CN115074105A - 页岩油勘探开发中储层的杀菌除硫化氢方法 - Google Patents
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- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 5
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical group NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 4
- 239000010779 crude oil Substances 0.000 description 4
- 238000011010 flushing procedure Methods 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical group O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
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- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
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Abstract
本发明提供了一种页岩油勘探开发中储层的杀菌除硫化氢方法。该方法包括:在页岩油的体积压裂作业过程中,将杀菌除硫化氢压裂液注入储层,以对页岩勘探开发中油井筒、近井筒区域及储层深部进行杀菌和/或除硫化氢。其中,杀菌除硫化氢压裂液包括稠化剂、杀菌除硫化氢药剂、pH调节剂、破胶剂及水;杀菌除硫化氢药剂为亚氯酸钠。应用本发明的技术方案,可实现井筒、近井筒区域及储层深部中硫化氢、硫酸盐还原菌的有效去除与杀灭,从而达到了对页岩油油气井生产过程中储层深部硫化氢的更有效地清除,治理硫化氢的效果更好,且硫化氢治理保持期较长,进一步避免了硫化氢对井下设备的腐蚀。
Description
技术领域
本发明涉及页岩油勘探开发技术领域,具体而言,涉及一种页岩油勘探开发中储层的杀菌除硫化氢方法。
背景技术
石油与天然气作为一种化石能源,对我国工业发展、国防建设具有重要的支撑作用。在石油的勘探开发过程中,随着钻井、压裂等作业的实施易使储层中原生或次生的硫化氢通过地层-井筒运移到地面,其中,储层中原生硫化氢由地壳产生,次生硫化氢由开发作业中生成的硫酸盐还原菌产生。
由于硫化氢是一种有毒气体,在油气井生产过程中对井下设备及人员安全造成威胁,因此急需对油气井生产过程中产生的硫化氢进行治理。国内外对硫化氢治理技术的研究主要有物理法、生物法和化学法。目前,针对油气井生产阶段产生的硫化氢,主要是采用地面除硫方式,地面除硫工艺可以消除硫化氢对人员的伤害,但无法避免硫化氢对井下管柱的腐蚀伤害,且地面除硫工艺需要配备相应的地面加药泵、吸收塔等相关设备增加了治理成本和管理难度。
中国专利CN208486868U公开了一种油井套管喷雾脱除硫化氢的装置,该装置由外筒、活动喷雾管、前进机构、后退机构、定位机构和进液闸阀组成。该装置是在洗井过程中,将具有喷雾功能的喷头伸入油套环空,利用洗井泵车提供的具有一定动能的含脱硫剂洗井液经喷头雾化,在油套环空内形成细小的雾滴,增大气液接触面积,从而实现气相硫化氢的彻底去除。但是,该方法对储层中原生的硫化氢及储层中次生的生成硫化氢的硫酸盐还原菌未能从源头上消除,且在洗井作业后,储层中的硫化氢依然会通过地层-井筒运移到地面,其硫化氢治理保持期较短。
