CN104245890B - 对原油进行集成加氢处理、蒸汽热解和浆液加氢处理以生产石油化学产品 - Google Patents
对原油进行集成加氢处理、蒸汽热解和浆液加氢处理以生产石油化学产品 Download PDFInfo
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- CN104245890B CN104245890B CN201380015174.9A CN201380015174A CN104245890B CN 104245890 B CN104245890 B CN 104245890B CN 201380015174 A CN201380015174 A CN 201380015174A CN 104245890 B CN104245890 B CN 104245890B
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Classifications
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Abstract
在氢气存在下将原油加到在可有效产生经过加氢处理的流出物的条件下操作的加氢处理区,在蒸汽存在下在蒸汽热解区中对其进行热裂化,以产生混合产物流。对来源于所述经过加氢处理的流出物、所述蒸汽热解区内的加热蒸汽或所述混合产物流中的一者或多者的重质组分加到浆液加氢处理区,以产生浆液中间产物,然后对其进行热裂化。从所分离的混合产物流回收烯烃和芳烃作为产物。
Description
相关申请
本申请要求2012年3月20日提交的美国临时专利申请号61/613,294和2013年3月14日提交的美国临时专利申请号61/785,894的优先权权益,该两文献以引用的方式并入本文中。
发明背景
发明领域
本发明涉及一种由进料(包括原油)生产如轻质烯烃和芳烃等石油化学产品的集成加氢处理、蒸汽热解和浆液加氢处理工艺。
相关技术说明
低级烯烃(例如乙烯、丙烯、丁烯和丁二烯)和芳烃(例如苯、甲苯和二甲苯)是广泛用于石油化工和化学工业的基本中间物。热裂化或蒸汽热解是典型地在蒸汽存在下和在无氧条件下形成这些材料的工艺的一种主要类型。蒸汽热解的原料可以包括石油气体和馏分,如石脑油、煤油和瓦斯油。在原油精炼中,这些原料的可用性常常受到限制,并且需要昂贵的能量密集型工艺步骤。
已经使用重质烃作为蒸汽热解反应器的原料进行了研究。常规重质烃热解操作中的一个主要缺点是焦炭形成。举例来说,用于重质液体烃的蒸汽裂化工艺公开在美国专利号4,217,204中,其中将熔融盐雾引入到蒸汽裂化反应区中,以试图将焦炭形成减到最少。在一个使用康拉逊残碳为3.1重量%的阿拉伯轻质原油的实施例中,在熔融盐 存在下,裂化设备能够连续操作624小时。在不加入熔融盐的对比例中,蒸汽裂化反应器在仅5小时后就因为反应器中形成焦炭而被阻塞并且变得不可操作。
另外,使用重质烃作为蒸汽热解反应器的原料时烯烃和芳烃的产率和分布与使用轻质烃原料时的不同。重质烃与轻质烃相比具有较高的芳烃含量,如较高的矿务局相关指数(BMCI)所指示。BMCI是原料芳香度的度量,且计算如下:
BMCI=87552/VAPB+473.5*(sp.gr.)-456.8 (1)
其中:
VAPB=体积平均沸点(兰氏度),且
sp.gr.=原料的比重。
当BMCI减小时,预期乙烯产率增加。因此,高石蜡或低芳烃进料通常优选进行蒸汽热解,以便在反应器旋管部分中获得所需烯烃的较高产率且避免存在较多不希望的产物和焦炭形成。
Cai等,“Coke Formation in Steam Crackers for Ethylene Production,”Chem.Eng.&Proc.,第41卷,(2002),199–214中已经报告了蒸汽裂化器中的绝对焦炭形成速率。总体来说,绝对焦炭形成速率呈烯烃>芳烃>石蜡烃这样的升序,其中烯烃表示重烯烃。
为了能够响应于对这些石油化学产品的不断增长的需求,能以较大的量使用的其它类型进料,如未处理的原油,对生产商具有吸引力。使用原油进料将最小化或消除精炼的可能性,精炼是这些必需的这些石油化学产品生产中的瓶颈。
发明概述
本文中的系统和工艺提供了一种集成有加氢处理区和浆液加氢 处理区以便允许直接处理原料(包括原油原料)以生产石油化学产品(包括烯烃和芳烃)的蒸汽热解区。
在氢气存在下将原油加到在可有效生产经过加氢处理的还原流出物的条件下操作的加氢处理区,所述流出物具有降低的污染物含量、增加的链烷烃含量、减小的矿务局相关指数和增加的美国石油学会比重。在蒸汽热解区中对经过加氢处理的流出物进行热裂化,以产生混合产物流。来源于经过加氢处理的流出物、蒸汽热解区内经过加热的蒸汽或由蒸汽裂化产生的混合产物流中的一者或多者加到浆液加氢处理区,以产生浆液中间产物,然后对其进行热裂化。从所分离的混合产物流回收烯烃和芳烃作为产物。
