CN105593343A - 用于增强蒸汽裂化器及铂重整进料的灵活方法 - Google Patents

用于增强蒸汽裂化器及铂重整进料的灵活方法 Download PDF

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CN105593343A
CN105593343A CN201480054243.1A CN201480054243A CN105593343A CN 105593343 A CN105593343 A CN 105593343A CN 201480054243 A CN201480054243 A CN 201480054243A CN 105593343 A CN105593343 A CN 105593343A
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CN105593343B (zh
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G·A·芬克
S·T·阿拉卡瓦
M·利普曼
M·J·威尔
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Honeywell UOP LLC
Universal Oil Products Co
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Abstract

本发明提供用于增加轻质烯烃的产率或转化以增加从烃进料至汽油掺和池的烃组分的方法。该方法包括将石脑油进料分离成更易于在裂化单元中进行处理的至第一料流的组分及更易于在重整单元中进行处理的第二料流中组分。该方法包括将组分从该裂化料流转化至该重整料流及将组分从该重整料流转化至该裂化料流的能力。

Description

用于增强蒸汽裂化器及铂重整进料的灵活方法
优先权声明
本申请主张于2014年4月24日提出申请的美国申请第14/260,812号(其主张于2013年8月7日提出申请的美国临时申请第61/863,019号的权益)的优先权，该申请的全部内容皆以引用方式并入本文中。
技术领域
本发明涉及从较重烃料流产生芳香族化合物的方法及系统。具体而言，此方法增加从烃进料产生芳香族化合物及轻质烯烃的产率及灵活性。
背景技术
重整石油原材料是用于产生有用产品的重要方法。一种重要方法是分离并升级用于发动机燃料的烃，例如在汽油生产中产生石脑油进料流并升级石脑油的辛烷值。然而，来自原始石油来源的烃进料流包括生产有用的化学前体用于生产塑料、洗涤剂及其他产品。
汽油升级是重要的方法，且改良石脑油进料流的转化率来增加辛烷值已在美国专利3,729,409；3,753,891；3,767,568；4,839,024；4,882,040；及5,242,576中给出。这些方法涉及多种方式以增加辛烷值、且尤其增加汽油的芳香族化合物含量。
方法包括使用不同催化剂(例如对于较低沸点烃使用单金属催化剂或非酸性催化剂，且对于较高沸点烃使用双金属催化剂)分流进料及操作若干重整器。其他改良包括新的催化剂，如美国专利4,677,094；6,809,061；及7,799,729中所呈现。然而，这些专利中所呈现的方法及催化剂存在限制，且可使成本显著增加。
轻质烯烃通常是经由蒸汽或催化裂化方法而产生，且包括乙烯及丙烯。轻质烯烃亦源自与汽油相同的进料。由于石油来源的可用度有限且成本较高，故从这些石油来源生产轻质烯烃的成本持续增加。转化进料中的组分用于轻质烯烃及汽油池的能力使得制造商能够经济地选择最重要的产品线，且能够以有效方式转化一些烃组分。
发明内容
本发明给出在加工石脑油进料中用于改良轻质烯烃、重整物的产率且提供灵活性的方法。本发明的第一实施方案是增加轻质烯烃及重整物产率的方法，其包括将烃进料流的第一部分传送至分馏塔，以产生包含C6化合物及较轻组分的塔顶料流及包含较重烃的底部料流；将塔顶料流传送至裂化单元，将底部料流传送至分离单元，以产生包含正构烃的萃取物料流及包含非正构烃的萃余物料流；及将萃取物料流传送至裂化单元以生产轻质烯烃。
本发明的第二实施方案是用于增加轻质烯烃产率的方法，其包括将烃料流传送至分馏塔以产生包含nC4及较轻烃的第一塔顶料流及包含C5及较重烃的第一底部料流；将第一底部料流传送至分离单元，以产生包含正构烃的萃取物料流及包含非正构烃的萃余物料流；将萃余物料流传送至重整单元以产生重整物料流；及将萃取物料流传送至裂化单元以生产轻质烯烃。本发明的一个实施方案是此段落中直至此段落中的该第二实施方案的一个、任一个或所有先前实施方案，其进一步包括将萃余物料流传送至萃余物分离系统，以产生包含C5及C6烃的第二塔顶料流、包含C7及较重烷烃与C6及较重芳香族化合物及环烷烃的中间料流以及包含解吸剂的第二底部料流。
