阳离子型酸液胶凝剂的合成与性能研究
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摘要
酸化是油气藏重要的增产措施之一,酸化工作液及酸液添加剂的性能直接影响酸化效果,对低渗透、高温深井尤为突出。目前常规的酸液体系在深井高温条件下,缓速和降滤失能力有限,不能形成较长和具有一定支撑能力的刻蚀裂缝。
本文以碳酸岩油藏的高温、深井的酸化增产为切入点,从提高胶凝酸液体系抗温性、配伍性和溶解性以及减少地层伤害等实际应用性能出发,选用阳离子单体甲基丙烯酰氧乙基三甲基氯化铵(DMC)为原料,分别采用水溶液聚合和反相乳液聚合法合成了新型酸液胶凝剂聚甲基丙烯酰氧乙基三甲基氯化铵(P(DMC)):在均聚的基础上,引入丙烯酰胺单体为辅助原料通过自由基水溶液共聚合成了甲基丙烯酰氧乙基三甲基氯化铵(DMC)一丙烯酰胺(AM)二元共聚物(P(DMC-AM));分别讨论了单体浓度、单体配比、引发剂用量、温度、pH值等反应条件对聚合产物特性粘数的影响,得出了最佳合成方案;探讨了共聚物的溶液性质。
结果表明:三种聚合产物在所确定的最佳条件下的特性粘数分别达到672ml/g、236ml/g和723ml/g。聚合物P(DMC-AM)溶液的比浓粘度随聚合物浓度增加先降低后增加;提出了外加盐对聚合物溶液粘度产生影响的模型,比浓粘度随盐中阳离子半径的增大而减小;所合成的聚合物在酸中较稳定,在碱中容易降解;DMC单体的加入大大提高了聚合物的耐温性能;并从理论推导的角度对常用的吸附架桥理论提出了质疑。
采用红外光谱对共聚条件下的产物结构的表征结果证实了产物中共聚物P(DMC-AM)的存在。用中华人民共和国石油天然气行业标准"SY/T6214-1996,酸液稠化剂评价方法”对产品酸液性能进行了评价,结果表明溶液聚合条件下的两种胶凝剂均具有良好的热稳定性和剪切稳定性,缓速性能好,将通常酸液体系中聚合物胶凝剂含量从2.5%降到1.0%,大大减少了聚合物的用量,从而减小了酸化过程中聚合物残渣对储层造成的潜在伤害,具有较好的开发前景。
Acidizing treatment is one important measure for hydrocarbon reservoir to increase production,the performance of acidizing working liquids and acidizing fluid additives directly affect the effect of acidizing treatment,especially for deep wells with high temperature and low permeability.At present,under the deep well condition with high temperature,the routine acidizing fluid has limited ability of slowing rate,and can not form the longer acid etching fracture that has some sustaining ability.
In this paper,considered the pratical application of acid fluid system with improved temperature resistant,compatibility and reduced potential resevior damage, methylacryloyloxyethyltrimethyl ammonium chloride(DMC) is chosed as raw material according to documents investigation,and a kind of new acid fluid gelling agent P(DMC) is synthesized with both of aqueous solution polymerization and inverse phase emulsion polymerization;on the basis of homopolymerization,methylacryloyloxyethyltrimethyl ammonium chloride (DMC) and acrylamide (AM) binary copolymer P(DMC-AM) is prepared through free radical aqueous solution copolymerization;meanwhile,the influences of reaction conditions such as monomer concentration,monomer ratio,initiator amounts,temperature,pH value etc.on the intrinsic viscosity of polymer are also discussed,and as a result,the optimum synthesis scheme are proposed,and under which their intrinsic viscosities are respectively 672ml/g、236ml/g and 723ml/g.The properties of polymer P(DMC-AM)solution are explored,and the model of the effect of added salts on the viscosity of dilute polymer solution are also put forward.At last,through theoretical derivation, some doubts about the conventional adsorption-bridging theory are raised.
In laboratory tests,the above synthesised homopolymers and copolymers are estimated as gelling agent in acid fluids. Evaluation standard of acid fluid gelling agent refers to the People Republic of China petroleum natural gas profession standard(SY/T6214-1996).The experimental result shows that the two kinds of polymers P(DMC) and P(DMC-AM) both have good properties in thermal stability,shear thinning,corrosion inhibition and salts resistant,good compatibility with other kinds of acid fluids additives, the content of polymer gelling agnet is droped from 2.5 wt % to 1.0 wt % in common acid fluid,so the potential damage of polymer residues is also reduced. We believe they have a broad researching and application prospect in petroleum industry and some other fields.
