CN115322764B - 一种抗高温缓阻泡排剂及其制备方法 - Google Patents
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Abstract
本发明公开了一种抗高温缓阻泡排剂及其制备方法。其原料组成及各组分质量百分含量为:发泡剂主剂15‑60%,稳泡剂1‑10%,金属螯合剂0.02‑0.5%;发泡剂主剂包括至少一种阴离子表面活性剂和至少一种非离子表面活性剂。优点是:通过添加金属螯合剂,既能解决阴离子与现场水不配伍,发挥其最佳发泡性能,又能起到缓垢作用。通过阴离子和非离子表面活性剂的协同增效作用,改性含氟表面活性剂优异的抗温性能,改性硅树脂聚醚能增强液膜抗压能力,提高液膜结构稳定性,赋予泡沫良好的弹性和自修复能力,从而达到良好的稳泡效果。该泡排剂在深层页岩气井开采中后期,排采动液面接近井底,高温高钙镁离子的环境中起泡、稳泡、携液能力均能满足排采需求。
Description
技术领域
本发明涉及一种深层页岩气井泡排剂及其制备方法,具体地说是一种抗高温缓阻泡排剂及其制备方法,属于页岩气开发排采工艺技术领域。
背景技术
随着页岩气井的深度开发,气藏压力逐渐衰减,井筒中气体流速逐渐降低,气井无法实现自喷,地层产水无法带出地面,气井井筒内不断积水,造成油压与产量下降,因此,需要采取多种措施排出井底积液,从而提高页岩气井的采收率;其中,开采中使用的泡排剂种类繁多,机理复杂,加之每个工区具体工况、地层温度、压力、地层水质、矿化度等不同,对泡排剂的使用效果有很大影响,所以每个地区使用的泡排剂都存在一定的局限性,一般泡排剂在深井的泡排措施效果不明显,无法满足现场施工需求。
经过实践表明,表征矿化度中各类金属离子对泡排剂的影响差异较大,有研究表明钙镁等二价金属离子对泡沫性能影响远大于其他离子,矿化度含量并不能作为抗盐性能的直接指标。且二价金属离子易结垢,固相含量对泡沫稳定性具有较强的破坏作用。
泡排剂实质上是一种表面活性剂体系,能有效改善液体表面张力,按照有效成分主要分为阴离子型、阳离子型、两性离子型、非离子型和特殊型表面活性剂等。目前市场上泡排剂的室内评价在100℃以下、矿化度100000mg/L的样品中能起到良好的发泡效果,但是当井深超过3500米、井底温度超过120℃的深层页岩气井上应用效果不佳。因为目前行业内无高温泡排剂统一检验标准,所以现有泡排剂实际运用情况与室内实验数据存在较大差距。针对高温高钙镁离子含量地层环境,急需研制一种针对性的抗高温缓阻泡排剂。
发明内容
本发明要解决的技术问题是提供一种起泡、稳泡和携液性能强,具有耐高温、抗高钙镁离子含量且具有一定缓阻性能的页岩气井泡排剂及其制备方法。
为了解决上述技术问题,本发明的页岩气井泡排剂,原料组成及各组分质量百分含量为:发泡剂主剂15-60%,稳泡剂1-10%,金属螯合剂0.02-0.5%;所述发泡剂主剂包括至少一种阴离子表面活性剂和至少一种非离子表面活性剂。
所述阴离子表面活性剂为脂肪醇聚氧乙烯醚硫酸盐、α—烯基磺酸盐、十二烷基硫酸钠中的一种或几种。
所述非离子表面活性剂为改性含氟表面活性剂。
所述改性含氟表面活性剂由聚氧乙烯醚、2-溴异丁酰溴、N,N’-二乙基丙烯酰胺、4-二甲氨基吡啶(DMAP)、有机胺、全氟己基磺酸钠材料制成。
所述改性含氟表面活性剂的制作方法为:
将聚氧乙烯醚、2-溴异丁酰溴按物质的量比1:2在0℃冰浴和N2保护下,在有机胺和4-二甲氨基吡啶催化下酯化反应2-4小时,再加入与2-溴异丁酰溴同等物质的量的N,N’-二乙基丙烯酰胺,通N230-60分钟后加入金属催化剂和有机胺,在55-85℃条件下与酯化后的产物进行接枝改性1-2小时,最终产物即为改性含氟表面活性剂。
所述改性含氟表面活性剂的具体改性流程如下:
所述稳泡剂为改性硅油树脂聚醚、聚乙二醇中的一种或几种;
所述金属螯合剂为乙二胺四乙酸二钠、酒石酸钠中的一种或几种。
一种如上述泡排剂的制备方法,包括以下步骤:
步骤A:将去离子水加热至55-65℃,添加发泡剂主剂混合物,低速搅拌0.2-0.5小时;
步骤B:在步骤A中添加稳泡剂,并逐渐增加搅拌速度,低速搅拌0.2-0.5小时;
步骤C:在步骤B中添加金属螯合剂;
