CN101959994B - 增效性酸共混物提取助剂和其使用方法 - Google Patents

增效性酸共混物提取助剂和其使用方法 Download PDF

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CN101959994B
CN101959994B CN200980107284.1A CN200980107284A CN101959994B CN 101959994 B CN101959994 B CN 101959994B CN 200980107284 A CN200980107284 A CN 200980107284A CN 101959994 B CN101959994 B CN 101959994B
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A·E·戈利亚塞夫斯基
C·R·麦丹尼尔
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Abstract

已经发现用于提高原油中污染物(例如金属和胺)的去除率的提取助剂，其使用脱盐处理中合乎需要的组分作为组分，所述组分为水溶性的，具有低毒性，具有高生物降解性并显示高热稳定性。根据本发明的一个实施方案，提供增强的提取性质的提取助剂由酸(特别是水溶性酸)的共混物组成。更具体地讲，选自乙酸、硫酸、乙醇酸、柠檬酸和甲磺酸的两种酸的组合。

Description

增效性酸共混物提取助剂和其使用方法
发明领域
本发明涉及提取助剂和其在石油开采和炼油厂脱盐处理中的用途。更详细地讲，本发明涉及用于在开采和加工期间从原油中除去污染物(特别是金属和胺)的提取助剂。
发明背景
液态烃介质例如原油和粗制馏分(包括石脑油、汽油、煤油、喷气燃料、燃料油、瓦斯油和真空残渣)常含有可对加工或产品质量有害的污染物。所述污染物可引起炼油厂和其他处理中的腐蚀、换热器结垢、炉结焦(furnace cooking)、催化剂失活和产物降解。所述污染物大致分为盐、底部沉积物和水、固体和金属。这些杂质的量根据特定原油和其加工而不同。
脱盐或脱水是一种用以在输送和炼油之前从原油中除去污染物(主要是水和无机盐)的方法。最初的脱水步骤通常使用例如游离水分离器(FWKO)的装置来从油中分离生成的水而实地进行。一般来说，生成的油含有远高于0.5％典型管输规格(pipeline specification)的量的水且FWKO的目的是将水移除到低于管输规格的程度。炼油厂中的脱盐步骤通过加入数体积百分数的新鲜水并将其与原油混合以接触原油中以乳液形式留下的盐水并使该盐水除去。脱盐提供给原油加工或炼油的益处包括：减少原油装置腐蚀；减少原油预热体系结垢；降低蒸馏塔毁坏的可能性；降低能量消耗；和减少后续处理和产物污染。
在原油脱盐中，油包水乳液特意用基于原油计算在约四(4)至约十(10)体积百分比范围内的水形成。将水加到原油中并密切混合以将原油中的杂质转移到水相中。由于小水滴聚结成逐渐变大的液滴且油与下层水相最后重力分离而出现各相分离。
在美国专利第4,778,589号中，公开了一种从含烃原料中除去金属污染物(特别是钙)的方法。所述方法包括将原料与金属螯合剂(特别是羟基羧酸，且更详细地讲是柠檬酸，或其盐或混合物)的水溶液混合，并分离含有金属的水溶液形成脱金属的原料。
美国专利第5,078,858号公开并要求保护从液态烃例如原油中提取铁物类例如环烷酸铁和硫化铁的方法。将选自草酸或柠檬酸的螯合剂直接加到液态烃中并与其混合。加入洗涤水以形成油包水乳液，解析所述乳液并分离含铁的水相。
在美国专利申请公开案第US 2004/0045875A1号中，人们发现在破乳处理中通过使用含有水溶性羟基酸的组合物可将金属和/或胺除去或从烃相转移到水相中。所述组合物还可包含至少一种无机酸以降低脱盐装置洗涤水的pH。溶剂可任选包含在所述组合物内。所述方法容许在几乎没有或没有烃相被带进水性pH中的情况下将金属和/或胺转移到水相中。
