CN102753657A - 从原油中去除金属和胺的改进的方法 - Google Patents

从原油中去除金属和胺的改进的方法 Download PDF

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CN102753657A
CN102753657A CN2010800429996A CN201080042999A CN102753657A CN 102753657 A CN102753657 A CN 102753657A CN 2010800429996 A CN2010800429996 A CN 2010800429996A CN 201080042999 A CN201080042999 A CN 201080042999A CN 102753657 A CN102753657 A CN 102753657A
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crude oil
washing water
acid
metal
emulsion
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J·M·加西亚三世
S·A·罗窦
M·L·布雷登
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ChampionX LLC
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Abstract

一种从原油中去除金属和胺的方法，所述方法包括向所述原油中加入有效金属去除量的一种或多种选自乳酸和苹果酸的羟基羧酸及其盐；向所述原油中加入洗涤水；混合所述原油、酸和洗涤水，以形成乳液；和使得所述乳液解析成水相和金属含量减少的原油。

Description

从原油中去除金属和胺的改进的方法
技术领域
本发明涉及在精炼脱盐工艺中从具有不可接受的高含量金属的石油原油中去除金属(特别是钙)的方法，在所述工艺中向原油(crude oil)而非洗涤水中加入某种羟基羧酸。
发明背景
一些，但日益重要的石油原油原料包含的金属(如铁和钙)含量使其难以(如果可能的话)使用常规的精炼技术进行加工。例如，导致具体问题的钙污染物可能是非卟啉、有机金属结合的化合物的形式。一类这种含钙化合物包括环烷酸钙(calcium naphthenates)和其同系物。这些有机钙化合物通过常规的脱盐工艺不能从原料中分离，在常规精炼技术中它们可能导致焦炭炉结垢，将不符合金属技术要求(off specification for metal)的剩余燃料馏出，并使得加氢处理催化剂非常迅速失活。证实具有不可接受的高含量钙化合物的原料的一个例子是西非多巴原油(West African Doba crudes)。
美国专利第4,778,589号和第4,789,463号分别公开了在精炼脱盐工艺中使用羟基羧酸以帮助从原油中去除包括钙和铁的金属。
美国专利第7,497,943号公开了一种精炼脱盐工艺中从原油中去除金属的方法，该方法中在洗涤水与原油接触之前，向洗涤水中加入各种酸，包括C2-C4羟基羧酸。
美国专利第5,080,779号公开了一种精炼脱盐工艺中从原油中去除铁的方法，该方法中在加入洗涤水之前，向原油中加入各种螯合剂。
发明概述
我们意外地发现在常规的原油脱盐操作中，向原油中分开加入包括乳酸和苹果酸的羟基羧酸和洗涤水能促进从原油中去除胺以及结合和未结合的金属污染物。
因此，在一个实施方式中，本发明提供一种从原油中去除金属和胺的方法，所述方法包括向所述原油中加入有效金属去除量的选自乳酸和苹果酸的一种或多种羟基羧酸及其盐；向所述原油中加入洗涤水；混合所述原油、酸和洗涤水，以形成乳液；和使得所述乳液解析(resolve)为水相和金属含量减少的原油。
发明的详细说明
在精炼原油脱盐操作中，通过向原油中加入水(通常称为“洗涤水”)来有意地形成油包水(w/o)乳液，以所述原油为基准计，允许加入的洗涤水约为3-10体积％。洗涤水添加至原油中并紧密混合，从而使得原油中的杂质例如氯化物转移至水相中。将w/o乳液再泵送至脱盐设备单元中，在脱盐设备单元中由于小的水滴聚结成逐渐增大的液滴并最终在重力作用下分离成油和下层水相而发生相分离。
脱盐设备通常设置有电极，从而使脱盐设备中形成电场。这用来使分散的水分子极化。这样形成的偶极分子在带相反电荷的两极之间施加吸引力，同时增大的吸引力使得水滴的聚结速度增加10-100倍。水滴还在电场中快速移动，从而促进能进一步增加聚结(coalescence)的随机碰撞。
同样，脱盐设备通常设置有加热装置和压力控制装置来分别控制容器中的温度和压力。脱盐设备温度通常保持在约200-300℉。加热降低了连续相(即油)的粘度，从而加速聚结水滴的沉降。这也增加了主体油溶解某些可能已加入原油中或者在原油中天然存在的有机乳液稳定剂的能力。
