CN105612138A - 制造汽油或芳香族化合物的整合工艺 - Google Patents

制造汽油或芳香族化合物的整合工艺 Download PDF

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CN105612138A
CN105612138A CN201480054344.9A CN201480054344A CN105612138A CN 105612138 A CN105612138 A CN 105612138A CN 201480054344 A CN201480054344 A CN 201480054344A CN 105612138 A CN105612138 A CN 105612138A
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G·A·芬克
S·T·阿拉卡瓦
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Honeywell UOP LLC
Universal Oil Products Co
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    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
    • C10G69/14—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural parallel stages only
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    • C10G61/00—Treatment of naphtha by at least one reforming process and at least one process of refining in the absence of hydrogen
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    • C10G61/00—Treatment of naphtha by at least one reforming process and at least one process of refining in the absence of hydrogen
    • C10G61/08—Treatment of naphtha by at least one reforming process and at least one process of refining in the absence of hydrogen plural parallel stages only
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    • C10G61/00—Treatment of naphtha by at least one reforming process and at least one process of refining in the absence of hydrogen
    • C10G61/10—Treatment of naphtha by at least one reforming process and at least one process of refining in the absence of hydrogen processes also including other conversion steps
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G63/00—Treatment of naphtha by at least one reforming process and at least one other conversion process
    • C10G63/06—Treatment of naphtha by at least one reforming process and at least one other conversion process plural parallel stages only
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    • C10G63/00—Treatment of naphtha by at least one reforming process and at least one other conversion process
    • C10G63/06—Treatment of naphtha by at least one reforming process and at least one other conversion process plural parallel stages only
    • C10G63/08—Treatment of naphtha by at least one reforming process and at least one other conversion process plural parallel stages only including at least one cracking step
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    • C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
    • C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
    • C10G67/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including solvent extraction as the refining step in the absence of hydrogen
    • C10G67/0409—Extraction of unsaturated hydrocarbons

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Abstract

本发明呈现用于增加烃组分自烃原料至汽油掺配池的产率的工艺。该工艺包含将石脑油原料分离为较易于在裂化单元中加工的第一流的组分及较易于在重整单元中加工的第二流的组分。该工艺包含将组分自裂化流转化为重整流的能力。