如本文中所使用,术语“原油”应理解为包括来自于常规来源的全原油,包括已经进行了一定的预处理的原油。术语原油还应该理解为包括已经进行了水-油分离和/或气-油分离和/或脱盐和/或稳定的原油。
下文详细论述本发明工艺的其它方面、实施方案和优点。此外,应理解,前述信息和以下详细描述都仅仅是各种方面和实施方案的说明性实例,并且打算为理解所要求的特征和实施方案的特性和特征提供综述或框架。附图是说明性的,并且是为了加深对本发明工艺的各种方面和实施方案的理解而提供。
附图简述
将在下文且参考附图更详细地描述本发明,其中:
图1是本文中所描述的集成工艺的一个实施方案的工艺流程图;且
图2A-2C是本文中所描述的集成工艺的某些实施方案中所使用的气-液分离装置的透视图、顶视图和侧视图的示意性说明;且
图3A-3C是本文中所描述的集成工艺的某些实施方案中所使用的闪蒸容器中的气-液分离装置的截面视图、放大截面视图和顶部截面视图的示意性说明。
发明详述
图1中示出了包括集成加氢处理、蒸汽热解和浆液加氢处理的工艺流程图。所述集成系统总体上包括选择性加氢处理区、蒸汽热解区、浆液加氢处理区和产物分离区。
所述选择性加氢处理区总体上包括加氢处理反应区4,所述加氢处理区具有用于接收混合物3的入口,所述混合物含有进料1和从蒸汽热解产物流再循环而来的氢气2,以及必要时存在的补充氢气(未示出)。加氢处理反应区4还包括用于排出经过加氢处理的流出物5的出口。
在热交换器(未示出)中冷却来自于加氢处理反应区4的反应器流出物5,且送到高压分离器6。在胺单元12中净化分离器顶部物质7,且将产生的富氢气体流13传送到再循环压缩器14以用作加氢处理反应器中的再循环气体15。来自于高压分离器6的底部物流8基本上呈液相,将其冷却并引入到低压冷分离器9中,在其中将它分离成气体物流和液体物流10。来自于低压冷分离器的气体包括氢气、H2S、NH3和任何轻质烃,如C1-C4烃。典型地,将这些气体送出以便进行进一步处理,如闪光处理或燃料气体处理。根据本文中的工艺和系统的某些实施方案,通过将物流11与蒸汽裂化器产物44组合作为产物分离区的组合进料来从其中回收氢气和其它烃。液体物流10a的全部或一部分充当加到蒸汽热解区30的经过加氢处理的裂化进料。
蒸汽热解区30总体上包括可基于本领域中已知的蒸汽热解单元操作(例如在蒸汽存在下将热裂化进料加到对流部分)进行操作的对流部分32和热解部分。
在某些实施方案中,气-液分离区36包括在部分32与34之间。来自于对流区32的经过加热的裂化进料所通过被分馏的气-液分离区36可以是闪蒸分离装置、基于对蒸气和液体进行物理或机械分离的分离装置或包括这些装置类型中的至少一种的组合。
在其它实施方案中,气-液分离区18包括在部分32的上游。物流10a在气-液分离区18中被分馏成气相和液相,所述气-液分离区可以是闪蒸分离装置、基于对蒸气和液体进行物理或机械分离的分离装置或包括这些装置类型中的至少一种的组合。
有用的气-液分离装置示范为且参考图2A-2C和3A-3C。气-液分离装置的类似配置描述于美国专利公开号2011/0247500中,该案以全文引用的方式并入本文中。在这个装置中,蒸气和液体流经气旋几何结构,该装置在此以等温方式且以非常短的停留时间(在某些实施方案中小于10秒)并且以相对较低的压降(在某些实施方案中小于0.5巴)进行操作。总体来说,蒸气以循环模式旋转以产生力,其中较重的液滴和液体被捕获并且引导到液体出口作为可以传送到浆液加氢处理区22的液体残余物(任选地经由浆液加氢处理掺合单元20),而蒸气被引导通过蒸气出口。在设置气-液分离装置36的实施方案中,液相38作为残余物排出,而气相是热解部分34的装料37。在设置气-液分离装置18的实施方案中,液相19作为残余物排出,而气相是对流部分32的装料10。改变蒸发温度和流体速度以调节近似温度截止点,例如在与残余燃油掺合物相容的某些实施方案中,例如约540℃。
在本文中的工艺中,使所有不合格残余物或再循环的底部物质,例如物流19、38和72,经过加氢处理区且与初始进料相比,含有减少量的杂原子化合物,包括含硫、含氮和金属化合物。可以将这些残余物流的全部或一部分加到如本文中所描述的浆液加氢处理区22(任选地经由浆液加氢处理掺合单元20)。
淬火区40也集成在蒸汽热解区30的下游,且包括与蒸汽热解区30的出口流体连通的用于接收混合产物流39的入口、用于接收淬火溶液42的入口、用于将经过淬火的混合产物流44排到分离区的出口和用于排出淬火溶液46的出口。