维持足够高的脱盐设备压力以防止原油或水蒸发。蒸发使得引入原油中的水分离开脱盐设备。在操作温度下脱盐设备的压力通常应超过原油或水蒸气压力(不管哪个压力更低)约20psi。
从w/o乳液中分离相后，原油通常从脱盐设备的顶部排出，并送至原油蒸馏装置或其它精炼工艺中的分馏塔。含水溶性金属盐化合物和沉淀物的水相以流出物形式排出。
本发明提供一种改进的精炼脱盐操作，其包括(i)提供原油；(ii)向所述原油中加入洗涤水并混合，形成乳液；和(iii)使得所述乳液解析，以提供水相以及金属和胺含量减少的原油，所述改进包括向原油中加入有效金属去除量的选自苹果酸和乳酸的一种或多种羟基羧酸及其盐，所述加入与洗涤水的加入分开进行。羟基羧酸盐包括例如碱金属盐，如钠盐，钾盐和铵盐。“所述加入与洗涤水的加入分开进行”表示分开加入的位置可以在洗涤水的上游或下游。
“原油”表示精炼操作中使用的任意烃原料，包括石油原油(crudepetroleum)、常压或真空渣油、来自这些原油和渣油的溶剂脱沥青油、页岩油、液化煤(liquefied coal)、精选的沥青砂等及其掺混物。所述原油也可以用一种或多种加工助剂包括溶剂、破乳剂、腐蚀抑制剂等进行处理。在一个实施方式中，所述原油是石油原油。在一个实施方式中，所述石油原油是多巴原油或包含多巴原油的原油板岩(crude oil slate)。
适合用本发明方法去除的金属包括但不限于钙、铁、锌、硅、镍、钠、钾、钒等及其混合物。在一个实施方式中，所述金属包括铁和钙。在一个实施方式中，所述金属是结合和未结合形式的钙。
适合用本发明方法去除的胺包括但不限于单乙醇胺、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、甲氧基丙基胺、N-乙基吗啉、N-甲基乙醇胺、N-甲基二乙醇胺等及其混合物。
苹果酸和/或乳酸可以水溶液形式添加。在一个实施方式中，所述水溶液包含约40-70重量％的酸。
苹果酸和/或乳酸的有效量是指实现从原油中去除所需量的金属或胺所需要的酸的量，可以由本领域技术人员通过考虑所述酸的性质、要处理的原油和任意其它工艺参数来确定。
在一个实施方式中，向所述原油中加入的酸的量足以使得分开的水溶液的pH值约为3-6。
通常，向所述原油中加入约1-2,000ppm的羟基羧酸。在一个实施方式中，向所述原油中加入约10-500ppm的羟基羧酸。
在一个实施方式中，所述羟基羧酸是苹果酸。
所述羟基羧酸可以与精炼脱盐工艺中使用的一种或多种辅助剂结合使用，所述辅助剂包括腐蚀抑制剂、破乳剂、pH调节剂、金属配位剂、污垢抑制剂、烃溶剂等。所述辅助剂可以单独加入原油中，加入洗涤水中或者与酸溶液一起配制。例如，油溶性辅助剂如破乳剂和腐蚀抑制剂可以直接加入所述原油中，而水溶性辅助剂可以与酸一起配制或加入所述洗涤水中。
在一个实施方式中，向所述原油或洗涤水中加入一种或多种破乳剂。
在一个实施方式中，向所述原油或洗涤水中加入一种或多种腐蚀抑制剂。
在一个实施方式中，向所述洗涤水中加入一种或多种腐蚀抑制剂。
在一个实施方式中，在含腐蚀抑制剂的洗涤水的上游，向所述原油中加入羟基羧酸。
在一个实施方式中，在含腐蚀抑制剂的洗涤水的下游，向所述原油中加入羟基羧酸。
在一个实施方式中，向所述原油或洗涤水中加入一种或多种金属配位剂，所述金属配位剂不包括苹果酸和乳酸。
金属配位剂包括一大类能与金属离子配位或络合的化学物质。代表性的金属配位剂包括但不限于乙二胺四乙酸(EDTA)、乙醇酸、葡糖酸、巯基乙酸、酒石酸、扁桃酸、柠檬酸、乙酸、草酸、氨三乙酸(nitrolotriacetic acid)(NTA)、乙二胺(EDA)、甲磺酸、丙二酸、琥珀酸、马来酸、二硫代氨基甲酸盐和聚合的二硫代氨基甲酸盐等及其盐。
在代表性的精炼应用中，在常规的脱盐操作中加工含约70ppm钙的原油，所述脱盐操作包括预热系统(preheat train)，所述预热系统包括预热交换器、所述预热系统下游的混合阀和静电脱盐设备。对150,000bbl/天以上的包含约20％(30,000bbl)多巴原油的原油进行加工。以约5％(7,500bbl/天)的速率向原油物流中加入经腐蚀抑制剂处理的洗涤水。在洗涤水上游以约2,000-3500加仑/天的剂量速率向所述原油进料加入50％的羟基羧酸水溶液。混合阀形成的原油乳液在脱盐设备中通过静电聚结解析，使得原油中钙的去除率最高可达约95％。
通过以下实施例可以更好地理解本发明的上述内容，提供以下实施例仅是为了说明，不是用来限制本发明的范围。
实施例1
在180℉，将50重量％的原油的甲苯溶液加热约20分钟，再将加热的原油样品与10重量％的羟基羧酸水溶液混合。加热并摇振混合物约30分钟。萃取循环结束时，立刻加热样品进行第二个10分钟加热循环，之后，在分液漏斗中使各相分离。用ICP分析确定回收相中的钙和铁含量。结果总结在表1中。
表1
Figure BPA00001530321300051
虽然上文本发明结合代表性或说明性的实施方式进行描述，但这些实施方式并不是完全的或者不对本发明构成限制。而是，本发明是用来覆盖包括在其精神和范围内的所有替代方式、改进形式和等同形式，本发明由所附权利要求书所限定。

