CN101326258B - 用于油田维护液的无溶剂流体化聚合物悬浮体 - Google Patents

用于油田维护液的无溶剂流体化聚合物悬浮体 Download PDF

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CN101326258B
CN101326258B CN200680046105.4A CN200680046105A CN101326258B CN 101326258 B CN101326258 B CN 101326258B CN 200680046105 A CN200680046105 A CN 200680046105A CN 101326258 B CN101326258 B CN 101326258B
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M·麦尔布西
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Abstract

本发明涉及在油田应用如完井液、钻井液、压裂液和油井水泥浆中作为流变/粘度调节剂和降滤失剂的、用于将对海洋环境的影响最小化的水溶性多糖和/或聚乙烯醇(PVA)的含水流体化聚合物悬浮体的组合物和应用领域。

Description

用于油田维护液的无溶剂流体化聚合物悬浮体
相关申请
本申请主张2005年12月8日提出的美国临时申请序列第60/748,452号的权益，其内容通过引用结合在此。
技术领域
本发明涉及在油田应用如完井液、钻井液和油井水泥浆中作为流变/粘度调节剂和降滤失剂的、纤维素衍生物和/或聚乙烯醇(PVA)的无溶剂流体化聚合物悬浮体的组合物和应用。该浆液组合物包含PLONOR(几乎不对环境形成危险)目录的成分，尤其是适合用于北海地区。
背景技术
在各种添加剂当中，羟乙基纤维素(HEC)广泛被用于油田水基流体。虽然高粘度类型的HEC因为流变和降滤失性能而通常应用在完井液中，但低粘度HEC由于其降滤失性能而通常用在油井水泥浆和钻井液中。有时，高粘度和低粘度的HEC可一起使用来更加优化总体特性，特别是在水泥浆液中。尽管低重均分子量(Mw)的HEC对于中等温度的固井是优选的降滤失添加剂，但PVA对低温条件则更为优选。
为了容易在尤其是海上的油井和气井钻探平台、油田操作中进行处理，要求使用的流体物质/制剂从海上装置的排放不需要被严格地管制。在过去的几年里，已经采用了基于环境可接受的溶剂的各种聚合物悬浮体。这些悬浮体基于矿物油或乙二醇。然而，这类悬浮体由于不满足全部受规章限制的有关水生生物毒性、可生物降解性和生物聚积的要求而仍面临一些应用限制。对北海严格的环境保护法规要求油田服务公司重新配制其产品，以便其对海洋环境的影响能减到最少，而且产品的组分包含许可的组分。
对于化学品在北海的应用，根据组分的生态毒物学特性其被划分为四(4)类。各由颜色表明的所述四种类型如下：
黑色：禁止使用或排放；
红色：高优先级的经由替代逐渐淘汰；
黄色：环境可接受的；和
绿色：仅适于有关东北大西洋海洋环境保护的OSPAR协定中PLONAR(几乎不形成危险)数据库所列化学制品。
对于北海的油和气钻探作业，公司必需逐步淘汰产品中的黑色和红色组分的使用，并且仅使用完全由“绿色”组分构成的新化学制品。
Burdick的美国专利5,268,466公开了选自HEC、CMHEC、HM-HEC、HM-EHEC、MC、MHEC、MHPC、EC和瓜尔胶/瓜尔胶衍生物的水溶性多糖的稳定悬浮体，其可以在12-40重量％的磷酸氢二钾的溶液中制备。所述悬浮体包括15-30重量％的所述多糖。所述悬浮体还包括稳定量的黄原胶。列举的这些稳定悬浮体的工业应用为在建筑和涂料中，如在接缝化合物和乳胶漆上的使用。
从海上装置的排放对海洋环境不形成明显危险的流体物质/制剂存在的需要是基于以下的事实：所述流体物质/制剂的组分包含被许可过的PLONAR组分，同时保持了这些流体物质/制剂在油田维护液如钻井液、完井液/修井液、压裂液和油井固井液中的功能。
发明内容
