CN1088184A - 用于油田水净化的分散聚合物 - Google Patents
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Abstract
本发明提供从油田生产水中除去乳化油的方
法。据此方法,用有效量的水溶性阳离子聚合物的分
散液处理该含油水。
Description
本发明涉及一种从油田生产水中除去残留油的组合物和方法,更具体地,本发明涉及一种使用分散在浓缩盐介质中的水溶性聚合物来从油田生产水中除去残留油的方法。
当油田蓄积变得日益枯竭时,提高油产量的一种方法是,通过向地层中注入水或蒸气而保护地层中的压力。水或蒸气使油压出地层到达表面。维持油生产的该方法称为二次油回收。二次回收是回收方法中最广泛使用的。
在二次油回收中,产生的流体包括被油乳化的注射水。为了出售该油,首先必须将其从水中分离出来。但是,油分离方法不是完全有效的。在生产水中,一定量(200-10,000ppm)的油仍在生产水中保持乳化。引起关注的正是这种废水。生产水在排出前必须用某种方式处理以除去残留的油。
在生产水中存在的乳化油通常在几百几万ppm的范围内,不仅从出售油的经济观点,而且从环境观点考虑,必需除去这种残留油。美国环境保护署严格限制向公公饮水供应***和向公开水体排放水中油和脂(TOG)的总量。除了政府规定之外,必须除去残留油是为了保持清洁的重新注入地层的水源或蒸气源。不这样做最终会造成地层堵塞和产量下降。
除去乳化油的最有效的方法是使用化学助剂。历史上,干聚合物,溶液聚合物,反乳化胶乳和金属离子均用于处理生产水。每种物质各有其优缺点。
尽管干聚合物具有极浓缩的好处,因此降低了运输成本,但溶解聚合物的设备是昂贵的,在油田得不到。
胶乳聚合物也有问题,但是仍相当频繁地使用。胶乳聚合物制品包括30-35%的分散在油中的固体。在使用之前,胶乳聚合物也必须转化。象干聚合物一样,在油田中用于前转化的设备得不到,于是被迫直接将聚合物送入到***中。与此送入方法有关的许多问题使得许多客户不用胶乳聚合物。另外,胶乳通常具有很窄的处理范围,在较高剂量时常会导致过度处理。
尽管溶液聚合物不需要预加工,但由于材料的性质,百分比固体和分子量被严格地限制。这些材料常用于破坏可逆的乳化液,但是它们不能絮凝和分散油,于是需要其它化学品来完成。
金属离子,例如Fe3+,Zn2+,Al3+,等,长期以来用于破坏可逆的乳化液,但近来政府法规限制了它们在排出流中的浓度。尽管它们对破坏可逆的乳化液有效,但也需要另一种化学品来絮凝油。
本发明的水溶性分散聚合物对这些问题提供了很多解决方案,并且描述了一种处理油田产生的废水的新方法。
按照这些问题的解决方案,本发明提供了一种从油田生产水中除去乳化油的方法,该方法的特征在于,包括用有效量的水溶性阳离子聚合物的分散液处理含油水的步骤,所述水溶性阳离子聚合物的分散液是在多价阴离子盐的水溶液中,使含至少5%mole由通式(Ⅰ)代表的阳离子单体和至少5mol%的丙烯酰胺或甲基丙烯酰胺的水溶性单体混合物聚合,所述聚合在分散剂聚合物的存在下进行,所述分散剂聚合物是水溶性阳离子聚合物,它在所述多价阴离子盐的水溶液中是可溶的,并且它含有至少20mol%由通式(Ⅱ)表示的阳离子单体单元:
其中R1和R4各是H或CH3;R2,R3,R5和R6各是具有1-2个C原子的烷基,R7是H原子或具有1-2个C原子的烷基;A1和A2各是O原子或NH;B1和B2各是2-4个C原子或羟丙基,以及X1-和X2-各是相反阴离子。
本发明的又一方面是提供在接种聚合物存在下的聚合。接种聚合物是水溶性阳离子聚合物,它在多价阴离子盐的水溶液中是不溶的。接种聚合物还含有至少5mol%通式为(Ⅰ)的阳离子单体单元。
按照一个优选的实施方案,水溶性单体混合物进一步包含至少5mol%由通式(Ⅱ)表示的阳离子单体,多价阴离子盐优选包括磷酸盐,硫酸盐或其混合物。
图1是条形图,总结了对胶乳聚合物与本发明所用的水溶性聚合物分散液比较的评价数据。