Description

制造汽油或芳香族化合物的整合工艺
优先权的声明
本申请主张2014年4月24日提出申请的美国申请第14/260,784号的优先权，该美国申请主张2013年8月7日提出申请的美国临时申请第61/863,025号的权益，该两个申请的内容以全文引用方式并入本文中。
技术领域
本发明涉及用于自较重烃流制造芳香族化合物的工艺及系统。特定而言，该工艺提供自烃原料制造芳香族化合物及轻烯烃的增加的产率及灵活性。
背景
石油原材料的重整是用于制造有用产品的重要工艺。在汽油的制造中，一个重要工艺是对用于马达燃料的烃的分离及升级，诸如制造石脑油进料流及升级石脑油的辛烷值。然而，来自原油来源的烃进料流包含有用化学前体的制造以供在塑料、清洁剂及其它产品的制造中使用。
汽油的升级是重要工艺，且已在美国专利第3,729,409号、第3,753,891号、第3,767,568号、第4,839,024号、第4,882,040号及第5,242,576号中呈现对石脑油进料流的转化的改良以增加辛烷值。这些工艺涉及用以增强辛烷值及特定而言用于增强汽油芳香族化合物含量的多种手段。
该工艺包含使用诸如用于较低沸点烃的单金属催化剂或非酸催化剂及用于较高沸点烃的双金属催化剂的不同催化剂来分裂进料及操作数个重整器。如在美国专利第4,677,094号、第6,809,061号及第7,799,729号中所呈现，其它改良包含新催化剂。然而，存在对这些专利中所呈现的方法及催化剂的限制，且这样的限制可需要成本的显著增加。
传统上已透过蒸汽或催化剂裂化工艺来制造轻烯烃，且轻烯烃包括乙烯及丙烯。轻烯烃也自与汽油相同的原料衍生。由于石油来源的有限可获得性及高成本，因此自这样的石油来源制造轻烯烃的成本已稳步地增加。使轻烯烃及汽油池的原料中的组分转换的能力使得生产者能够经济地挑选最重要产品线且能够以有效方式使烃组分中的某些烃组分转换。
发明内容
呈现了用于改良汽油产率的工艺。本发明的第一实施方案是用于转化已处理烃进料流的工艺，该工艺包括：将该已处理烃进料流传递至分离单元以产生富含正链烷烃的萃取物流及具有减小的正烃含量的萃余物流；将该萃取物流传递至萃取物分离系统以产生包括nC5及nC6化合物的萃取物顶部流、包括nC7至nC11化合物的萃取物中间流及包括解吸剂的萃取物底部流；将该萃余物流传递至萃余物分离系统以产生包括iC5及iC6化合物的萃余物顶部流、包括C6至C11碳范围中的芳香族化合物及非正烃的中间萃余物流以及包括解吸剂的萃余物底部流；及将该中间萃余物流传递至重整单元以产生芳香族化合物流。本发明的实施方案是向上直至此段落中的第一实施方案的此段落中的先前实施方案中的一项、任何或所有先前实施方案，该实施方案进一步包括：将烃进料流传递至分馏单元以产生包括C4及较轻烃的顶部流以及包括C5+烃的底部流；对该底部流进行加氢处理以产生已处理氢化流；将该已处理氢化流传递至分离单元。本发明的实施方案是向上直至此段落中的第一实施方案的此段落中的先前实施方案中的一项、任何或所有先前实施方案，该实施方案进一步包括将该萃取物顶部流的一部分传递至异构化单元以产生包括C5及C6化合物的已异构化流。本发明的实施方案是向上直至此段落中的第一实施方案的此段落中的先前实施方案中的一项、任何或所有先前实施方案，该实施方案进一步包括将该已异构化流传递至该分离单元。
本发明的第二实施方案是用于转化石脑油进料流的工艺，该工艺包括：将该石脑油进料流分馏以产生包括C4及较轻烃的石脑油顶部流以及包括C5+烃的石脑油底部流；对该石脑油底部流进行加氢处理以产生具有减少的乙炔、二烯、硫及氮含量的已氢化流；将该已氢化流传递至分离单元以产生富含正烃的萃取物流及萃余物流；将该萃取物流传递至萃取分离系统以产生包括nC5及nC6化合物的萃取物顶部流、包括nC7至nC11化合物的萃取物中间流以及包括解吸剂的萃取物底部流；将该萃余物流传递至萃余物分离系统以产生包括iC5及iC6化合物的萃余物顶部流、包括C6至C11芳香族化合物及非正烃的中间萃余物流以及包括解吸剂的萃余物流；将该中间萃取物流及该石脑油顶部流传递至石脑油裂化单元以产生轻烯烃；及将该中间萃余物流传递至重整单元以产生芳香族化合物流。本发明的实施方案是向上直至此段落中的第二实施方案的此段落中的先前实施方案中的一项、任何或所有先前实施方案，该实施方案进一步包括将该萃取物顶部流的一部分传递至异构化单元以产生包括C5及C6化合物的已异构化流。本发明的实施方案是向上直至此段落中的第二实施方案的此段落中的先前实施方案中的一项、任何或所有先前实施方案，该实施方案进一步包括将该已异构化流传递至该分离单元。
依据以下详细说明及附图，本领域技术人员将明了本发明的其它目标、优点及应用。
附图简单说明
图1是工艺的流程示意图；且
图2是本发明工艺的特定实施方案。
实施方式
本发明实施方案提供烃原料的有效使用。自较低价值烃原料制造有用较高价值产品对石油加工厂的经济而言是重要的。人们期望较高价值产品的制造的灵活性以响应不同产品线的需求转换。