总体来说,中间淬火混合产物流44被转化为中间产物流65和氢气62。对所回收的氢气进行纯化,且用作加氢处理反应区中的再循环氢气流2。在分离区70中,中间产物流65总体上被分馏成最终产物和残余物,所述分离区可以是一个或多个分离单元,如多个分馏塔,包括如本领域技术人员已知的脱乙烷塔、脱丙烷塔和脱丁烷塔。举例来说,合适的设备描述于“Ethylene,”Ullmann’s Encyclopedia of Industrial Chemistry,第12卷,第531–581页中,特别是图24、图25和图26,该文献以引用的方式并入本文中。
产物分离区70与产物流65流体连通且包括多种产物73-78,其包括用于排出甲烷的出口78、用于排出乙烯的出口77、用于排出丙烯的出口76、用于排出丁二烯的出口75、用于排出混合丁烯的出口74和用于排出热解汽油的出口73。另外,回收热解燃料油71,例如,作为将在异地精炼厂进行进一步处理的低硫燃料油掺合物。可以将所排出的热解燃料油的部分72加到浆液加氢处理区(如虚线所指示)。注意,尽管示出了六个产物出口以及氢气再循环出口和底部出口,但可以设置更少或更多个,这取决于例如所采用的分离单元的配置以及产率和分布要求。
浆液加氢处理区22可以包括现有的或经过改良的(例如,尚有待开发的)浆液加氢处理操作(或单元操作系列),其将具有相当低的值的残余物或底部物质(例如,通常来自于真空蒸馏柱或大气压蒸馏柱,且在本发明中系统来自于蒸汽热解区30)转化成相对较低分子量的烃气体、石脑油以及轻瓦斯油和重瓦斯油。加到加氢处理区22的进料包括来自于气-液分离区18的底部物质19的全部或一部分,或来自于气-液分离区36的底部物质38的全部或一部分。另外,如本文中 所描述,可以将来自于产物分离区70的热解燃料油71的全部或一部分72组合,作为流化催化裂化区25的装料。
浆液床反应器单元操作的特征在于存在具有非常小的平均尺寸且可以有效地均匀分散并维持在介质中的催化剂粒子,使得加氢工艺有效且立即在反应器的整个体积内进行。浆液相加氢处理在相对较高的温度(400℃-500℃)和高压(100巴-230巴)下操作。由于所述工艺的严格度较高,故可以实现相对较高的转化率。所述催化剂可以是均匀的或不均匀的,并且设计为在高严格度条件下起作用。所述机制是热裂化工艺,并且基于自由基形成。在催化剂存在下利用氢气来稳定所形成的自由基,从而防止焦炭形成。所述催化剂促进重质原料在裂化之前部分氢化,从而减少长链化合物的形成。
浆液加氢裂化工艺中所使用的催化剂可以是小粒子,或可以作为总体上呈反应期间或预处理步骤中形成的金属硫化物形式的油溶性前体引入。组成分散催化剂的金属总体上是一种或多种过渡金属,其可以选自Mo、W、Ni、Co和/或Ru。钼和钨是特别优选的,因为它们的性能优于钒或铁,而钒或铁与镍、钴或钌相比又是优选的。催化剂能以低浓度,例如,数百百万分率(ppm),以一次通过配置加以使用,但在那些条件下,在较重产品的升级方面不是特别有效。为了获得更好的产品质量,以较高的浓度使用催化剂,且有必要对催化剂进行再循环以使得所述工艺足够经济。可以通过使用如沉降、离心或过滤等方法来回收催化剂。
总体来说,浆液床反应器可以是两相或三相反应器,取决于所利用的催化剂的类型。当采用均匀的催化剂时,它可以是气体和液体的两相系统,或当采用小粒度不均匀催化剂时,是气体、液体和固体的三相系统。可溶性液体前体或小粒度催化剂允许催化剂高度分散在液体中且在催化剂与原料之间产生密切接触,从而获得高转化率。
对于本文中的系统和工艺中的浆液床加氢处理区22来说,有效 的处理条件包括介于375与450℃之间的反应温度和介于30与180巴之间的反应压力。合适的催化剂包括由油溶性催化剂前体就地产生的非负载型纳米尺寸活性粒子,包括例如一种第VIII族金属(Co或Ni)和一种第VI族金属(Mo或W)的硫化物形式。
在采用图1中所示的配置的工艺中,将原料1与有效量的氢气2和15(和任选地存在的补充氢气,未示出)混合,且在300℃到450℃范围内的温度下将混合物3加到选择性加氢处理反应区4的入口。在某些实施方案中,加氢处理反应区4包括一个或多个如共同拥有的美国专利公开号2011/0083996和PCT专利申请公开号WO2010/009077、WO2010/009082、WO2010/009089和WO2009/073436中所描述的单元操作,所有这些文献都以全文引用的方式并入本文中。举例来说,加氢处理反应区可以包括一个或多个含有有效量的加氢脱金属催化剂的床,和一个或多个含有有效量的具有加氢脱芳烃、加氢脱氮、加氢脱硫和/或加氢裂化功能的加氢处理催化剂的床。在其它实施方案中,加氢处理反应区4包括多于两个催化剂床。在其它实施方案中,加氢处理反应区4包括多个反应容器,各反应容器含有具有不同功能的催化剂床。