步骤D:将步骤C所制混合物置于容器中,于40-50℃低速搅拌0.2-0.5小时,降温冷却即可。
本发明的优点在于:
通过理论和大量实验数据证明阴离子表面活性剂和含氟类表面活性剂具有良好的抗温性,阴离子型表面活性剂起泡能力最好,但抗电解质能力较差,高钙镁离子含量下会与水中的多价阳离子生成沉淀,本发明通过添加金属螯合剂,既能解决阴离子与现场水不配伍,发挥其最佳发泡性能,又能起到缓垢作用。
通过阴离子和非离子表面活性剂的协同增效作用,改性含氟表面活性剂优异的抗温性能,改性硅树脂聚醚能增强液膜抗压能力,提高液膜结构稳定性,赋予泡沫良好的弹性和自修复能力,从而达到良好的稳泡效果。按照一定比例复配所制备的泡排剂具有耐高温环境(150℃以内)、耐高钙镁离子含量(总量3000mg/L)并且该泡排剂具有优异的泡沫综合性能和阻垢性能,适合于深层高温高钙镁离子页岩气井;该泡排剂在深层页岩气井开采中后期,排采动液面接近井底,高温高钙镁离子的环境中起泡、稳泡、携液能力均能满足排采需求。
具体实施方式
下面结合具体实施方式,对本发明的页岩气井泡排剂及其制备方法作进一步详细说明。
实施例一:
本实施例的页岩气井泡排剂,通过单剂评价及复配正交实验,实验结果表明,其原料组成及各组分质量百分含量为:发泡剂主剂51%(阴离子表面活性剂34%,非离子表面活性剂17%),稳泡剂5%,金属螯合剂0.1%,余量为去离子水,发泡剂主剂包括阴离子表面活性剂和非离子表面活性剂。
上述发泡剂主剂中,优选的,阴离子表面活性剂为脂肪醇聚氧乙烯醚硫酸盐,非离子表面活性剂为改性含氟表面活性剂;
上述稳泡剂中,优选的,所述稳泡剂为改性硅油树脂聚醚;
上述金属螯合剂中,优选的,所述金属螯合剂为乙二胺四乙酸二钠。
实施例二:
本实施例的页岩气井泡排剂,其原料组成及各组分质量百分含量为:发泡剂主剂51%(阴离子表面活性剂17%,非离子表面活性剂34%),稳泡剂5%,金属螯合剂0.1%,余量为去离子水,发泡剂主剂包括阴离子表面活性剂和非离子表面活性剂。
上述发泡剂主剂中,优选的,阴离子表面活性剂为脂肪醇聚氧乙烯醚硫酸盐,非离子表面活性剂为改性含氟表面活性剂;
上述稳泡剂中,优选的,所述稳泡剂为改性硅油树脂聚醚;
上述金属螯合剂中,优选的,所述金属螯合剂为乙二胺四乙酸二钠。
实施例三:
本实施例的页岩气井泡排剂,其原料组成及各组分质量百分含量为:发泡剂主剂51%(阴离子表面活性剂25.5%,非离子表面活性剂25.5%),稳泡剂5%,金属螯合剂0.1%,余量为去离子水,发泡剂主剂包括阴离子表面活性剂和非离子表面活性剂。
上述发泡剂主剂中,优选的,阴离子表面活性剂为脂肪醇聚氧乙烯醚硫酸盐,非离子表面活性剂为改性含氟表面活性剂;
上述稳泡剂中,优选的,所述稳泡剂为改性硅油树脂聚醚;
上述金属螯合剂中,优选的,所述金属螯合剂为乙二胺四乙酸二钠。
实施例四:
本实施例的页岩气井泡排剂,其原料组成及各组分质量百分含量为:发泡剂主剂51%(阴离子表面活性剂25.5%,非离子表面活性剂25.5%),稳泡剂5%,金属螯合剂0.1%,余量为去离子水,发泡剂主剂包括阴离子表面活性剂和非离子表面活性剂。
上述发泡剂主剂中,优选的,阴离子表面活性剂为脂肪醇聚氧乙烯醚硫酸盐,非离子表面活性剂为改性含氟表面活性剂;
上述稳泡剂中,优选的,所述稳泡剂为聚乙二醇;
上述金属螯合剂中,优选的,所述金属螯合剂为乙二胺四乙酸二钠。
实施例五:
本实施例的页岩气井泡排剂,其原料组成及各组分质量百分含量为:发泡剂主剂51%(阴离子表面活性剂25.5%,非离子表面活性剂25.5%),稳泡剂5%,金属螯合剂0.1%,余量为去离子水,发泡剂主剂包括阴离子表面活性剂和非离子表面活性剂。
上述发泡剂主剂中,优选的,阴离子表面活性剂为脂肪醇聚氧乙烯醚硫酸盐,非离子表面活性剂为改性含氟表面活性剂;
上述稳泡剂中,优选的,所述稳泡剂为改性硅油树脂聚醚;
上述金属螯合剂中,优选的,所述金属螯合剂为酒石酸钠。
上述任一实施例均采用如下制备方法进行制备,它包括以下步骤:
步骤A:将去离子水加热至55-65℃,添加发泡剂主剂混合物,低速搅拌0.2-0.5小时;
步骤B:在步骤A中添加稳泡剂,并逐渐增加搅拌速度,低速搅拌0.2-0.5小时;
步骤C:在步骤B中添加金属螯合剂;
