥接(后交联)由前述交联共聚物珠粒来制备。后交联可以通过在非反应性条件下首先将共聚物珠粒用溶胀剂以及卤烷基化剂(haloalkylating agent)和有效量的弗里德-克拉夫茨催化剂(Friedel-Crafts catalyst)溶胀来实现。卤烷基化剂有利地将弗里德-克拉夫茨催化剂并入其中。随后将溶胀的共聚物珠粒维持在以下温度下：足以使卤烷基化剂与共聚物珠粒反应，直到获得所期望的反应程度，通常每个芳香族环0.6到0.7个卤烷基。反应温度可以是20℃到180℃。更优选地，温度是60℃到85℃。用于使共聚物珠粒卤烷基化的方法描述于以下中：US2642417、US2960480、US2992544、US4191813、US4263407以及US4950332，它们以引用的方式并入本文中。
弗里德-克拉夫茨催化剂是路易斯酸(Lewis acid)并且包括例如AlCl3、FeCl3、BF3以及HF。AlCl3和FeCl3是优选的。优选的卤烷基化剂包括氯甲基甲基醚和α,α'-二氯二甲苯，其中氯甲基甲基醚是最优选的。合适的溶胀剂是如下溶剂：其在卤烷基化的共聚物的后交联期间基本上是惰性的，并且包括氯化烃，如二氯乙烷、氯苯、二氯苯、二氯甲烷以及丙烯二氯化物，或氮取代的芳香族物，如硝基苯。
当使共聚物基质氯甲基化时，氯甲基与相邻共聚物链的芳香族环的反应使得在两个共聚物链之间形成亚烷基桥，或在此实例中形成亚甲基桥，即(-CH2-)部分，如以下反应路径中所说明。
在形成桥接部分后，可以通过常规方法如溶剂萃取、洗涤、干燥或其组合来去除卤烷基化剂和溶胀剂。如果使用干燥步骤，那么在高于正常室温的温度下优选地避免含氧气氛。
随后可使用文献中所描述的经典方法将亚烷基桥接的基质官能化(磺化、胺化等)。参见例如：US2500149、US2631127、US2664801、US2764564、US3037052、US3266007、US4950332、US5248435、US5616622、US2002/002267以及US2004/0006145；它们的相关教示内容以引用的方式并入本文中。一般来说，通过在足以获得所期望的磺化度的温度下，使亚烷基桥接的共聚物基质与磺化剂如浓硫酸(按总重量计具有至少约95重量百分比硫酸的酸)、发烟硫酸、氯磺酸或三氧化硫反应，持续足以获得所期望的磺化度的时间，来制备磺化吸附剂。优选的磺化剂是浓硫酸。浓硫酸的量应足以在反应期间提供充分的混合，一般约2:1到约20:1的酸与珠粒的重量比是足够的。通常，将酸和共聚物珠粒维持在约0℃到约200℃的温度下，持续足以获得干重容量是至少约0.5毫当量/克(meq/g)的吸附剂的时间。可以在溶胀剂存在下进行磺化。代表性溶胀剂包括：二氯甲烷、二氯化乙烯、二氯丙烷、二氧化硫、苯、甲苯、二甲苯、乙苯、异丙基苯、氯苯、硝基苯、硝基甲烷、四氯乙烷以及四氯乙烯。
可应用的胺化反应的实例描述于以下中：US5134169、US5141965、US6756462、US6924317、US7282153、US2004/0256597以及US4950332。优选的胺官能团包括二甲胺、三甲胺以及二亚乙基三胺(DETA)，其也称为N-(2-氨基乙基-1,2-乙二胺)。
已经描述了本发明的多个实施例并且在一些情况下已将某些实施例、选择、范围、组分或其它特征表征为“优选的”。对“优选”特征的表征决不应解释为将这类特征视作是本发明所需的、必需的或关键的。
实例
实例1：如下文所描述测试两种可商购的亚烷基桥接的大孔吸附剂的NGL吸附容量和穿透特性。
样品1(DOWEXTMOPTIPORETMV493)(非官能化的)
样品2(DOWEXTMOPTIPORETMV503)残余氯甲基通过与二乙基苯反应的后反应产生已增加疏水性的介质。
甲烷、乙烷、丙烷以及丁烷：使用Micromeritics ASAP 2020表面积和孔隙度分析仪来分析308K下的甲烷(西格玛-奥德里奇公司(Sigma-Aldrich)，99.0％)、乙烷(西格玛-奥德里奇公司，99.99)、丙烷(西格玛-奥德里奇公司，99.97％)以及丁烷(Matheson Tri-Gas，99.9％)吸附。在分析之前，在石英U形管中在423K下在真空下将所测试的大孔聚合物吸附剂(0.3至0.5克)脱气到低于5μmHg的压力持续12小时。采用在5到600mmHg之间的压力点，具有45秒平衡间隔。随后在真空下将样品抽空1小时，之后重复压力点。
戊烷：使用配备有蒸气引入选项与双区温度控制的Micromeritics ASAP 2020表面积和孔隙度分析仪来分析在273K下的静态戊烷吸附。使用冷却器露水内含有的乙二醇/水混合物作为样品的温度控制。将戊烷(西格玛-奥德里奇公司，无水，≥99％)置于位于控制到308K的温度调节蒸气炉中的石英容器中。在戊烷分析之前，在石英管中在373K下在真空下将所测试的大孔聚合物吸附剂脱气到低于5μmHg的压力持续至少12小时。采用在0.005<P/P0<0.50之间的相对压力点。饱和压力P0基于戊烷吸附特性和分析浴温被计算为183.526mmHg。
吸附穿透(Adsorption Breakthrough)：