加氢处理反应区4在可对油原料(其在某些实施方案中为原油)进行有效的加氢脱金属、加氢脱芳烃、加氢脱氮、加氢脱硫和/或加氢裂化的参数下操作。在某些实施方案中,使用以下条件进行加氢处理:在300℃到450℃范围内的温度下操作;在30巴到180巴的压力下操作;和液体时空速度在0.1h-1到10h-1范围内。值得注意的是,当使用原油作为加氢处理反应区4中的原料时,显示出了许多优点,例如,如与相同加氢处理单元操作用于大气压残余物时相比。举例来说,在开始时或运行温度在370℃到375℃范围内时,钝化速率在1℃/月左右。相反,如果要对残余物进行处理,那么钝化速率将更接近于约3℃/月到4℃/月。对大气压残余物的处理典型地采用200巴左右的压力,而处理原油的本发明工艺可以在低达100巴的压力下操作。另外,为了实现增加进料的氢气含量所需的高水平的饱和,当与大气压残余物 相比时,这一工艺可以在高吞吐量下操作。LHSV可以高达0.5h-1,而大气压残余物的则典型地为0.25h-1。意外的发现是当处理原油时钝化速率处于通常观察到的结果的反方向。低吞吐量(0.25h-1)下的钝化是4.2℃/月,而较高吞吐量(0.5h-1)下的钝化是2.0℃/月。在工业上考虑的每次进料下,观察结果相反。这可以归因于催化剂的洗涤作用。
在热交换器(未示出)中冷却来自于加氢处理区4的反应器流出物5并且送到高压冷或热分离器6。在胺单元12中净化分离器顶部物质7,且将产生的富氢气体流13传送到再循环压缩器14以用作加氢处理反应区4中的再循环气体15。来自于高压分离器6的分离器底部物质8基本上呈液相,将其冷却,然后引入到低压冷分离器9。可以用常规方式净化来自于低压冷分离器的其余气体,即物流11,包括氢气、H2S、NH3和任何轻质烃(其可以包括C1-C4烃),且送出以便进行进一步处理,如闪光处理或燃料气体处理。在本发明工艺的某些实施方案中,通过组合物流11(如虚线所指示)与裂化气体,即来自于蒸汽裂化器产物的物流44来回收氢气。
在某些实施方案中,底部物流10a是加到蒸汽热解区30的进料10。在其它实施方案中,将来自于低压分离器9的底部物质10a送到分离区18,其中所排出的蒸气部分是加到蒸汽热解区30的进料10。蒸气部分可以具有例如对应于物流10a的沸点的初始沸点和在约350℃到约600℃范围内的最终沸点。分离区18可以包括合适的气-液分离单元操作,如闪蒸容器、基于对蒸气和液体进行物理或机械分离的分离装置或包括这些装置类型中的至少一种的组合。呈独立式装置形式或安装在闪蒸容器入口处的气-液分离装置的某些实施方案分别描述于图2A-2C和3A-3C中。
蒸汽热解进料10含有降低的污染物(例如,金属、硫和氮)含量、增加的链烷烃含量、减小的BMCI和增加的美国石油学会(API)比重。在有效量的蒸汽(例如,经由蒸汽入口接收的)的存在下,将含有与进料1相比增加的氢气含量的蒸汽热解进料10传输到蒸汽热解区30的对流部分32的入口。在对流部分32中,将混合物加热到预定温度,例如,使用一个或多个废热流或其它合适的加热配置。在某些实施方案中,将混合物加热到温度为400℃到600℃范围内的温度,并且将沸点低于所述预定温度的材料汽化。
蒸汽热解区30在可使进料10有效裂化成所需产物(包括乙烯、丙烯、丁二烯、混合丁烯和热解汽油)的参数下操作。在某些实施方案中,使用以下条件进行蒸汽裂化:在对流部分和热解部分中温度在400℃到900℃范围内;对流部分中的蒸汽对烃比率在0.3∶1到2∶1范围内;以及在对流部分和热解部分中的停留时间在0.05秒到2秒范围内。
在某些实施方案中,气-液分离区36包括一个或多个气液分离装置80,如图2A-2C中所示。气液分离装置80具有操作经济性且无需维护,因为它不需要能量或化学产品供应。总体来说,装置80包括三个端口,包括用于接收气-液混合物的进入口82、分别用于排出和收集所分离的气相和液相的蒸气排出口84和液体排出口86。装置80基于包括以下各项的现象组合进行操作:利用球形流体预旋转部分将来料混合物的线性速度转化成旋转速度,用于预分离蒸气与液体的受控离心作用和用于促进蒸气与液体分离的气旋作用。为了实现这些作用,装置80包括预旋转部分88、受控气旋垂直部分90和液体收集器/沉降部分92。
如图2B中所示,预旋转部分88包括介于横截面(S1)与横截面(S2)之间的受控预旋转元件和通到受控气旋垂直部分90且位于横截面(S2)与横截面(S3)之间的连接元件。来自于具有直径(D1)的入口82的气液混合物在横截面(S1)上沿切线方向进入所述设备。根据以下等式,来料流的进入截面(S1)的面积是入口82的面积的至少10%:
预旋转元件88限定曲线流动路径,并且其特征在于从入口横截面S1向出口横截面S2,横截面恒定、减小或增加。在某些实施方案中,受控预旋转元件的出口横截面(S2)与入口横截面(S1)之间的比率在0.7≤S2/S1≤1.4之间。