本发明的第三实施方案是用于在汽油生产中提供灵活性的方法，将烃料流传送至分馏塔，以产生包含nC4及较轻烃的第一塔顶料流以及包含C5及较重烃的第一底部料流；将第一底部料流传送至氢化单元，以产生炔、二烯烃、硫及氮含量减小的经处理底部料流；将经处理底部料流传送至分离单元，以产生包含正构烃的萃取物料流及包含非正构烃的萃余物料流；将萃余物料流传送至重整单元以产生重整物料流；及将萃取物料流的一部分传送至裂化单元以生产轻质烯烃。本发明的一个实施方案是此段落中直至此段落中的该第三实施方案的一个、任一个或所有先前实施方案，其进一步包括将萃取物料流传送至萃取物分离系统，以产生包含C5及C6正构烷烃的第二塔顶料流、包含C7及较重正构烷烃的中间料流以及包含解吸剂的第二底部料流。
在一个实施方案中，该方法包括使用异构化单元来转化C5-C6料流。异构化单元可用于将iC5-iC6料流转化成iC5-iC6及正构C5及C6组分的混合物以增加轻质烯烃的产率。在替代性实施方案中，可使nC5-nC6的料流通过异构化单元以将该料流转化成iC5-iC6与正构C5及C6组分的混合物来增加汽油池的产率。
根据以下实施方式及附图，本领域技术人员将明了本发明的其他目标、优点及应用。
附图简述
图1是显示将石脑油流分流成至裂化单元的进料及至重整单元的进料的方法的基本情形；
图2是显示分离石脑油分流器底部料流以增加轻质烯烃产率的实施方案；
图3是显示分离石脑油分流器底部料流并异构化以增加轻质烯烃产率的实施方案；且
图4是显示分离石脑油分流器底部料流并异构化以增加汽油掺和池产率的实施方案。
实施方式
本发明提供用于增加轻质烯烃的产率或转化以增加从烃进料至汽油掺和池的烃组分的方法。该方法包括将石脑油进料分离成更易于在裂化单元中进行加工的第一料流或裂化单元进料流组分及更易于在重整单元中进行加工的第二料流或重整单元进料流组分。该方法包括将组分从裂化料流转化至重整料流并将组分从重整料流转化至裂化料流的能力。
石脑油进料流的加工可用于生产轻质烯烃，并为汽油掺和池或重整组分提供烃组分，以产生欲传送至芳香族化合物复合物的芳香族化合物。如图1中所显示的基本方法包括将石脑油进料流分裂成两部分，第二部分6及第一部分8。第二部分的量可少至0，或可包含所有石脑油进料流，这取决于产物的选择。将第二部分6传送至裂化单元20以产生具有轻质烯烃的工艺料流22。轻质烯烃包括乙烯及丙烯。将石脑油进料流的第一部分8传送至石脑油分流器10以产生塔顶料流12及底部料流14。塔顶料流12包含石脑油进料流中的C6及较轻组分。底部料流14包含石脑油进料流中的C6及较重组分。较重组分的典型范围是C5至C11烃。基于烃组分的相对沸点操作的分流器10及分流器塔顶料流12可包含沸点等于或低于甲基环戊烷(MCP)的组分。可改变操作条件以调节所期望塔顶组合物，包括改变操作条件以具有包含C4及较轻组分的塔顶料流12以及包含C5及较重组分的底部料流14。将塔顶料流12传送至裂化单元20。将底部料流14传送至氢化处理单元30以产生经处理料流32。将经处理料流32传送至重整单元40以产生芳香族化合物含量增加的重整物料流42。
烃料流中的正构组分比非正构组分更容易裂化形成轻质烯烃。正构组分亦比非正构组分更难重整成芳香族化合物。此外，支化链烷烃是用于汽油掺和池的相对于正构组分优选的组分。正构与非正构组分的分离，结合将不同料流传送至适宜下游处理单元改良裂化及重整石脑油的灵活性及经济效益。将正构组分转化成非正构组分的能力允许烃组分从进给至裂化单元的料流转移至用于产生汽油组分的料流。
在一个实施方案中，如图2中所显示，该方法是用于增加轻质烯烃及重整物产率。该方法包括将烃进料流的第一部分8传送至分馏塔10，以产生包含C6及较轻组分的塔顶料流12以及包含较重组分的底部料流14。将塔顶料流12传送至裂化单元20以产生包含轻质烯烃的工艺料流22。将底部料流14传送至氢化处理单元30以产生经处理底部料流32。氢化处理单元30移除杂质以保护下游催化剂及吸附剂。所移除的杂质包含硫化合物及氮化合物。此外，可对烃化合物(例如炔及二烯烃)实施一定程度的氢化。这些化合物是反应性更强的化合物，且这些化合物的氢化可减少一些下游副反应，例如聚合。
将经处理底部料流32传送至分离单元50以产生萃取物料流52及萃余物料流54。分离单元50优选是吸附分离单元，且包含选择性吸附来自经处理底部料流的组分的吸附剂。在一个实施方案中，吸附剂是经选择以从料流32优先吸附正构组分，同时排斥非正构组分。萃取物料流52包含在C5至C11范围内的正构烃，且萃余物料流54包含来自底部料流的非正构组分。非正构组分包括支化链烷烃、环烷烃及芳香族化合物。将萃取物料流52传送至裂化单元20以增加来自烃进料流的轻质烯烃产率。在一个实施方案中，烃进料流是石脑油进料流。尽管本发明实施方案是通过石脑油进料流来例示，但该方法并不限于石脑油进料流，且可包括具有与石脑油进料流重叠的组成的任何进料流。对于石脑油进料流，裂化单元20可为石脑油蒸汽裂化单元。
在一个实施方案中，该方法进一步包括将萃余物料流54传送至重整单元40以产生芳香族化合物含量增加的重整物料流42。
该方法可进一步包括将烃进料流的第二部分6传送至裂化单元20。