使用GC/质谱仪(mass spec)确定吸附剂的穿透曲线数据。校准GC/质谱，随后将40g样品负载到样品柱。分析包含40/40/40/40标准立方厘米/分钟(SCCM)的比率的CH4/C2H6/C3H8/C4H10的混合气体。气体开始流动。这一流动分流通过填充床(即柱)。使系统平衡2小时。随后通过质谱仪分析分流的气体。在两分钟延迟后，打开三通阀门以使得混合气体进入填充床柱。记录离开填充床柱的混合气体的质谱分析数据。允许系统运行直到所有气体已在质谱仪中分析并且记录为止。表1列举每一种气体的穿透时间。分别在图2和3中提供样品1和2的等温线。
表1
实例2：为了证实本亚烷基桥接的大孔吸附剂的官能化实施例的独特的微波吸附特性，在相同条件下将三种可商购的吸附剂(在下文标注)暴露于微波。根据时间监测吸附剂的温度，其中温度充当微波吸附的替代项。结果概述在图4和5中。
样品吸附剂：
◇DOWEXTMOPTIPORETMV503(非官能化的
■DOWEXTMOPTIPORETMV493(非官能化的)
▲DOWEXTMOPTIPORETMSD-2(官能化的)
实例3：为了证实本吸附剂的优异的丙烷吸附特征，将五种不同的吸附剂与可商购的大孔离子交换树脂相比较。所有样品是基于大孔交联共聚物基质，所述大孔交联共聚物基质衍生自包含苯乙烯和二乙烯基苯的单体混合物。
使用Micromeritics ASAP 2020表面积和孔隙度分析仪来分析308K下的丙烷(西格玛-奥德里奇公司，99.97％)吸附。在分析之前，在石英U形管中在423K下在真空下将所测试的大孔聚合物吸附剂(0.3至0.5克)脱气到低于5μmHg的压力持续12小时。采用400、500以及600mmHg的压力点，具有45秒平衡间隔。
如通过表2中所概述的结果所说明，本亚烷基桥接的吸附剂具有良好的丙烷吸附，然而相对应的无亚烷基桥接的大孔树脂具有极少到无丙烷吸附。
表2
样品3-1：DowexTMOptiporeTMV493
样品3-2：DowexTMOptiporeTMSD-2
样品3-3：亚烷基桥接的大孔吸附剂，类似于3-2但用三甲基胺官能化
样品3-4：亚烷基桥接的大孔吸附剂，类似于3-2但用二亚乙基三胺官能化
样品3-5：亚烷基桥接的大孔吸附剂，类似于3-2但用硫酸官能化
*样品3-6：DowexTM22(大孔2型强碱阴离子交换树脂)
*样品3-7：DowexTM66(大孔弱碱阴离子交换树脂)
*样品3-8：DowexTMMarathon MSC(大孔阳离子交换树脂)
*样品3-9：DowexTMMarathon MSA(大孔阴离子交换树脂)
*仅进行比较(不是本发明的一部分)。

Claims (10)

1.一种用于从烃气体混合物中分离甲烷或乙烷的方法，所述烃气体混合物包含甲烷或乙烷或甲烷与乙烷的组合以及C2+链烷烃，其中所述方法包含以下步骤：
i)提供对C2+链烷烃的选择性优于甲烷和乙烷的吸附剂床；
ii)使烃气体混合物穿过所述吸附剂床，以从所述气体混合物中至少部分地去除C2+链烷烃，以产生：(a)负载C2+链烷烃的吸附剂和(b)C2+链烷烃被消耗的烃气体混合物；
iii)回收所述C2+链烷烃被消耗的烃气体混合物；
iv)通过从所述吸附剂中至少部分地去除C2+链烷烃使所述负载C2+链烷烃的吸附剂再生；以及
v)使用来自步骤(iv)的再生吸附剂依序重复步骤(ii)和(iii)。
2.根据权利要求1所述的用于从烃气体混合物中分离甲烷的方法，所述烃气体混合物包含甲烷和包含乙烷和C2+链烷烃的天然气液(NGL)，其中所述方法包含以下步骤：
i)提供对NGL的选择性优于甲烷的吸附剂床；
ii)使烃气体混合物穿过所述吸附剂床，以从所述气体混合物中至少部分地去除NGL，以产生：(a)负载NGL的吸附剂和(b)NGL被消耗的烃气体混合物；
iii)回收所述NGL被消耗的烃气体混合物；
iv)通过从所述吸附剂中至少部分地去除NGL使所述负载NGL的吸附剂再生；以及
v)使用来自步骤(iv)的再生吸附剂依序重复步骤(ii)和(iii)。
3.根据权利要求2所述的方法，其中步骤(i)发生在吸附室中，并且步骤(iv)发生在解吸附室中，并且其中负载NGL的吸附剂从所述吸附室连续地转移到所述解吸附室，并且再生吸附剂从所述解吸附室连续地转移到所述吸附室。
4.根据权利要求3所述的方法，其中位于所述吸附室中的所述吸附剂形成填充移动床。
5.根据权利要求2所述的方法，其中使所述负载NGL的吸附剂再生的所述步骤包含用微波照射所述吸附剂。
6.根据权利要求1所述的方法，其中所述吸附剂包含亚烷基桥接的大孔吸附剂。
7.根据权利要求1所述的方法，其中所述吸附剂的亚烷基桥接与酚的比率是0.4到0.8:1。
8.根据权利要求1所述的方法，其中所述吸附剂包含官能化的亚烷基桥接的大孔吸附剂。
9.根据权利要求8所述的方法，其中所述吸附剂包含干重容量是0.5到2.0毫当量/克的官能化的亚烷基桥接的大孔吸附剂。
10.根据权利要求8所述的方法，其中所述亚烷基桥接的大孔吸附剂包含含胺或硫的官能团。
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