因此，仍然需要使用水溶性组分改进原油中污染物提取以使得污染物在脱盐处理中不分配到原油中、不导致原油装置塔顶馏分酸化(可导致中和剂需求)、在高温下稳定并且易于实施的方法。
发明概述
已经发现用于提高原油中污染物(例如金属和胺)的去除率的提取助剂，其使用采油和脱盐处理中合乎需要的组分作为组分，所述组分为水溶性的，具有低毒性，具有高生物降解性并显示高热稳定性。
根据本发明的一个实施方案，提供增强的提取性质的提取助剂由酸(特别是水溶性酸)的共混物组成。更具体地讲，选自乙酸、硫酸、乙醇酸、柠檬酸和甲磺酸的两种酸的组合。
在提取中显示增效效应的替代实施方案由甲磺酸(MSA)和柠檬酸组成，已经发现所述组合比使用单一酸例如柠檬酸效果好。
在本发明的另一替代实施方案中，通过探索发现，甲磺酸与柠檬酸的组合的增效效应在甲磺酸的存在量为提取助剂的约5-约50％体积时明显。增效效应在甲磺酸在提取助剂中的存在量为约10％体积和约20％体积时似乎最大。
用本说明书随附并形成本说明书的一部分的权利要求书详细地指出表征本发明的各种特征的新颖性。为了更透彻地理解本发明、其操作优势和通过使用其得到的益处，参考附图和说明事项。所述附图旨在显示本发明的实施例。附图并非想要显示可产生并使用本发明的所有方式的限制。当然可产生本发明的各种组分的改变和替换。本发明还包括所述要素的子组合和子体系以及使用其的方法。
附图简述
图1为根据本发明的一个实施方案相对于未处理的废水胺提取增强的图示。
图2为根据本发明的一个实施方案表现组合酸提取助剂的增效作用的曲线图。
图3为根据本发明的一个实施方案表现相对于柠檬酸提取助剂胺提取增强的曲线图。
发明详述
在本文中贯穿说明书和权利要求书使用的近似语言可用来修饰可容许在不引起所涉及的基本功能改变的情况下变化的任何定量表述。因此，通过一个或多个术语例如“约”修饰的值不限于所指定的精确值。在至少一些情况下，近似语言可对应于用于测量所述值的仪器的精确度。范围界限可组合和/或互换，这些范围得以确定，并且除非上下文或语言指明相反情况，否则包括本文所包括的所有子范围。除了在操作实施例或指明相反情况之处以外，本说明书和权利要求书中使用的关于成分的量、反应条件等的所有数值或表达将被理解为在所有情形下都由术语“约”修饰。
本文所用的术语“包含”、“包括”、“具有”或其任何其它变体意欲涵盖非排他性的包括。例如，包含例举要素的工艺、方法、制品或设备并非必然仅仅限于这些要素，而是可包括其它没有明确列出或所述工艺、方法、制品或设备所固有的要素。
根据本发明的一个实施方案，用于在炼油的脱盐处理期间从原油中除去污染物的提供增强的提取性质的提取助剂由酸(特别是水溶性酸)共混物组成。已经发现向原油中加入酸组合可在其经过炼油厂中的脱盐装置时显著降低烃中钙和其它金属的量以及胺的量。已经发现酸组合比在将单一酸用作提取助剂时以更高程度减少烃中的污染物，特别是金属和胺污染物。
与原油一起进入炼油厂的各种化学物类对于加工或产品质量可能有害。一种这样的群组或化学实体为胺族。根据相对沸点，例如某些烷基胺在脱盐和经常压塔蒸馏之后可保留在原油中。这些胺的盐酸盐可引起沉积并且引起高侵蚀性沉积物下腐蚀或熔盐腐蚀。已经确定速率大于1000mpy(密耳/年腐蚀渗透)。如果胺盐酸盐的盐点在水露点前面位于塔顶或取出管线上，这将尤其成问题。胺的来源有许多，包括来自酸气洗涤装置、排气或泄漏的胺。胺还可能因来自脱盐装置洗涤水并分配到脱盐装置中的原油中而进入原油塔。存在并显示这些特性且通过加入提取助剂而显著减少的胺在工业中已知，包括但不限于乙醇胺、二乙醇胺、三乙醇胺、N-甲基乙醇胺、N，N-二甲基乙醇胺、吗啉、N-甲基吗啉、乙二胺、甲氧基丙胺、N-乙基吗啉、N-甲基乙醇胺、N-甲基二乙醇胺、二丁胺和其组合。
在原油加工中不需要并且引起问题的另外化学物质为金属。在本发明中有意提及的金属包括但不限于周期表(CAS版)的IA族、IIA族、VB族、VIII族、IIB族和IVA族的金属。在另一非限制性实施方案中，所述金属包括但不限于钙、铁、锌、硅、镍、钠、钾、钒和其组合。未从脱盐装置中的油中提取的金属例如铁可终止于常压蒸馏的塔底物和由这些塔底物制成的焦炭。这产生金属方面不合格的焦炭。残留钙可导致焦化装置熔炉结垢，驱使剩余燃料在金属含量方面不合格或充当FCC进料中的催化剂毒物。
