CN103827060A - 由天然油共制备烷基苯和生物燃料的方法 - Google Patents

由天然油共制备烷基苯和生物燃料的方法 Download PDF

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CN103827060A
CN103827060A CN201280046370.8A CN201280046370A CN103827060A CN 103827060 A CN103827060 A CN 103827060A CN 201280046370 A CN201280046370 A CN 201280046370A CN 103827060 A CN103827060 A CN 103827060A
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alkane
alkylbenzene
natural oil
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A·G·博萨诺
M·J·格里菲斯
A·阿努玛康达
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Universal Oil Products Co
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Abstract

本发明提供由天然油共制备直链烷基苯和生物燃料的方法的实施方案。一种方法包括使天然油脱氧以形成包含烷烃的料流的步骤。使烷烃的第一部分脱氢以得到单烯烃。随后，在烷基化条件下用单烯烃使苯烷基化以得到包含烷基苯和苯的烷基化流出物。此后，分离烷基苯以得到烷基苯产物。处理烷烃的第二部分以形成生物燃料。

Description

由天然油共制备烷基苯和生物燃料的方法
优先权说明
本申请主张2011年9月23日申请的美国申请第13/242,833号的优先权，其内容据此以全文引用的方式并入本文中。
技术领域
本发明大体上涉及共制备烷基苯和生物燃料的方法，且更具体地涉及由天然油制备可再生烷基苯和生物燃料的方法。
现有技术
直链烷基苯为具有式C6H5CnH2n+1的有机化合物。尽管n可具有任何实际值，但烷基苯的当前商业用途要求n处于10与16之间，或更特别地处于10与13之间、处于12与15之间或处于12与13之间。当烷基苯在制备清洁剂的表面活性剂中用作中间体时，通常要求这些特定范围。由于自烷基苯产生的表面活性剂可生物降解，故烷基苯制备自其1960年代最初用于清洁剂制备以来已快速增长。
尽管使用基于烷基苯的表面活性剂制备的清洁剂可生物降解，但产生烷基苯的方法并不基于可再生来源。特别地，烷基苯目前自由土壤提取的煤油制备。由于关于化石燃料提取的环境问题日益增多且关于正在耗竭的化石燃料储备存在经济担忧，故可能支持在清洁剂和其它工业中使用生物可降解表面活性剂的替代性来源。
对使用生物燃料还存在日益增加的需求以便降低对化石燃料的需求且减少其使用。此需求尤其适用于运输需要，其中难以利用其它可再生能源。举例而言，生物柴油或绿色柴油和生物喷射机燃料或绿色喷射机燃料可使基于石油的燃料的需求和使用显著减少。
因此，需要提供由天然油(亦即并非自土壤提取的油)共制备烷基苯和生物燃料的方法和系统。另外，需要提供自来自蔬菜、坚果和/或种子油的易于处理的甘油三酯和脂肪酸提供可再生烷基苯和生物燃料的方法和系统。此外，本发明的其它所需特点和特征将由随后本发明的详细描述和随附权利要求结合本发明的附图和背景技术而变得显而易见。
发明内容
本申请提供由天然油共制备烷基苯产物和生物燃料的方法。根据一个例示性实施方案，该方法使天然油脱氧以形成包含烷烃的料流。随后，使烷烃的第一部分脱氢以得到单烯烃。在该方法中，在烷基化条件下使用单烯烃使苯烷基化。通过烷基化产生包含烷基苯和苯的烷基化流出物。自流出物分离烷基苯，得到烷基苯产物。处理烷烃的第二部分以形成生物燃料。
在另一例示性实施方案中，提供一种由天然油来源甘油三酯共制备烷基苯产物和生物燃料的方法。在此实施方案中，使甘油三酯脱氧以形成包含水、二氧化碳、丙烷、烷烃的第一部分和烷烃的第二部分的料流。使此料流分馏以分离烷烃的第一部分与第二部分。随后，使烷烃的第一部分脱氢以得到单烯烃。在烷基化条件下使用单烯烃使苯烷基化，得到包含烷基苯和苯的烷基化流出物。此后，分离烷基苯得到烷基苯产物。处理烷烃的第二部分以形成生物燃料。