本发明涉及悬浮体组合物，其包含选自钻井液、完井液/修井液、压裂液和油井固井液的油田维护液；并包含水溶性聚合物悬浮于磷酸钾化合物的水溶液中的流体聚合物悬浮体。水溶性聚合物选自水溶性多糖和合成聚合物。水溶性多糖可选自纤维素醚、瓜尔胶和瓜尔胶衍生物。合成聚合物可以是聚乙烯醇。纤维素醚可以是羟乙基纤维素(HEC)、甲基纤维素(MC)、羟丙基纤维素(HPC)、乙基羟乙基纤维素(EHEC)、甲基羟乙基纤维素(MHEC)、疏水改性的羟乙基纤维素(HMHEC)、疏水改性的乙基羟乙基纤维素(HMEHEC)、疏水改性甲基羟乙基纤维素(HMMHEC)、乙基纤维素(EC)、甲基羟丙基纤维素(MHPC)、和羧甲基羟乙基纤维素(CMHEC)。油田维护液包括钻井液、完井液/修井液、压裂液和油井固井液。
具体实施方式
人们已经意外地发现，环境可接受的磷酸钾化合物可用于油田维护液，以在油田使用中提供有效的和较好的结果。本发明提供改进的基于描述于美国专利5,268,466中的物质组成的水溶性聚合物在浓缩的磷酸钾盐水溶液中的悬浮体，该专利的全部内容通过引用结合在此。本发明组合物的一个优点在于，全部悬浮体组分可选自东北大西洋海洋环境保护的OSPAR协定中批准用于北海地区的PLONOR目录中的添加剂。应当注意不是全部磷酸钾盐都在该PLONOR目录上。
据发现水溶性聚合物的悬浮体，优选水溶性多糖、更优选纤维素醚、瓜尔胶或瓜尔胶衍生物，还更优选为选自HEC、MC、HPC、EHEC、MHEC、HMHEC、HMEHEC、HMMHEC、EC、MHPC和CMHEC的纤维素醚、又更优选HEC在浓缩的含水磷酸钾化合物中、优选在无水磷酸氢二钾(CAS#7758-11-4)中时可由此提供完全由PLONOR物质所列组分构成的组合物。该组合物可以用少量的低分子量CMC、黄原胶和/或藻酸钠来稳定。
本发明中所用磷酸钾化合物可选自磷酸钾、磷酸氢二钾(K2HPO4)、磷酸三钾(K3PO4)、磷酸二氢钾(KH2PO4)和磷酸钾盐(2∶1)(KH5(PO4)2)、及它们的混合物。优选磷酸钾化合物为磷酸氢二钾(K2HPO4)。本发明悬浮体组合物中采用磷酸钾化合物的一个优点在于所述悬浮体组合物基本变为自防腐，不需要通常PLONAR材料不容许的其它防腐剂。
本发明的悬浮体组合物包含以下组分：水、磷酸钾化合物，优选无水磷酸氢二钾，其占流体聚合物悬浮体的约10-40重量％，优选为约20-30重量％，更优选约25重量％，和水溶性聚合物，优选水溶性多糖，更优选纤维素醚，更优选HEC。本发明的悬浮体组合物可另外包含有效量的稳定剂，其功能是使流体聚合物悬浮体具有长期稳定性和防止组分的沉降。有效量的稳定剂可占流体聚合物悬浮体的至多约2重量％，优选至多约1重量％，还更优选至多约0.5重量％。稳定剂可以是低分子量(Mw)羧甲基纤维素钠(CMC)，例如购自Hercules公司的Blanose
Figure S2006800461054D00031
7L1羧甲基纤维素钠。或者所述稳定剂可以是黄原胶，例如购自Rhodia USA的Rhodopol23标准级黄原胶或藻酸钠。或者可以采用CMC和黄原胶的组合。将CMC和黄原胶加入流体聚合物悬浮体中以提供长期稳定性。
据发现除了水溶性多糖之外，合成聚合物例如聚乙烯醇(PVA)也可悬浮于所述流体聚合物悬浮体中。根据水溶性聚合物的类型，可制备稳定且可流动的流体化聚合物悬浮体，该流体聚合物悬浮体包含约5-50重量％、优选约10-40重量％、更优选约20-25重量％的水溶性聚合物。
以下提供实施例来说明本发明，除非另外指明，份数和百分数为基于重量。
实施例
典型的流体聚合物悬浮体和相关的长期稳定性在表1和2中给出。在室温下储存6个星期后没有观察到聚合物沉降。另外，对流体聚合物悬浮体进行冷冻/解冻稳定性试验(3个循环)。该流体聚合物悬浮体仍然是稳定且可流动的。
                表1：详细的悬浮体组合物
Figure S2006800461054D00041
                    表2：长期粘度稳定性
 布氏粘度   悬浮体1cPs   悬浮体2cPs   悬浮体3cPs   悬浮体4cPs
  T0   1570   1660   2040   805
