CN102971398A - 从石油流去除硫化合物 - Google Patents
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Abstract
本发明涉及一种用于通过将油流与水流混合并使其经受处于或高于水的超临界温度及压力的条件来提高所述油流的质量的方法。所述方法进一步包含冷却及后续碱萃取步骤。可将所得的硫醇及硫化氢气体与产品流隔离,从而产生质量提高的油流,与所述油流相比,所述质量提高的油流为具有低硫、低氮及低金属杂质的较高值油。
Description
技术领域
本发明涉及一种用于通过使碳氢化合物流与超临界水流体接触且随后接着引入碱性溶液以萃取含硫化合物来提高油的质量的方法。特定来说,在不存在外部提供的氢或催化剂的情况下进行水热质量提高方法以产生具有低硫、低氮、低金属杂质以及增加的API比重的高值原油以供用作碳氢化合物原料。
背景技术
全球对石油产品的需求在近年来已急剧增加,这耗尽了许多已知的高值轻质原油储层。因此,生产公司已将其兴趣转向使用低值重质油以便满足将来不断增加的需求。然而,由于使用重质油的当前精炼方法比使用轻质原油的那些方法效率低,因此为了获得相同体积的最终产品,从较重质原油生产石油产品的精炼厂必须精炼更大体积的较重质原油。遗憾地,尽管这样,此也并非是造成将来需求的预期增加的原因。使所述问题进一步加剧的是,许多国家已实施或计划实施关于基于石油的运输燃料的规格的更严格的法规。因此,石油工业正在设法寻找用于在精炼之前处理重质油的新方法以力图满足对石油原料的不断增加的需求并改善在精炼厂工艺中所使用的可用油的质量。
一般来说,重质油提供较低量的更有价值的轻质及中间馏分。另外,重质油通常含有增加量的杂质,例如硫、氮及金属,所有这些杂质通常均需要增加量的氢及能量来进行加氢处理以便满足关于最终产品中的杂质含量的严格法规。
通常定义为来自大气及真空蒸馏器的底馏分的重质油还含有高沥青质含量、高硫含量、高氮含量及高金属含量。这些性质使得难以通过常规精炼方法精炼重质油而生产具有满足严格政府法规的规格的最终石油产品。
可通过使用此项技术中已知的各种方法使重质馏分裂解而将低值重质油转变成高值轻质油。常规上,一直在存在氢的情况下使用催化剂在高温下进行裂解及清洁。然而,此类型的加氢处理在处理重质及含硫油方面具有若干限制。
另外,重质原油原料的蒸馏及/或加氢处理产生必须经进一步裂解及氢化处理才能利用的大量沥青质及重质碳氢化合物。用于沥青质及重质馏分的常规氢化裂解及氢化处理方法还需要高的资本投资及相当多的处理。
许多石油精炼厂在将油蒸馏成各种馏分之后执行常规加氢处理,其中单独地对每一馏分进行加氢处理。因此,精炼厂必须针对每一馏利用复杂的单元操作。此外,在常规氢化裂解及氢化处理方法中利用显著量的氢及昂贵的催化剂。这些方法是在苛刻的反应条件下执行以增加从重质油到更有价值中间馏分的产率且去除例如硫、氮及金属的杂质。
当前,使用大量的氢来调整从常规精炼方法产生的馏分的性质以便:满足最终产品的所需低分子量规格;去除例如硫、氮及金属的杂质;且增加基质的氢碳比。沥青质及重质馏分的氢化裂解及氢化处理是需要大量氢的方法的实例,此两者均导致催化剂具有减少的使用寿命循环。
石油仍旧是用于为世界的能量需要进行供应的主要来源。然而,随着对空气质量关注的增加,世界上的政府已极力要求生产者从石油流去除杂质(例如,硫化合物)。举例来说,要求运输燃料(例如,汽油及柴油)大致无硫化合物(即,大约小于10wt ppm硫)。为了满足关于运输燃料硫含量的此严格法规,通常用经蒸馏的流或经裂解的流(其具有汽油及柴油的沸点范围)来执行超深脱硫。
