CN115433559B - 使用生态环境友好型粘度稳定剂制备适用于含硫产出水的高温高盐油藏采油用聚丙烯酰胺 - Google Patents
使用生态环境友好型粘度稳定剂制备适用于含硫产出水的高温高盐油藏采油用聚丙烯酰胺 Download PDFInfo
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- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/588—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/84—Compositions based on water or polar solvents
- C09K8/86—Compositions based on water or polar solvents containing organic compounds
- C09K8/88—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/882—Compositions based on water or polar solvents containing organic compounds macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
Abstract
本发明涉及一种使用生态环境友好型粘度稳定剂制备适用于含硫产出水的高温高盐油藏采油用聚丙烯酰胺,该稳定剂选用一种或多种混合的以绿色多元酸螯合剂为基体的有机锌类化合物。选用草酸锌、衣糠酸锌、亚氨基二琥珀酸锌、酒石酸锌、柠檬酸锌、葡萄糖酸锌、有机多元磷酸锌、氨基酸型EDTA‑Zn、NTA‑Zn、DTPA‑Zn、聚羧酸锌、聚膦酸锌中一种或多种。在其应用时,将聚丙烯酰胺和稳定剂有机锌按一定质量占比混合均匀,即得改进型聚丙烯酰胺。
Description
技术领域
本发明属于油田提高采收率技术,具体涉及一种使用生态环境友好型粘度稳定剂制备适用于含硫产出水的高温高盐油藏采油用聚丙烯酰胺。
背景技术
聚合物驱三次采油方法是提高原油采收率的重要方法,成为我国许多油田增产的主要技术。目前油田用聚丙烯酰胺水溶液做驱油剂已在现场上得到广泛应用并取得成功,影响聚合物驱油效果的因素是多方面的,其中聚丙烯酰胺溶液的稳定性是影响聚合物驱效果的主要因素(驱油用聚合物溶液黏度影响因素的研究,孙秀芝,精细石油化工进展,2018,19(3):25-28)。
目前配制聚合物水溶液所用水越来越多采用产出污水。其中的钙镁离子、亚铁离子(基于Fe2+质量浓度变化的聚合物黏度损失影响因素,断块油气田,王刚,2019,26(3):371-374;Fe2+对聚合物的影响及其处理方法研究,陈斌等,石油天然气化工,2014,43(2):168-173)等高价离子及硫离子(S2-离子对凝胶体系成胶影响及检测方法研究,刘家林等,精细石油化工进展,2014,15(4):18-20;还原性物质对低浓度PHPAM溶液性能的影响,鲁红升,西南石油大学学报,2010,32(4):156-159),硫酸还原菌等均会导致粘度降低(污水配制聚合物溶液粘度降低的影响因素研究,樊剑等,油田化学,2011,28(3):250-262)。特别是硫离子与细菌的协同作用,会引起聚合物断链形成低聚物,其又是细菌的营养底物,硫酸还原菌又加速产生硫离子,该过程加剧了聚合物的降解及粘度损失。
