CN102627577A - 基于多胺和脂肪酸/马来酸酐的乳化剂 - Google Patents
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Abstract
本发明总体涉及一种通过多胺和脂肪酸和酸酐、优选马来酸酐反应获得的聚酰胺乳化剂，还涉及含有所述乳化剂的钻井液以及使用该钻井液组合物在地层中钻井眼的方法。
Description
本申请是中国专利申请200680038330.3的分案申请，该中国专利申请的申请日为2006年10月12日，发明名称是“基于多胺和脂肪酸/马来酸酐的乳化剂”。
发明领域
本发明涉及一种基于通过多胺和脂肪酸/马来酸酐的用于油基钻井液的乳化剂。本发明还涉及含有本发明乳化剂的油基或合成基钻井液以及使用该钻井液的钻井方法。
发明背景
钻井液是一种特别设计的流体，在井筒被钻孔时循环流过井筒以促进钻孔操作。钻井液促进了从井筒除去钻孔碎屑、冷却和润滑钻头，帮助支撑钻杆和钻头，并提供静水压力以保持井筒壁的完整性，从而使井破裂的趋势最小化。根据特定地质组成的特征选择特定的钻井液体系，从而使钻井操作最优化。
油基或合成基钻井液，或反相乳液，通常用于钻孔溶胀或膨胀性页岩、盐、石膏、硬石膏或其它蒸发岩地层，含硫化氢的地层，以及热(高于约300°F)洞，但是可以用于其它能穿透地层的洞中。这种钻井液通常含有油或合成油或其它合成材料或合成流体(“合成”)作为连续相，还可以含有通过乳化分散在水中的水，从而在流体中没有明显的水层。术语“油基钻井液”或“油基或合成基钻井液”一般表示反相油基钻井乳液或反相乳液。所有油基钻井液简单地含有100体积％油作为液相；也就是说，没有含水的内相。反相乳液钻井液可以一般含有约50∶50至95∶5体积的油相/水相比率。
用于转井的反相乳液一般含有：用于外相的基础油或合成流体；用于内相的盐水溶液(通常是含有约30％氯化钙的溶液)；和其它用于悬浮、降滤失、密度、油润湿、乳化、过滤和流变控制的试剂或添加剂。
美国专利6006831公开了电子测井液和其使用方法。在第2栏第40行起，此专利描述了通过多胺与脂肪酸和基础酸例如马来酸和富马酸反应获得的乳化剂。但是，没有公开本发明中的从马来化松浆油脂肪酸和高级多胺衍生的特殊乳化剂或它们在高温/高压应用中作为乳化剂的有效性。
美国专利4,508,628公开了快速钻井反相乳液钻井液。优选的聚酰胺乳化剂如下制备：先使多胺与脂肪酸反应形成酰氨基胺，然后使酰氨基胺中间体与二羧酸、优选马来酸或富马酸反应。但是，从此专利的公开内容可见，多胺限制为非常短链的多胺(第5栏第30行)。另外，此专利的乳化剂必须溶解在溶剂中以在室温下是液体。
美国专利3,169,113公开了用于油包水型酸性压裂液的乳化剂。公开的乳化剂具有两种组分：
(a)具有C2-6亚烷基和3-5个氨基氮的多亚烷基多胺的偏酰胺的C9-18单脂肪羧酸盐，其中至少两个氨基被C9-18单脂肪羧酸酰胺化，并且其中有至少一个与酸形成盐的未被酰胺化的氨基，和
(b)具有C2-6亚烷基和2-5个氨基氮的多亚烷基多胺与C9-18单脂肪羧酸形成的聚酰胺。
美国专利4,501,672公开了用于油基操作液的降滤失添加剂。此添加剂通过使1mol二亚烷基三胺与2mol脂肪酸反应获得。实施例1具体公开了二亚乙基三胺二油基酰胺与马来酸酐的桥接。
WO 89/11516公开了用于钻井液的油基乳化剂，其是1或2摩尔酰胺-胺或羟基烷基酰胺与1-5摩尔二羧酸或酸酐的反应产物。此专利的第5页起说明了考虑使用非常短链的多胺。
美国专利4,658,036公开了反相乳液及其制备方法。乳化剂是通过至少一种松浆油脂肪酸与丙烯酸、马来酸酐或富马酸反应、然后与二亚乙基三胺和至少一种松浆脂肪酸反应制备，得到反相乳化剂。
