CN111961162A - 一种可膨胀选择性长效堵水剂及其制备方法 - Google Patents

一种可膨胀选择性长效堵水剂及其制备方法 Download PDF

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CN111961162A
CN111961162A CN202010641393.XA CN202010641393A CN111961162A CN 111961162 A CN111961162 A CN 111961162A CN 202010641393 A CN202010641393 A CN 202010641393A CN 111961162 A CN111961162 A CN 111961162A
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曾斌
徐太平
李栓
周京伟
丁小惠
袁发明
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Jetbeton Petroleum Technology Group Co ltd
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Abstract

本发明公开了一种可膨胀选择性长效堵水剂及其制备方法，包括A、B两组分，所述A组分为聚氨酯预聚体，占堵水剂原料总质量的60％‑85％，所述B组分为1％‑20％亲水性功能性单体、1％‑10％亲水性纳米材料、0.01％‑1％引发剂、0.01％‑5％催化剂、1％‑10％扩链剂与水混合形成的混合溶液，B组分中各原料的含量为单剂在堵水剂原料总质量中所占的比例；所述堵水剂由A、B两组分混合后，聚氨酯预聚体、亲水性功能性单体、亲水性纳米材料在引发剂、催化剂和扩链剂的共同作用下聚合而成。本发明在传统的聚氨酯材料中引入亲水性功能单体和亲水性纳米材料，增强了堵水剂的吸水膨胀型、稳定性和封堵能力，具有堵水不堵油的特点，适用于高含水区块油水井的堵水作业。