混合物的旋转速度取决于预旋转元件88的中心线的曲率半径(R1),其中所述中心线定义为接合预旋转元件88的连续横截面表面的所有中心点的曲线。在某些实施方案中,曲率半径(R1)在2≤R1/D1≤6范围内,其中张角在150°≤αR1≤250°范围内。
入口截面S1处的横截面形状虽然被描述为总体上呈正方形,但它可以是矩形、圆角矩形、圆形、椭圆形或其它直线、曲线或上述形状的组合。在某些实施方案中,沿流体通过的预旋转元件88的曲线路径的横截面的形状逐渐变化,例如从大体上正方形变成矩形。元件88的横截面的逐渐变成矩形有利地使开口面积最大化,因而允许气体在早期与液体混合物分离且实现均匀速度分布并且使流体流中的剪切应力最小化。
来自于受控预旋转元件88的截面(S2)的流体流经由连接元件通过截面(S3)到达受控气旋垂直部分90。连接元件包括开放区域,所述开放区域对气旋垂直部分90的入口开放并且与其连接或成一体。流体流以高旋转速度进入所述受控气旋垂直部分90,以产生气旋效应。连接元件出口截面(S3)与入口截面(S2)之间的比率在某些实施方案中处于2≤S3/S1≤5范围内。
处于高旋转速度下的混合物进入气旋垂直部分90。动能降低,且蒸气在气旋作用下与液体分离。在气旋垂直部分90的上部90a和下部90b中形成气旋。在上部90a中,混合物的特征在于高蒸气浓度,而在下部90b中,混合物的特征在于高液体浓度。
在某些实施方案中,气旋垂直部分90的内径D2在2≤D2/D1≤5范围内,且可以沿其高度方向恒定不变,上部90a的长度(LU)在1.2≤ LU/D2≤3范围内,且下部90b的长度(LL)在2≤LL/D2≤5范围内。
气旋垂直部分90在蒸气出口84附近的端部连接到部分开放的释放上升管并且连接到蒸汽热解单元的热解部分。部分开放的释放上升管的直径(DV)在某些实施方案中处于0.05≤DV/D2≤0.4范围内。
因此,在某些实施方案中,且取决于来料混合物的性质,其中较大体积分数的蒸气通过具有直径DV的部分开放的释放管从出口84排出装置80。具有低蒸气浓度或不存在蒸气浓度的液相(例如,残余物)通过气旋垂直部分90的具有横截面积S4的底部部分排出,且收集在液体收集器和沉降管92中。
气旋垂直部分90与液体收集器和沉降管92之间的连接区域的角度在某些实施方案中是90°。在某些实施方案中,液体收集器和沉降管92的内径在2≤D3/D1≤4范围内,且在整个管长度上是恒定的,并且液体收集器和沉降管92的长度(LH)在1.2≤LH/D3≤5范围内。通过具有直径DL且位于沉降管底部或邻近沉降管底部的管子86从所述设备中去除具有低蒸气体积分数的液体,所述直径在某些实施方案中处于0.05≤DL/D3≤0.4范围内。
在某些实施方案中,设置在操作和结构方面类似于装置80而不具有液体收集器和沉降管送回部分的气-液分离装置18或36。举例来说,气-液分离装置180用作闪蒸容器179的入口部分,如图3A-3C中所示。在这些实施方案中,容器179的底部充当来自于装置180的回收液体部分的收集和沉降区。
总体来说,通过闪蒸容器179的顶部194排出气相,并且从闪蒸容器179的底部196回收液相。气-液分离装置180具有操作经济性且无需维护,因为它不需要能量或化学产品供应。装置180包括三个端口,包括用于接收气-液混合物的进入口182、用于排出所分离的蒸气的蒸气排出口184和用于排出所分离的液体的液体排出口186。装置180基于包括以下各项的现象组合进行操作:利用球形流体预旋转 部分将来料混合物的线性速度转化成旋转速度,用于预分离蒸气与液体的受控离心作用和用于促进蒸气与液体分离的气旋作用。为了实现这些作用,装置180包括预旋转区188和具有上部190a和下部190b的受控气旋垂直部分190。具有低液体体积分数的蒸气部分通过具有直径(DV)的蒸汽排出口184排出。上部190a是部分或完全开放的,且具有在某些实施方案中处于0.5<DV/DII<1.3范围内的内径(DII)。具有低蒸气体积分数的液体部分由具有在某些实施方案中处于0.1<DL/DII<1.1范围内的内径(DL)的液体端口186排出。收集液体部分并且从闪蒸容器179的底部排出。
为了增强或控制相分离,总体上通过抑制烃的沸点和减少焦炭形成,向气-液分离装置80或180的进料中加入加热蒸汽。还可以利用如本领域技术人员已知的常规热交换器来加热进料。调节装置80或180的进料的温度,使得所需的残余物馏分作为液体部分排出,例如在约350℃到约600℃范围内。
尽管已经独立地且以独立的部分描述了气-液分离装置的不同部件,但本领域技术人员应理解,设备80或设备180可以形成为单片式结构,例如,它可以浇铸或模制,或者它可以由独立的零件组装,例如,通过将独立的组件焊接或以其它方式连接在一起,所述组件可能或可能不精确对应于本文中所描述的部件或部分。
