CN114621110A - 一种油基泡沫钻井液用含氟表面活性剂及其制备方法 - Google Patents
一种油基泡沫钻井液用含氟表面活性剂及其制备方法 Download PDFInfo
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 27
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- PGFXOWRDDHCDTE-UHFFFAOYSA-N hexafluoropropylene oxide Chemical class FC(F)(F)C1(F)OC1(F)F PGFXOWRDDHCDTE-UHFFFAOYSA-N 0.000 claims description 15
- -1 amino compound Chemical class 0.000 claims description 14
- AQQBRCXWZZAFOK-UHFFFAOYSA-N 2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctanoyl chloride Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(Cl)=O AQQBRCXWZZAFOK-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
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- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
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- HSDJWNJDPDJOEV-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6,6-tridecafluorohexane-1-sulfonyl fluoride Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)S(F)(=O)=O HSDJWNJDPDJOEV-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 6
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- MCEDOKUQJYNLKR-UHFFFAOYSA-N 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-nonadecafluorodecanoyl chloride Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(Cl)=O MCEDOKUQJYNLKR-UHFFFAOYSA-N 0.000 claims description 5
- BHHGXPLMPWCGHP-UHFFFAOYSA-N Phenethylamine Chemical compound NCCC1=CC=CC=C1 BHHGXPLMPWCGHP-UHFFFAOYSA-N 0.000 claims description 5
- LUYQYZLEHLTPBH-UHFFFAOYSA-N perfluorobutanesulfonyl fluoride Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)S(F)(=O)=O LUYQYZLEHLTPBH-UHFFFAOYSA-N 0.000 claims description 5
- 239000013638 trimer Substances 0.000 claims description 5
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 claims description 4
- BHFJBHMTEDLICO-UHFFFAOYSA-N Perfluorooctylsulfonyl fluoride Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)S(F)(=O)=O BHFJBHMTEDLICO-UHFFFAOYSA-N 0.000 claims description 4
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 claims description 4
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- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 3
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 claims description 3
- VDNQHHBRKZQBPY-UHFFFAOYSA-N 2-octyldodecan-1-amine Chemical compound CCCCCCCCCCC(CN)CCCCCCCC VDNQHHBRKZQBPY-UHFFFAOYSA-N 0.000 claims description 3