Description

一种可膨胀选择性长效堵水剂及其制备方法
技术领域
本发明涉及油田开发技术领域，特别涉及一种可膨胀选择性长效堵水剂及其制备方法。
背景技术
油井出水是油田开发中后期遇到的普遍现象，特别是水驱油田。油井出水不仅会降低产量、加快设备腐蚀，还会导致地层原有结构破坏，加重油井出砂，同时还会增加污水处理量，减缓油田开采进度等。目前，油田的堵水方法主要是机械堵水法和化学堵水法。化学堵水是目前研究最多、最有效的方法。常见有化学堵剂主要有聚丙烯酰胺类的高分子聚合物凝胶、树脂类堵水剂、水泥类堵水剂、无机盐类堵水剂、泡沫堵水剂等。随着油田开采难度的日益增加，现有的化学堵水剂存在很多问题及使用局限，非选择性堵水常常会造成误堵，将水和油同时堵死，沉淀类的堵水剂还会造成严重储层伤害，影响产量。另外，堵水剂的耐盐性差、耐腐蚀性和冲刷性弱等问题，导致堵水剂的有效期短。
发明内容
针对上述问题，本发明旨在提供一种可膨胀选择性长效堵水剂及其制备方法，所述堵水剂可用于油井各种条件下的堵水作业，具有堵水不堵油、弹性好、粘接力强、封堵强度高等优点，具有很好的堵水效果，且堵水有效期长，适用于高含水区块油水井的堵水作业。
本发明的技术方案如下：
一方面，提供一种可膨胀选择性长效堵水剂，包括A、B两组分，所述A组分为聚氨酯预聚体，所述B组分为亲水性功能性单体、亲水性纳米材料、引发剂、催化剂、扩链剂与水混合形成的混合溶液；所述堵水剂由A、B两组分混合后，聚氨酯预聚体、亲水性功能性单体、亲水性纳米材料在引发剂、催化剂和扩链剂的共同作用下聚合而成。
作为优选，各组分的质量百分比如下：聚氨酯预聚体60％-85％、亲水性功能性单体1％-20％、亲水性纳米材料1％-10％、引发剂0.01％-1％、催化剂0.01％-5％、扩链剂1％-10％，余量为水。
作为优选，所述亲水性功能性单体为含有酰胺基或磺酸基的功能性单体。
作为优选，所述亲水性功能性单体为丙烯腈、丙烯酰胺、丙烯酸、苯乙烯磺酸、乙烯磺酸、2-丙烯酰胺-2-甲基丙磺酸、N-乙烯基乙酰胺、N-乙烯基-N-甲基乙酰胺、N,N-二甲基乙酰胺、丙烯酰胺或丙烯酸季铵盐衍生物中的一种或多种。
作为优选，所述亲水性纳米材料为纳米二氧化硅、纳米碳酸钙、纳米三氧化二铝中的一种或多种。
作为优选，所述引发剂为偶氮二异丁基脒盐酸盐、偶氮二异丁咪唑啉、过硫酸盐、氧化还原引发剂中的任一种。
作为优选，所述催化剂为三乙醇胺、二月桂酸二丁基锡、辛酸亚锡、有机铋中的任一种。
作为优选，所述扩链剂为三羟甲基丙烷、1,4-丁二醇、三异丙醇胺、二甲硫基甲苯二胺中的任一种。
作为优选，所述聚氨酯预聚体由多元醇和异氰酸酯反应制备而成，
所述多元醇为聚乙二醇、聚氧化丙烯二醇、聚己内酯二醇、聚碳酸酯二醇、聚四亚甲基醚二醇、聚四氢呋喃二醇、聚氧化丙烯三醇中的一种或多种；
所述异氰酸酯为甲苯二异氰酸酯、1，6-己二异氰酸酯、甲基环己基二异氰酸酯、六亚甲基二异氰酸酯、二苯基甲烷二异氰酸酯中的一种或多种。
另一方面，提供一种可膨胀选择性长效堵水剂的制备方法，所述A组分的制备方法为：将多元醇和异氰酸酯分别进行脱水干燥，搅拌混合后升温至80℃，反应2h，然后在80℃下真空脱气0.5h，得到所述聚氨酯预聚体；
所述B组分的制备方法为：将B组分中的各原料依次加入水中，混合均匀，得到所述B组分；
所述堵水剂的制备方法为：将A组分与B组分混合均匀，在30℃-100℃条件下反应1-8h，得到所述堵水剂。
作为优选，所述多元醇的脱水干燥条件为105℃真空脱水2h，所述异氰酸酯的脱水干燥条件为100℃真空干燥2h。
与现有技术相比，本发明具有如下优点：
本发明不仅具有聚氨酯组分的高膨胀性能，还通过引入的亲水性功能单体使得本发明具有高分子材料的亲水性、耐温耐盐和高吸附性能，通过引入的亲水性纳米材料增强本发明的封堵性能，通过引入的亲水性功能单体和亲水性纳米材料使得本发明具有油水选择性，能够堵水不堵油，这是由于聚氨酯组分和亲水单体聚合的高分子材料，聚合物的分子链具有极强的亲水性，分子链在水中舒展并将水分包裹在其中，分子链遇到油则收缩，最终实现堵水剂的膨胀及堵水效果。综上使得本发明具有良好的吸水膨胀性、稳定性和封堵能力，具有堵水不堵油、弹性好、粘接力强、封堵强度高等优点，具有很好的堵水效果，且堵水有效期长，适用于高含水区块油水井的堵水作业。
具体实施方式
下面结合实施例对本发明进一步说明。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技术特征可以相互结合。除非另外定义，本发明公开使用的技术术语或者科学术语应当为本公开所属领域内具有一般技能的人士所理解的通常意义。本公发明开中使用的“包括”或者“包含”等类似的词语意指出现该词前面的元件或者物件涵盖出现在该词后面列举的元件或者物件及其等同，而不排除其他元件或者物件。
实施例1
一种可膨胀选择性长效堵水剂的制备方法，包括如下步骤：
步骤1、制备聚氨酯预聚体：称取30克聚乙二醇(预先去除水分)、20克聚四氢呋喃二醇(预先去除水分)放入三口烧瓶中，搅拌下加入30克甲苯二异氰酸酯(预先去除水分)、升温至80℃，反应2h，在80℃下真空脱气0.5h，得到所述聚氨酯预聚体，称取70克聚氨酯预聚体，其为A组分。
步骤2、配制功能性液体：将6克丙烯酰胺、2克2-丙烯酰胺-2-甲基丙磺酸、0.01克偶氮二异丁咪唑啉、2克亲水性纳米二氧化硅、0.05克三乙醇胺、3克三羟甲基丙烷依次加入16.94克水中，搅拌均匀，得到B组分。
步骤3、将A组分与B组分液体倒入反应器中搅拌均匀，放入60℃恒温加热器中反应4h，得到可膨胀选择性长效堵水剂。
该堵水剂在60℃的膨胀倍数为5倍，将堵水剂放入煤油中，产品不固化不膨胀。对岩心的封堵率为99.1％，封堵性能好、膨胀倍数高。大量注水后对渗透率影响小，现场堵水有效期长。
实施例2
一种可膨胀选择性长效堵水剂的制备方法，包括如下步骤：
步骤1、制备聚氨酯预聚体：称取25克聚己内酯二醇(预先去除水分)、35克聚碳酸酯二醇(预先去除水分)放入三口烧瓶中，搅拌下加入30克1，6-己二异氰酸酯、升温至80℃，反应2h，在80℃下真空脱气0.5h，得到聚氨酯预聚体，称取80克聚氨酯预聚体，其为A组分。
步骤2、配制功能性液体：将4克丙烯酰胺、1克丙烯酸、2克纳米三氧化二铝、0.01克过硫酸铵、0.01克亚硫酸氢钠、0.03克二月桂酸二丁基锡，3克三异丙醇胺依次加入9.95克水中，搅拌均匀，得到B组分。
步骤3、将A组分与B组分液体倒入反应器中搅拌均匀，放入40℃恒温加热器中反应8h，得到可膨胀选择性长效堵水剂。
该堵水剂在40℃的吸水膨胀倍数为4倍，将堵水剂放入煤油中，产品不固化不膨胀。对岩心的封堵率为98.2％，封堵性能好、膨胀倍数高。大量注水后对渗透率影响小，现场堵水有效期长。
实施例3
一种可膨胀选择性长效堵水剂的制备方法，包括如下步骤：
步骤1、制备聚氨酯预聚体：称取50克聚四亚甲基醚二醇(预先去除水分)、放入三口烧瓶中，搅拌下加入40克甲基环己基二异氰酸酯、升温至80℃，反应2h，在80℃下真空脱气0.5h，得到聚氨酯预聚体，称取60克聚氨酯预聚体，其为A组分。
步骤2、配制功能性液体：将12克丙烯酰胺、2克2-丙烯酰胺-2-甲基丙磺酸、1克丙烯酸、5克纳米碳酸钙、0.05克过硫酸铵、1克辛酸亚锡，2克1,4-丁二醇依次加入16.95克水中，搅拌均匀，得到B组分。
步骤3、将A组分与B组分液体倒入反应器中搅拌均匀，放入80℃恒温加热器中反应3h，得到可膨胀选择性长效堵水剂。
该堵水剂在80℃的吸水膨胀倍数为5.5倍，将堵水剂放入煤油中，产品不固化不膨胀。对岩心的封堵率为98.7％，封堵性能好、膨胀倍数高。大量注水后对渗透率影响小，现场堵水有效期长。
以上所述，仅是本发明的较佳实施例而已，并非对本发明作任何形式上的限制，虽然本发明已以较佳实施例揭露如上，然而并非用以限定本发明，任何熟悉本专业的技术人员，在不脱离本发明技术方案范围内，当可利用上述揭示的技术内容做出些许更动或修饰为等同变化的等效实施例，但凡是未脱离本发明技术方案的内容，依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与修饰，均仍属于本发明技术方案的范围内。