中国专利CN108643882A公开了一种原油中硫化氢的消除方法,该方法将脱硫剂制成固体脱硫棒体并将若干个该固体脱硫棒体从进口加入井内,使固体脱硫棒之间形成原油和天然气的多孔通道,当原油出井时,使固体脱硫棒与原油接触发生反应。该固体脱硫棒的原料是,一二乙基乙醇胺、碳酸钠、三乙醇胺、聚丙烯酞胺。该方法可实现硫化氢在井筒中的消除,且不需要添加地面设备。但是,该方法在处理产液量较大的页岩油油井时,由于井筒中流体的高速流动,使固体脱硫棒在井筒中无法形成稳定的多孔通道,会降低脱硫棒的脱硫效果。且页岩油粘度较高,脱硫棒形成的多孔通道易被页岩油封堵,无法实现硫化氢与脱硫棒的有效接触,硫化氢去除效果差。
页岩油是油藏中的一种特殊类型,在页岩油勘探开发中,现有的除硫化氢技术对页岩油储层深部中原生和次生的硫化氢去除率较低,且硫化氢治理保持期较短。因此,如何针对页岩油储层进行更有效地硫化氢治理,是一个亟需解决的问题。
发明内容
本发明的主要目的在于提供一种页岩油勘探开发中储层的杀菌除硫化氢方法,以解决现有技术中对页岩油储层深部中原生和次生的硫化氢去除率较低,且硫化氢治理保持期较短的问题。
为了实现上述目的,根据本发明的一个方面,提供了一种页岩油勘探开发中储层的杀菌除硫化氢方法,在页岩油的体积压裂作业过程中,将杀菌除硫化氢压裂液注入储层,以对页岩勘探开发中油井筒、近井筒区域及储层深部进行杀菌和/或除硫化氢;其中,杀菌除硫化氢压裂液包括稠化剂、杀菌除硫化氢药剂、pH调节剂、破胶剂及水;杀菌除硫化氢药剂为亚氯酸钠。
进一步地,按重量百分比计,杀菌除硫化氢压裂液中稠化剂的含量为0.01~0.5wt%、pH调节剂的含量为0.001~0.02wt%、破胶剂的含量为0.08~0.5wt%、杀菌除硫化氢药剂的含量为0.05~0.5wt%。
进一步地,稠化剂为胍胶、聚丙烯酰胺类聚合物中的一种。
进一步地,破胶剂为过硫酸钠和/或过硫酸铵。
进一步地,pH调节剂为乳酸、盐酸、醋酸、氢氧化钠中的一种或多种。
进一步地,储层中的硫化氢含量为10~1000ppm。
进一步地,储层中的硫化氢为硫酸盐还原菌代谢产生的硫化氢,和/或地壳产生的硫化氢。
应用本发明的技术方案,可实现井筒、近井筒区域及储层深部中硫化氢、硫酸盐还原菌的有效去除与杀灭,从而达到了对页岩油油气井生产过程中储层深部硫化氢的更有效地清除,治理硫化氢的效果更好,硫化氢治理保持期大于12个月,进一步避免了硫化氢对井下设备的腐蚀。而且,本发明无需长期投用地面附加设备,只需在页岩油的体积压裂作业过程中,利用液体传压的原理,将杀菌除硫化氢压裂液压入储层裂缝及孔隙中,即可完成杀菌除硫化氢操作,成本更低,操作更便捷。另外,本发明所使用的杀菌除硫化学药剂亚氯酸钠对压裂液、压裂设备、储层等均不产生不利影响,可满足页岩油体积压裂需求。
具体实施方式
需要说明的是,在不冲突的情况下,本申请中的实施例及实施例中的特征可以相互组合。下面将结合实施例来详细说明本发明。
正如背景技术部分所描述的,现有技术中对页岩油储层深部中原生和次生的硫化氢去除率较低,且硫化氢治理保持期较短。为了解决这一问题,本发明提供了一种页岩油勘探开发中储层的杀菌除硫化氢方法,在页岩油的体积压裂作业过程中,将杀菌除硫化氢压裂液注入储层,以对页岩勘探开发中油井筒、近井筒区域及储层深部进行杀菌和/或除硫化氢;其中,杀菌除硫化氢压裂液包括稠化剂、杀菌除硫化氢药剂、pH调节剂、破胶剂及水;杀菌除硫化氢药剂为亚氯酸钠。