通常,可通过在存在高压氢气的情况下进行催化氢化处理来实现石油馏分(经蒸馏及经裂解的流)的脱硫。对于石油的较重质馏分,通常借助非常高的氢压力来施加催化氢化裂解及催化氢化处理以便将高分子量碳氢化合物转化为低分子量碳氢化合物,借此满足对运输燃料的沸点范围要求。用于氢化处理及氢化裂解的催化剂遭受主要由焦化导致的失活以及原料中所含有的有毒物质的影响。因此,使用高氢压力来维持催化剂使用寿命。然而,催化剂在氢化处理及氢化裂解方面具有有限的使用寿命,且因此必须经定期且频繁地更换。另外,在氢化处理及氢化裂解期间所消耗的大量氢表示一显著缺点,因为氢是精炼及石化工业中最重要且有价值的化学品之一。
还使用石油流的非催化及非氢化热裂解来去除杂质。然而,这些类型的精炼方法仅能够进行中度杂质去除。此外,这些方法通常产生显著量的焦炭。
生产清洁运输燃料的另一选项是使用具有较少量的杂质(例如,硫化合物)的低硫原油。通过使用低硫原油,可以较低的操作成本来执行复杂且密集的氢化处理及氢化裂解。然而,低硫原油的供应相当有限,而发现含硫原油具有大得多的量。
作为常规催化氢化处理/氢化裂解及热裂解的替代方案,在存在超临界水的情况下接触碳氢化合物开始获得更多关注。在现有技术中,已采用超临界或近临界水来作为反应介质以去除杂质且还将大分子裂解成小分子而不产生大量焦炭。然而,尚未清楚地识别出在超临界水介质中发生的反应。
水的临界点是374℃及22.06MPa。水的性质在临界点附近会剧烈改变。水的介电常数从在环境条件下的约ε=78改变为在临界点下的约ε=7。此外,超临界条件的小的温度及压力改变会导致水的介电常数的宽广变化(ε=2-30)。介电常数的此宽广范围覆盖了例如乙烷(ε=1.8)的非极性有机溶剂及例如甲醇(ε=32.6)的极性有机溶剂。水的密度在近临界点处也剧烈改变。在超临界条件下,水的密度从0.05g/ml到0.3g/ml地变化。此外,超临界水具有比次临界水低得多的粘度及高得多的扩散率。
已利用超临界水的独特性质来促进某些反应。举例来说,利用有机物质及氧气在超临界水中的高溶解度来分解有毒废料(超临界水氧化=SCWO)。
石油流中所含有的碳氢化合物分子也较容易溶解于超临界水中,但碳氢化合物分子的溶解度取决于其分子量及化学结构。超临界水的高温条件(>374℃)从碳氢化合物分子产生较容易通过复杂的反应网络转化为各种碳氢化合物的基团物质。一般来说,通过双基团反应的终止导致二聚作用,后续接着焦炭产生。另一方面,携带基团的碳氢化合物分子容易分解为更小分子。一般来说,分子间基团反应产生例如焦炭的较大分子,而分子内基团反应产生较小子。在石油流的常规热裂解中产生大量焦炭是由此分子间基团反应导致,而存在超临界水作为反应介质则通过“笼罩效应”减少分子间基团反应,借此促进例如分解及异构化的分子内基团反应。因此,超临界水的使用允许以可忽略不计的焦炭量将石油流转化为较轻质流。
也可在超临界水的辅助下进行杂质去除;然而,现有技术教示超临界水在降低粘度方面比在脱硫方面更有效。
举例来说,木下淳史(Atsushi Kishita)等人(日本石油研究院的期刊,第46卷,第215到221页,2003年)曾通过使用分批反应器而用超临界水处理加拿大沥青。在430℃下15分钟的反应之后,沥青的粘度从2.8×104mPa*S降低到28mPa*S,而硫含量仅从4.8wt%硫降低到3.5wt%硫。通过所揭示的处理产生的焦炭量为进给沥青的9.6wt%。
超临界水在从石油流去除杂质(特定来说,硫)方面的有限性能归因于氢的有限可用性。虽然较高的操作温度必定有益于改善脱硫性能,但达到如此高的操作温度(例如,超过450℃)需要重型反应器材料及大量能量。
向石油流进给氢还有益于改善脱硫。可通过氢气或可通过特定反应产生氢的其它化学品来供应氢。举例来说,一氧化碳可通过水煤气交换反应产生氢。此外,可使用氧通过石油流中所包含的碳氢化合物的氧化及接下来的水煤气交换反应来产生氢。然而,随同石油流及水一起注入高压气体导致在搬运及安全方面的许多困难。另外,还可使用例如甲醛的化学品通过分解来产生氢;然而,在超临界水内添加化学品会降低工艺经济性且导致更大的复杂性。