文献介绍(注入水水质对聚合物黏度的影响及水质处理剂的筛选,王增林等,油田化学,2019,36(4):681-687;硫离子对聚丙烯酰胺黏度影响机制研究,杜春安,中国石油大学学报,2016,40(5):166-172;埕东油田聚驱过程聚合物黏度影响因素,林翔,油气地面工程,2010,29(3):34-35)要使胜利油田现场配注的聚合物溶液具有较高的粘度,Fe2+/和Fe3+含量最高应分别不超过0.5mg/L和2mg/L,S2-含量应该控制在1mg/L以内,溶解氧含量应控制在0.3mg/L以下。其中硫脲是与聚合物体系配伍性良好的且应用效果最好的除氧剂。200mg/L的硫脲在模拟水和现场水条件下均能保证聚合物体系老化60天的粘度保留率在75%以上。
专利CN101993686B 公布了一种污水配制聚合物溶液粘度保护剂,含10.0-20%的阴离子或非离子表活剂,10.0-20%的有机磷酸,2.0-10%的多元醇,余量为水。通过对油,亚铁离子、硫离子等离子的捕集和掩蔽,以及对聚合物伸展增粘,在矿化度为40g/L的采出污水中,粘度保护剂浓度600mg/L、聚合物浓度为1000mg/L溶液的粘度可以达到15-20mPa.s。
专利CN111517482A 公布了一种油田污水中硫化物控制的方法,通过加入生物硫化物控制剂母液提高配聚粘,将控制剂与油田污水混合后作为稀释聚合物母液用水,粘度损失率控制在20%以内。
专利CN112980417A 公开了一种油田污水配制聚合物溶液粘度保护剂,由螯合阻垢剂、复合细菌培养物和激活剂组成。通过螯合高价离子,抑制硫酸还原菌和硫离子的产生,调控激活剂浓度,改变注聚系统微生物群落结构,从而保证在沿程输送、注聚井注入及油层环境下聚合物溶液粘度均具有较高保留率。
文献介绍(采油污水中保留聚合物对污水配制聚合物溶液黏度的影响,方洪波,油田化学,2021,38(1):173-178)含聚产出水中保留聚合物(r-HPAM)为低分子量(200万左右)、高水解度(46%)的聚合物,用此产出水配制新鲜HPAM溶液,可以降低溶液的粘度损失。污水中的r-HPAM可以作为牺牲剂与二价离子相互作用,抵消这些离子对新配制HPAM溶液粘度的损耗,从而起到保粘、增粘作用。
针对硫化氢对聚合物粘度的影响,目前油田现场防治硫化氢技术主要包括瀑氧法,物理化学吸附法,燃烧法,中和法等(陆梁油田油井H2S综合治理技术分析,魏勇等,油气田环境保护,2015,25(4):24-26)。文献介绍(硫化氢对聚合物粘度的影响及对策,吴运强等,特种油气藏,2008,25(2):76-77;硫离子与部分水解聚丙烯酰胺溶液作用的分子动力学研究,施雷庭,2021,应用化工,1-7)可以用碳酸钠中和处理,可以明显提高聚合物粘度,但是因为硫化氢只是转化成了硫化钠,并没有根本消除具有还原性的硫化物。无机金属化合物除硫剂广泛用于油田污水处理(高含硫油田污水处理技术的试验应用,张雪萍,化工管理,2018,(7):191;复合除硫+絮凝净化处理高含硫气田碱性采出水,工业水处理,惠小敏,2015,35(9):79-81;油田含油污水除硫实验研究,李杰等,化工技术与开发,2015,44(3):11-13;除硫剂性质的热力学研究,徐行同,油田化学,1994,11(3):194-196;几种钻井液用除硫剂脱除硫化氢效果的研究,赵树凯等,钻井液和完井液,2008,25(1):73-75;一种新型无机复合除硫剂的应用,王均,钻井液和完井液,2010,27(2):70-71; 一种新型的锌基硫化氢清除剂,左宏刚,西部探矿工程,2013(1):43-48),但有时并不彻底或者输送过程中又产生新的硫化物。在配制聚合物溶液时,不可避免的导致聚合物粘度下降。
以上方法均取得了一定效果,但也存在一些问题;如消除硫离子影响侧重于掩蔽、生物氧化利用等措施,用药量高,需要单独溶解添加系统,增加现场地面设备。有些化学品,如硫脲具有致癌作用。也很少见对配制好的聚合物溶液在沿程输送与注入过程中的粘度保护措施。
发明内容
本发明针对胜利油田现场存在的问题,提出一种使用生态环境友好型粘度稳定剂制备适用于含硫产出水的高温高盐油藏采油用聚丙烯酰胺。