随着在一些钻井地点的空间受到限制，例如在海外平台上，以及随着将材料运输到钻井地点的成本增加，在工业上十分关注和需要更有效的浓缩的钻井液添加剂，并且与现有技术的常规钻井液相比能以较少量的添加剂配制并保持的钻井液。
发明概述
本发明总体涉及基于多胺和脂肪酸/马来酸酐的用于油基钻井液的乳化剂，表示该乳化剂含有至少一种由脂肪酸衍生的结构部分、至少一种由多胺衍生的结构部分和至少一种由酸酐衍生的结构部分。优选，本发明的乳化剂基本由这些结构部分的任何组合组成。本发明的乳化剂可以通过使多胺与脂肪酸(或脂肪酸的混合物)和酸酐反应制备，酸酐特别是马来酸酐。本发明还涉及含有本发明乳化剂的油基或合成基钻井液，以及使用此钻井液的钻井方法。
附图说明
图1显示了基于柴油的且含有不同含量乳化剂1的钻井液在300°F老化16小时后的HTHP降滤失性能。
本发明的详细描述
本发明的聚酰胺是衍生自脂肪酸/马来酸酐以及与二亚乙基三胺(“DETA”)不同的高级多胺。它们提供了乳化作用，并允许得到浓缩的产品，是固体或液体的，并具有优异的性能。用于油基钻井液的常规乳化剂一般在高温和高压条件下降解，这导致油基钻井液的性能变差。这要求向钻井液体系中加入更多的乳化剂以保持所需的性能，这显著增加了体系的成本。本发明的乳化剂在高温和高压条件下更有效，以减少乳化此体系所需要的额外乳化剂的量，从而改进体系的性能和成本。另外，本发明的聚酰胺乳化剂在室温下是液体，不需要添加溶剂。
本发明的聚酰胺乳化剂由下式表示：
R3O-C(O)-R4-C(O)-N(R1)-(CH2)n-NH-C(O)-R2
其中R1和R2独立地选自C10-C24亚烷基，R3是氢或C1-C5烷基，R4是C1-C5烷基/烯基，在另一个实施方案中是C2-C4烷基/亚烷基，n是2-5的整数，在另一个实施方案中是3-4。在另一个实施方案中，R1和R2选自C12-C22亚烷基；在另一个实施方案中，R1和R2选自C14-C18亚烷基。有利的是，R1和R2衍生自脂肪酸源。优选的脂肪酸源包括但不限于椰子、棕榈、棕榈壳、大豆、牛油、松浆油以及它们的混合物。理想的来源包括但不限于松浆油和牛油。
本发明优选的聚酰胺乳化剂由下式表示：
HO-C(O)-CH＝CH-C(O)-N(R1)-(CH2)3-NH-C(O)-R2
其中R1和R2独立地选自C10-C24亚烷基。优选，R1和R2衍生自松浆油。
本发明的乳化剂在以低剂量使用时是非常有效的，并且当用于常规油基钻井液配剂中时，得到具有高电子稳定性的钻井液。另外，本发明的乳化剂是高度浓缩的，即达到100％的活性成分，并且是不含石灰的，即不需要向钻井液体系中加入石灰以活化乳化剂。本发明的乳化剂也在高温和高压下在使用较低剂量时具有低的滤失(过滤性能)，不需要使用其它降滤失或过滤添加剂。
本发明的聚酰胺乳化剂通常从脂肪酸(I)和多胺(II)的缩合反应制备。脂肪酸和多胺反应的比例使得形成酰氨基胺中间产物(III)，其具有反应性酸位与反应性胺位(例如氮结合的氢)之间的摩尔比在约0.25∶1至约0.75∶1的范围内，最优选是约0.5∶1。
这种酰氨基胺中间体(III)然后进一步与马来酸酐(IV)按照0.75∶1.25的摩尔比率反应，得到本发明的聚酰胺乳化剂(V)。
R-NH(CH2)nNH2+R’-CO2H→R-NH(CH2)nNHCO-R’
(I) (II) (III)
R-NH(CH2)nNHCO-R’+马来酸酐
(III) (IV) →
HO-CO-CH＝CH-CO-N(R)-(CH2)n-NH-CO-R’(V)
用于制备反应中的脂肪酸(I)一般选自下式的脂肪酸：R’-CO2H，其中R’是饱和或不饱和的、支链或直链的、取代或未取代的具有6-22个碳原子的烷基。松浆油脂肪酸和/或牛油特别优选用于本发明乳化剂制备方法中的脂肪酸源化合物。松浆油是常规的产品，通过对来自木浆生产的碱液进行酸处理得到，松浆油及其衍生物已经用于油井钻井液中。