本文中所描述的气-液分离装置可以设计用于容纳一定的流速和组成以实现所需的分离,例如,在540℃下。在一个实施例中,对于540℃和2.6巴下的总流速2002m3/天和入口处具有密度分别为729.5kg/m3、7.62kg/m3和0.6941kg/m3的7%液体、38%蒸气和55%蒸汽的流体组成来说,装置80(不存在闪蒸容器)的合适的尺寸包括D1=5.25cm;S1=37.2cm2;S1=S2=37.2cm2;S3=100cm2;αR1=213°;R1=14.5cm;D2=20.3cm;LU=27cm;LL=38cm;LH=34cm;DL=5.25cm;DV=1.6cm;和D3=20.3cm。对于相同的流速和特征来说,闪蒸容器中所使用的装置180包括D1=5.25cm;DV=20.3cm; DL=6cm;和DII=20.3cm。
应了解,虽然陈述了不同的尺寸作为直径,但在组件零件不是圆柱形的实施方案中,这些值也可以是当量有效直径。
将混合产物流39传送到具有经由独立的入口引入的淬火溶液42(例如,水和/或热解燃料油)的淬火区40的入口,以产生具有降低的温度,例如约300℃的中间经淬火混合产物流44,且排出用过的淬火溶液46。来自于裂化器的气体混合物流出物39典型地为氢气、甲烷、烃类、二氧化碳和硫化氢的混合物。在利用水或油淬火进行冷却之后,在多阶段压缩区51中,典型地在4-6个阶段中压缩混合物44,以产生压缩气体混合物52。在碱性处理单元53中处理压缩气体混合物52,以产生脱除了硫化氢和二氧化碳的气体混合物54。在压缩区55中进一步压缩气体混合物54,且所得裂化气体56典型地在单元57中进行低温处理以脱水,且通过使用分子筛进行进一步干燥。
将来自于单元57的冷裂化气流58传送到脱甲烷塔59,从中由裂化气流产生含有氢气和甲烷的塔顶物流60。然后将来自于脱甲烷塔59的底部物流65送出以便在包括分馏塔(包括脱乙烷塔、脱丙烷塔和脱丁烷塔)的产物分离区70中进行进一步处理。还可以采用脱乙烷塔、脱丙烷塔和脱丁烷塔的顺序不同的工艺配置。
根据本文中的工艺,在脱甲烷塔59处与甲烷分离且在单元61中进行氢气回收之后,获得纯度典型地为80-95体积%的氢气62。单元61中的回收方法包括低温回收(例如,在约-157℃的温度下)。然后将氢气流62传送到氢气纯化单元64,如变压吸附(PSA)单元,以获得纯度为99.9%+的氢气流2,或膜分离单元,以获得纯度为约95%的氢气流2。然后将经过纯化的氢气流2反向再循环,以充当加氢处理反应区的必需氢气的主要部分。另外,较小比例可以用于乙炔、甲基乙炔和丙二烯的氢化反应(未示出)。另外,根据本文中的工艺,甲烷流63可以任选地再循环到蒸汽裂化器以用作燃烧器和/或加热器的燃 料(如虚线所指示)。
将来自于脱甲烷塔59的底部物流65传输到产物分离区70的入口,以便分离成甲烷、乙烯、丙烯、丁二烯、混合丁烯和热解汽油,分别经由78、77、76、75、74和73排出。热解汽油总体上包括C5-C9烃,且可以从这个切入点提取芳烃,包括苯、甲苯和二甲苯。将氢气传送到氢气纯化区64的入口以产生高纯度氢气流2,所述氢气流经由其出口排出且再循环到加氢处理反应区4的入口。将热解燃料油经由出口71排出(例如,在高于沸点最低的C10化合物的沸点的温度下沸腾的材料,称为“C10+”物流),所述热解燃料油可以用作热解燃料油掺合物,例如,低硫燃料油掺合物,以便在异地精炼厂进行进一步处理。此外,如本文中所示,燃料油72(其可以是热解燃料油71的全部或一部分)可以经由掺合区20引入到浆液加氢处理区22。
加到浆液加氢处理区的进料包括如本文中所描述的物流19、38和/或72的组合。在浆液加氢处理区22中对这个材料进行处理,任选地经由掺合区20。在掺合区20中,将残余液体馏分与包括催化剂活性粒子的浆液状未转化残余物25混合,以形成浆液加氢处理区22的进料。然后在浆液加氢处理区22中,在氢气23存在下对此进料进行升级,以产生包括中间馏分的浆液中间产物24。在某些实施方案中,浆液加氢处理区22处于普通高压回路下,其中一个或多个反应器在加氢处理区4中。将浆液中间产物24再循环且与经过加氢处理的反应器流出物10混合,之后在蒸汽热解区30中进行处理以便进行转化。
在一系列分离单元70中分离蒸汽热解区后淬火和分离流出物流65,以产生主要产物73-78,包括甲烷、乙烷、乙烯、丙烷、丙烯、丁烷、丁二烯、混合丁烯、汽油和燃料油。使氢气流62通过氢气纯化单元64,以形成高品质氢气2,以便与加氢处理反应单元4的进料混合。
在某些实施方案中,加氢处理工艺可以通过饱和化然后对芳烃,尤其是聚芳烃进行温和加氢裂化来增加原料的链烷烃含量(或降低BMCI)。当加氢处理原油时,可以通过使原料通过执行脱金属、脱硫和/或脱氮等催化功能的一系列层状催化剂来去除如金属、硫和氮等污染物。
