CN105308158B - 通过整合减压蒸馏与溶剂脱沥青来提高燃料产量 - Google Patents

通过整合减压蒸馏与溶剂脱沥青来提高燃料产量 Download PDF

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CN105308158B
CN105308158B CN201480010515.8A CN201480010515A CN105308158B CN 105308158 B CN105308158 B CN 105308158B CN 201480010515 A CN201480010515 A CN 201480010515A CN 105308158 B CN105308158 B CN 105308158B
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D·B·吉利斯
J·伍德森
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Amec Foster Wheeler USA Corp
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    • 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
    • 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
    • C10G67/0454—Solvent desasphalting
    • C10G67/049—The hydrotreatment being a hydrocracking
    • 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
    • C10G51/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more cracking processes only
    • C10G51/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more cracking processes only plural serial stages only
    • 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
    • C10G55/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process
    • 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
    • C10G55/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process
    • C10G55/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process plural serial stages only
    • C10G55/04—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process plural serial stages only including at least one thermal cracking step
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1077—Vacuum residues
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4081—Recycling aspects

Abstract

本发明的实施方案涉及通过将未转化油馏分进料至减压闪蒸器并对由其中获得的馏分进行处理，来将由加氢裂化单元得到的未转化油馏分再循环的方法和设备。原油中含有杂原子、聚芳族分子，其包括化合物例如硫、氮、镍、钒和其它化合物，其量能够不利地影响原油馏分的炼油厂处理。

