CN101817909A - 水合物抑制剂聚合物及制备方法 - Google Patents
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Abstract
本发明涉及一种用于石油海洋深水钻井液中的水合物抑制剂聚合物及制备方法。它能捕获钻井液中渗入的天然气,形成超分子聚集体,达到高效抑制水合物的效果。其技术方案是:该水合物抑制剂由甲基丙烯酸乙酯(EM)、烯丙基环糊精(ACD)、二甲基二烯丙基氯化铵(DMDAAC)和N-乙烯基吡咯烷酮(NVP)四种单体构成的聚合物;先在DMDAAC水溶液中搅拌下加入EM,高速搅拌10-20min使之为乳液,再将该乳液和NVP溶液加入ACD水溶液中;然后依次加入螯合剂、氧化剂和还原剂;最后搅拌混和均匀后充氮气20-40min除氧,30-60℃下反应6-12h,得水合物抑制剂聚合物产品。该聚合物制备方法简便可行,反应条件温和;该聚合物有很好的水合物抑制效果,用于石油天然气海洋深水钻井液中。
Description
技术领域
本发明涉及一种用于石油天然气钻井工程海洋深水钻井液中的水合物抑制剂聚合物及制备方法。
背景技术
随着石油天然气勘探开发向海洋的发展,海洋钻井数量和深度逐年增加。海洋深水钻井作业中钻遇裂缝隙地层时,钻井液易与地层天然气形成水合物,阻碍井控作业。虽然全油基钻井液可减少水合物的生成(WilliEM Halliday.New Gas Hydrate Inhibitors for DeepwaterDrilling Fluids.IDAC/SPE 39316,201-211;宁伏龙,张凌,蒋国盛等.深水油基钻井液中抑制水合物形成的实验研究,石油学报,2009,30(5)440-443),但成本明显高于水基或油包水基钻井液,基于成本和应用角度考虑,本发明制备了一种可用于海洋深水钻井液中抑制水合物形成的EM/ACD/DMDAAC/NVP聚合物。
发明内容
本发明的目的是:为了使制备的聚合物能捕获钻井液中渗入的天然气,形成超分子聚集体,达到高效抑制水合物的效果,特提供一种水合物抑制剂聚合物及制备方法。
为了达到上述目的,本发明采用以下技术方案:水合物抑制剂聚合物及制备方法,其特征是,该水合物抑制剂包含甲基丙烯酸乙酯(EM)、烯丙基环糊精(ACD)、二甲基二烯丙基氯化铵(DMDAAC)和N-乙烯基吡咯烷酮(NVP)四种结构单元构成的聚合物,简写成EM/ACD/DMDAAC/NVP聚合物,其结构式如下:
红外分析认为3423.06cm-1是环糊精分子中羟基的O-H伸缩振动吸收峰,1655.02cm-1是羰基伸缩振动峰,1300cm-1是C-N伸缩振动峰,1226.00cm-1和1167.00cm-1是甲基丙烯酸乙酯的特征吸收峰,1167.00cm-1是环糊精中C-O-C的伸缩振动峰,965.00cm-1处为季铵基-(CH2)N(CH3)2Cl的伸缩振动吸收峰。
吸收峰归属如表1。
表1红外分析(v伸缩振动,δ弯曲振动)
出峰位置cm-1 | 归属 |
3427.43 | v(O-H) |
2929.06 | v(CH2) |
1655.02 | v(C=O) |
1457.56 | δ(CH2) |
1408 | δ(OH)平面弯曲 |
1340 | δ(CCH)+δ(COH) |
1300 | v(C-N) |
1226 | v(CO)+δ(CCH)+δ(OOH)(O-H平面弯曲) |
1167 | v(C-O-C) |
1026.22 | vCC+δ(CCH)+δ(OCH) |
965 | 铵基-(CH2)N(CH3)2Cl的伸缩振动吸收峰 |
960 | 含α-1,4-键在内的CD骨架振动 |
880 | δ(CCH)+v(C-O)+v(C-C振动) |
575.28 | 骨架振动(环振动) |
从EM/ACD/DMDAAC/NVP聚合物扫描电镜图谱分析认为,该聚合物的表面呈典型的高分子凝胶网络结构。这是由于烯丙基环糊精形成超分子链聚集体,发生分子间或分子内缔合以及凝胶之间相互交联,从而形成包含空腔的立体网状结构。该结构易于捕获天然气分子,从而减少水合物形成的可能性。