Claims (14)

1.一种从原油中去除金属和胺的方法，所述方法包括向所述原油中加入有效金属去除量的一种或多种选自乳酸和苹果酸的羟基羧酸及其盐；向所述原油单独地加入洗涤水，混合所述原油、酸和洗涤水，以形成乳液；和使得所述乳液解析成水相和金属和/或胺含量减少的原油。
2.如权利要求1所述的方法，其特征在于，所述羟基羧酸是苹果酸或其盐。
3.如权利要求1所述的方法，其特征在于，所述金属是钙。
4.如权利要求1所述的方法，其特征在于，所述羟基羧酸的有效金属去除量是使得分开的水相的pH调节至约3-6所需的羟基羧酸的量。
5.如权利要求1所述的方法，所述方法还包括向所述原油或所述洗涤水中加入一种或多种破乳剂。
7.如权利要求1所述的方法，所述方法还包括向所述原油或所述洗涤水中加入一种或多种腐蚀抑制剂。
8.如权利要求1所述的方法，所述方法还包括向所述原油或洗涤水中加入一种或多种金属配位剂，所述金属配位剂不包括苹果酸和乳酸。
9.如权利要求8所述的方法，其特征在于，向所述洗涤水中加入一种或多种腐蚀抑制剂。
10.如权利要求9所述的方法，其特征在于，在所述洗涤水的上游，向所述原油加入所述羟基羧酸。
11.如权利要求9所述的方法，其特征在于，在所述洗涤水的下游，向所述原油加入所述羟基羧酸。
12.如权利要求1所述的方法，其特征在于，利用静电聚结使所述乳液解析。
13.如权利要求1所述的方法，其特征在于，所述原油是石油原油。
14.如权利要求13所述的方法，其特征在于，所述石油原油包括多巴原油。
15.一种用于从原油中去除金属和胺的改进的精炼脱盐方法，其包括：
(i)提供原油；
(ii)向所述原油中加入洗涤水；
(iii)混合所述原油和所述洗涤水，以形成乳液，以及
(iv)使所述乳液解析，以提供水相以及金属和胺含量减少的原油，所述改进包括向所述原油中加入有效金属去除量的选自苹果酸和乳酸的一种或多种羟基羧酸，所述加入与所述洗涤水的加入分开进行。
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