因此,将需要具有一种用于借助超临界水流体来提高油的质量的既不需要外部氢供应也不需要存在外部供应的催化剂的经改善方法。形成一种允许提高油而非个别馏分的质量以达到所要质量使得可简化精炼方法及各种支持设施的方法及设备将为有利的。
另外,具有如下一种经改善方法将为有益的:其不需要与需要氢供应或除焦炭系统的其它方法相关联的复杂设备或设施,使得可在生产站点处实施所述方法。
发明内容
本发明是针对一种满足这些需要中的至少一者的方法。本发明包含一种用于使用超临界水及后续碱萃取来提高重质油的质量的方法。有利地,所述方法可在不存在外部供应的氢或外部供应的催化剂的情况下实践。所述方法通常包含将含硫碳氢化合物与水的反应混合物引入到反应区中并使所述反应混合物经受处于或超过水的超临界条件的操作条件,使得所述反应混合物中的碳氢化合物的至少一部分经历裂解以形成质量提高的混合物,其中所述硫化合物的至少一部分被转化为硫化氢及硫醇化合物。所述反应区基本上无外部提供的催化剂及外部提供的碱性溶液。在质量提高步骤之后,将所述质量提高的混合物冷却到低于水的临界温度的第一冷却温度以形成经冷却的质量提高的混合物,其中所述经冷却的质量提高的混合物界定油相及水相。所属领域的技术人员将认识到,可充分混合所述经冷却的质量提高的混合物使得形成具有在一种相内的另一相的乳剂(水中油、油中水或复乳剂)。可在萃取区中将碱性溶液与所述经冷却的质量提高的混合物混合,以便将所述硫醇化合物的相当大部分从所述油相萃取到所述水相中。在一个实施例中,所述碱性溶液由碱金属盐及水制成。优选碱金属盐包含氢氧化钠、氢氧化钾及其组合。可将所述经冷却的质量提高的混合物分离成气体流及质量提高的液体流,其中所述气体流含有所述硫化氢的相当大部分。可接着将所述质量提高的液体流分离成质量提高的油及回收水。与所述反应混合物内的碳氢化合物相比,所述质量提高的油具有减少量的含沥青质、硫、氮或金属的物质及增加的API比重。所述回收水包含水及经转变的硫醇化合物。
在另一实施例中,所述方法可进一步包含在混合所述碱性溶液的步骤之后且在分离所述经冷却的质量提高的混合物的步骤之前将所述经冷却的质量提高的混合物冷却到第二冷却温度。所述第一冷却温度优选地在100℃与300℃之间,更优选地在150℃与250℃之间。在一个实施例中,所述反应区大致无外部提供的氢源。
在另一实施例中,所述方法进一步包含在混合区中将碳氢化合物流与水流组合以形成反应混合物,同时使所述反应混合物的温度保持低于150℃。另外,可使所述反应混合物经受超声波能以形成亚微乳剂。可接着使用高压泵将所述亚微乳剂泵送穿过预热区。所述高压泵在将所述反应混合物引入到所述反应区中的步骤之前将所述亚微乳剂的压力增加到处于或高于水的临界压力的目标压力。在另一实施例中,所述方法可进一步包含在将所述反应混合物引入到所述反应区中的步骤之前且在将所述碳氢化合物流与所述水流组合的步骤之后将所述亚微乳剂加热到第一目标温度以形成经预热的亚微乳剂的步骤。优选地,所述第一目标温度在约150℃到350℃的范围内。
在一个实施例中,所述反应混合物优选地具有在标准条件下所述碳氢化合物流对所述水流的约10∶1到约1∶50的体积流量比。更优选地,所述体积流量比为在标准条件下所述碳氢化合物流对所述水流的约10∶1到约1∶10。
在另一实施例中,所述方法还可包含通过将所述回收水的至少一部分与所述水流组合以形成所述反应混合物来使所述回收水再循环的步骤。另外,所述方法可进一步包含在处于或高于水的超临界条件的条件下在存在氧化剂的情况下处理所述回收水以便产生清洁的回收水流,使得所述清洁的回收水流含有比所述回收水实质更少的碳氢化合物含量的步骤。优选地,通过选自由空气、液化氧、过氧化氢、有机过氧化物及其组合组成的群组的氧源供应所述氧化剂。