  1-星期   1600   1690   2120   -
  2-星期   1560   1690   2140   -
  3-星期   1620   1690   2120   -
  6-星期   1620   1690   2140   -
以下实施例说明本发明的这类悬浮体在完井液和低温油井水泥浆组合物中的典型性能。
在完井液中的应用
通过将2.8lb/bbl(0.8重量％)当量的干燥HEC溶于NaCl饱和盐水中，对悬浮体3(Natrosol
Figure S2006800461054D00051
HIVIS HEC悬浮体)相对于其前体的增稠效率进行评价。首先，通过将360克NaCl溶解于1000mL去离子水中来制备NaCl饱和盐水。然后，将2.8克干燥的HEC或14.0克原样的悬浮体3加入420克NaCl饱和水溶液中，同时在Hamilton Beach混合器上混合(～11,500rpm)。为了加速聚合物的水合，将1mL 10％的NaOH溶液加入聚合物溶液中以提高pH。为了减少/消除过多的泡沫，加入几滴消泡剂(Advantage
Figure S2006800461054D00052
A96消泡剂，购自Hercules公司)。将溶液混合经过90分钟的时间。然后，在25℃水浴中静态老化16小时后，进行Fann流变学以及滤失性能的测量。
表3中的数据表明，当以相同活性物剂量用于NaCl饱和水溶液中时，悬浮体3(实施例2)的性能稍微好于其干燥的前体(对比例1)。对于悬浮体，Fann表观粘度和屈服点性能较高，而滤失较低(较好)。
表3：NaCl饱和盐水的流变和滤失特性
Figure S2006800461054D00061
从表3可以看出，本发明主题HEC的含水悬浮体是完井液/修井液的有效增稠剂和降滤失剂。
在油井水泥浆中的应用
以下实施例对在低温油井水泥浆组合物中的HEC含水悬浮体(1&2，相应的)的性能进行说明。以相当的活性物含量将悬浮体的性能与其相应的干燥前体进行比较。
油井水泥浆使用通常工业中所采用的、如美国石油学会(API)推荐的添加剂和混合/配制技术进行配制。浆料组合物中的所有添加剂的浓度(实施例3-6)都是基于水泥的重量(bwoc)。
油井水泥浆通过将水泥干燥混合物加入混合水中、以及在最后加入降滤失剂(FLAC)来制备。该干燥混合物由600克Cemoil G水泥、3.3克浓缩的萘磺酸钠盐分散剂(Lomar
Figure S2006800461054D00071
D水泥分散剂，购自Cognis)(0.55重量％bwoc)和2.7克干燥的FLAG(0.45重量％bwoc)组成。因为其低Mw，所以以较高剂量使用Natrosol
Figure S2006800461054D00072
250LR HEC(4.8克或0.80％bwoc)。就FLAC悬浮体(悬浮体1&2)的对比试验而言，在添加干燥混合物前将聚合物悬浮体加入混合水中。在整个制备中，添加几滴消泡剂(Advantage
Figure S2006800461054D00073
A96消泡剂，购自Hercules公司)以减少水泥浆过多的泡沫。
在相对低的温度下进行油井水泥浆的流变和降滤失性能试验。典型地，“混合流变行为”用Fann型粘度计在室温约27℃(～80℉)下在浆液刚刚制备后进行测量，以模拟在地面上的混合和泵入，而“API流变行为”在27℃(80℉)下对浆液调理20分钟后进行测量。降滤失性能在27℃(80℉)下调理浆液后测量。
表4中的数据显示FLAC悬浮体提供了优异的降滤失性能。滤液体积相当于其相应的干燥前体。有趣的是发现，悬浮体2甚至在较高剂量也比悬浮体1提供了在具有显著的降滤失性能下更低的流变。
表4：水泥浆的对比流变行为和滤失性能
Figure S2006800461054D00081
从表4可见，本发明主题的FLAG悬浮体(悬浮体1&2)是油井水泥浆的有效降滤失剂。
尽管本发明已经通过在各种条件下的实践中推测的某些实施方案或变更进行了描述、公开、说明和显示，但其不意味也不应认为本发明的保护范围因此受到限制，并且特别保留可作为在此的教导所暗示的这种其它变更或实施方案，尤其是当其落入本发明所附权利要求书的外延和范围内时。