用于上述方法中的多胺一般具有下式：
R-NH(CH2)nNH2
其中R是饱和或不饱和的、支链或直链的、取代或未取代的具有6-22个碳原子的烷基，n＝2-5。特别优选的是多胺，脂肪多胺，二胺，包括单烷基或二烷基对称或不对称的乙二胺、丙二胺和它们的多胺类似物。合适的工业脂肪多胺是Duomeen C(N-椰油-1，3-二氨基丙烷)、Duomeen S(N-大豆-1，3-二氨基丙烷)、Duomeen T(N-牛油-1，3-二氨基丙烷)和/或DuomeenO(N-油基-1，3-二氨基丙烷)。Duomeen产品可以从Akzo Nobel SurfaceChemistry LLC，Chicago，Illinois获得。
马来酸酐(酸酐)是优选用于本发明反应的酸酐。但是，本领域技术人员将认识到可以使用其它酸酐，包括但不限于戊二酸酐等，以及它们的混合物。
反应一般在化学计量条件下进行，即1摩尔的Duomeen T在第一步中与0.5-1.5摩尔、优选1摩尔的松浆油脂肪酸(TOFA)反应，并在第二步中1摩尔的中间体与0.75-1.25摩尔、优选1摩尔马来酸酐反应。第一步的反应温度一般是150-175℃，优选约165℃，一般进行约10-17小时，直到酸减少到小于约0.2meq/g。第二步一般在80-100℃的温度进行2-3小时(反应是放热的)，直到胺值降低到低于约0.5meq/g且酸值降低到低于约1.5meq/g。在反应的任何步骤中都不需要使用催化剂。
本发明的乳化剂是用于油基或合成基钻井液的优异添加剂，提供了改进的乳化作用，并改进了电子稳定性和降滤失控制，且与现有技术的钻井流体添加剂相比显著减少了添加剂的体积。本发明的乳化剂以通常用现有技术乳化剂乳化油基或合成基钻井液所需常规量的约1/3的添加率就达到了满意的乳化效果。通常，约3-5磅本发明乳化剂/每桶钻井液对于乳化是有效的。甚至更低的量也能改进钻井液的电子稳定性和滤失控制，即使已经用其它乳化剂乳化时也是如此。
一般，0.1-10重量％、优选约0.5-1.5重量％的本发明乳化剂用于钻井液组合物中。在另一个实施方案中，使用约0.75-1.25重量％。典型的含有本发明乳化剂的油基钻井液是基于油(柴油或聚烯烃)，也可以含有组分例如有机粘土、盐水、增重剂、分散剂、稳定剂和重晶石。额外的组分也是本领域技术人员公知的。
本发明的乳化剂不需要载体，是高活性的，并且能用于所有或基本所有的公知用于钻井液的合成基和油基体系。本发明的乳化剂也可以向钻井液赋予更高的粘度，因此优选在加入任何增重剂之前加入基础钻井液中。
本发明的乳化剂有效地在高温和高压下操作，并且在不需要过滤添加剂的情况下即使在达到约150℃(300°F)的温度也是稳定的，在使用过滤添加剂时在达到约180℃(350°F)的温度也是稳定的。在乳化剂包中一起加入润湿剂和本发明产品可以提高钻井液在一些基础油中的油润湿性质，但不需要其它油。润湿剂也可以改进在达到约300°F的温度下的流变稳定性，并进一步提高一些流体体系的性能。
本发明的钻井液组合物优选含有至少一种油或合成基钻井油。这些钻井油称为油泥，是本领域技术人员公知的。本发明的钻井液组合物也优选包括盐水。在大多数情况下，使用钠、钙和/或镁的盐水。
本发明的方法包括在地层中钻井眼时，将本发明的聚酰胺乳化剂加入油基或合成基钻井液中，或使用包含本发明聚酰胺乳化剂的钻井液。在另一个方案中，本发明方法包括向油基或合成基钻井液中加入本发明的聚酰胺乳化剂以促进钻井液的乳化或反相乳液的形成。最后，本发明涉及一种在钻井的同时改进穿透速率的方法，包括在含有下端与井眼底部接触的旋转钻头的一串钻杆进行旋转的同时，使本发明的钻井液组合物循环通过井眼，从而促进从井眼除去由所述钻头形成的钻孔碎屑。