- PLZVEHJLHYMBBY-UHFFFAOYSA-N Tetradecylamine Chemical compound CCCCCCCCCCCCCCN PLZVEHJLHYMBBY-UHFFFAOYSA-N 0.000 claims description 3
- MJCJUDJQDGGKOX-UHFFFAOYSA-N n-dodecyldodecan-1-amine Chemical compound CCCCCCCCCCCCNCCCCCCCCCCCC MJCJUDJQDGGKOX-UHFFFAOYSA-N 0.000 claims description 3
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- 239000002283 diesel fuel Substances 0.000 description 5
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- 230000007935 neutral effect Effects 0.000 description 3
- 125000006736 (C6-C20) aryl group Chemical group 0.000 description 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
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- YWGHUJQYGPDNKT-UHFFFAOYSA-N hexanoyl chloride Chemical compound CCCCCC(Cl)=O YWGHUJQYGPDNKT-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
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- C07C231/00—Preparation of carboxylic acid amides
- C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
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- C07C233/02—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
- C07C233/04—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with carbon atoms of carboxamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C233/05—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with carbon atoms of carboxamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton having the nitrogen atoms of the carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
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- C07C235/04—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton being acyclic and saturated
- C07C235/06—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton being acyclic and saturated having the nitrogen atoms of the carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
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Abstract
本发明提供了一种具有式(I)结构的油基泡沫钻井液用含氟表面活性剂。具体制备方法为:胺基化合物、缚酸剂和含氟化合物混合,反应,得到式(I)结构的油基泡沫钻井液用含氟表面活性剂。本发明所得油基泡沫钻井液用表面活性剂可降低油相表面张力,具有较强的发泡能力和泡沫稳定性,可用于油基泡沫钻井液配制。
Description
技术领域
本发明涉及钻井液技术领域,尤其是涉及一种油基泡沫钻井液用含氟表面活性剂及其制备方法。
背景技术
在低压易漏地层钻井过程中,使用常规钻井液体系极易造成钻井液漏失,影响井下施工安全。而泡沫钻井液是解决上述技术难题的有效手段。但对于强水敏地层(如页岩气层钻井等),由于黏土极易水化分散,使用水基泡沫钻井液极易引发井壁失稳。因此,在低压强水敏地层钻进时,必须使用油基泡沫钻井液体系。