根据另一实施方案，提供一种由天然油共制备烷基苯产物和生物燃料的方法。在该方法中，用氢气使天然油脱氧以形成包含烷烃的料流。使烷烃的第一部分脱氢，得到单烯烃和氢气。根据例示性实施方案，使通过脱氢得到的氢气再循环以使天然油脱氧。在烷基化条件下使用单烯烃使苯烷基化，得到包含烷基苯和苯的烷基化流出物。随后，自流出物中分离烷基苯以得到烷基苯产物。处理烷烃的第二部分以形成生物燃料。
附图简述
下文将结合以下图式描述本发明的实施方案。
图1示意性地显示根据示例性实施方案共制备烷基苯和生物燃料的系统。
具体实施方式
以下详细描述本质上仅为例示性的且不欲限制本发明或本发明的应用和用途。此外，不欲受前述背景技术或以下详细描述中所呈现的任何理论约束。
本文中所涵盖的各种实施方案涉及由天然油共制备烷基苯产物和生物燃料的方法和系统。图1中说明用于由天然油进料14制备烷基苯产物12和生物燃料13的例示性系统10。如本文所用，天然油为来源于植物或藻类物质的天然油，且通常称为可再生油。天然油并不基于煤油或其它化石燃料。在某些实施例中，天然油包括椰子油、巴巴苏油、蓖麻油、烹调油和其它蔬菜、坚果或种子油中的一种或多种。天然油通常包含甘油三酯、游离脂肪酸或甘油三酯与游离脂肪酸的组合。
在所说明的实施方案中，将天然油进料14传递至脱氧单元16中，脱氧单元16还接受氢气进料18。在脱氧单元16中，使进料14中的甘油三酯和脂肪酸脱氧且转化为正烷烃。甘油三酯在结构上由三个(通常不同)脂肪酸分子形成，所述脂肪酸分子用甘油桥键结在一起。甘油分子包括三个羟基(HO-)且各脂肪酸分子具有羧基(COOH)。在甘油三酯中，甘油的羟基与脂肪酸的羧基连接，形成酯键。因此，在脱氧期间，脂肪酸自甘油三酯结构中游离出来且转化成正烷烃。甘油转化成丙烷，且羟基和羧基中的氧转化成水或二氧化碳。脂肪酸和甘油三酯的脱氧反应分别说明如下：
在脱氧反应期间，所产生烷烃链Rn的长度将取决于确切反应途径而变化某一值。举例而言，若形成二氧化碳，则该链将比脂肪酸来源(Rn)少一个碳。若形成水，则该链将与脂肪酸来源中Rn链的长度相等。通常形成大致等量的水与二氧化碳，使得形成等量的CX烷烃和CX-1烷烃。
在图1中，使含有正烷烃、水、二氧化碳和丙烷的脱氧料流20离开脱氧单元16且进入分离器22中。分离器22可为多级分馏单元、蒸馏系统或类似已知装置。在任何情况下，分离器22自脱氧料流20中移除水、二氧化碳和丙烷。另外，分离器22可提供烷烃的第一部分24和烷烃的第二部分26。在某些实施方案中，烷烃的第一部分24具有C10至C14的碳链长度。在其它实施方案中，烷烃的第一部分24具有下限CL(其中L为四(4)至三十一(31)的整数)和上限CU(其中U为五(5)至三十二(32)的整数)的碳链长度。与烷烃的第一部分24相比，烷烃的第二部分26可具有较短、较长或较短与较长的组合的碳链。在一优选实施方案中，烷烃的第一部分24包含具有C10至C13链的烷烃，且烷烃的第二部分26包含具有C17至C18链的烷烃。
如图1中所示，将烷烃的第一部分24引入烷基苯制备区28中。具体而言，将烷烃的第一部分24供入烷基苯制备单元28中的脱氢单元30中。在脱氢单元30中，烷烃的第一部分24脱氢成与烷烃的第一部分24碳数相同的单烯烃。脱氢通常通过已知催化方法发生，例如商业上常用的帕科尔方法(Pacolprocess)。如以下等式中所表示，二烯烃(亦即二烯)和芳族化合物还作为脱氢反应的不当结果产生：
单烯烃形成：
Figure BDA0000480866450000041
二烯烃形成：
Figure BDA0000480866450000042
芳族化合物形成：
Figure BDA0000480866450000043
在图1中，使包含单烯烃和氢气以及一些二烯烃和芳族化合物的脱氢料流32离开脱氢单元30。将脱氢料流32传递至相分离器34中以自脱氢料流32移出氢气。如所示，氢气以氢气再循环流36的形式离开相分离器34，该氢气再循环流36可添加至氢气进料18中以支持上游脱氧方法。
在相分离器34处，形成液流38且其包含脱氢期间形成的单烯烃和任何二烯烃和芳族化合物。液流38离开相分离器34且进入选择性氢化单元40(例如德法恩反应器(DeFine reactor))中。氢化单元40选择性氢化液流38中二烯烃的至少一部分以形成额外单烯烃。从而形成具有增加单烯烃浓度的增强流42。
