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CN1263581A - 作为原油中沥青质的分散剂的醚羧酸 - Google Patents

作为原油中沥青质的分散剂的醚羧酸 Download PDF

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CN1263581A
CN1263581A CN98807194A CN98807194A CN1263581A CN 1263581 A CN1263581 A CN 1263581A CN 98807194 A CN98807194 A CN 98807194A CN 98807194 A CN98807194 A CN 98807194A CN 1263581 A CN1263581 A CN 1263581A
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asphaltenes
ether carboxylic
crude oil
dispersants
carboxylic acids
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D·米勒
A·沃尔莫
M·费尤斯泰尔
P·克鲁格
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Clariant Produkte Deutschland GmbH
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Abstract

本发明涉及原油和由其得到的产物,它们含有下式所示的、以醚羧酸形式存在的沥青质分散剂：RO(CH2CHR1O)x(CH2CHR2O)yCH2－CO2H各取代基如说明书中所定义。

Description

作为原油中沥青质的分散剂的醚羧酸
沥青质是原油中的成分，其包括多种结构，特别是包括杂原子的高分子量的冷凝的芳香族成分。由于他们的化学复杂性，沥青质被当成可溶于苯、但不溶于正戊烷的油馏分。
在原油中沥青质通常以胶体分散体形式存在，其可被油树脂稳定。
沥青质可于原油和其产物例如重燃料油或航海油的生产，精炼，运输和储存过程中沉淀出来。产生这种沉淀作用的部分原因是温度的降低或是组成的改变(例如挥发性物质的蒸发)。沥青质也可从流过多孔介质过程中沉淀出来。在运输过程中用CO2溢流可引起沥青质的絮凝或沉淀。
某些油类含有烃蜡，其于低温时沉淀出来。蜡和沥青质的沉淀产生的相互作用会增加沉淀物质的总量或其形成速率。
在原油的生产制造过程中，沉淀的沥青质会引起一些问题。沥青质会沉淀在活门，管子和运输设备中。在热表面例如热交换器中，这些沉淀物的碳化作用会造成他们的除去很困难。沉淀物会减低工厂的效率，更严重的情形是会导致完全堵塞和停止生产，而造成高成本。
重油常被用于航海推进，其包括相当量的沥青质。沥青质的沉淀作用会导致不完全燃烧和引擎燃料的处理和储存的困难。
沥青质、重油和残余物有时用溶剂稀释，以降低运输时的粘稠度。若沥青质于这个过程中沉淀出来，在处理上会产生问题。
沥青质的沉淀作用可经由少量的分散剂而被预防或降低。这些物质有下列一个或多个效果：
a)降低沉淀物的量；
b)使沉淀物的形成较缓慢；
c)沉淀物会更微小地分布；和
d)沉淀物聚集在表面的倾向会减少。
若沥青质的沉淀物已形成，其可通过使用溶剂予以除去。分散剂的加入可改进这些溶剂的效率。
众多的沥青质分散剂是已知的。
CA2029465和CA2075749描述了烷基酚—甲醛树脂与亲水—亲脂的乙烯基聚合物的组合。十二烷基苯磺酸具有的分散沥青质的性质已被描述于US4414035，和D.-L.Chang和H.S.Fogler(SPE论文第25185号，1993)和M.N.Bouts等等(石油工艺杂志，47，782-7，1995)。
至今已知的分散剂仅能部分解决因沥青质的沉淀作用所引起的问题。因为油的组成不同，个别分散剂仅在有限的范围内有作用效果。有时，甚至在油组成上有小的改变，却对沥青质的分散性质会有极大的影响。因此，于某些例子中，已知的分散剂不是令人满意的，这就要求开发另外的类型。