本发明的油基或合成基钻井液也可以包含各种本领域技术人员已知的任选组分。这些任选组分包括但不限于滤失控制剂、流变改性剂、湿润剂等。
本发明将由以下非限制性实施例说明。
实施例1制备钻井液
用于以下非限定性实施例的基于柴油的钻井液如下制备：在常规实验室钻井液混合器中将20-30重量％的#2柴油、0.25-1.5重量％的乳化剂、0.3-1重量％的有机粘土、5-15重量％的CaCl2溶液(25重量％活性)和50-70重量％的重晶石(顶部尺寸＝200微米(μm))在7000-12000rpm混合30-90分钟。
实施例2.检测钻井液的性能
钻井液流变性能的检测使用具有R1-B1同心圆柱几何形状的Fann35A粘度计在120°F(50℃)进行。在检测粘度600rpm(DR1)、然后检测300(DR2)、200、100、6和3rpms之后，根据下式计算塑性粘度和屈服点：塑性粘度(PV)＝DR1-DR2
屈服点(YP)＝2DR2-DR1.
钻井液滤失性能的检测根据American Petroleum Institute(API)Recommended Practice 13B(RP 13B)，第12版(09/01/1988)，11-13页，3.4节“高温/高压过滤实验”所述进行。
钻井液乳液稳定性的检测使用OFI检测设备(Houston，TX)乳液稳定计按照标准程序进行。
实施例3
表1乳化剂1和2的制备和分析结果
| 乳化剂1 | 乳化剂2 | |
| TOFA∶Duomeen T∶MA的摩尔比 | 1.1∶1∶1.08 | 1∶1∶1 |
| 最终产品的胺含量(meq/g) | 0.287 | 0.104 |
| 最终产品的酸含量(meq/g) | 1.208 | 1.444 |
实施例4
表2含有1重量％乳化剂的基于柴油的钻井液在150℃(300°F)老化16小时之前和之后的HTHP性能
实施例5
图1显示了含有不同含量乳化剂1的基于柴油的钻井液在150℃(300°F)老化16小时之后的HTHP滤失性能。
Claims (15)
1.具有下式的化合物：
R3O-C(O)-R4-C(O)-N(R1)-(CH2)n-NH-C(O)-R2
其中R1和R2独立地选自C10-C24亚烷基，R3是氢或C1-C5烷基，R4是C1-C5烷基/烯基，n是2-5的整数。
2.权利要求1的化合物，其中R1和R2选自C12-C22亚烷基。
3.权利要求1的化合物，其中R1和R2选自C14-C18亚烷基。
4.权利要求1-3中任一项的化合物，其中R1和R2衍生自选自以下的脂肪酸源：椰子、棕榈、棕榈壳、大豆、牛油、松浆油以及它们的混合物。
5.权利要求4的化合物，其中脂肪酸源是松浆油脂肪酸。
6.权利要求1的化合物，其具有下式：
HO-C(O)-CH＝CH-C(O)-N(R1)-(CH2)3-NH-C(O)-R2
其中R1和R2独立地选自C10-C24亚烷基。
7.一种乳化剂，其含有乳化有效量的至少一种权利要求1-6中任一项的化合物。
8.权利要求7的乳化剂，其含有乳化有效量的至少一种权利要求6的化合物。
9.一种钻井液组合物，其含有油或合成基料和至少一种权利要求1-6中任一项定义的聚酰胺乳化剂。
10.权利要求9的组合物，其中所述至少一种乳化剂的存在量是约0.5-1.5重量％，基于钻井液组合物的总重量计。
11.权利要求10的组合物，其中所述至少一种乳化剂的存在量是约0.75-1.25重量％，基于钻井液组合物的总重量计。
12.权利要求9的钻井液组合物，其进一步含有至少一种湿润剂、盐水、有机粘土、重晶石以及它们的混合物。
13.一种在地层中钻井眼的方法，所述方法包括在钻所述井眼的同时使用油基或合成基钻井液组合物，其中所述钻井液组合物含有至少一种油或合成基料和至少一种权利要求1-6中任一项的聚酰胺乳化剂。