在页岩油的勘探开发过程中,随着钻井、压裂等作业的实施易使储层中原生和次生的硫化氢通过地层-井筒运移到地面。其中,储层中的原生硫化氢主要由地壳产生,次生硫化氢主要由开发作业中生成的硫酸盐还原菌产生。本发明通过在压裂液中加入杀菌除硫化氢药剂亚氯酸钠,继而在体积压裂作业过程中加入上述压裂液使其进入储层深部,在完成体积压裂作业的同时达到杀菌除硫化氢的目的。一方面,杀菌除硫化氢药剂可以杀灭储层深部的硫酸盐还原菌,从源头上消除次生的硫化氢。另一方面,杀菌除硫化氢药剂可以与硫化氢反应生成钠盐和硫磺,进一步实现原生和次生硫化氢的有效去除。基于此,本发明可实现井筒、近井筒区域及储层深部中硫化氢、硫酸盐还原菌的有效去除与杀灭,从而达到了对页岩油油井生产过程中储层深部硫化氢的更有效地去除,避免了硫化氢对井下设备的腐蚀。且本发明无需长期投用地面附加设备,只需在页岩油的体积压裂作业过程中,利用液体传压的原理,将杀菌除硫化氢压裂液注入储层,即可完成杀菌除硫化氢操作,成本更低,操作更便捷。另外,本发明所使用的杀菌除硫化学药剂亚氯酸钠对压裂液、压裂设备、储层等均不产生不利影响,可满足页岩油体积压裂需求。
总之,本发明在满足页岩油体积压裂需求的基础上,可实现储层深部原生和次生硫化氢的有效去除,治理硫化氢效果更好,在页岩油储层压裂作业后,井口取样口检测到的硫化氢体积浓度<10ppm,且硫化氢治理保持期大于12个月。
具体地,在页岩油的体积压裂作业过程中,地面设置有高压大排量的泵组,其作业压力为60~90MPa,利用液体传压的原理,即可将前述杀菌除硫化氢压裂液以大于储层的吸收能力的压力向储层中注入,前述杀菌除硫化氢压裂液在页岩油井底憋起高压,在储层深部形成人工裂缝,从而促使前述杀菌除硫化氢压裂液可通过储层中的人工裂缝与天然裂缝进入储层深部,进而实现对储层深部中原生及次生硫化氢的有效消除。
优选地,按重量百分比计,杀菌除硫化氢压裂液中稠化剂的含量为0.01~0.5wt%、pH调节剂的含量为0.001~0.02wt%、破胶剂的含量为0.08~0.5wt%、杀菌除硫化氢药剂的含量为0.05~0.5wt%。在此范围内,可以促使各个组分的性能得以更好地发挥,同时协同效果更好。从而可以更好地平衡杀菌除硫化氢药剂的除硫化氢作用和页岩油体积压裂需求,从而达到了对页岩油油井生产过程中储层深部硫化氢的更有效地清除。
基于促使杀菌除硫化氢压裂液在满足页岩油体积压裂需求的基础上,杀菌除硫化氢效果更好的目的,优选杀菌除硫化氢药剂和稠化剂的重量比为(10~2):1。
优选地,稠化剂可以为本领域常规稠化剂,这是本领域技术人员可以自行选择的,在此不多赘述。更优选地,稠化剂为聚丙烯酰胺类聚合物。在满足页岩油体积压裂需求的基础上,稠化剂和杀菌除硫化氢药剂的协同作用更佳,能更大程度上地发挥杀菌除硫化氢药剂的除硫化氢的作用。在一种优选的实施方案中,破胶剂为过硫酸钠和/或过硫酸铵。
优选地,pH调节剂为乳酸、盐酸、醋酸、氢氧化钠中的一种或多种。pH调节剂选自上述种类,可以和稠化剂的协同增效作用更佳,并且可以调节压裂液体系的pH在6.0~10.0,从而杀菌除硫化氢药剂的除硫化氢效果更佳。
优选地,杀菌除硫化氢压裂液中可选地还包括交联剂,优选交联剂为硼砂、有机硼、有机锆中的一种或多种,更优选交联剂的用量为压裂液的0.1~2%。这样,能够更好的平衡压裂液的压裂需求和杀菌除硫化氢药剂的除硫化氢的作用。
在一种优选的实施方案中,页岩油勘探开发中储层中的硫化氢含量为10~1000ppm。本发明的杀菌除硫化氢压裂液可以杀灭储层深部的硫酸盐还原菌,从源头上消除次生的硫化氢。同时还可以与硫化氢反应生成钠盐和硫磺,进一步实现原生和次生硫化氢的有效去除。
在一种优选的实施方案中,储层中的硫化氢为硫酸盐还原菌代谢产生的硫化氢,或者为地质、热化学作用形成的硫化氢。
以下结合具体实施例对本申请作进一步详细描述,这些实施例不能理解为限制本申请所要求保护的范围。
实施例1
杀菌除硫化氢压裂液配方,总计为100份,以重量百分比计,包括下列成分:
水 | 99.389wt% |
胍胶 | 0.15wt% |
pH调节剂盐酸 | 0.001wt% |
过硫酸钠 | 0.01wt% |
亚氯酸钠 | 0.45wt% |
将上述杀菌除硫化氢压裂液在页岩油储层压裂作业中注入储层,作业压力为60MPa,页岩油储层压裂作业后井口取样口检测到的硫化氢体积浓度为0ppm。
实施例2
