CN101679844B - 用于油田的羟乙基纤维素的稳定硫代硫酸钠基流化聚合物悬浮液 - Google Patents

用于油田的羟乙基纤维素的稳定硫代硫酸钠基流化聚合物悬浮液 Download PDF

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CN101679844B
CN101679844B CN200880007658.8A CN200880007658A CN101679844B CN 101679844 B CN101679844 B CN 101679844B CN 200880007658 A CN200880007658 A CN 200880007658A CN 101679844 B CN101679844 B CN 101679844B
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M·迈尔伯西
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Abstract

本发明涉及一种悬浮在硫代硫酸钠中的羟乙基纤维素(HEC)的水性流化聚合物悬浮液组合物及其应用，该悬浮液在油田应用如完井液、钻井液、压裂液和油井水泥浆中用作流变/粘度改进剂和钻井液降滤失剂，以实现对海洋环境的影响最小化。

Description

用于油田的羟乙基纤维素的稳定硫代硫酸钠基流化聚合物悬浮液
本申请要求2007年3月9日提交的临时申请60/906,149的相关权利并将其并入作为参考。
技术领域
本发明涉及一种组合物以及羟乙基纤维素的硫代硫酸钠基流化聚合物悬浮液在油田应用例如完井液、钻井液和油井水泥浆中作为流变/粘度改进剂和钻井液降滤失剂的用途。
背景技术
羟乙基纤维素(HEC)被广泛地用于油田水基流体中。由于其流变性能和控制失液量性能，高粘型通常被用于完井液中。由于其过滤控制性能，低粘型一般被用于油井水泥浆和钻井液中。然而，高粘型与低粘型在油井水泥浆中可用作自由水控制添加剂。
为了在油气井钻探平台中易于处理，以及在近海操作中方便储存，液体添加剂是最优选的。然而，由于排放到近海中的潜在环境危害，液体添加剂的使用受到严格地管制。过去几年里已经使用了各种环境上可接受的溶剂基聚合物悬浮液。这些悬浮液是基于矿物油或乙二醇。然而，由于这些类型的悬浮液都没有满足水生生物毒性、生物降解能力和生物体内积累方面的规范要求，它们仍然面临一些使用限制。
目前正在寻找完全由PLONOR(对环境很少或没有风险)组分组成的油井和气井产品。所有不满足PLONOR组分要求的现有产品都在逐步淘汰，一旦有可用的“绿色”添加剂，就需要被取代。
Burdick的美国专利5,268,466中公开了选自HEC(羟乙基纤维素)、HPC(羟丙基纤维素)、MC(甲基纤维素)、EHEC(乙基羟乙基纤维素)等的水溶性多糖与瓜尔胶/瓜尔胶衍生物的稳定悬浮液可在12-40wt.％的磷酸氢二钾溶液中制备，该专利的全部内容在此并入作为参考。该悬浮液包含15-30wt.％的所述多糖。该悬浮液还包括稳定量的黄原胶。这些稳定的悬浮液在工业上用于建筑涂料例如粘结化合物和乳胶漆。
美国专利5,407,475公开了一种HEC在硫代硫酸钠或铵盐溶液中的悬浮液组合物。该组合物要求用于钻井液(完井液)，并提高HEC的热稳定性。该悬浮液组合物包含至少30％w/w的硫代硫酸钠或铵。该专利并未公开这样的组合物在油井水泥浆中的用途。
美国专利公开号2007/0135312A1公开了一种PLONOR定级的HEC流化悬浮液，其全部内容在此并入作为参考。该专利申请具体地教导了HEC的磷酸氢二钾基水性悬浮液在油井维修流体中的用途。
为了提供与其它的水泥浆添加剂的更广泛的相容性以及提高HEC的热稳定性，显然需要开发大量PLONOR定级的悬浮液以满足特定的应用要求。
附图说明
图1描述了本发明的悬浮液和对比前体材料在NaCl饱和盐水中室温下和高温下的流变性分布。
发明内容
一种包含流体聚合物悬浮液的悬浮液组合物，所述流体聚合物悬浮液包含悬浮在硫代硫酸钠水溶液中的羟乙基纤维素(HEC)，所述悬浮液组合物还包含稳定剂，所述稳定剂为黄原胶或PLONOR定级防腐剂如苯甲酸钠。该组合物可与选自钻井液、完井/油井维修液、增产液如压裂液、固井液、砾石填充液和提高采收率流体的油田维修流体混合使用。
具体实施方式
本发明的目的是提供一种在浓硫代硫酸钠盐水溶液中的改善的HEC悬浮液，其与用于油田维修流体的其它添加剂具有改善的相容性。
硫代硫酸钠的优点在于其列于PLONOR核准的用于北海的产品目录中。
为了改善硫代硫酸钠悬浮液的长期稳定性，已经对该组合物进行了改良。对硫代硫酸钠悬浮液的一种改进是其包含悬浮剂和选自PLONOR目录核准的化学品中的防腐剂。观察发现包含悬浮剂的悬浮液物理稳定超过3个月。