水合物抑制剂EM/ACD/DMDAAC/NVP聚合物的制备方法,包括以下步骤:
先取浓度为0.5g/mL二甲基二烯丙基氯化铵(DMDAAC)水溶液3-6mL,放入150mL烧杯中,磁力搅拌下准确加入甲基丙烯酸乙酯(EM)1-2g,再高速搅拌10-20min使之成为乳液;将上述乳液和浓度为0.5g/mL的N-乙烯基吡咯烷酮(NVP)水溶液4-8mL加入到浓度为0.02g/mL烯丙基环糊精(ACD)水溶液35-70mL中;EM、DMDAAC、烯丙基环糊精和NVP四者摩尔比依次为15-30∶15-30∶1-8∶32-69;然后依次加入0.3-0.7g乙二胺四乙酸二钠(EDTA)螯合剂、0.4-0.6g过硫酸钾氧化剂和0.4-0.6g亚硫酸氢钠还原剂;最后,在磁力搅拌器上充分搅拌混和均匀后充氮气20-40min除氧,3060℃下反应6-12h,得水合物抑制剂EM/ACD/DMDAAC/NVP聚合物产物。
本聚合物的制备方法所使用的烯丙基环糊精(ACD)是烯丙基α-环糊精、烯丙基β-环糊精、或烯丙基γ-环糊精的一种。
与现有技术相比,本发明具有以下有益效果:EM/ACD/DMDAAC/NVP聚合物的制备方法简便可行,反应条件温和;该方法制备的聚合物由于含有环糊精单元能够捕获钻井液中渗入的天然气,形成超分子聚集体,吡咯烷酮的五元环结构可以镶嵌在水合物晶核的笼型结构中,阻止气体分子占据笼型结构,酯基对水合物晶核有较强的吸附作用,以上三种结构单元协调作用,达到高效抑制水合物的效果,季铵盐单体有利于提高钻井液的抗温等其他性能。
具体实施方式
下面通过实施例对本发明进一步说明。
实施例1EM/ACD/DMDAAC/NVP聚合物的制备方法
取浓度为0.5g/mL二甲基二烯丙基氯化铵(DMDAAC)水溶液3.8mL于150mL烧杯中,磁力搅拌下准确加入甲基丙烯酸乙酯(EM)1.2g,再高速搅拌10-20min使之成为乳液。
将上述乳液和浓度为0.5g/mL的NVP水溶液5mL加入到浓度为0.01g/mL烯丙基β-环糊精(ACD)水溶液50mL中。然后依次加入0.6g乙二胺四乙酸二钠(EDTA)螯合剂、0.6g过硫酸钾氧化剂和0.6g亚硫酸氢钠还原剂。在磁力搅拌器上充分搅拌混和均匀后充氮气40min除氧,50℃下反应9h,得EM/ACD/DMDAAC/NVP四元聚合物。
按GB12005.1-89所述标准测定EM/ACD/DMDAAC/NVP聚合物的特性粘数,再根据GB/T12005.10-92标准测定聚合物的分子量,测得EM/CD/DMDAAC/NVP聚合物的分子量为M=3.55×106。
实施例2EM/ACD/DMDAAC/NVP聚合物在钻井液中水合物的抑制效果
为了评价EM/ACD/DMDAAC/NVP聚合物在钻井液中水合物的抑制效果,使用可视化高压流体测试系统。该系统由带蓝宝石双视窗高压釜、恒温浴槽、温度控制系统、压力控制系统和测量系统构成。
水合物的生成虽然可通过视窗观察,但本发明采用釜内压力和温度的突然变化来判断。因为水合物生成反应是放热反应,温度会升高,同时压力明显下降。实验确定的水合物形成时间为釜内通入气体且压力恒定为16Mpa至压力下降点所经历的时间。
本发明的聚合物评价是在海水膨润土浆和KCl/PLUS钻井液两种常用的海水钻井液中分别进行。海水膨润土浆的组成为:4%海水浆+0.3%CMC-MV+0.3%80A5;KCl/PLUS钻井液的组成为:3%海水浆+0.3%PF-PLUS+1.0%NPAN+0.2%HV-PAC+1.5%PF-TEX+1%TEMP+0.5%JFC+CaCO3(ρ=1.15g/cm3)。
表2为EM/ACD/DMDAAC/NVP四元聚合物在钻井液中的水合物抑制效果。从表2可以看出,本发明的聚合物在海水膨润土浆和KCl/PLUS钻井液中都具有很好的水合物抑制效果。
表2EM/ACD/DMDAAC/NVP四元聚合物水合物的抑制效果
试验基浆 | 气体组成 | 3℃时形成水合物时间min |
海水膨润土浆 | 99.99%CH4、0.01%C+ | 18.0 |