步骤D:将步骤C所制混合物置于容器中,于40-50℃低速搅拌0.2-0.5小时,降温冷却即可。
下面针对上述实施例一、实施例二、实施例三提供的泡排剂在不同温度和矿化度条件下的初始起泡体积V0、泡沫半衰期t1/2以及气流量为8L/min时15min的携液量进行了测试,并在相同测试条件下与东胜区块现场所用的广友生产的泡排剂和润达公司生产的泡排剂的性能进行了对比。
测试过程中所用的仪器为高温高压泡沫稳定仪(海安石油仪器有限公司定制);测试用水为:1、根据现场页岩气井产出水进行分析后,采用NaCl、CaCl2、MgCl2、KCl、Na2SO4、NaHCO3进行配制得到的,矿化度为50000~200000mg/L;2、钙镁离子矿化水采用CaCl2和MgCl2按现场页岩气井产出水中的比例配制得到,浓度为1000-3000mg/L;3、现场页岩气井产出水(平均矿化度为70000mg/L)。
具体测试方法如下所述:
1、泡排剂的发泡性与稳泡性测试:
先将评价装置内温度升至指定测试温度;
再将上述泡排剂配制成0.5%浓度200mL溶液,并将溶液注入实验装置;
将装置压力升至2MPa(氮气),记录初始起泡体积V0与5min后起泡体积。
2、泡排剂的携液量测试:
先将评价装置内温度升至指定测试温度;
再将上述泡排剂配制成1%浓度250mL溶液,并将溶液注入实验装置;
将氮气以5L/min的速度泵入实验装置内,收集并记录15min的携液量。
3、泡排剂的缓阻性能测试:
本实验采用Q/SHCG0133-2021《油田水处理用防垢剂技术要求》中6.6.2抑制碳酸钙垢性能中步骤实验,其中实验标准水样用现场页岩气井产出水替代。
表1:不同温度下各种泡排剂在50000mg/L模拟矿化水中的性能对比
表2:不同矿化度下各种泡排剂的性能对比(120℃)
表3:不同钙镁离子浓度水中各种泡排剂的性能对比(120℃)
表4:各种泡排剂的缓阻性能对比(现场页岩气井产出水)
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该泡排剂适应150℃、矿化度200000mg/L、钙镁离子3000mg/L的页岩气储层,综合能力比现场使用的泡排剂提升20%以上,且具有一定缓阻性能,在高温、高钙镁离子含量页岩气深井中具有良好的起泡、稳泡和携液能力,该泡排剂在页岩气后期排采中具有广阔的应用前景。
Claims (5)
1.一种页岩气井泡排剂,其特征在于:其原料组成及各组分质量百分含量为:发泡剂主剂15-60%,稳泡剂1-10%,金属螯合剂0.02-0.5%,余量为去离子水,所述发泡剂主剂包括至少一种阴离子表面活性剂和至少一种非离子表面活性剂;非离子表面活性剂为改性含氟表面活性剂;所述改性含氟表面活性剂由聚氧乙烯醚、2-溴异丁酰溴、N,N’-二乙基丙烯酰胺、4-二甲氨基吡啶、有机胺、全氟己基磺酸钠材料制成;所述改性含氟表面活性剂的制备方法为:
将聚氧乙烯醚、2-溴异丁酰溴按物质的量比1:2在0℃冰浴和N2保护下,在有机胺和4-二甲氨基吡啶催化下酯化反应2-4小时,再加入与2-溴异丁酰溴同等物质的量的N,N’-二乙基丙烯酰胺,通N230-60分钟后加入金属催化剂和有机胺,在55-85℃条件下与酯化后的产物进行接枝改性1-2小时,最终产物即为改性含氟表面活性剂。
2.按照权利要求1所述的页岩气井泡排剂,其特征在于:所述阴离子表面活性剂为脂肪醇聚氧乙烯醚硫酸盐、α—烯基磺酸盐、十二烷基硫酸钠中的一种或几种。
3.按照权利要求1所述的页岩气井泡排剂,其特征在于:所述稳泡剂为改性硅油树脂聚醚、聚乙二醇中的一种或几种。
4.按照权利要求1所述的页岩气井泡排剂,其特征在于:所述金属螯合剂为乙二胺四乙酸二钠、酒石酸钠中的一种或几种。
5.一种如权利要求1-4之一所述页岩气井泡排剂的制备方法,其特征在于,包括以下步骤:
步骤A:将去离子水加热至55-65℃,添加发泡剂主剂混合物,低速搅拌0.2-0.5小时;
步骤B:在步骤A中添加稳泡剂,并逐渐增加搅拌速度,低速搅拌0.2-0.5小时;
步骤C:在步骤B中添加金属螯合剂;
步骤D:将步骤C所制混合物置于容器中,于40-50℃低速搅拌0.2-0.5小时,降温冷却即可。
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