在本发明的另一实施例中,用于从碳氢化合物流去除硫化合物的方法包含以下步骤:将反应混合物引入到反应区中;使所述反应混合物经受处于或超过水的超临界条件的操作条件,使得所述反应混合物中的碳氢化合物的至少一部分经历裂解以形成质量提高的混合物,其中所述硫化合物的至少一部分被转化为硫化氢及硫醇化合物,且其中所述反应区基本上无外部提供的催化剂及外部提供的碱性溶液。可将所述质量提高的混合物冷却到低于水的临界温度的第一冷却温度以形成经冷却的质量提高的混合物。可将所述经冷却的质量提高的混合物分离成气体流及液体流。优选地,所述气体流含有所述硫化氢的相当大部分。引入碱性进料并在混合区中将其与所述液体流混合以产生质量提高的液体流,其中所述质量提高的液体流具有水相及油相。在混合步骤期间,将所述硫醇化合物的相当大部分从所述油相萃取到所述水相中。可将所述质量提高的液体流分离成质量提高的油及回收水。与所述碳氢化合物流相比,所述质量提高的油具有减少量的含沥青质、硫、氮或金属的物质及增加的API比重,且所述回收水包含水及经转变的硫醇化合物。
附图说明
考虑以下描述、所附权利要求书及附图,本发明的这些及其它特征、方面以及优点将变得更好理解。然而,应注意,图式仅图解说明本发明的数个实施例且因此不应视为限制本发明的范围,因为本发明可容许有其它等效的实施例。
图1是本发明的一实施例。
图2展示本发明的替代实施例。
图3展示本发明的替代实施例。
具体实施方式
尽管将结合数个实施例来描述本发明,但将理解并不打算将本发明限制于那些实施例。相反,本发明打算涵盖可包含在所附权利要求书所界定的本发明精神及范围内的所有替代方案、修改形式及等效物。
参考图1,在混合区30中组合水流2与碳氢化合物流4以形成反应混合物32。可使用高压泵35来传送反应混合物32以将反应混合物32的压力提升为超过水的临界压力。在未展示的实施例中,可在组合之前个别地加压及/或个别地加热水流2及碳氢化合物流4。示范性压力包含22.06MPa到30MPa,优选地24MPa到26MPa。在一个实施例中,在标准条件下碳氢化合物流4对水流2的体积流量率为0.1∶1到1∶10,优选地0.2∶1到1∶5,更优选地0.5∶1到1∶2。碳氢化合物流4的示范性温度在50℃到650℃内,更优选地在150℃到550℃内。可接受的加热装置可包含带式加热器、浸没式加热器、管式炉或此项技术中已知的其它加热装置。
在一个实施例中,所述方法包含将反应混合物32引入到预热装置40,在预热装置40中,优选地将反应混合物32加热到约250℃的温度,之后经由线路42将其进给到反应区50中。反应区50内的操作条件处于或高于水的临界点,水的临界点为大约374℃及22.06MPa。在此极高热量及压力期间,所述反应混合物经历裂解且形成质量提高的混合物52。此时,曾处于碳氢化合物流4中的硫化合物被转化为H2S及硫醇化合物,其中硫醇化合物通常可见于质量提高的混合物的油相中。示范性反应区50包含管型反应器、配备有搅拌器的容器型反应器或此项技术中已知的其它装置。可使用水平及/或垂直型反应器。优选地,反应区50内的温度在380℃到500℃之间,更优选地在390℃到500℃之间,最优选地在400℃到450℃之间。在反应区50内的优选停留时间在1秒到120分钟之间,更优选地在10秒到60分钟之间,最优选地在30秒到20分钟之间。