本发明实施方案提供加工烃进料流以制造轻烯烃及/或芳香族化合物的灵活性。如图1中所展示，该工艺包含将已处理烃流8传递至分离单元10。分离单元10产生富含正烃的萃取物流12及具有减少的正烃含量的萃余物流14。将萃取物流12传递至萃取物分离系统20以产生萃取物顶部流22。萃取物分离系统20也可产生萃取物中间流24及萃取物底部流26。
烃流中的正组分比非正组分更易于裂化以形成轻烯烃。正组分也比非正组分更难以重整为芳香族化合物。与将不同流传递至适当下游加工单元组合的正组分与非正组分的分离改良了裂化及重整石脑油的灵活性及经济。将正组分转化为非正组分的能力允许将烃组分自进料至裂化单元的流转换至用于产生汽油组分的流。
萃取物顶部流22可包括正C5及C6化合物，萃取物中间流24可包括正C7及较重化合物，且萃取物底部流26可包括传递回至分离单元10的循环流。将萃取物中间流24传递至裂化单元40以产生轻烯烃。在一个实施方案中，裂化单元40是石脑油流裂化单元。
在一个实施方案中，分离单元10是吸附分离单元，且循环流26是自萃取物分离系统20至分离单元10循环的解吸剂。萃取物分离系统20可包括用于自解吸剂分离萃取物流的一或多个分馏塔。萃取物分离系统20也可将萃取物流12分离成多个流。分离工艺的选项包含分隔壁塔或用于分离烃流的其它手段。
将萃余物流14传递至萃余物分离系统30以产生萃余物顶部流32、中间萃余物流34及萃余物底部流36。萃余物顶部流32将包括异戊烷及异己烷，中间萃余物流34包括C6至C11范围中的芳香族化合物、环烷及非正烃，且萃余物底部流36包括返回至分离单元10的循环流。
借助吸附分离系统10，萃余物循环是吸附分离工艺中所使用的解吸剂。将中间萃余物流34传递至重整单元50以产生包括芳香族化合物的重整油流52。
在特定实施方案中，如图2中所展示，该工艺加工石脑油进料流。石脑油进料流包括诸多烃组分，且通常被传递至裂化单元以制造轻烯烃。然而，石脑油流的组成包含不能良好地裂化为轻烯烃的组分且这导致进一步加工。石脑油进料流也包含用于转化为芳香族化合物的有用烃。本实施方案试图分离石脑油进料流以增加石脑油裂化单元及重整单元的产率及效率。将石脑油进料流76传递至分馏单元70以产生包括C4及较轻烃的顶部流72以及包括C5及较轻烃的底部流74。将顶部流72传递至裂化单元40以产生轻烯烃产品流42。
石脑油进料流将通常包括C4至C11范围中的烃。吸附分离单元10将因此利用通常在该范围之外的适当解吸剂。对具有C4至C11范围中的组分的轻石脑油起作用的一种解吸剂是n-C12。
将石脑油底部流74传递至加氢处理单元80以产生已处理烃流8。对石脑油底部流74的加氢处理移除硫杂质及氮杂质。加氢处理也可执行诸如乙炔及二烯的反应性组分的一些氢化。加氢处理或氢化之后，将流8传递至吸附分离单元10以产生萃取物流12及萃余物流14。选择吸附分离单元10中的吸附剂以自非正烃分离正烃及特定而言正链烷烃。萃取物流12包括正烃且萃余物流14包括非正及芳香烃。
将萃余物流14传递至萃余物分离系统30。萃余物分离系统30产生萃余物顶部流32、中间萃余物流34及萃余物底部流36。萃余物分离系统30可包括两个分馏塔、分隔壁塔或用于将混合物分离成两个或三个流的其它手段。分馏是优选的，这是因为萃余物流中的组分因其沸点差而易于分离。吸附分离系统10使用解吸剂，且萃余物底部流36包括循环至吸附分离系统10的解吸剂。萃余物顶部流包括iC5及iC6化合物，且可用于下游加工，包含添加至汽油掺配池。将包括具有比iC5或iC6化合物高的沸点的芳香族化合物及非正烃的中间萃余物流34传递至重整单元50以产生具有增加的芳香族化合物含量的重整油52。
将萃取物流12传递至萃取分离系统20以产生萃取物顶部流22、萃取物中间流24及萃取物底部流26。萃取物分离系统20可包括多个分馏塔并且优选的系统使用分隔壁塔。萃取物底部流26包含循环至分离单元10的解吸剂。将萃取物中间流24传递至裂化单元40以将正链烷烃转化为轻烯烃42。典型裂化单元是石脑油流裂化单元，但也可包括催化剂裂化单元。也可将萃取物顶部流22传递至裂化单元40，但在替代方案中，可将萃取物顶部流传递至异构化单元60。
异构化单元60将具有正C5及C6烷烃的顶部流22转化为具有正及异C5及C6烷烃的混合物的已异构化流62。将已异构化流62传递至分离单元10，其中然后在萃余物流14中移除已异构化流62的非正组分。这提供较多烃传递至重整单元50以增加重整油52或传递至萃余物顶部流32以供下游处理(包含传递至重整单元50作为选项)。
优选实施方案是用于将分离系统、异构化系统及催化剂重整工艺整合至一体化炼油厂石油操作中。该工艺提供在用以产生轻烯烃的裂化工艺与用于产生芳香族化合物的重整工艺之间的烃转换。因此给工厂提供产生所要产品流的灵活性。
在优选实施方案中，萃取物分离系统或萃余物分离系统将利用分隔壁塔来制造三个分离的流。这将节省资金及操作成本。该工艺将透过石脑油进料流中的烃组分以及(特定而言)C5及C6组分自裂化流至重整流或引导至汽油掺配池的转换而允许汽油制造领域的灵活性。
虽然已借助当前视为优选实施方案的内容而阐述本发明，但应理解，本发明并不限于所揭示实施方案，而意欲涵盖随附权利要求范围的范畴内所包含的各种修改及等效配置。