图2是条形图,总结了对胶乳聚合物与本发明所用的水溶性聚合物分散液的比较的评价数据。
本发明提供从油田生产水中除去乳化油的先进方法。在从油田生产水中除去乳化油中,已经发现了一类新的水溶性分散聚合物比现用的化学处理更为有效。如下面的详细讨论,在多价阴离子盐的水溶液中制备本发明的聚合物分散液。本发明的聚合物分散液具有细颗粒尺寸和水溶解度,这在此类应用中使用其它聚合物无法获得的。本发明中所用的聚合物分散液示于实施例中,从生增废水中除去了是现行化学处理法两倍之多的乳化油。而且,当过量送入聚合物分散液时,不会出现问题,而用胶乳聚合物则是个缺陷。
按照本方法,将本发明的聚合物加入到油田生产水中。加入聚合物的有效量是0.5至约100ppm。更优选地,生产水中聚合物的量是2至约40ppm;最优选的是,约4至约20ppm。但是,应该注意到,好象没有一个聚合物会对***产生有害影响的最大剂量。好象在较高剂量下存在有利效应的平台,而且就成本来说,这样的高剂量,可能为大于大约100ppm,在成本上是不合算的。优选地,以纯净形式将本发明的聚合物加入到***中去。但是,在某些应用中,聚合物可以水溶液形式加入。
一旦本发明的聚合物加入到生产水中,当经处理的生产水从净化***中通过时,自然地被搅拌。本发明的聚合物使得乳化油从水中分离出来并且浮在水的表面成为絮片。随后从油表面除去絮片并加入到油生产中。经处理的水或者排入河,湖或海,或者重新注入地层中以迫使油喷出地面。本发明的优选的聚合物由日本的Hymo Corporation制备。优选的聚合物制品从Hymo Corporation购得,商标名为DR-2570,DR-3000和DR-4000。在美国专利US5,006,590和US4,929,655(转让给Kyoritsu Yuki Co.Ltd.,Tokyo,Japan)中,详细地描述了本发明所用的聚合物分散液的制备方法。这两篇专利的说明书合并在此作为参考。
按照本发明,从含有至少5mol%由通式(Ⅰ)表示的阳离子单体的水溶性单体混合物来制备用于处理生产水的聚合物分散液:
其中R1是H或CH3;R2和R3各是具有1-2个C原子的烷基;A1是O原子或NH;B1是具有2-4个C原子的烷基或羟丙基,X1是相反离子。上述水溶性单体混合物在多价阴离子盐的水溶液中是可溶的。但是,由该单体混合物产生的聚合物在多价阳离子盐水溶液中是不溶的。该单体混合物的聚合物也可用作接种聚合物。接种聚合物在下面详述。
上述阳离子单体用通式(Ⅰ)表示,优选的是通过苄基氯与丙烯酸二甲氨基乙酯,丙烯酸二乙氨基乙酯,丙烯酸二甲氨基羟丙酯,二甲氨基丙在丙烯酰胺,甲基丙烯酸二甲氨基乙酯,甲基丙烯酸二甲氨基乙酯,甲基丙烯酸二乙氨基乙酯,和二甲氨基丙基甲基丙烯酰胺反应而获得的季铵盐。
优选地与通式(Ⅰ)所代表的阳离子单体共聚的单体包括丙烯酰胺,甲基丙烯酰胺和由通式(Ⅱ)所代表的阳离子单体:
其中R4是H或CH3;R5和R6各是具有1-2个C原子的烷基;R7是H或具有1-2个C原子的烷基;A2是O原子或NH;B2是具有2-4个C原子的烷基或羟丙基,X2是相反离子。
通式(Ⅱ)所代表的优选的单体包括丙烯酸二甲氨基乙酯,丙烯酸二乙氨基乙酯,二甲基氨基丙基丙烯酰胺,二乙基氨基丙基丙烯酰胺和丙烯酸二甲基羟丙酯,甲基丙烯酸二甲基氨基乙酯,甲基丙烯酸二乙基氨基乙酯,甲基丙烯酸二甲基氨基丙酯,甲二乙基氨基丙基丙烯酰胺和甲基丙烯酸二甲基羟丙酯的铵盐,以及甲基化和乙基化的季盐。由通式(Ⅱ)所代表的更优选的阳离子单体是丙烯酸二烷基氨乙酯和甲基丙烯酸二烷基氨乙酯的盐和甲基化季盐。在该聚合反应物中的上述单体的浓度宜在5-30%(wt)的范围内。
按照本发明,掺入到水溶液中的多价阴离子盐合适的是硫酸盐,磷酸盐或其混合物。优选的盐包括硫酸铵,硫酸钠,硫酸镁,硫酸铝,磷酸氢铵,磷酸氢钠和磷酸氢钾。在本发明中,这些盐各用其水溶液,浓度为15%或更高。