质量提高的混合物52接着经由线路52移动到第一冷却器60,在第一冷却器60中,将混合物52冷却到低于水的临界温度的温度,之后在萃取区70中将其与碱性溶液64混合。第一冷却器60可为骤冷器、热交换器或此项技术中已知的任何其它冷却装置。在一个实施例中,经冷却的质量提高的混合物62的温度在5℃与200℃之间,更优选地在10℃与150℃之间,最优选地在50℃与100℃之间。在一个实施例中,设备可包含压力调节装置(未展示)以在质量提高的混合物进入萃取区70之前减小其压力。所属领域的技术人员将容易认识到可接受的压力调节装置。在一个实施例中,萃取流体在萃取区70中的停留时间为1分钟到120分钟,优选地10分钟到30分钟。在此混合步骤期间,碱有助于将硫醇化合物从油相萃取到水相中。示范性萃取区70包含管型或容器型。在一些实施例中,萃取区70可包含混合装置,例如旋转叶轮。优选地,用氮气或氦气吹扫萃取区70以去除萃取区70内的氧气。在一个实施例中,使萃取区70内的温度维持处于10℃到100℃,更优选地30℃到70℃。
在萃取步骤之后,将萃取流体72进给到液气分离器80,在液气分离器80中,在对萃取流体72进行减压之后去除气体流82。优选压力在0.1MPa到0.5MPa之间,更优选地在0.01MPa到0.2MPa之间。
接着将质量提高的液体流84送到油水分离器90,在油水分离器90中,分离回收水94与质量提高的油92。与碳氢化合物流4相比,质量提高的油92具有减少量的含沥青质、硫、氮或金属的物质及增加的API比重。在任选步骤中,可随同氧化剂流96一起将回收水94引入到氧化反应器110中以便帮助从回收水94去除污染物以形成清洁的水112。
图2表示其中在液气分离器80之后而非在液气分离器80之前将经冷却的质量提高的混合物62引入到萃取区70的替代实施例。在此实施例中,可在反应区50与液气分离器80之间的任何点处采用压力调节装置(未展示)。
图3表示类似于图1中所展示的实施例但添加了第二冷却器75的替代实施例。在其中第一冷却器60及第二冷却器75两者均存在的实施例中,可更精确地控制经冷却的质量提高的混合物62及萃取流体72的温度分布曲线。优选地,经冷却的质量提高的混合物62的温度在100℃与300℃之间,更优选地在150℃到200℃之间。在其中萃取区70位于第一冷却器60与第二冷却器75之间的实施例中,方法有利地允许维持借助碱性溶液萃取的蒸气的温度(优选地处于高于150℃的温度)同时维持流的液相,因为在萃取区70之前不存在压力减小元件。在较高萃取温度下,硫醇在水中的溶解度也增加。因此,净效应是增加的萃取产率。另外,由于水处于次临界状态,因此碱性化合物不在萃取区70中沉淀,此有助于保持所述方法高效地运行。
基线产品
通过计量泵将整个阿拉伯重质原油(AH)及去离子水(DW)加压到25MPa。在标准条件下AH与DW的质量流量率分别为0.509kg/小时及0.419kg/小时。在将经加压水预热到490℃之后将经加压AH与水组合。使反应区维持处于450℃。估计AH与水混合物的停留时间为大约3.9分钟。在冷却及减压之后,获得液体产品。总液体产率为91.4wt%。AH及产品的总硫含量经测量为2.91wt%硫及2.49wt%硫(大致0.4wt%减小)。
经改进产品
通过含有10wt%NaOH的碱性溶液来处理基线产品。以1∶1wt/wt将碱性溶液添加到基线产品。在通过磁搅拌器混合之后,使混合物经受超声波辐照达1.5分钟。在10分钟之后,以2500rpm对混合物进行离心达20分钟。将油相与水相分离且通过总硫分析仪对其进行分析。总硫含量降低到2.30wt%硫(额外的0.2wt%减小)。
尽管已结合本发明的特定实施例描述了本发明,但显而易见,所属领域的技术人员鉴于前文描述将明了许多替代方案、修改形式及变化形式。因此,本发明打算包含归属于所附权利要求书的精神及宽广范围的所有此些替代方案、修改形式及变化形式。本发明可适当地包括所揭示的元件、由所述元件组成或基本上由所述元件组成,且可在不存在未揭示的元件的情况下实践。
Claims (17)
1.一种用于从碳氢化合物流(4)去除硫化合物的方法,所述方法包括以下步骤:
(a)将反应混合物(32)引入到反应区(50)中,其中所述反应混合物包括所述碳氢化合物流(2)与水流(4)的混合物,其中所述碳氢化合物流(4)含有硫化合物;