Claims (10)

1.一种用于转化已处理烃进料流的方法，其包括：
将该已处理烃进料流传递至分离单元以产生富含正链烷烃的萃取物流及具有减少的正烃含量的萃余物流；
将该萃取物流传递至萃取物分离系统以产生包括nC5及nC6化合物的萃取物顶部流、包括nC7至nC11化合物的萃取物中间流以及包括解吸剂的萃取物底部流；
将该萃余物流传递至萃余物分离系统以产生包括iC5及iC6化合物的萃余物顶部流、包括芳香族化合物及非正烃的中间萃余物流以及包括解吸剂的萃余物底部流；和
将该中间萃余物流传递至重整单元以产生芳香族化合物流。
2.如权利要求1的方法，其进一步包括：
将烃进料流传递至分馏单元以产生包括C4及较轻烃的顶部流以及包括C5+烃的底部流；
对该底部流进行加氢处理以产生已处理氢化流；
将该已处理氢化流传递至该分离单元。
3.如权利要求2的方法，其进一步包括将该顶部流传递至裂化单元。
4.如权利要求1的方法，其进一步包括将该萃取物中间流传递至裂化单元。
5.如权利要求1的方法，其进一步包括将该萃取物顶部流的一部分传递至异构化单元以产生包括C5及C6化合物的已异构化流。
6.如权利要求5的方法，其进一步包括将该已异构化流传递至该分离单元。
7.如权利要求1的方法，其进一步包括将该萃取物顶部流的一部分传递至裂化单元。
8.如权利要求7的方法，其中该烃进料流是石脑油进料流。
9.如权利要求7的方法，其中该裂化单元是石脑油裂化单元。
10.如权利要求1的方法，其进一步包括将该萃余物顶部流传递至汽油掺配池。
CN201480054344.9A 2013-08-07 2014-06-23 制造汽油或芳香族化合物的整合工艺 Expired - Fee Related CN105612138B (zh)

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