在发生上述单体的聚合作用的阴离子盐水溶液中存在分散剂聚合物。分散剂聚合物是水溶性的高分子量阳离子聚合物。分散剂聚合物在上述盐水溶液中是可溶的。分散剂聚合物优选的用量是为单体总重量的1-10%(wt)。分散剂聚合物包括20mol%或更多的由式(Ⅱ)所代表的阳离子单体单元。优选地,剩余的mol%是丙烯酰胺或甲基丙烯酰胺。分散剂的性能受分子量的影响不大。但是,分散剂优选的分子量在10,000在10,000,000的范围内。按照本发明的一个实施方案,象丙三醇或聚乙二醇这样的多官能团醇在聚合***中共存。在这些醇的存在下,细颗粒的沉积缓慢地进行。
为了聚合,可以使用常用的形成水溶性基的试剂,但是,优选的是水溶性的偶氮化合物,例如使用2,2′-偶氨双(2-脒基丙烷)氢氯化物和2,2′-偶氮双(N,N′-二亚甲基异丁胺)氢氯化物。
按照本发明的一个实施方案,为了获得一种细分散液,在开始上述单体的聚合之前,加入一种接种聚合物。接种聚合物是水溶性阳离子聚合物,它在多价阴离子盐的水溶液中是不溶的。接种聚合物优选地是一种聚合物,它是用本文所述工艺,由上述单体混合物制备的。但是,接种聚合物的单体组成不必总是等于在聚合中形成的水溶性阳离子聚合物的单体组成。然而,象在聚合中形成的水溶性聚合物那样,接种聚合物应该含有至少5mol%的由通式(Ⅰ)代表的阳离子单体单元。按照本发明的一个实施方案,在一个聚合反应中所用的接种聚合物是在先前反应中用相同的单体混合物制备的水溶性聚合物。
下述实施例用来描述本发明的优选实施方案和用途,除非在权利要求书中另有说明之外,并不意味着限制本发明。
实施例1
为了评价本发明的聚合物和胶乳聚合物制品的处理能力,轮流用手摇动,和通过几组搅拌直观地比较水的清澈度。收集了2至大约5加仑的油田生产水。6盎司的干妆玻璃瓶充满了100ml的水,颠倒几次,使乳化油涂覆瓶子。以1%水溶液向单个瓶子中加入处理化学品。用于比较的处理化学品是NALCO
3374和NALCO
3390(从Nalco Chemical Company,Naperville,Illinois获得),以及DR-3000,DR-2570和DR-4000(从Hymo Corporation,Japan获得)。NALCO3374和NALCO3390是胶乳聚合物制品,它在油田中常用于此用途。DR-3000,DR-2570和DR-4000是本发明所用的水溶性阳离子聚合物分散液的市售制品。盖上瓶子,编号及搅拌。所有的样品均相同地搅拌。搅拌是为了配合水净化***的条件。搅拌分组进行,在每组之后进行观察和评价。观察如水的清澈度,未破坏的乳液,分散的油滴以及残留在水中的油的相对数量,转换成1-10的分数级,10为最佳。在废水中经处理的化学品的最终浓度是20ppm,在几组搅拌之后,随后立即记录水的清澈度,絮片的尺寸和持久性,以及水的相对清澈度,以避免乳化液的冷却和老化。
下面的表1总结了采集的数据。如表1所示,本发明中所用的水溶性阳离子聚合物的分散液大大优于为此用途现售的胶乳聚合物制剂。
实施例2
向搅拌槽中放入2升油田生产水。WemcoR混合机安装好。Wemco混合机混合并分散空气进入生产水。每个生产水的样品中,加入1%水溶液的处理化学品。样品的配料量为2,8和20ppm。化学处理剂采用NALCO3390,DR-3000,DR-2570和DR-4000。在1800RPM下,将每组样品搅动1分钟。在搅动样品之后,使样品静置,直至溶解的空气冒泡完毕。在每组样品上面是絮凝的油,从每组样品表面之下取出40ml经处理的水。用20ml的Frcon
-113(从Fisher Scieatigic Corporation得到)萃取40ml经处理的水。用Whatman
No.541过滤纸过滤所得到的萃取液。经过滤的萃取液放在石英容器中,并放在Miran
固定波长红外光谱仪下(波长为2874cm-1)。得到了经过滤的萃取液的吸收。该吸收和配料曲线相比,以确定残留在水样品中的剩余乳化油的量。在实验之前,通过取已知量的在水中的油,并获得其红外吸收,绘制了配料曲线。获得的数据总结在图1中。如图1所示,本发明中所用的分散液聚合物在其全部配料浓度上都优于为此用途现用的胶乳制剂。而且,图1表示,在20ppm,胶乳聚合物制剂过度处理体系。这种现象实际上导致了生产水清澈度的下降。