Claims (27)

1.一种悬浮体组合物，其包括： 
a)选自以下组中的油田维护液：钻井液、完井液或修井液、压裂液和油井固井液，和 
b)流体聚合物悬浮体，其包含悬浮于磷酸钾化合物水溶液中的水溶性聚合物，其中所述水溶性聚合物选自以下组中：水溶性多糖和合成聚合物，其中所述磷酸钾化合物选自以下组中：磷酸钾、磷酸氢二钾K2HPO4、磷酸三钾K3PO4、2:1的磷酸二氢钾KH2PO4和磷酸钾盐KH5(PO4)2、及它们的混合物，并且， 
其中所述磷酸钾化合物占流体聚合物悬浮体的10-40重量%，和 
其中所述水溶性聚合物占流体聚合物悬浮体的5-50重量%。 
2.权利要求1的悬浮体组合物，其还包含稳定剂。 
3.权利要求2的悬浮体组合物，其中所述稳定剂选自以下组中：羧甲基纤维素CMC、黄原胶、及它们的混合物。 
4.权利要求1的悬浮体组合物，其中所述水溶性聚合物是水溶性多糖。 
5.权利要求4的悬浮体组合物，其中所述水溶性多糖选自以下组中：纤维素醚、瓜尔胶和瓜尔胶衍生物。 
6.权利要求5的悬浮体组合物，其中所述水溶性多糖是纤维素醚。 
7.权利要求5或6的悬浮体组合物，其中所述纤维素醚选自以下组中：羟乙基纤维素HEC、甲基纤维素MC、羟丙基纤维素HPC、乙基羟乙基纤维素EHEC、甲基羟乙基纤维素MHEC、疏水改性的羟乙基纤维素HMHEC、疏水改性的乙基羟乙基纤维素HMEHEC、疏水改性的甲基羟乙基纤维素HMMHEC、乙基纤维素EC、甲基羟丙基纤维素MHPC、和羧甲基羟乙基纤维素CMHEC。 
8.权利要求4的悬浮体组合物，其中所述磷酸钾化合物包含磷酸氢二钾K2HPO4。 
9.权利要求8的悬浮体组合物，其中所述水溶性聚合物包含HEC。 
10.权利要求1的悬浮体组合物，其中所述合成聚合物包含聚乙烯醇PVA。 
11.权利要求9的悬浮体组合物，其中所述悬浮体组合物还包含有效量的稳定剂，其中所述稳定剂选自以下组中：羧甲基纤维素CMC、黄原胶、及它们的混合物。 
12.权利要求10的悬浮体组合物，其中所述悬浮体组合物还包含有效量的稳定剂，其中所述稳定剂选自以下组中：羧甲基纤维素CMC、黄原胶、及它们的混合物。 
13.权利要求1的悬浮体组合物，其中所述磷酸钾化合物占流体聚合物悬浮体的20-30重量%。 
14.权利要求13的悬浮体组合物，其中所述磷酸钾化合物占流体聚合物悬浮体的25重量%。 
15.权利要求1的悬浮体组合物，其中所述水溶性聚合物占流体聚合物悬浮体的10-40重量%。 
16.权利要求15的悬浮体组合物，其中所述水溶性聚合物占流体聚合物悬浮体的20-25重量%。 
17.权利要求9的悬浮体组合物，其中磷酸氢二钾K2HPO4占流体聚合物悬浮体的10-40重量%，并且其中HEC占组合物悬浮体的5-50重量%。 
18.权利要求17的悬浮体组合物，其中磷酸氢二钾K2HPO4占流体聚合物悬浮体的20-30重量%，并且其中HEC占流体聚合物悬浮体的10-40重量%。 
19.权利要求18的悬浮体组合物，其中磷酸氢二钾K2HPO4占流体聚合物悬浮体的25重量%，并且其中HEC占流体聚合物悬浮体的20-25重量%。 
20.权利要求17的悬浮体组合物，其还包含稳定剂，其中所述稳定剂选自以下组中：羧甲基纤维素CMC、黄原胶、藻酸钠、及它们的混合物，并且其中所述稳定剂占流体聚合物悬浮体的至多2重量%。 
21.权利要求20的悬浮体组合物，其中所述稳定剂占流体聚合物悬浮体的至多1重量%。 
22.权利要求21的悬浮体组合物，其中所述稳定剂占流体聚合物悬浮体的至多0.5重量%。 
23.权利要求19的悬浮体组合物，其还包含稳定剂，其中所述稳定剂选自以下组中：羧甲基纤维素CMC、黄原胶、藻酸钠、及它们的混合物，并且其中所述稳定剂占流体聚合物悬浮体的至多0.5重量%。 
24.权利要求1的悬浮体组合物，其中所述油田维护液是钻井液。 
25.权利要求1的悬浮体组合物，其中所述油田维护液是完井液或修井液。 
26.权利要求1的悬浮体组合物，其中所述油田维护液是油井固井液。 
27.权利要求1的悬浮体组合物，其中所述油田维护液是压裂液。 
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