Description

通过整合减压蒸馏与溶剂脱沥青来提高燃料产量
交叉引用的相关申请
本申请依据35 U.S.C.§119(e)要求2013年2月25日提交的美国临时专利申请第61/769062号、和2013年3月13日提交的美国临时专利申请第61/780678号的权益，通过引用如同其完全在此阐述地将其全部内容并入本文。
技术领域
本发明涉及减压蒸馏与溶剂脱沥青的整合以提高燃料的产量。
背景技术
原油含有杂原子、聚芳族(polyaromatic)分子，其包括化合物例如硫、氮、镍、钒和其它化合物，其量能够不利地影响原油馏分的炼油厂处理。轻质原油或冷凝物的硫浓度低至0.01重量％(W％)。与之相比，重质原油和重质石油馏分的硫浓度高达5-6W％。类似地，原油中的氮含量范围可在0.001-1.0W％。这些杂质必须在精制过程中除去，以符合针对最终产品(例如汽油、柴油、燃料油)或中间精制物流而制定的环境规范，该中间精制物流待被处理以用于进一步提质(upgradubg)，例如异构化或重整。此外，已知污染物例如氮、硫和重金属使催化剂失活或中毒，因此必须除去。
性质上为固体且包括存在于较小芳族化合物和树脂分子的溶液中的多核芳族化合物的沥青质，也以不同的量存在于原油和重质馏分中。沥青质不会存在于所有的冷凝物或存在于轻质原油中；然而，它们以相对大量存在于重质原油和石油馏分中。沥青质浓度定义为通过向原料添加正链烷烃溶剂来沉淀的沥青质的量。
在典型的炼油厂中，原油首先在常压蒸馏塔中分馏，以分离包括甲烷、乙烷、丙烷、丁烷和硫化氢的酸气，石脑油(典型沸点范围：36-180℃)，煤油(典型沸点范围：180-240℃)，瓦斯油(典型沸点范围：240-370℃)和常压渣油(其为沸点高于瓦斯油的烃馏分)。基于炼油厂的配置，来自常压蒸馏塔的常压渣油或是用作燃料油，或是被送至减压蒸馏单元。来自减压蒸馏的主要产物是减压瓦斯油(典型沸点范围：370-520℃)和减压渣油，其包括沸点高于减压瓦斯油的烃。
减压蒸馏是将常压渣油(AR)物理分离为减压瓦斯油(VGO)和减压渣油(VR)的非常经过证实的技术。对源自原油或其它天然来源例如页岩油、沥青(bitumen)和焦油砂的石脑油、煤油和瓦斯油物流处理以将超过针对最终产物(一种或多种)所设定的规格的污染物例如硫除去。加氢处理是用于除去这些污染物的最常规的精制技术。在加氢裂化单元中处理减压瓦斯油以得到汽油和柴油，或者在流化催化裂化(FCC)单元中进行处理以主要产生汽油，和作为副产物的轻质循环油(LCO)和重质循环油(HCO)，前者用作柴油池或燃料油中的共混组分，后者被直接送入燃料油池。
按照惯例，油品炼油厂采用溶剂脱沥青(SDA)工艺以用来从渣油原料中萃取有价值的组分，所述渣油原料是作为精制原油的副产物产生的重质烃。将经萃取的组分进料回炼油厂，其中将其转化成有价值的较轻馏分，例如汽油、柴油或润滑油。可以用于SDA工艺中的合适的渣油原料包括例如常压塔底产物、减压塔底产物、原油、拔顶原油、煤馏油萃取物、页岩油和从焦油砂回收的油。
溶剂脱沥青(SDA)用于根据渣油的分子类型对渣油进行物理分离。图1中显示了典型的SDA流程方案。关键容器是萃取器，在其中发生脱沥青油(DAO)和沥青(pitch)的分离。在典型的SDA过程中，将轻质烃溶剂添加到来自炼油厂的渣油进料中，并在可称为沥青质分离器的容器中处理。使用的常规溶剂包括轻质石蜡溶剂。轻质石蜡溶剂的实例包括，但不限于，丙烷、丁烷、异丁烷、戊烷、异戊烷、新戊烷、己烷、异己烷、庚烷和类似的已知用于脱沥青的溶剂，及其混合物。在升高的温度和压力下，沥青质分离器中的混合物分离成多个液体物流，通常为基本上不含沥青质的脱沥青油(DAO)物流，树脂和溶剂，以及沥青质和其中可能溶解一些DAO的溶剂的混合物。
一旦已经除去了沥青质，通常使基本上不含沥青质的DAO物流、树脂和溶剂经历溶剂回收系统。通过使用超临界分离技术或者通过煮沸出溶剂(通常使用来自火焰加热器的蒸汽或热油)，SDA单元的溶剂回收系统从富溶剂的DAO中萃取溶剂级分。然后将经分离的溶剂再循环回去以在SDA单元中使用。
发明内容
本发明的一个实施方案涉及将由加氢裂化单元产生的未转化油馏分再循环的方法，该方法包括：将常压渣油馏分进料至减压蒸馏单元；在溶剂脱沥青萃取器中处理来自减压蒸馏单元的减压渣油，以获得脱沥青馏分；在加氢裂化单元中处理脱沥青馏分，以获得未转化的油馏分和烃产物馏分；并在减压闪蒸器(VF)中处理未转化的油馏分，以获得VF馏出物馏分和VF塔底馏分，其中所述VF塔底馏分在溶剂脱沥青萃取器中经历额外处理。
附图说明
图1显示了依照本发明的一个实施方案的典型的溶剂脱沥青流程方案。
图2显示了依照本发明的一个实施方案的典型的VDU-SDA-HC流程方案。
图3显示了依照本发明的一个实施方案的相对于渣油类型和产率的脱沥青油的品质。
图4显示了依照本发明的一个实施方案的多环芳族化合物的沸点范围；和
图5显示了依照本发明的一个实施方案的典型的整合VDU-VF-SDA流程方案的图解。
示例性实施方案的详细描述
DAO的产率由处理原料性质限制所决定，例如下游过程的有机金属的金属含量和康氏残炭(CCR)。这些限制通常低于在SDA过程中最大可回收的DAO。表1举例说明了依照本发明的一个实施方案在SDA过程中获得的产率。如果DAO产率能够提高，那么基于渣油进料的总的有价值的运输燃料产率可提高，并且总的收益率增加。在SDA和随后延迟焦化结合的情况下将出现类似的益处。相对于热转化，最大化DAO产率使渣油的催化转化最大化，这在延迟焦化中发生。
表1
进料 DAO 沥青
体积-％ 100.00 53.21 46.79
重量-％ 100.00 50.00 50.00
API 5.37 14.2 -3.4
Sp.Gr. 1.0338 0.9715 1.1047
S，wt-％ 4.27 3.03 5.51
N，wppm 3000 1250 4750