本发明的目的是提供新颖的沥青质分散剂，其不具有至今已知的分散剂的缺点。
令人惊异地发现，下式醚羧酸：
RO(CH2CHR1O)x(CH2CHR2O)yCH2-CO2H可用于防止沥青质于原油和其产物中的沉淀作用和/或淀积作用。
本发明涉及原油和其产物，它们包含用作分散剂的下式醚羧酸：
RO(CH2CHR1O)x(CH2CHR2O)yCH2-CO2H其中，R是C6-C22、较佳是C9-C18-烷基或烯基，C6-C20-烷芳基，R1和R2相互独立地是H或甲基，较佳是H，和x和y相互独立地是0至20的一个数，x和y的总和是1至20，较佳是1.5至8。
源自原油的产物是例如重燃料油，航海油或沥青质。
根据本发明的醚羧酸，除了其它方法外，可由烷基酚或天然的或合成的脂族醇与环氧乙烷和/或环氧丙烷反应成相应的氧烷基化的醇，且随后与碱(氢氧化钠，氢氧化钾)和氯乙酸钠或氯乙酸衍生物反应而制得，混合物被酸化且醚羧酸从含盐的水相中分离出来。
得到的产物是具有不同的聚烯化氧链长度的众多分子的混合物。数目x和y应了解其平均值。
适合于分散沥青质的产品是纯的醚羧酸和工业级的醚羧酸，其除了醚羧酸(含量＞50％，较佳是60-90％)外，通常亦包括少量的氧烷基化的醇(含量1-40％，较佳是5-30％)和水(含量＜20％，较佳2-10％)。于实施例中提到的醚羧酸是工业级的，其包括60和80％的纯醚羧酸。
根据本发明的分散剂的使用浓度是0.5至10000ppm，较佳是2至2000ppm。
分散剂可在油可溶的溶剂诸如芳香烃或烃和脂族醇的混合物中形成一种溶液，以方便使用。
除了根据本发明的分散剂外，烷基酚—甲醛树脂、氧烷基化胺、蜡分散剂或其任何混合物也可被使用。同样地，其它具有界面活性剂性质的有机酸例如单-或双烷基苯磺酸、石油磺酸和烷磺酸也可当作另外的添加物。
测试沥青质分散剂的效率
沥青质的分散或沉淀与烃介质的性质有关。沥青质可溶于芳香族的烃，但不溶于脂族的烃。可通过将油或萃取了的沥青质溶解在芳香族溶剂中，且向其中加入脂族烃，以产生沉淀物而测试分散剂。因为沥青质有较黑的颜色，沉淀物的含量可由清液层的比色测量予以测定。上清液层越黑，则有越多的沥青质保持分散了，那就是较好的分散剂。此测试方法已叙述于CA2029465中。在我们的测试方法中，沉淀介质这样选择，它使大多数但并非全部沥青质沉淀。分散化测试的步骤
a)将一种在甲苯中的25％油溶液过滤，以除去杂质。
b)将9.5ml作为沥青质沉淀剂的庚烷以及0.5ml甲苯/分散剂混合物(25∶1)倒入有刻度的玻璃试管中，其刚好为10ml，且充分摇晃。这相当于2000ppm的分散剂浓度。若需要，分散剂浓度可不同。于空白样品中使用纯甲苯。
c)然后加0.1ml已过滤的油溶液于玻璃试管中，且同样地充分摇晃；
d)静置整个混合物2小时，收集已沉淀在试管底的沥青质；
e)时间结束后，以刻度计算沉淀物的体积，记录整个样品的外观，且以吸管小心地吸取1ml的上清液溶液；
f)将吸出来的物质溶于5ml 99∶1的甲苯/三—乙醇胺混合物中，且在600nm时以光度计分析之。分散化测试的评价
下面式子被当作对分散作用的相对度量
A＝100(D-D0)/D0，其中D和D0是测试溶液和空白样品的光密度。最大可得之A值、即Amax相当于沥青质完全分散。其可由一未加分散剂、即以甲苯取代庚烷来使沥青质完全分散，从而计算得之。沉淀物的体积可对分散剂的效率提供进一步的讯息。沉积量愈少，物质分散得愈好。
实施例
使用一种来自委内瑞拉富含沥青质的油对根据本发明的物质作分散化测试。剂量是2000ppm。
序号 R R1 x y 分散化作用A[％] 沉积物体积毫升
1 油基 H 2 0 108 0
2 C14/15烷基 H 3 0 110 0
3 C14/15烷基 H 7 0 106 0
4 C12烷基 H 3 0 112 0
5 异构C9芳基烷基 H 4 0 115 0
空白样品 -- -- -- -- 0 0.45
在该实验系列中，最大的分散作用Amax达到约120％。