14.一种在地层中钻井眼的同时提高穿透速率的方法，包括在含有下端与井眼底部接触的旋转钻头的一串钻杆进行旋转的同时，使钻井液组合物循环通过所述井眼，从而促进从井眼除去由所述钻头产生的钻孔碎屑，其中所述钻井液组合物含有至少一种权利要求7所述的聚酰胺乳化剂。
15.权利要求7的乳化剂，其在室温下是液体且不需要添加溶剂。
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| CN114479780B (zh) * | 2022-02-22 | 2023-05-30 | 西南石油大学 | 一种双亲改性纳米颗粒及其乳状液和抗高温高密度可逆油基钻井液 |
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- 2006-10-12 GB GB0806662A patent/GB2445693B/en not_active Expired - Fee Related
- 2006-10-12 CN CN2012100377206A patent/CN102627577A/zh active Pending
- 2006-10-12 WO PCT/EP2006/067320 patent/WO2007045592A1/en active Application Filing
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103566816A (zh) * | 2013-10-22 | 2014-02-12 | 中国石油化工股份有限公司 | 一种三聚酰胺类非离子型表面活性剂及制备方法和用途 |
| CN103566816B (zh) * | 2013-10-22 | 2016-03-23 | 中国石油化工股份有限公司 | 一种三聚酰胺类非离子型表面活性剂及制备方法和用途 |
| CN107011877A (zh) * | 2016-03-04 | 2017-08-04 | 中国石油天然气集团公司 | 一种油基泥浆降粘剂及降粘方法 |
| CN107011877B (zh) * | 2016-03-04 | 2020-10-09 | 中国石油天然气集团公司 | 一种油基泥浆降粘剂及降粘方法 |
| CN110872497A (zh) * | 2018-08-30 | 2020-03-10 | 中石化石油工程技术服务有限公司 | 一种生物质醇醚基钻井液及其制备方法 |
| CN110872497B (zh) * | 2018-08-30 | 2022-03-15 | 中石化石油工程技术服务有限公司 | 一种生物质醇醚基钻井液及其制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2445693B (en) | 2010-01-13 |
| GB2445693A (en) | 2008-07-16 |
| WO2007045592A8 (en) | 2007-07-12 |
| WO2007045592A1 (en) | 2007-04-26 |
| US8163675B2 (en) | 2012-04-24 |
| GB0806662D0 (en) | 2008-05-14 |
| US20070093393A1 (en) | 2007-04-26 |
| CN101287808A (zh) | 2008-10-15 |
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Application publication date: 20120808 |