脱盐处理通常用作从原油中除去不良物类的方式。单独水洗可提取一些污染物，包括一些金属和胺。酸通常可通过使胺质子化并使其更加可溶于水而帮助除去污染物，特别是胺。酸的有益效应借助于使用亲水性胺来表现。提供增强的提取性质的提取助剂由酸(特别是水溶性酸)的共混物组成。更具体地讲，选自乙酸、硫酸、乙醇酸、柠檬酸和甲磺酸的两种酸的组合。
优选可溶于水的酸，特别是柠檬酸，其不仅显示水溶性，而且不可溶于烃，因此并不导致酸残存或进入原油装置塔顶馏分中。这一行为将导致需要增加中和剂的量。柠檬酸(C6H8O7)是一种弱有机酸，水溶性为133g/100ml(20℃)，不溶于烃，对环境友好，因此是优选的酸。
甲磺酸(CH3SO2OH)是磺酸家族的一员，是有机酸。其可溶于水，但不溶于烃，在高温下显示稳定性且具有可生物降解性。
通过组合两种酸产生提取助剂，对于从原油中提取污染物，特别对于提取金属(例如但不限于铁和锌)和/或胺显示增效效应。组合酸的增效值根据提取助剂的组成而不同。在由约5-约50％体积的甲磺酸与包括柠檬酸的第二酸组成的提取助剂中显示增效效应。本发明的一个实施方案包括包含甲磺酸和柠檬酸的提取助剂，其中所述甲磺酸包括约10-约20％体积的甲磺酸。
当与单独的洗涤水或单一酸提取助剂例如柠檬酸比较时，用组合酸提取助剂见到增效效应。在将甲磺酸和柠檬酸组合成提取助剂的实施方案中，相对于未处理的洗涤水，见到提取增强作用高达约70％。相对于未处理的洗涤水，该实施方案中的平均提取增强作用为约20-约40％。这些增效效应在多种原油中见到，所述原油显示多种污染物，包括各种胺。这类原油的实例包括但不限于Syncrude PZ、Maya、Arab Medium和Heidrun。所述增效作用还相对于不同胺例如二丁胺(DBA)、二甲基乙醇胺(DMEA)、吗啉(MORPH)、二乙醇胺(DEA)和单乙醇胺(MEA)而不同。
增效效应还通过使用由甲磺酸和柠檬酸组成的提取助剂表现出来，其优于使用仅由一种酸例如柠檬酸组成的提取助剂。这对于提取胺特别理想，对于提取极性胺甚至更加理想。
实施例
脱盐装置模拟实验使用5种工业有关的胺：DBA、DMEA、MORPH、DEA和MEA在多种不同性质的原油中进行，具体地说，所述原油为Syncrude PZ、Maya、Arab Medium和Heidrun。所述原油中加有200ppm胺，实验室脱盐装置模拟实验用处理过的洗涤水和未处理的洗涤水进行。所述处理在加有剪切力的情况下在240-300℉下使用4-8％洗涤水。结果示于下表中。
相对于未处理的洗涤水，胺的提取增强作用的百分数示于附图1中，而图3显示优于用单一酸(具体地说是柠檬酸)的提取助剂的增强的提取作用。图2表现出根据本发明的组合酸的增效作用。虽然已参考优选的实施方案描述了本发明，但本发明所属领域的普通技术人员在不脱离本发明的技术范围的情况可对这些实施方案进行各种改变或替换。因此，本发明的技术范围不仅涵盖上文所述的那些实施方案，而且涵盖属于附加权利要求书的范围的所有内容。

Claims (6)

1.一种用于在炼油处理期间除去原油中的污染物的提取助剂，其中所述提取助剂由甲磺酸和柠檬酸组成，其中所述甲磺酸的存在量为所述助剂的5-50％体积。
2.权利要求1的提取助剂，其中所述提取在脱盐装置处理中进行。
3.权利要求1的提取助剂，其中所述甲磺酸的存在量为所述助剂的10-20％体积。
4.权利要求1的提取助剂，其中所提取的污染物包括金属和/或胺。
5.一种用于提高炼油厂脱盐处理期间污染物的去除率的提取助剂，其中所述提取助剂由甲磺酸和柠檬酸组成，其中所述甲磺酸的存在量为所述助剂的5-50％体积。
6.一种除去原油炼油厂中污染物的方法，其中用于脱盐处理的提取助剂由甲磺酸和柠檬酸组成，其中所述甲磺酸的存在量为所述助剂的5-50％体积。
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