康氏碳，wt％ 23 7.7 38.3
C7不溶物，wt-％ 6.86 0.05 13.7
Ni+V，wppm 118 7 229
经回收的脱沥青油(DAO)通常用于下游过程，例如VGO加氢裂化(HC)过程，或者作为润滑油工厂的原料。在图2中显示了典型的VDU-SDA-HC流程方案。当在HC中处理DAO时，DAO的产率通常由HC原料品质限制所决定，例如有机金属的金属、康氏残炭(CCR)和沥青质的浓度。在SDA过程中最大可回收DAO下的DAO产率通常导致高于下游单元原料品质限制的污染物水平(表1，图3)。
当在HC中处理DAO时，最大转化率通常低于处理直馏减压瓦斯油时的转化率，这是由于处理DAO对于HC催化剂的稳定性的不利的影响。该当处理DAO时降低转化率以保持HC催化剂稳定性的要求导致显著更高的未转化油(UCO)的产率，所述未转化油具有比运输燃料例如柴油或汽油显著更低的价值。
最大化HC进料转化率以最小化UCO物流，并且最大化HC的收益率将是理想的。实际上，只有UCO组分的小部分需要净化。这些为存在于UCO中的多核芳族化合物(PNA)。如果不从HC过程中净化，这些PNA将导致重质多核芳族化合物(HPNA)的浓度增加，这将导致催化剂迅速失活。UCO的其余部分非常适合于在HC中转化。不幸的是，用常规分馏不能将这些PNA与UCO分子的其余部分分离。
除非炼油厂有其它方法，例如流化催化裂化(FCC)，其可以催化转化UCO，否则将UCO送至低价值的燃料油池或用作沥青稀释油(cutter stock)。这导致低于AR至较高价值的运输燃料的所需的总转化率。
SDA DAO已经在HC商业方法中进行处理，然而UCO的产率通常远高于理想产率，和/或在HC中处理的DAO的最大可允许的百分比被限制在总的进料的少数部分。
当VGO和VR之间的蒸馏分馏点被降低到相比于典型的VDU操作相对低的值时，将UCO再循环回上游的减压蒸馏单元(VDU)也已经在商业上实行。该操作与最大化VGO回收(并因此最大化HC原料)的目标相悖，因为一些VGO沸腾材料留在了VR中。除非VGO/VR的分馏点显著降低，否则不存在多环芳族化合物与VGO和UCO的足够的分离，这是因为多环芳族化合物的宽沸点范围，如图4所示。此外，如果将VR送至SDA过程，则能够留在渣油中的增加的重质VGO将充当助溶剂，从而增加来自SDA过程的DAO的污染物和PNA的含量。
本发明包括若干关键组成部分，所述关键组成部分当在VDU-SDA-HC流程方案中处理AR时增加有价值的运输燃料的产率。当与上游VDU整合不可实现时，或当SDA处理AR或AR+VR的组合而不仅仅是VR时，本发明还可以单独应用于SDA-HC组合工艺。
在本发明的一个实施方案中，所述UCO单独在减压闪蒸器(VF)中分馏，其VGO终馏点等于或低于处理AR时在VDU中获得的典型的终馏点。
在本发明的进一步的实施方案中，当可能时将所述VF与上游VDU整合，以降低VF的资金和操作成本。
在本发明的其它实施方案中，将VF塔底产物(UCO HVGO)发送至SDA单元(通常与来自VDU的减压分馏塔的VR联合)。另外，在某些实施方案中，将VF闪蒸馏出物(UCO LVGO)发送至VDU减压分馏塔以用于进一步分离。在本发明的其它实施方案中，当可能时将减压系统与VDU共享，并且在某些情况下，存在VDU和SDA过程的热整合。
图5是对典型的整合的VDU-VF-SDA流程方案的图解，其中将UCO发送至VF。在本发明的一个替代的实施方案中，所述VF是独立的单元，其可以与SDA过程热整合。进一步的实施方案为其中UCO减压闪蒸器被包含内构件的减压塔所代替以改进轻质和重质UCO馏分之间的分离的实施方案。
相对于通常的VDU-SDA-HC流程方案，总的AR转化率可以提高超过5.0wt％。表2中显示了产率改变的实例。对于该情形，在本发明之前的基本操作将使SDA DAO产率限制在75wt％且从HC的UCO净化在5wt％的最小值。这将导致总的AR转化率为86.9wt％。表2显示了选择性的UCO回收之前和之后总的材料平衡。表2中的所有数值都以wt％显示。
表2
根据本发明的实施方案，由于包括PNA的增加的污染物将与UCO一起被净化，DAO产率能够提高到80wt％。由于将UCO从HC再循环回到VDU-SDA，大部分UCO作为优质HC进料回收，且有效HC转化率增加至超过99wt％。较高的DAO产率与较高的HC转化率的结合导致总的AR转化率为92.4wt％，总共增加了5.5wt％。
对于50,000BPD的AR进料量，基于与将UCO送入燃料油池时的UCO相比运输燃料的$60/bbl的提质价值，这种替代的流程方案的年度收益可以超过每年5千万美元。
在此引用的所有文献，包括出版物、专利申请和专利，通过引用并入本文，至如同各个参考文献被个体地和具体地指明通过引用并入并以其全部内容在本文中阐述的程度。
在描述本发明的上下文中(特别是在以下权利要求书的上下文中)所使用的术语“一种”、“一个”、“所述”以及类似的指代词应解释为涵盖单数和复数两者，除非在本文中另行指明或与上下文明显矛盾。本文对数值范围的叙述仅仅旨在用作个体地指代落入该范围内的每个单独值的简写方法，除非本文中另行指明，并且每个单独的值被并入到该说明书中，如同其在本文中被个体地叙述。在此描述的所有方法可以以任何合适的顺序实施，除非本文中另行指明或另外与上下文明显矛盾。本文提供的对任何和全部的实例、或者示例性语言(如“例如”)的使用仅旨在用于更好地说明本发明，而不是提出对本发明的范围的限制，除非另行主张。说明书中的语言不应被解释为指明任何未要求保护的要素对实行本发明而言是必不可少的。
本文中描述了本发明优选的实施方案，包括发明人已知的实施本发明的最佳模式。当阅读了前面的描述，这些优选的实施方案的变型对于本领域普通技术人员而言将得以明确。因此，本发明包括在此处所附权利要求中叙述的主题的全部改进和等同内容。