Claims (5)

1.一种原油和其产物，它们含有作为沥青质分散剂的下式醚羧酸：
RO(CH2CHR1O)x(CH2CHR2O)yCH2-CO2H其中，R是C6-C22烷基或-烯基，C6-C20烷基芳基；R1和R2相互独立地为H或甲基，和x和y相互独立地是0至20的一个数，x和y的总和是1至20。
2.如权利要求1的原油，其特征在于，R是C9-C18烷基或-烯基，C6-C20烷基芳基，R1和R2是H和x和y相互独立地是0至20的一个数，x和y的总和是1.5至8。
3.按权利要求1的醚羧酸的应用，用作原油和其产品中的沥青质的分散剂。
4.一种分散原油和其产物中的沥青质的方法，其特征在于，将按权利要求1的醚羧酸以0.5至10000、较佳是2至2000ppm的量加入到原油和其产物中。
5.按权利要求4的方法，其特征在于，可另外使用烷基酚-甲醛树脂、氧烷基化的胺、单-或双烷基磺酸、石油磺酸、烷磺酸、蜡分散剂或其任何混合物。
CN98807194A 1997-07-14 1998-07-06 作为原油中沥青质的分散剂的醚羧酸 Pending CN1263581A (zh)

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CN108290876A (zh) * 2015-11-30 2018-07-17 Bp北美公司 用于沥青质稳定剂的筛选方法
CN112831362A (zh) * 2020-12-26 2021-05-25 中海油天津化工研究设计院有限公司 一种船用燃料油稳定性助剂及其制备方法
CN112844219A (zh) * 2021-02-24 2021-05-28 江苏四新界面剂科技有限公司 低泡型两性表面活性剂
CN115505378A (zh) * 2021-06-23 2022-12-23 中国石油天然气股份有限公司 一种复合型沥青质析出抑制剂

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CN108290876A (zh) * 2015-11-30 2018-07-17 Bp北美公司 用于沥青质稳定剂的筛选方法
CN106866640A (zh) * 2017-01-19 2017-06-20 中国石油化工股份有限公司 用于高凝稠油沥青质分散剂
CN106866640B (zh) * 2017-01-19 2019-04-02 中国石油化工股份有限公司 用于高凝稠油沥青质分散剂
CN112831362A (zh) * 2020-12-26 2021-05-25 中海油天津化工研究设计院有限公司 一种船用燃料油稳定性助剂及其制备方法
CN112844219A (zh) * 2021-02-24 2021-05-28 江苏四新界面剂科技有限公司 低泡型两性表面活性剂
CN115505378A (zh) * 2021-06-23 2022-12-23 中国石油天然气股份有限公司 一种复合型沥青质析出抑制剂
CN115505378B (zh) * 2021-06-23 2024-02-02 中国石油天然气股份有限公司 一种复合型沥青质析出抑制剂

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TW466269B (en) 2001-12-01
EP0995012B1 (de) 2001-03-21
EP0995012A1 (de) 2000-04-26
NO20000165D0 (no) 2000-01-12
US6063146A (en) 2000-05-16
CO5050398A1 (es) 2001-06-27
ID24250A (id) 2000-07-13
NO316403B1 (no) 2004-01-19
DE19730085A1 (de) 1999-01-21
NO20000165L (no) 2000-01-12
WO1999004138A1 (de) 1999-01-28
BR9811691A (pt) 2000-09-26

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