如所示，增强流42自氢化单元40穿至轻质物分离器44(例如汽提塔)中，该轻质物分离器44移除含有产生自上游处理期间的裂解或其它反应的任何轻质物(例如丁烷、丙烷、乙烷和甲烷)的轻馏分流46。移除轻馏分46后，形成料流48且可传递至芳族化合物移除装置50(例如购自UOP的帕科尔增强方法(Pacol Enhancement Process；PEP)单元)中。如由其名称所指示，芳族化合物移除装置50自料流48移除芳族化合物且形成单烯烃流52。
在图1中，将单烯烃流52和苯流54供入烷基化单元56中。烷基化单元56容纳催化剂58，例如固体酸催化剂，其支持用单烯烃52使苯54烷基化。氟化氢(HF)和氯化铝(AlCl3)为商业上用于用直链单烯烃使苯烷基化的两种主要催化剂，且可用于烷基化单元56中。通过烷基化，根据以下反应形成烷基苯(通常称为直链烷基苯(LAB))：
Figure BDA0000480866450000051
且其存在于烷基化流出物60中。
为使烷基化方法最佳化，将过剩量的苯54供应至烷基化单元56中。因此，离开烷基化单元56的烷基化流出物60含有烷基苯和未反应的苯。另外，烷基化流出物60还可包括一些未反应的烷烃。在图1中，将烷基化流出物60送至苯分离单元62(例如分馏塔)中，以自烷基化流出物60分离未反应的苯。此未反应的苯以苯再循环流64的形式离开苯分离单元62，使该苯再循环流64传递回烷基化单元56中以减少料流54中所要新鲜苯的体积。
如所示，苯经汽提的料流66离开苯分离单元62且进入烷烃分离单元68(例如分馏塔)中。在烷烃分离单元68中，将未反应的烷烃以再循环烷烃流70的形式自苯经汽提的料流66移出，且在如上所述进行脱氢以前投送至烷烃的第一部分24中且与该烷烃的第一部分24混合。
另外，通过烷烃分离单元68分离烷基苯流72且进入烷基化物分离单元74中。烷基化物分离单元74(其可为例如多塔分馏系统)分离重质烷基化物底部流76与烷基苯流72。
通过后烷基化分离方法，分离直链烷基苯产物12且使其离开装置10。应注意，并非所有实施例均需要分离方法来分离烷基苯产物12。举例而言，烷基苯产物12可能需要具有宽范围的碳链长度且无需任何分馏来去除比所需长的碳链(亦即重质物)或比所需短的碳链(亦即轻质物)。另外，进料14可具有足够质量以无需分馏，而不管所需链长范围。
在某些实施例中，进料14为实质上均质的且包含在所需范围内的游离脂肪酸。举例而言，进料可为棕榈脂肪酸馏出物(PFAD)。或者，进料14可包含甘油三酯和游离脂肪酸，其均具有适用于所需烷基苯产物12的碳链长度。
在某些实施例中，天然油来源为蓖麻，且进料14包含蓖麻油。蓖麻油基本上由在碳12位置处具有其它内部羟基的C18脂肪酸组成。举例而言，蓖麻油甘油三酯的结构为：
Figure BDA0000480866450000061
在使包含蓖麻油的进料14脱氧期间，已发现碳链的一些部分在碳12位置处裂解。因此，脱氧产生一组在脱氧期间由裂解产生的具有C10至C11链的较轻质烷烃，和一组具有C17至C18链的未裂解较重质烷烃。较轻质烷烃可形成烷烃的第一部分24，且较重质烷烃可形成烷烃的第二部分26。应注意，尽管蓖麻油作为具有其它内部羟基的油的实例展示，但可存在其它实例。同样，可能需要基因工程改造的生物体以通过设计制备油。因此，任何具有内部羟基的油均可为所需进料油。
如图1中所示，将烷烃的第二部分26供入系统80中以制备生物燃料13，例如柴油或喷射机燃料。生物燃料制备系统80中通常不需要进一步脱氧。更确切而言，在系统80中，烷烃的第二部分26通常在异构化单元82中异构化或在裂解单元84中裂解，产生与烷烃的第二部分26相比具有相等或较轻分子量的异烷烃。可自所得生物燃料13中分离出这些方法期间消耗的氢气，形成再循环至脱氧单元16中的氢气流86。尽管显示直接供入脱氧单元16中，但可将氢气流86供入氢气进料18中。
为产生生物柴油，生物燃料制备系统80主要使烷烃的第二部分26异构化而具有最小裂解。为制备生物喷射机燃料或绿色喷射机燃料，执行一些裂解反应以便获得较小分子(具有降低的分子量)来满足喷射机技术要求所要求的较严格的冻结点。
尽管已在上述详细描述中呈现至少一个例示性实施例，但应了解，存在大量变化形式。亦应了解，例示性实施例仅为实例，且不欲以任何方式限制本发明的范围、适用性或构成。更确切而言，上述详细描述将为本领域技术人员提供用于实施本发明的例示性实施例的便利路线图，应了解，在不背离如随附权利要求及其合法等效物中所阐述的本发明的范围的情况下，可对例示性实施例中所述的组件的功能和配置进行各种改变。