海水膨润土浆 | 99.00%CH4、0.60%C2H6、0.40%C3H8 | 18.6 |
KCl/PLUS钻井液 | 99.99%CH4、0.01%C+ | 21.8 |
KCl/PLUS钻井液 | 99.00%CH4、0.60%C2H6、0.40%C3H8 | 21.1 |
海水膨润土浆+1.5%实例1样 | 99.99%CH4、0.01%C+ | 34.6 |
海水膨润土浆+1.5%实例1样 | 99.00%CH4、0.60%C2H6、0.40%C3H8 | 35.0 |
KCl/PLUS钻井液+1.5%实例1样 | 99.99%CH4、0.01%C+ | 44.2 |
KCl/PLUS钻井液+1.5%实例1样 | 99.00%CH4、0.60%C2H6、0.40%C3H8 | 45.0 |
Claims (3)
1.水合物抑制剂聚合物,其特征是:该水合物抑制剂包含甲基丙烯酸乙酯(EM)、烯丙基环糊精(ACD)、二甲基二烯丙基氯化铵(DMDAAC)和N-乙烯基吡咯烷酮(NVP)四种结构单元构成的聚合物,简写成EM/ACD/DMDAAC/NVP聚合物,其结构式如下:
其中:X的摩尔百分比为15-30%、Y的摩尔百分比为1-8%,符号表示环糊精结构单元,Z的摩尔百分比为15-30%。
2.如权利要求1所述聚合物的制备方法,其特征在于:先取浓度为0.5g/mL二甲基二烯丙基氯化铵(DMDAAC)水溶液3-6mL,放入150mL烧杯中,磁力搅拌下准确加入甲基丙烯酸乙酯(EM)1-2g,高速搅拌10-20min使之成为乳液;再将上述乳液和浓度为0.5g/mL的N-乙烯基吡咯烷酮(NVP)水溶液4-8mL加入到浓度为0.02g/mL烯丙基环糊精(ACD)水溶液35-70mL中;然后依次加入0.3-0.7g乙二胺四乙酸二钠(EDTA)螯合剂、0.4-0.6g过硫酸钾氧化剂和0.4-0.6g亚硫酸氢钠还原剂;最后,在磁力搅拌器上充分搅拌混和均匀后充氮气20-40min除氧,30-60℃下反应6-12h,得水合物抑制剂EM/ACD/DMDAAC/NVP聚合物产品。
3.根据权利要求2所述聚合物的制备方法,其特征在于:所使用的烯丙基环糊精(ACD)是烯丙基α-环糊精、烯丙基β-环糊精、或烯丙基γ-环糊精的一种。
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US20090054268A1 (en) * | 2007-08-06 | 2009-02-26 | Clariant International Ltd. | Use of substituted polyethyleneimines as gas hydrate inhibitors with improved biodegradability |
CN101608111A (zh) * | 2009-07-03 | 2009-12-23 | 华南理工大学 | 一种高效无腐蚀的水合物抑制剂 |
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US20090054268A1 (en) * | 2007-08-06 | 2009-02-26 | Clariant International Ltd. | Use of substituted polyethyleneimines as gas hydrate inhibitors with improved biodegradability |
CN101608111A (zh) * | 2009-07-03 | 2009-12-23 | 华南理工大学 | 一种高效无腐蚀的水合物抑制剂 |
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CN113388379A (zh) * | 2021-07-21 | 2021-09-14 | 中国石油大学(北京) | 一种水合物动力学抑制剂及其制备方法与应用 |
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