使用石脑油来产生乙烯及丙烯是常见的。已知正构链烷烃、n-链烷烃优选比非正构链烷烃相对容易裂化。同样，使用石脑油作为重整进料以产生可用于芳香族化合物复合物中或用作汽油掺和池的一部分的芳香族化合物。非正构链烷烃亦是可用于汽油掺和池或重整的组分。增加转化石脑油进料以生产轻质烯烃或产生汽油或芳香族化合物的能力可提高精炼厂的经济效益。
在一个实施方案中，如图3中所显示，该方法增加轻质烯烃产率。该方法包括将烃进料流8传送至分馏单元10。分馏单元10产生包含C4及较轻烃组分的塔顶料流12以及包含C5及较重组分的底部料流14。将塔顶料流12传送至裂化单元20以产生具有轻质烯烃的工艺料流22。将底部料流14传送至氢化处理单元30以产生经处理底部料流32。将经处理底部料流32传送至分离单元50以产生包含正构烃的萃取物料流52及包含非正构烃的萃余物料流54。非正构烃包括支化链烷烃、环烷烃及芳香族化合物。将萃取物料流52传送至裂化单元20。
将萃余物料流54传送至萃余物分离系统60，且产生萃余物塔顶料流62、中间萃余物料流64及萃余物底部料流66。分离单元50包括吸附分离系统，且包含使用解吸剂作为吸附分离方法中的工作流体。萃余物底部料流66包含解吸剂且再循环回分离单元50。中间萃余物料流包含萃余物料流中的非正构C7至C11链烷烃及C6至C11芳香族化合物以及环烷烃组分。萃余物塔顶料流62包含来自萃余物料流的iC5及iC6组分。
将萃余物塔顶料流62传送至异构化单元70以产生异构料流72。异构化单元70包括携载烃组分的混合物且将这些组分异构化以产生异构料流72的新组成的催化反应器。异构化方法可将支化链烷烃转化成正构链烷烃，或可用于将正构链烷烃转化成支化链烷烃。在此实施方案中，至异构化单元的进料是由支化链烷烃组成，且将产生支化及正构链烷烃的混合物。将异构料流72传送至分离单元50。此实施方案增加所产生正构链烷烃的量且增加至裂化单元20的进料。增加至裂化单元的正构链烷烃的进料增加产生的裂化工艺料流22的轻质烯烃的量。
在一个实施方案中，如图4中所显示，该方法提供增加汽油生产或增加芳香族化合物生产的灵活性。该方法包括将烃进料流8传送至分馏单元10。分馏单元10产生包含C4及较轻烃组分的塔顶料流12以及包含C5及较重组分的底部料流14。将塔顶料流12传送至裂化单元20以产生具有轻质烯烃的工艺料流22。将底部料流14传送至氢化处理单元30以产生经处理底部料流32。将经处理底部料流32传送至分离单元50以产生包含正构烃的萃取物料流52及包含非正构烃的萃余物料流54。非正构烃包含支化链烷烃及烯烃、环烷烃及芳香族化合物。
将萃余物料流54传送至萃余物分离系统60，且产生萃余物塔顶料流62、中间萃余物料流64及萃余物底部料流66。分离单元50包括吸附分离系统，且包含使用解吸剂作为吸附分离方法中的工作流体。萃余物底部料流66包含解吸剂且再循环回分离单元50。中间萃余物料流包含萃余物料流中的非正构C7至C11链烷烃及C6至C11芳香族化合物以及环烷组分。萃余物塔顶料流62包含来自萃余物料流的iC5及iC6组分，然后可将其传送至汽油掺和池或其他期望下游工艺。
将萃取物料流52传送至萃取物分离系统80，且产生萃取物塔顶料流82、中间萃取物料流84及萃取物底部料流86。萃取物底部料流86包含解吸剂且再循环至吸附分离单元50。萃取物中间料流84包含C7至C11正构链烷烃且传送至裂化单元20以生产轻质烯烃。
萃取物塔顶料流82包含nC5及nC6链烷烃，且传送至异构化单元70以产生异构化工艺料流72。将异构化工艺料流72传送至分离单元10以将正构链烷烃料流转化成正构及支化链烷烃的混合物。此实施方案增加支化链烷烃的量且增加来自分离单元10的萃余物的量。此提供iC5及iC6的增加，且使萃余物塔顶料流62增加或使至汽油掺和池的进料增加。
萃取物分离系统及/或萃余物分离系统可包括一或多个分馏塔用于将各个萃取物或萃余物料流分离成多个料流。萃取物分离及/或萃余物分离系统的选择包括分隔壁塔或用于分离烃料流的其他构件。
在以下结果中可见分离单元10的添加，其中正构物含量及芳香族化合物含量实质增加。此有助于增加用于裂化的轻质烯烃。添加异构化亦显示其可增加正构物及芳香族化合物。此提供现有设备的有用增加。
表-情形的比较
描述 正构物％ N+2A
情形1 基本情形-无分离单元 26 57
情形2 具有分离单元 59 71
情形3 具有分离及异构化 94 73
情形1提供目前工业中所用标准处理的比较，其中将直馏石脑油在最少准备的情况下进料至蒸汽裂化器。直馏石脑油可与来自单独石脑油料流的经处理用于催化重整单元的轻馏分组合。石脑油中的正构物通常在15重量％至30重量％范围内。通过添加分离单元，分离可增加用于至裂化单元的进料的正构物的量，如情形2中所显示。添加异构化单元允许进一步改良至裂化单元及至重整单元的进料的质量。至重整单元的进料的质量(N+2A或芳香族潜含量)显示处理改进来自重整单元的产率。
添加异构化单元亦允许设备操作者更灵活性地控制至裂化单元或重整单元的进料但不改变烃料流的质量。异构化单元允许增加正构链烷烃的量或呈iC5及iC6形式的支化链烷烃的量。
尽管已通过当前视为优选实施方案的实施方案来阐述本发明，但应理解，本发明并不限于所揭示的实施方案，而意欲涵盖随附权利要求的范畴内所包含的各种修改及等效配置。