Claims (10)

1.一种可膨胀选择性长效堵水剂，其特征在于，包括A、B两组分，所述A组分为聚氨酯预聚体，所述B组分为亲水性功能性单体、亲水性纳米材料、引发剂、催化剂、扩链剂与水混合形成的混合溶液；所述堵水剂由A、B两组分混合后，聚氨酯预聚体、亲水性功能性单体、亲水性纳米材料在引发剂、催化剂和扩链剂的共同作用下聚合而成。
2.根据权利要求1所述的可膨胀选择性长效堵水剂，其特征在于，各组分的质量百分比如下：聚氨酯预聚体60％-85％、亲水性功能性单体1％-20％、亲水性纳米材料1％-10％、引发剂0.01％-1％、催化剂0.01％-5％、扩链剂1％-10％，余量为水。
3.根据权利要求2所述的可膨胀选择性长效堵水剂，其特征在于，所述亲水性功能性单体为含有酰胺基或磺酸基的功能性单体。
4.根据权利要求3所述的可膨胀选择性长效堵水剂，其特征在于，所述亲水性功能性单体为丙烯腈、丙烯酰胺、丙烯酸、苯乙烯磺酸、乙烯磺酸、2-丙烯酰胺-2-甲基丙磺酸、N-乙烯基乙酰胺、N-乙烯基-N-甲基乙酰胺、N,N-二甲基乙酰胺、丙烯酰胺或丙烯酸季铵盐衍生物中的一种或多种。
5.根据权利要求2所述的可膨胀选择性长效堵水剂，其特征在于，所述亲水性纳米材料为纳米二氧化硅、纳米碳酸钙、纳米三氧化二铝中的一种或多种。
6.根据权利要求2所述的可膨胀选择性长效堵水剂，其特征在于，所述引发剂为偶氮二异丁基脒盐酸盐、偶氮二异丁咪唑啉、过硫酸盐、氧化还原引发剂中的任一种。
7.根据权利要求2所述的可膨胀选择性长效堵水剂，其特征在于，所述催化剂为三乙醇胺、二月桂酸二丁基锡、辛酸亚锡、有机铋中的任一种。
8.根据权利要求2所述的可膨胀选择性长效堵水剂，其特征在于，所述扩链剂为三羟甲基丙烷、1,4-丁二醇、三异丙醇胺、二甲硫基甲苯二胺中的任一种。
9.根据权利要求2-8中任一项所述的可膨胀选择性长效堵水剂，其特征在于，所述聚氨酯预聚体由多元醇和异氰酸酯反应制备而成，
所述多元醇为聚乙二醇、聚氧化丙烯二醇、聚己内酯二醇、聚碳酸酯二醇、聚四亚甲基醚二醇、聚四氢呋喃二醇、聚氧化丙烯三醇中的一种或多种；
所述异氰酸酯为甲苯二异氰酸酯、1，6-己二异氰酸酯、甲基环己基二异氰酸酯、六亚甲基二异氰酸酯、二苯基甲烷二异氰酸酯中的一种或多种。
10.如权利要求9所述的可膨胀选择性长效堵水剂的制备方法，其特征在于，所述A组分的制备方法为：将多元醇和异氰酸酯分别进行脱水干燥，搅拌混合后升温至80℃，反应2h，然后在80℃下真空脱气0.5h，得到所述聚氨酯预聚体；
所述B组分的制备方法为：将B组分中的各原料依次加入水中，混合均匀，得到所述B组分；
所述堵水剂的制备方法为：将A组分与B组分混合均匀，在30℃-100℃条件下反应1-8h，得到所述堵水剂。
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