在一个实施方案中,用于执行加氢脱金属(HDM)和加氢脱硫(HDS)的催化剂的顺序如下:
a.HDM部分中的催化剂总体上基于γ氧化铝载体,其表面积为约140-240m2/g。这种催化剂最好描述为具有非常高的孔隙体积,例如,超过1cm3/g。孔隙尺寸本身典型地主要是大孔。需要如此来为催化剂表面上的金属和任选地存在的掺杂剂的吸收提供较大的容量。典型地,催化剂表面上的活性金属是镍和钼的硫化物,其比率为Ni/Ni+Mo<0.15。HDM催化剂上的镍浓度低于其它催化剂,因为预计一些镍和钒将在去除过程中自动从原料中沉积,从而充当催化剂。所使用的掺杂剂可以是磷(参见例如美国专利公开号US2005/0211603,该文献以引用的方式并入本文中)、硼、硅和卤素中的一者或多者。所述催化剂可以呈氧化铝挤出物或氧化铝珠粒形式。在某些实施方案中,使用氧化铝珠粒来促进反应器中的催化剂HDM床的卸荷,因为在床顶部,金属吸收将在30%到100%范围内。
b.还可以使用中间催化剂在HDM与HDS功能之间进行过渡。其具有中间金属载荷和孔隙尺寸分布。HDM/HDS反应器中的催化剂大体上是呈挤出物形式的基于氧化铝的载体,任选地存在至少一种VI族催化金属(例如,钼和/或钨),和/或至少一种VIII族催化金属(例如,镍和/或钴)。所述催化剂还任选地含有至少一种选自硼、磷、卤素和硅的掺杂剂。物理性质包括约140–200m2/g的表面积、至少0.6cm3/g的孔隙体积,和介孔且在12到50nm范围内的孔隙。
c.HDS部分中的催化剂可以包括具有基于γ氧化铝的载体材料 的那些催化剂,其中典型表面积接近HDM范围的较高端,例如,约在180-240m2/g范围内。这就要求较高的HDS表面,产生相对较小的孔隙体积,例如,低于1cm3/g。所述催化剂含有至少一种VI族元素,如钼,和至少一种VIII族元素,如镍。所述催化剂还包括至少一种选自硼、磷、硅和卤素的掺杂剂。在某些实施方案中,钴是用于提供相对较高水平的脱硫。活性相的金属载荷较高,因为所需的活性较高,使得Ni/Ni+Mo摩尔比在0.1到0.3范围内,且(Co+Ni)/Mo摩尔比在0.25到0.85范围内。
d.设计最终催化剂(其可以任选地替换第二和第三催化剂)以进行原料氢化(而不是加氢脱硫的主要功能),例如,如Appl.Catal.A General,204(2000)251中所描述。还将利用Ni提升催化剂活性,且载体将为宽孔γ氧化铝。物理性质包括接近HDM范围的较高的一端的表面积,例如,180-240m2/g。这就要求较高的HDS表面,产生相对较小的孔隙体积,例如,低于1cm3/g。
本文中的方法和系统与已知的蒸汽热解工艺相比提供了以下改良:
使用原油作为原料来生产石油化学产品,如烯烃和芳烃;
从初始全原油中大量去除焦炭前体,这就允许减少蒸汽热解单元的辐射盘管中的焦炭形成;
还从起始进料中显著去除其它杂质,如金属、硫和氮化合物,这就避免了最终产物的后处理。
另外,将由蒸汽裂化区产生的氢气再循环到加氢处理区以使对新的氢气的需求最小化。在某些实施方案中,本文中所描述的集成系统仅需要新的氢气来开始操作。一旦反应达到平衡后,氢气纯化系统就可以提供足够高纯度的氢气来维持整个系统的操作。
实施例
以下是本文中所公开的工艺的一个实施例。表1示出了以阿拉伯轻质油作为原料的常规加氢处理步骤的性质。
表1
下表2是按照浆液加氢处理工艺,使用所公开的油分散催化剂对阿拉伯轻质油进行处理的结果。此工艺可以经过优化以实现更高程度的转化和脱硫。
表2
表3示出了利用常规加氢处理步骤对升级的阿拉伯轻质油进行蒸汽裂化的预测石化产品产率。
表3
产物 | 产率,Wt%FF |
H2 | 0.6% |
甲烷 | 10.8% |
乙炔 | 0.3% |
乙烯 | 23.2% |
乙烷 | 3.6% |
甲基乙炔 | 0.3% |
丙二烯 | 0.2% |
丙烯 | 13.3% |
丙烷 | 0.5% |
丁二烯 | 4.9% |
丁烷 | 0.1% |
丁烯 | 4.2% |
热解汽油 | 21.4% |
热解燃料油 | 16.4% |
上文和附图中已经描述了本发明的方法和系统;然而,修改对于本领域技术人员来说应是显而易见的,且本发明的保护范围将由以下权利要求书来限定。
Claims (15)
1.一种集成加氢处理、蒸汽热解和浆液加氢处理工艺,用于直接转化原油以产生烯烃类和芳香族石油化学产品,所述工艺包括:
a.在氢气存在下,在可有效产生经过加氢处理的流出物的条件下对原油进行加氢处理,所述流出物具有降低的污染物含量、增加的链烷烃含量、减小的矿务局相关指数和增加的美国石油学会比重;
b.在蒸汽存在下,在蒸汽热解区中,在可有效产生混合产物流的条件下对所述经过加氢处理的流出物和浆液中间产物进行热裂化;