Claims (4)

1.一种将加氢裂化单元产生的未转化油馏分再循环的方法，该方法包括：
将常压渣油馏分进料至减压蒸馏单元中；
在溶剂脱沥青萃取器中处理来自减压蒸馏单元的减压渣油或来自原油蒸馏单元的常压渣油以获得脱沥青馏分；
在加氢裂化单元中处理所述脱沥青馏分以获得未转化油的馏分和烃产物的馏分；以及
在减压闪蒸器中处理所述未转化油的馏分以获得减压闪蒸器馏出物馏分和减压闪蒸器塔底馏分，其中所述减压闪蒸器塔底馏分在溶剂脱沥青萃取器中经历额外处理；
其中该方法进一步包括将所述减压闪蒸器馏出物馏分传送至减压蒸馏单元的步骤；以及
将所述减压闪蒸器塔底馏分传送至溶剂脱沥青萃取器的步骤。
2.根据权利要求1所述的方法，其进一步包括将所述减压闪蒸器与所述减压蒸馏单元整合的步骤。
3.根据权利要求1所述的方法，其中所述减压闪蒸器塔底馏分在被传送至溶剂脱沥青萃取器之前，与来自减压蒸馏单元的减压渣油结合。
4.根据权利要求1所述的方法，其中所述的减压闪蒸器被减压蒸馏塔代替。
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