(b)使所述反应混合物(32)经受处于或超过水的超临界条件的操作条件,使得所述反应混合物(32)中的碳氢化合物的至少一部分经历裂解以形成质量提高的混合物(52),其中所述硫化合物的至少一部分被转化为硫化氢及硫醇化合物,且其中所述反应区(50)基本上无外部提供的催化剂及外部提供的碱性溶液;
(c)将所述质量提高的混合物(52)冷却(60)到低于水的临界温度的第一冷却温度以形成经冷却的质量提高的混合物(62),所述经冷却的质量提高的混合物(62)界定油相及水相;
(d)在萃取区(70)中将碱性溶液(64)与所述经冷却的质量提高的混合物(62)混合,使得所述硫醇化合物的相当大部分被从所述油相萃取到所述水相中,所述碱性溶液包括碱金属盐及水;
(e)将所述经冷却的质量提高的混合物分离成气体流(82)及质量提高的液体流(84),其中所述气体流(82)含有所述硫化氢的相当大部分;及
(f)将所述质量提高的液体流(84)分离成质量提高的油(92)及回收水(94),其中与所述碳氢化合物流(4)相比,所述质量提高的油(92)具有减少量的含沥青质、硫、氮或金属的物质及增加的API比重,且所述回收水(94)包含水及经转变的硫醇化合物。
2.根据权利要求1所述的方法,其进一步包括在所述混合所述碱性溶液的步骤之后且在所述分离所述经冷却的质量提高的混合物的步骤之前将所述经冷却的质量提高的混合物(62)冷却(75)到第二冷却温度的步骤,其中所述第一冷却温度在约100℃到300℃之间。
3.根据权利要求2所述的方法,其中所述第一冷却温度在约150℃到250℃之间。
4.根据权利要求1所述的方法,其进一步包括在所述将所述反应混合物(32)引入到所述反应区(50)中的步骤之前在混合区(30)中将所述碳氢化合物流(4)与所述水流(2)组合以形成所述反应混合物(32)的步骤,其中所述反应混合物(32)的温度不超过150℃。
5.根据权利要求4所述的方法,其进一步包括使所述反应混合物(32)经受超声波能以形成亚微乳剂并使用高压泵(35)将所述亚微乳剂泵送穿过预热区(40)的步骤,其中所述高压泵(35)在所述将所述反应混合物(32)引入到所述反应区(50)中的步骤之前且在所述将所述碳氢化合物流(4)与所述水流(2)组合的步骤之后将所述亚微乳剂的压力增加到处于或高于水的临界压力的目标压力。
6.根据权利要求5所述的方法,其进一步包括在所述将所述反应混合物(32)引入到所述反应区(50)中的步骤之前且在所述将所述碳氢化合物流(4)与所述水流(2)组合的步骤之后将所述亚微乳剂加热到第一目标温度以形成经预热的亚微乳剂的步骤,所述第一目标温度在约150℃到350℃的范围内。
7.一种用于从碳氢化合物流(4)去除硫化合物的方法,所述方法包括以下步骤:
(a)将反应混合物(32)引入到反应区(50)中,其中所述反应混合物包括所述碳氢化合物流(4)与水流(2)的混合物,其中所述碳氢化合物流(4)含有硫化合物;
(b)使所述反应混合物(32)经受处于或超过水的超临界条件的操作条件,使得所述反应混合物(32)中的碳氢化合物的至少一部分经历裂解以形成质量提高的混合物(52),其中所述硫化合物的至少一部分被转化为硫化氢及硫醇化合物,且其中所述反应区(50)基本上无外部提供的催化剂及外部提供的碱性溶液;
(c)将所述质量提高的混合物(52)冷却(60)到低于水的临界温度的第一冷却温度以形成经冷却的质量提高的混合物(62);
(d)将所述经冷却的质量提高的混合物(62)分离成气体流(82)及液体流(84),其中所述气体流(82)含有所述硫化氢的相当大部分;
(e)在萃取区(70)中将碱性进料(64)与所述液体流(84)混合以产生质量提高的液体流(72),所述质量提高的液体流(72)界定水相及油相,使得所述硫醇化合物的相当大部分被从所述油相萃取到所述水相中,所述碱性进料包括碱金属盐及水;及