已经发现，在浓硫代硫酸钠盐水中的HEC悬浮液用少量黄原胶稳定并任选包含防腐剂如苯甲酸钠，其提供了完全由被列为PLONOR物质的组分组成的稳定组合物。
该悬浮液组合物包含水、约5至约80wt％的HEC、约10至约30wt％的硫代硫酸钠、约0.01至约0.50wt％的黄原胶。另外任选地，可含有约0.1至约1.0wt％的苯甲酸钠防腐剂。
为了制备该悬浮液组合物，各组分以任何顺序进行添加，并在室温下混合。
以下实施例说明本发明的这种悬浮液在完井液和低温油井水泥浆组合物中的典型特性。
实施例1
用于实施例1的本发明的悬浮液组合物由下列组分组成：水；约24重量％的硫代硫酸钠；约20重量％的HEC；约0.15重量％至约0.20重量％的少量黄原胶；以及任选少量的防腐剂，比如有效量的苯甲酸钠，一般为约0.50重量％。所得悬浮液具有优良的流动特性(布氏粘度1600-2100cPs)。在室温下储存3个月后，没有观察到相分离的迹象。
另外，该悬浮液显示优良的冻熔稳定性。经测量，该悬浮液的冰点在-15℃以下。详细的悬浮液组成见表1，除非另有描述，所有份数和百分比均按重量计。
表1-详细的悬浮液组成
Figure G2008800076588D00041
制备后使用布氏粘度计测量得悬浮液1的粘度为2,100cPs，悬浮液2的粘度为1,660cPs以及悬浮液3的粘度为2,240cPs。
实施例2在完井液中的应用
相较于非悬浮液态而为干粉态的HEC(
Figure G2008800076588D00042
HIVIS HEC，由Hercules Incorporated获得)，评价本发明的悬浮液(
Figure G2008800076588D00043
HIVIS HEC悬浮液，由Hercules Incorporated获得(悬浮液3))的增稠效率。将干粉态HEC与通过在NaCl饱和盐水中溶解21b/bbl(0.57wt.％)当量的干HEC的HEC悬浮液进行比较。首先通过在1000ml去离子水中溶解360gNaCl制得所述NaCl饱和盐水。然后，将2.0g干HEC或10.0g悬浮液3加入到420g NaCl饱和水溶液中，同时在Hamilton beach混合器中混合(～11,500rpm)。为了加速聚合物的水合，在聚合物溶液中加入1ml 10％NaOH溶液以提高pH值。为了减少/除去过量的泡沫，加入几滴消泡剂。将该溶液混合60分钟。制得两种溶液，均化，然后分成两份以进行老化。一份在室温(～25℃)下静态老化一晚，另一份在121℃下热轧一晚。老化后进行Fann流变测量。
表2中的数据显示，当以相同的活性量在NaCl饱和水溶液中使用时，悬浮液3(实施例2)表现出比其干燥前体(对比例1)略好的性能。悬浮液3(实施例2)提供比干燥前体(对比例1)更高的整体流变性。
而且，重要的是悬浮液3(实施例2)比其干燥前体(对比例1)显示出好得多的热稳定性。当在121℃下热轧一晚后，用悬浮液3(实施例2)增稠的盐水溶液保留了87.2％/78.7％的表观粘度/屈服值，而对比例1则为67.8％/41.8％。
表2-NaCl饱和盐水中的热稳定性比较
由表2和图1可看出，悬浮液3(实施例2)是完井/油井维修液的有效增稠剂，同时相对于其干燥前体提供额外的热稳定性。
实施例3在油井水泥浆中的应用
以下实施例说明HEC的水悬浮液(悬浮液2(
Figure G2008800076588D00061
250JR HEC，由Hercules Incorporated获得))在低温和中温油井水泥浆组合物中的典型性能。温度对低温和中温油井水泥浆组合物的影响评价到180°F(82℃)，以及耐盐性评价到依水的重量计(bwow)18％NaCl。
油井水泥浆通过使用添加剂以及本行业通常使用的美国石油组织(API)推荐的混合/配制技术配制而成。水泥浆组合物(实施例3-6)中所有的添加剂浓度均是基于水泥的重量(bwoc)。
通过将水泥干混合物加入搅拌水中，最后包含降滤失剂(FLAC)，制备得到油井水泥浆。所述干混合物由600g Calport G水泥、2.3％合成分散剂(1.15wt％活性)、0.10％消泡剂和2.0％悬浮液2(0.40％活性FLAC)组成。为了在180°F(82℃)下实验，在水泥浆中加入2.0％缓凝剂(38％木素磺酸钙溶液)。
对油井水泥浆的流变性和控制滤失性能进行测试。一般地，为了模拟井上混合和泵抽，在室温(～80°F，～27℃)下制备出水泥浆后即用Fann类型的粘度计测量“混合流变性”，而在试验温度下调理水泥浆20分钟后测量“API流变性”。在水泥浆调理后，在80°F(27℃)和180°F(82℃)下测量控制滤失性能。
表3的数据显示，在相当低的剂量下(0.40％活性)，作为本发明目标的悬浮液2提供了优良的流变性能和优良的控制滤失性能。
Figure G2008800076588D00071
Figure G2008800076588D00081