杀菌除硫化氢压裂液配方,总计为100份,以重量百分比计,包括下列成分:
水 | 99.32wt% |
胍胶 | 0.15wt% |
pH调节剂醋酸 | 0.02wt% |
亚氯酸钠 | 0.5wt% |
过硫酸钠 | 0.01wt% |
将上述杀菌除硫化氢压裂液在页岩油储层压裂作业中注入储层,作业压力为90MPa,页岩油储层压裂作业后井口取样口检测到的硫化氢体积浓度产出液中的硫化氢浓度为0ppm。
实施例3
杀菌除硫化氢压裂液配方,总计为100份,以重量百分比计,包括下列成分:
水 | 98.499wt% |
胍胶 | 0.3wt% |
pH调节剂氢氧化钠 | 0.001wt% |
亚氯酸钠 | 0.5wt% |
有机硼 | 0.2wt% |
过硫酸铵 | 0.5wt% |
将上述杀菌除硫化氢压裂液在页岩油储层压裂作业中注入储层,作业压力为60MPa,页岩油储层压裂作业后井口取样口检测到的硫化氢体积浓度产出液中的硫化氢浓度为0ppm。
实施例4
杀菌除硫化氢压裂液配方,总计为100份,以重量百分比计,包括下列成分:
水 | 97.58wt% |
胍胶 | 0.6wt% |
pH调节剂乳酸 | 0.02wt% |
亚氯酸钠 | 0.7wt% |
有机锆 | 0.5wt% |
过硫酸铵 | 0.6wt% |
将上述杀菌除硫化氢压裂液在页岩油储层压裂作业中注入储层,作业压力为60MPa,页岩油储层压裂作业后井口取样口检测到的硫化氢体积浓度为10ppm。
对比例1
杀菌除硫化氢压裂液配方,总计为100份,以重量百分比计,包括下列成分:
水 | 98.28wt% |
胍胶 | 0.6wt% |
pH调节剂乳酸 | 0.02wt% |
有机锆 | 0.5wt% |
过硫酸铵 | 0.6wt% |
将上述杀菌除硫化氢压裂液在页岩油储层压裂作业中注入储层,作业压力为90MPa,页岩油储层压裂作业后井口取样口检测到的硫化氢体积浓度为26ppm。
对比例2
和实施例1的区别仅在于将亚氯酸钠等含量替换为甲醛。
将上述杀菌除硫化氢压裂液在页岩油储层压裂作业中注入储层,作业压力为90MPa,页岩油储层压裂作业后井口取样口检测到的硫化氢体积浓度为24ppm。
以上仅为本发明的优选实施例而已,并不用于限制本发明,对于本领域的技术人员来说,本发明可以有各种更改和变化。凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (7)
1.一种页岩油勘探开发中储层的杀菌除硫化氢方法,其特征在于,在页岩油的体积压裂作业过程中,将杀菌除硫化氢压裂液注入储层,以对所述页岩勘探开发中油井筒、近井筒区域及储层深部进行杀菌和/或除硫化氢;
其中,所述杀菌除硫化氢压裂液包括稠化剂、杀菌除硫化氢药剂、pH调节剂、破胶剂及水;所述杀菌除硫化氢药剂为亚氯酸钠。
2.根据权利要求1所述的方法,其特征在于,按重量百分比计,所述杀菌除硫化氢压裂液中所述稠化剂的含量为0.01~0.5wt%、所述pH调节剂的含量为0.001~0.02wt%、所述破胶剂的含量为0.08~0.5wt%、所述杀菌除硫化氢药剂的含量为0.05~0.5wt%。
3.根据权利要求1或2中任一项所述的方法,其特征在于,所述稠化剂为胍胶、聚丙烯酰胺类聚合物中的一种。
4.根据权利要求1或2中任一项所述的方法,其特征在于,所述破胶剂为过硫酸钠和/或过硫酸铵。
5.根据权利要求1或2中任一项所述的方法,其特征在于,所述pH调节剂为乳酸、盐酸、醋酸、氢氧化钠中的一种或多种。
6.根据权利要求1至5中任一项所述的方法,其特征在于,所述储层中的硫化氢含量为10~1000ppm。
7.根据权利要求1至5中任一项所述的方法,其特征在于,所述储层中的硫化氢为硫酸盐还原菌代谢产生的硫化氢,和/或地壳产生的硫化氢。
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