c.在浆液加氢处理区中对来源于所述经过加氢处理的流出物、所述蒸汽热解区内的加热蒸汽或所述混合产物流中的一者或多者的舍弃的残余物或底部物质进行处理,以产生该浆液中间产物;
d.分离混合产物流;
e.对步骤(d)中所回收的氢气进行纯化且将它再循环到加氢处理步骤;和
f.从所分离的混合产物流中回收烯烃和芳烃。
2.如权利要求1所述的工艺,还包括从所述混合产物流回收热解燃料油以便用作步骤(c)中所裂解的舍弃的残余物或底部物质的至少一部分。
3.如权利要求1所述的工艺,还包括在气-液分离区中将来自于步骤(a)的经过加氢处理的流出物分离成气相和液相,其中在步骤(b)中对所述气相进行热裂化,且在步骤(c)中处理所述液相的至少一部分。
4.如权利要求3所述的工艺,其中所述气-液分离区是闪蒸分离设备。
5.如权利要求3所述的工艺,其中所述气-液分离区是用于分离蒸气与液体的物理设备。
6.如权利要求3所述的工艺,其中所述气-液分离区是用于分离蒸气与液体的机械设备。
7.如权利要求3所述的工艺,其中所述气-液分离区包括在入口处具有气-液分离装置的闪蒸容器,其包括
预旋转元件,其具有进入部分和过渡部分,所述进入部分具有用于接收所述经过加氢处理的流出物的入口和曲线型导管,
受控的气旋部分,其具有
通过会聚所述曲线型导管与所述气旋部分而连接到所述预旋转元件的入口,和
处于所述气旋部件的上端的上升管部分,蒸气通过所述上升管部分,
其中在液相的全部或一部分传递到步骤(c)之前,所述闪蒸容器的底部充当所述液相的收集和沉降区。
8.如权利要求1所述的工艺,其中步骤(b)还包括:
在所述蒸汽热解区的对流部分中加热经过加氢处理的流出物,
将经过加热的经加氢处理的流出物分离成气相和液相,
将所述气相传递到所述蒸汽热解区的热解部分,和
排出所述液相以用作步骤(c)中所处理的舍弃的残余物或底部物质的至少一部分。
9.如权利要求8所述的工艺,其中将所述经过加热的经加氢处理的流出物分离成气相和液相是利用基于物理分离的气-液分离装置。
10.如权利要求8所述的工艺,其中将所述经过加热的经加氢处理的流出物分离成气相和液相是利用基于机械分离的气-液分离装置。
11.如权利要求8所述的工艺,其中将所述经过加热的经加氢处理的流出物分离成气相和液相是利用包括以下各项的气-液分离装置
预旋转元件,其具有进入部分和过渡部分,所述进入部分具有用于接收所述经过加热的经加氢处理的流出物的入口和曲线型导管,
受控的气旋部分,其具有
通过会聚所述曲线型导管与所述气旋部分而连接到所述预旋转元件的入口,
处于所述气旋部件的上端的上升管部分,气相通过所述上升管部分;
和
在液相的全部或一部分传输到步骤(c)之前所述液相所通过的液体收集器/沉降部分。
12.如权利要求1所述的工艺,其中
步骤(d)包括
利用多个压缩阶段来压缩所述热裂化混合产物流;
对所述经过压缩的热裂化混合产物流进行碱处理以产生具有降低的硫化氢和二氧化碳含量的热裂化混合产物流;
对所述具有降低的硫化氢和二氧化碳含量的热裂化混合产物流进行压缩;
对所述具有降低的硫化氢和二氧化碳含量的经过压缩的热裂化混合产物流进行脱水;
从所述具有降低的硫化氢和二氧化碳含量的经过脱水的经压缩热裂化混合产物流回收氢气;和
从所述具有降低的硫化氢和二氧化碳含量的经过脱水的经压缩热裂化混合产物流的其余部分获得烯烃和芳烃;
和
步骤(e)包括对来自于所述具有降低的硫化氢和二氧化碳含量的经过脱水的经压缩热裂化混合产物流的回收氢气进行纯化,以便再循环到所述加氢处理区。
13.如权利要求12所述的工艺,其中从所述具有降低的硫化氢和二氧化碳含量的经过脱水的经压缩热裂化混合产物流回收氢气还包括分开地回收甲烷,以便在所述热裂化步骤中用作燃烧器和/或加热器的燃料。
14.如权利要求3所述的工艺,还包括
在高压分离器中分离所述经过加氢处理的流出物以回收气体部分和液体部分,对所述气体部分进行净化且再循环到所述加氢处理区作为另一个氢气来源,和
在低压分离器中将得自于所述高压分离器的液体部分分离成气体部分和液体部分,其中得自于所述低压分离器的液体部分是热裂化步骤的进料,并且在蒸汽热解区之后且在步骤(d)中进行分离之前,将得自于所述低压分离器的气体部分与所述混合产物流组合。
15.如权利要求3所述的工艺,还包括:
在高压分离器中分离所述经过加氢处理的流出物以回收气体部分和液体部分,对所述气体部分进行净化且再循环到所述加氢处理区作为另一个氢气来源,和
在低压分离器中将得自于所述高压分离器的液体部分分离成气体部分和液体部分,其中得自于所述低压分离器的液体部分是所述气-液分离区的进料,并且在蒸汽热解区之后且在步骤(d)中进行分离之前,将得自于所述低压分离器的气体部分与所述混合产物流组合。
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