Claims (10)

1.包含羟乙基纤维素和硫代硫酸钠的流体聚合物悬浮液的水性聚合物悬浮液组合物，所述悬浮液通过黄原胶和苯甲酸钠进行稳定，其中所述悬浮液组合物包含水、10-30重量%的硫代硫酸钠、5-80重量%的羟乙基纤维素和0.01-0.50重量%的黄原胶、以及0.1-1.0重量%的苯甲酸钠。
2.一种混合物，其为以下组分的混合物：a）羟乙基纤维素的流化水性聚合物悬浮液，其包含硫代硫酸钠，该悬浮液通过黄原胶和苯甲酸钠防腐剂进行稳定，其中所述悬浮液包含水、10-30重量%的硫代硫酸钠、5-80重量%的羟乙基纤维素和0.01-0.50重量%的黄原胶、以及0.1-1.0重量%的苯甲酸钠；和b）选自钻井液、完井/油井维修液、增产液、固井液、砾石填充液和提高采收率流体的油田流体。
3.如权利要求1所述的悬浮液组合物，其中所述悬浮液组合物包含水、24重量%的硫代硫酸钠、20重量%的羟乙基纤维素、0.15重量%至0.20重量%的黄原胶和0.50重量%的苯甲酸钠。
4.如权利要求2所述的混合物，其中所述油田流体为固井液。
5.如权利要求2所述的混合物，其中所述油田流体为钻井液。
6.如权利要求2所述的混合物，其中所述油田流体为完井／油井维修液。
7.如权利要求2所述的混合物，其中所述油田流体为增产液。
8.如权利要求7所述的混合物，其中所述增产液为压裂液。
9.如权利要求2所述的混合物，其中所述油田流体为砾石填充液。
10.如权利要求2所述的混合物，其中所述油田流体为提高采收率流体。
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US20080220993A1 (en) 2008-09-11
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