本发明采用的技术方案是:一种使用生态环境友好型粘度稳定剂制备适用于含硫产出水的高温高盐油藏采油用聚丙烯酰胺,其特征在于:油田油藏条件:TDS大于44000mg/L,钙镁二价离子含量大于2000mg/L,温度大于110度,稳定剂与聚丙烯酰胺混合配置成油田驱油聚合物溶液,稳定剂用量为4.5-5.5%。
所述聚丙烯酰胺优选磺化聚丙烯酰胺,稳定剂与磺化聚丙烯酰胺混合配置成油田驱油聚合物溶液,稳定剂用量为5%。
稳定剂选用一种或多种混合的以绿色多元酸螯合剂为基体的有机锌类化合物。
稳定剂选用草酸锌、衣糠酸锌、亚氨基二琥珀酸锌、酒石酸锌、柠檬酸锌、葡萄糖酸锌、有机多元磷酸锌、氨基酸型EDTA-Zn、NTA-Zn、DTPA-Zn、聚羧酸锌、聚膦酸锌中一种或多种。
进一步地,选用柠檬酸锌。
根据胜利油田现场污水硫化物含量,按比例直接和聚丙烯酰胺干粉复配,从而制备出满足胜利油田高温高盐高渗透非均质四类油藏三次采油调驱用驱油溶液。含稳定剂、聚丙烯酰胺的驱油聚合物溶液在溶解配注过程中,有机锌类化合物是可以发挥类似沉淀型无机除硫剂功能的环保型除硫剂,和产出水中硫化物结合置换,形成硫化锌胶体颗粒,而置换出的多元酸可以螯合部分产出水中的二价钙、镁或铁离子,从而保持聚丙烯酰胺粘度稳定,不受硫离子和减轻金属二价离子的干扰。此类改进型产品可以用现场含硫产出水配制,配注系统连续简单,具有降低地面设备投资,配注过程中,可以很好地保持聚合物粘度,从而有利于起到调驱增油作用。
所用聚丙烯酰胺可以是本领域专业人员熟悉的通过不同乙烯类单体和丙烯酰胺水溶液多元共聚或后水解工艺,经过造粒,干燥,粉碎和制备而来。磺化聚丙烯酰胺干粉可以是本领域专业人员熟悉的由丙烯酰胺、丙烯酸钠、AMPS钠盐共聚而成。
具体实施方式
一种使用生态环境友好型粘度稳定剂制备适用于含硫产出水的高温高盐油藏采油用聚丙烯酰胺,其中稳定剂选用一种或多种混合的以绿色多元酸螯合剂为基体的有机锌类化合物。稳定剂选用草酸锌、衣糠酸锌、亚氨基二琥珀酸锌、酒石酸锌、柠檬酸锌、葡萄糖酸锌、有机多元磷酸锌、氨基酸型EDTA-Zn、NTA-Zn、DTPA-Zn、聚羧酸锌、聚膦酸锌中一种或多种。
在其应用时,将聚丙烯酰胺和稳定剂有机锌按质量占比5%混合均匀,即得改进型聚丙烯酰胺。
以下用实施例、对比例的性能进行评价:
实施例与对比例
针对胜利油田,我们选用磺化聚丙烯酰胺(由丙烯酰胺/丙烯酸钠/AMPS钠盐共聚而成),稳定剂分别选用氧化锌、氯化锌、柠檬酸锌、葡萄糖酸锌、或柠檬酸锌和葡萄糖酸锌的混合。
胜利油田,TDS: 44465mg/L,钙镁二价离子含量2015mg/L,115度, 聚合物浓度2500mg/L。
聚合物:磺化聚丙烯酰胺,分子量:11-15 million。
对比了磺化聚丙烯酰胺加入稳定剂和不加稳定剂的情况,粘度和粘度保留率如下表所示:加入5%的稳定剂能够使聚合物具有抗10mg/L硫离子的能力, 115℃无氧条件下,1个月粘度保留率≥90.0%;115℃无氧条件下,3个月粘度保留率≥80.0%。
另外,需要说明的是,以上实施例描述了实施方式,但是,本发明并不限于此。在本发明的技术构思范围内,可以对本发明的技术方案进行多种简单变型,包括各个技术特征以任何其它的合适方式进行组合,这些简单变型和组合同样应当视为本发明所公开的内容,均属于本发明的保护范围。
Claims (1)
1.一种油田驱油聚合物溶液适用于含硫产出水的高温高盐油藏采油的应用,其特征在于:油藏条件:TDS44465mg/L,钙镁二价离子含量2015mg/L,温度115度,油田驱油聚合物溶液由3%柠檬酸锌、2%葡萄糖酸锌与浓度2500mg/L、分子量1000-1500万的磺化聚丙烯酰胺混合配置成,油田驱油聚合物溶液具有抗10mg/L硫离子的能力,115℃无氧条件下,1个月粘度保留率≥90.0%;115℃无氧条件下,3个月粘度保留率≥80.0%。
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