本文以碳酸岩油藏的高温、深井的酸化增产为切入点,从提高胶凝酸液体系抗温性、配伍性和溶解性以及减少地层伤害等实际应用性能出发,选用阳离子单体甲基丙烯酰氧乙基三甲基氯化铵(DMC)为原料,分别采用水溶液聚合和反相乳液聚合法合成了新型酸液胶凝剂聚甲基丙烯酰氧乙基三甲基氯化铵(P(DMC)):在均聚的基础上,引入丙烯酰胺单体为辅助原料通过自由基水溶液共聚合成了甲基丙烯酰氧乙基三甲基氯化铵(DMC)一丙烯酰胺(AM)二元共聚物(P(DMC-AM));分别讨论了单体浓度、单体配比、引发剂用量、温度、pH值等反应条件对聚合产物特性粘数的影响,得出了最佳合成方案;探讨了共聚物的溶液性质。
结果表明:三种聚合产物在所确定的最佳条件下的特性粘数分别达到672ml/g、236ml/g和723ml/g。聚合物P(DMC-AM)溶液的比浓粘度随聚合物浓度增加先降低后增加;提出了外加盐对聚合物溶液粘度产生影响的模型,比浓粘度随盐中阳离子半径的增大而减小;所合成的聚合物在酸中较稳定,在碱中容易降解;DMC单体的加入大大提高了聚合物的耐温性能;并从理论推导的角度对常用的吸附架桥理论提出了质疑。
采用红外光谱对共聚条件下的产物结构的表征结果证实了产物中共聚物P(DMC-AM)的存在。用中华人民共和国石油天然气行业标准"SY/T6214-1996,酸液稠化剂评价方法”对产品酸液性能进行了评价,结果表明溶液聚合条件下的两种胶凝剂均具有良好的热稳定性和剪切稳定性,缓速性能好,将通常酸液体系中聚合物胶凝剂含量从2.5%降到1.0%,大大减少了聚合物的用量,从而减小了酸化过程中聚合物残渣对储层造成的潜在伤害,具有较好的开发前景。
Acidizing treatment is one important measure for hydrocarbon reservoir to increase production,the performance of acidizing working liquids and acidizing fluid additives directly affect the effect of acidizing treatment,especially for deep wells with high temperature and low permeability.At present,under the deep well condition with high temperature,the routine acidizing fluid has limited ability of slowing rate,and can not form the longer acid etching fracture that has some sustaining ability.
In this paper,considered the pratical application of acid fluid system with improved temperature resistant,compatibility and reduced potential resevior damage, methylacryloyloxyethyltrimethyl ammonium chloride(DMC) is chosed as raw material according to documents investigation,and a kind of new acid fluid gelling agent P(DMC) is synthesized with both of aqueous solution polymerization and inverse phase emulsion polymerization;on the basis of homopolymerization,methylacryloyloxyethyltrimethyl ammonium chloride (DMC) and acrylamide (AM) binary copolymer P(DMC-AM) is prepared through free radical aqueous solution copolymerization;meanwhile,the influences of reaction conditions such as monomer concentration,monomer ratio,initiator amounts,temperature,pH value etc.on the intrinsic viscosity of polymer are also discussed,and as a result,the optimum synthesis scheme are proposed,and under which their intrinsic viscosities are respectively 672ml/g、236ml/g and 723ml/g.The properties of polymer P(DMC-AM)solution are explored,and the model of the effect of added salts on the viscosity of dilute polymer solution are also put forward.At last,through theoretical derivation, some doubts about the conventional adsorption-bridging theory are raised.
In laboratory tests,the above synthesised homopolymers and copolymers are estimated as gelling agent in acid fluids. Evaluation standard of acid fluid gelling agent refers to the People Republic of China petroleum natural gas profession standard(SY/T6214-1996).The experimental result shows that the two kinds of polymers P(DMC) and P(DMC-AM) both have good properties in thermal stability,shear thinning,corrosion inhibition and salts resistant,good compatibility with other kinds of acid fluids additives, the content of polymer gelling agnet is droped from 2.5 wt % to 1.0 wt % in common acid fluid,so the potential damage of polymer residues is also reduced. We believe they have a broad researching and application prospect in petroleum industry and some other fields.
引文
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