油基泡沫钻井液是在油基钻井液体系中加入具有发泡功能的表面活性剂,通过剧烈搅拌等方式将空气裹进油基钻井液中形成。由于表面活性剂的存在,显著降低了气-液之间的界面张力,最终形成了具有良好稳定性的油基泡沫。在ZL201210239981.6中公开了一种用于低压水敏地层的钻井液,其使用的表面活性剂是失水山梨胺脂肪酸酯;在ZL201110407297.X中公开了一种环保型抗高温合成基泡沫钻井液及其制备方法,其使用的表面活性剂是18~24个碳原子的烷基磺酸。这两种表面活性剂都是长烷基碳链结构的表面活性剂,由于自身表面张力较大,很难降低柴油的表面张力,在柴油中的发泡能力较差,难以形成稳定的油基泡沫。
发明内容
有鉴于此,本发明要解决的技术问题在于提供一种油基泡沫钻井液用含氟表面活性剂,本发明提供的油基泡沫钻井液用含氟表面活性剂具有较强的发泡性能和泡沫稳定性。
本发明提供了一种具有式(I)结构的油基泡沫钻井液用含氟表面活性剂,包括:
其中R1=CmF2m+1CnH2n或m为3~8的整数,n为0~1的整数,x为2~4的整数;R2为C6~C20的烷基、C6~C20环烷基、C6~C20的芳基;优选的,R2为C8~C20的含长链或芳环结构的烷基;R3为H、C3~C12的烷基、C3~C12的环烷基、C6~C12的芳基;Z为
优选的,所述
本发明提供了一种上述技术方案所述的式(I)结构的油基泡沫钻井液用含氟表面活性剂的制备方法,包括:
胺基化合物、缚酸剂和含氟化合物混合,反应,得到式(I)结构的油基泡沫钻井液用含氟表面活性剂;
所述含氟化合物选自全氟丁酰氯、全氟己酰氯、全氟辛酰氯、全氟丁基磺酰氟、全氟己基磺酰氟、全氟辛基磺酰氟、全氟丁基乙酰氯、全氟己基乙酰氯、全氟辛基乙酰氯、六氟环氧丙烷二聚体、六氟环氧丙烷三聚体和六氟环氧丙烷四聚体中的一种或几种。
优选的,所述胺基化合物选自十二胺、十四胺、十六胺、油胺、十八胺、2-苯乙胺、二正十二胺和2-辛基-1-十二胺中的一种或几种。优选的,所述缚酸剂为吡啶或三乙胺中的一种。
优选的,所述胺基化合物、缚酸剂和含氟化合物的摩尔比为1:(1~2):(0.5~2)。
优选的,所述反应的温度为0~100℃;所述反应的时间为1~3h。
优选的,所述反应后还包括在室温下用蒸馏水洗至中性。
本发明提供了一种油基泡沫钻井液,包括上述技术方案任意一项所述的含氟表面活性剂或上述技术方案任意一项所述的制备方法制备得到的含氟表面活性剂。
与现有技术相比,本发明提供了一种具有式(I)结构的油基泡沫钻井液用含氟表面活性剂。具体制备方法为:胺基化合物、缚酸剂和含氟化合物混合,反应,得到式(I)结构的油基泡沫钻井液用含氟表面活性剂。本发明所得油基泡沫钻井液用表面活性剂可降低油相表面张力,具有较强的发泡能力和泡沫稳定性,可用于油基泡沫钻井液配制。
具体实施方式
本发明提供了一种油基泡沫钻井液用含氟表面活性剂及其制备方法,本领域技术人员可以借鉴本文内容,适当改进工艺参数实现。特别需要指出的是,所有类似的替换和改动对本领域技术人员来说是显而易见的,它们都属于本发明保护的范围。本发明的方法及应用已经通过较佳实施例进行了描述,相关人员明显能在不脱离本发明内容、精神和范围内对本文的方法和应用进行改动或适当变更与组合,来实现和应用本发明技术。
本发明提供了一种具有式(I)结构的油基泡沫钻井液用含氟表面活性剂,包括:
R2为C6~C20的烷基、C6~C20环烷基、C6~C20的芳基;优选为C8~C20的含长链或芳环结构的烷基;更优选为C8~C18的烷基、C8~C18环烷基、C8~C18的芳基。最优选的,R2为C12~C18的烷基、C12~C18环烷基、C12~C18的芳基。
R3为H、C3~C12的烷基、C3~C12的环烷基、C6~C12的芳基;优选为H、C5~C10的烷基、C5~C10的环烷基、C8~C11的芳基。
在本发明其中一部分优选实施方式中,所述具有式(I)结构的油基泡沫钻井液用含氟表面活性剂具体为:
本发明提供了一种上述技术方案所述的式(I)结构的油基泡沫钻井液用含氟表面活性剂的制备方法,包括:
胺基化合物、缚酸剂和含氟化合物混合,反应,得到式(I)结构的油基泡沫钻井液用含氟表面活性剂;
所述含氟化合物选自全氟丁酰氯、全氟己酰氯、全氟辛酰氯、全氟丁基磺酰氟、全氟己基磺酰氟、全氟辛基磺酰氟、全氟丁基乙酰氯、全氟己基乙酰氯、全氟辛基乙酰氯、六氟环氧丙烷二聚体、六氟环氧丙烷三聚体和六氟环氧丙烷四聚体中的一种或几种。
本发明提供的式(I)结构的油基泡沫钻井液用含氟表面活性剂首先将胺基化合物和缚酸剂混合,搅拌,再加入含氟化合物混合。本发明对于所述搅拌的具体方式不进行限定,本领域技术人员熟知的即可。本发明所述反应优选在反应器中进行。
本发明所述胺基化合物优选选自十二胺、十四胺、十六胺、油胺、十八胺、2-苯乙胺、二正十二胺和2-辛基-1-十二胺中的一种或几种。
所述缚酸剂优选为吡啶或三乙胺中的一种。
本发明所述含氟化合物优选选自全氟丁酰氯、全氟己酰氯、全氟辛酰氯、全氟丁基磺酰氟、全氟己基磺酰氟、全氟辛基磺酰氟、全氟丁基乙酰氯、全氟己基乙酰氯、全氟辛基乙酰氯、六氟环氧丙烷二聚体、六氟环氧丙烷三聚体和六氟环氧丙烷四聚体中的一种或几种;更优选为全氟己酰氯、全氟辛酰氯、全氟丁基磺酰氟、全氟己基磺酰氟、全氟辛基磺酰氟、全氟丁基乙酰氯、全氟己基乙酰氯、全氟辛基乙酰氯、六氟环氧丙烷三聚体和六氟环氧丙烷四聚体中的一种或几种。
本发明对于上述胺基化合物、缚酸剂和含氟化合物的来源不进行限定,本领域技术人员熟知的即可。