Claims (10)

1.一种由天然油(14)共制备烷基苯产物(12)和生物燃料(13)的方法，其包括：
使天然油脱氧以形成包含烷烃的料流(20)；
使烷烃的第一部分(24)脱氢以得到单烯烃(52)；
在烷基化条件下用单烯烃使苯(54)烷基化以得到包含烷基苯和苯的烷基化流出物(60)；
分离烷基苯以得到烷基苯产物；和
处理烷烃的第二部分(26)以形成生物燃料。
2.根据权利要求1的方法，其中氢气流(36)由处理烷烃的第一部分产生，且其中该方法进一步包括使氢气流再循环以支持脱氧步骤。
3.根据权利要求1的方法，其中处理烷烃的第二部分包括使烷烃的第二部分异构化以形成异烷烃。
4.根据权利要求1的方法，其中二烯烃通过使烷烃脱氢得到，且其中该方法进一步包括选择性氢化二烯烃以形成额外单烯烃。
5.根据权利要求4的方法，其进一步包括在烷基化以前从单烯烃中移除芳族化合物。
6.根据权利要求1的方法，其中天然油包含具有第一链长范围的多种第一脂肪酸和具有第二链长范围的多种第二脂肪酸；其中通过使天然油脱氧形成第一链长烷烃和第二链长烷烃；
其中烷烃的第一部分包含第一链长烷烃；且其中烷烃的第二部分包含第二链长烷烃；该方法进一步包括：
在脱氢以前使该料流分馏以分离烷烃的第一部分与烷烃的第二部分。
7.根据权利要求1的方法，其中天然油包含具有内部羟基的脂肪酸，且其中使天然油脱氧引起裂解，且得到烷烃的第一部分和烷烃的第二部分。
8.根据权利要求8的方法，其中天然油为蓖麻油，其基本上由在碳12位置处具有羟基的C18脂肪酸组成，其中自裂解产生的烷烃的第一部分具有C10至C11链，且其中自裂解产生的烷烃的第二部分具有C17至C18链。
9.一种由天然油来源甘油三酯(14)共制备烷基苯产物(12)和生物燃料(13)的方法，其包括：
使甘油三酯脱氧以形成包含水、二氧化碳、丙烷、烷烃的第一部分(24)和烷烃的第二部分(26)的料流(20)；
使该料流分馏以分离烷烃的第一部分与烷烃的第二部分；
使烷烃的第一部分脱氢以得到单烯烃(52)；
在烷基化条件下用单烯烃使苯(54)烷基化以得到包含烷基苯和苯的烷基化流出物(60)；
分离烷基苯以得到烷基苯产物；和
处理烷烃的第二部分以形成生物燃料。
10.一种由天然油(14)共制备烷基苯产物(12)和生物燃料(13)的方法，其包括：
用氢气(18)使天然油脱氧以形成包含烷烃的料流(20)；
使该料流中的烷烃的第一部分(24)脱氢以得到单烯烃(52)和氢气(36)；
使该氢气再循环以支持天然油的脱氧；
在烷基化条件下用单烯烃使苯(54)烷基化以得到包含烷基苯和苯的烷基化流出物(60)；
分离烷基苯以得到烷基苯产物；和
处理烷烃的第二部分(26)以形成生物燃料。
CN201280046370.8A 2011-09-23 2012-08-14 由天然油共制备烷基苯和生物燃料的方法 Pending CN103827060A (zh)

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