(f)将所述质量提高的液体流(72)分离成质量提高的油(92)及回收水(94),其中与所述碳氢化合物流(4)相比,所述质量提高的油(92)具有减少量的含沥青质、硫、氮或金属的物质及增加的API比重,且所述回收水(94)包含水及经转变的硫醇化合物。
8.根据前述权利要求中任一权利要求所述的方法,其中所述反应区(50)基本上无外部提供的氢源。
9.根据前述权利要求中任一权利要求所述的方法,其中所述碱金属盐选自由氢氧化钠、氢氧化钾及其组合组成的群组。
10.根据前述权利要求中任一权利要求所述的方法,其进一步包括在所述将所述反应混合物(32)引入到所述反应区(50)中的步骤之前在混合区(30)中将所述碳氢化合物流(4)与所述水流(2)组合以形成所述反应混合物(32)的步骤,其中所述反应混合物(32)的温度不超过150℃。
11.根据权利要求10所述的方法,其进一步包括使所述反应混合物(32)经受超声波能以形成亚微乳剂并使用高压泵(35)将所述亚微乳剂泵送穿过预热区(40)的步骤,其中所述高压泵(35)在所述将所述反应混合物(32)引入到所述反应区(50)中的步骤之前且在所述将所述碳氢化合物流与所述水流组合的步骤之后将所述亚微乳剂的压力增加到处于或高于水的临界压力的目标压力。
12.根据权利要求7所述的方法,其进一步包括以下步骤:
在所述将所述反应混合物(32)引入到所述反应区(50)中的步骤之前在混合区(30)中将所述碳氢化合物流(4)与水(2)组合以形成所述反应混合物(32),其中所述反应混合物(32)的温度不超过150℃;及
在所述将所述反应混合物(32)引入到所述反应区(50)中的步骤之前且在所述将所述碳氢化合物流(4)与所述水流(2)组合的步骤之后将所述反应混合物(32)加热到第一目标温度,所述第一目标温度在约150℃到350℃的范围内。
13.根据前述权利要求中任一权利要求所述的方法,其中所述反应混合物(32)包括在标准条件下所述碳氢化合物流(4)对所述水流(2)的约10∶1到约1∶50的体积流量比。
14.根据前述权利要求中任一权利要求所述的方法,其中所述反应混合物(32)包括在标准条件下所述碳氢化合物流(4)对所述水流(2)的约10∶1到约1∶10的体积流量比。
15.根据前述权利要求中任一权利要求所述的方法,其进一步包括通过将所述回收水(94)的至少一部分与所述水流(2)组合以形成所述反应混合物(32)来使所述回收水再循环的步骤。
16.根据权利要求15所述的方法,其进一步包括在处于或高于水的所述超临界条件的条件下在存在氧化剂(96)的情况下处理所述回收水(94)以形成清洁的回收水流(112),使得所述清洁的回收水流(112)含有比所述回收水(94)实质更少的碳氢化合物含量的步骤。
17.根据权利要求16所述的方法,其中通过选自由空气、液化氧、过氧化氢、有机过氧化物及其组合组成的群组的氧源供应所述氧化剂(96)。
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WO2012005948A3 (en) | 2012-05-10 |
US20110315600A1 (en) | 2011-12-29 |
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EP2588569A2 (en) | 2013-05-08 |
CN102971398B (zh) | 2016-06-01 |
US9005432B2 (en) | 2015-04-14 |
KR101741871B1 (ko) | 2017-05-30 |
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