Claims (10)

1.一种增加轻质烯烃及重整物产率的方法，其包括：
将烃进料流的第一部分传送至分馏塔，以产生包含C6化合物及较轻组分的塔顶料流以及包含较重烃的底部料流；
将该塔顶料流传送至裂化单元；
将该底部料流传送至分离单元，以产生包含正构烃的萃取物料流及包含非正构烃的萃余物料流；及
将该萃取物料流传送至该裂化单元以生产轻质烯烃。
2.如权利要求1的方法，其中该烃进料流是石脑油。
3.如权利要求1的方法，其进一步包括：
将该底部料流传送至氢化处理单元以产生经处理底部料流；及
将该经处理底部料流传送至该分离单元。
4.如权利要求1的方法，其中该分离单元是吸附分离单元。
5.如权利要求1的方法，其进一步包括将该萃余物料流传送至重整单元以产生包含芳香族化合物的重整物料流。
6.如权利要求5的方法，其进一步包括将重整物料流传送至重整物分离系统，以产生包含C5及C6烃的第二塔顶料流、包含C7及较重烷烃、C6及较重芳香族化合物及环烷烃的中间料流以及包含解吸剂的第二底部料流。
7.如权利要求1的方法，其进一步包括将该烃进料流的第二部分传送至该裂化单元。
8.如权利要求1的方法，其中该裂化单元是石脑油蒸汽裂化单元。
9.如权利要求1的方法，其进一步包括将该萃余物料流的一部分传送至异构化单元，以产生包含异链烷烃及正构链烷烃的异构化工艺料流。
10.如权利要求9的方法，其进一步包括将该异构化工艺料流传送至该分离单元且将这些正构链烷烃传送至该裂化单元。
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