按照本发明,所述胺基化合物、缚酸剂和含氟化合物的摩尔比优选为1:(1~2):(0.5~2);更优选为1:(1~1.8):(0.5~1.8)。
本发明所述反应的温度优选为0~100℃;更优选为0~90℃;最优选为0~80℃;特别优选为0~70℃。
所述反应的时间优选为1~3h;具体可以为1h、2h或3h。
本发明所述反应后还包括在室温下用蒸馏水洗至中性,即得表面活性剂。
本发明所得油基泡沫钻井液用表面活性剂可降低油相表面张力,具有较强的发泡能力和泡沫稳定性,可用于油基泡沫钻井液配制。
本发明提供了一种油基泡沫钻井液,包括上述技术方案任意一项所述的含氟表面活性剂或上述技术方案任意一项所述的制备方法制备得到的含氟表面活性剂。
本发明提供的含氟表面活性剂可以用于制备油基泡沫钻井液,具有良好的技术效果。本发明对于制备油基泡沫钻井液的其余组分不进行限定,本领域技术人员熟知的即可。
本发明提供了一种具有式(I)结构的油基泡沫钻井液用含氟表面活性剂。具体制备方法为:胺基化合物、缚酸剂和含氟化合物混合,反应,得到式(I)结构的油基泡沫钻井液用含氟表面活性剂。本发明所得油基泡沫钻井液用表面活性剂可降低油相表面张力,具有较强的发泡能力和泡沫稳定性,可用于油基泡沫钻井液配制。
为了进一步说明本发明,以下结合实施例对本发明提供的一种油基泡沫钻井液用含氟表面活性剂及其制备方法进行详细描述。
实施例1
将1mol十二胺和1.5mol三乙胺加入反应器中搅拌均匀,然后将1.2mol全氟丁酰氯加入反应器中,在20℃反应1h,然后在室温下用蒸馏水洗至中性得到表面活性剂样品。其结构式如下:
实施例2
将1mol十八胺和2mol三乙胺加入反应器中搅拌均匀,然后将1.8mol全氟己基磺酰氟加入反应器中,在60℃反应3h,然后在室温下用蒸馏水洗至中性得到表面活性剂样品。其结构式如下:
实施例3
将1mol2-苯乙胺和1mol吡啶加入反应器中搅拌均匀,然后将0.5mol六氟环氧丙烷二聚体加入反应器中,在0℃反应2h,然后在室温下用蒸馏水洗至中性得到表面活性剂样品。其结构式如下:
对比例1~2,实施例4~12步骤与实施例1相同,反应物质及其用量如表1所示:
表1反应物质及用量表
将实施例1~12和对比例1和2中合成的表面活性剂进行性能评价。
(1)表面张力
在100mL柴油中加入1.0g表面活性剂,搅拌均匀后使用BZY-101型表面张力仪测定柴油表面张力。
表2实施例1~12表面活性剂表面张力值
由表2可知,相比于一般的表面活性剂如SP-80,本发明制得的表面活性剂可明显降低柴油表面张力。
(2)发泡性能
在100mL柴油中加入2g顺丁橡胶,充分溶解均匀后配制成基浆,将实施例中的样品和SP-80分别加入基浆中搅拌均匀,用高速搅拌机以10000r/min速度搅拌3min,然后将形成的泡沫浆倒入量筒中,记录泡沫体积及泡沫浆析出50mL发泡基液所用的时间,作为泡沫半衰期。结果参见表3。
表3表面活性剂性能评价
表面活性剂类型 | 起泡体积/mL | 半衰期/min |
实施例1 | 140 | 6.5 |
实施例2 | 165 | 7.5 |
实施例3 | 180 | 8.4 |
实施例4 | 180 | 9.1 |
实施例5 | 200 | 9.7 |
实施例6 | 190 | 8.8 |
实施例7 | 165 | 8.0 |
实施例8 | 140 | 5.6 |
实施例9 | 170 | 8.3 |
实施例10 | 160 | 7.2 |
实施例11 | 175 | 8.9 |
实施例12 | 160 | 7.7 |
SP-80 | 115 | 1.5 |
由表3可知,相比于一般的表面活性剂如SP-80,本发明制得的表面活性剂发泡性能好,形成的泡沫具有更好的稳定性。
以上所述仅是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以做出若干改进和润饰,这些改进和润饰也应视为本发明的保护范围。
Claims (9)
3.一种权利要求1或2所述的式(I)结构的油基泡沫钻井液用含氟表面活性剂的制备方法,其特征在于,包括:
胺基化合物、缚酸剂和含氟化合物混合,反应,得到式(I)结构的油基泡沫钻井液用含氟表面活性剂;
所述含氟化合物选自全氟丁酰氯、全氟己酰氯、全氟辛酰氯、全氟丁基磺酰氟、全氟己基磺酰氟、全氟辛基磺酰氟、全氟丁基乙酰氯、全氟己基乙酰氯、全氟辛基乙酰氯、六氟环氧丙烷二聚体、六氟环氧丙烷三聚体和六氟环氧丙烷四聚体中的一种或几种。
4.根据权利要求3所述的制备方法,其特征在于,所述胺基化合物选自十二胺、十四胺、十六胺、油胺、十八胺、2-苯乙胺、二正十二胺和2-辛基-1-十二胺中的一种或几种。
5.根据权利要求3所述的制备方法,其特征在于,所述缚酸剂为吡啶或三乙胺中的一种。
6.根据权利要求3所述的制备方法,其特征在于,所述胺基化合物、缚酸剂和含氟化合物的摩尔比为1:(1~2):(0.5~2)。
7.根据权利要求3所述的制备方法,其特征在于,所述反应的温度为0~100℃;所述反应的时间为1~3h。
8.根据权利要求3所述的制备方法,其特征在于,所述反应后还包括在室温下用蒸馏水洗至中性。
9.一种油基泡沫钻井液,其特征在于,包括权利要求1~2任意一项所述的含氟表面活性剂或权利要求3~8任意一项所述的制备方法制备得到的含氟表面活性剂。
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