实施例3
实施例3的步骤与实施例1相同,不同之处在于,使用了不同配料量的化学处理剂。在实施例3中获得的数据总结在图2中。如图2所示,在本发明中所用的所有聚合物,基本上完全超过了为此用途现用的胶乳聚合物。
在不偏离如权利要求书所限定的本发明概念和范围前提下,本文所述本发明的组成、操作和方法的安排可以有变化。
表1
处理化学的 | 投料量 PPM | 水清澈度 |
NALCO 3390NALCO 3374DR-2570DR-3000DR-4000空白 | 202020202020 | 338994 |
Claims (7)
1、一种从油田生产水中除去乳化油的方法,其特征在于,用有效量的水溶性阳离子聚合物的分散液处理含油水的步骤,所述水溶性阳离子聚合物的分散液制备如下,在多价阴离子盐的水溶液中,使含至少5mol%由通式(Ⅰ)代表的,阳离子单体与至少5mol%的丙烯酰胺或甲基丙烯酰胺的水溶性单体混合物聚合,所述聚合在分散剂聚合物的存在下进行,所述分散剂聚合物是水溶性阳离子聚合物,它在所述多价阴离子盐的水溶液中是可溶的,并且它含有至少20mole%由通式(Ⅱ)表示的阳离子单体单元:
其中R1和R4各是H或CH3;R2,R3,R5和R6各是具有1-2个C原子的烷基,R7是H原子或具有1-2个C原子的烷基;A1和A2各是O原子或NH;B1和B2各是2-4个C原子或羟丙基,以及X1-和X2-各是相反阴离子。
2、权利要求1的方法,其特征在于,聚合在接种聚合物的存在下进行;所述接种聚合物是水溶性阳离子聚合物,它在所述多价阴离子盐的水溶液中是不溶的,它含有至少5mol%用通式(Ⅰ)表示的阳离子单体单元。
3、权利要求1的方法,其特征在于,水溶性单体混合物还含有至少5mol%的由通式(Ⅱ)表示的阳离子单体。
4、权利要求1的方法,其特征在于,多价阴离子盐包括磷酸盐,硫酸盐或其混合物。
5、权利要求1的方法,其特征在于,加入到含油水中的水溶性阳离子聚合物分散液的有效量为至少0.5ppm。
6、权利要求1的方法,其特征在于,加入到含油水中的水溶性阳离子聚合物分散液的有效量为至少2ppm。
7、权利要求1的方法,其特征在于,加入到含油水中的水溶性阳离子聚合物分散液的有效量为至少4ppm。
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US968,763 | 1992-10-30 | ||
US07/968,763 US5330650A (en) | 1992-10-30 | 1992-10-30 | Dispersion polymers for oil field water clarification |
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EP (1) | EP0595156B1 (zh) |
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CN105873651A (zh) * | 2014-01-09 | 2016-08-17 | 陶氏环球技术有限责任公司 | 用于油田水澄清工艺的组合物和方法 |
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-
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CN105873651A (zh) * | 2014-01-09 | 2016-08-17 | 陶氏环球技术有限责任公司 | 用于油田水澄清工艺的组合物和方法 |
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