纳米复合破乳剂的研究与应用
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摘要
石油作为目前世界上最重要的能源受到了各国政府的高度重视,石油从地下开采出来时基本上都是含有不同数量水的原油乳状液,是不能直接应用和加工的,必须进行破乳脱水。破乳脱水方法主要分为物理方法和化学药剂法,由于物理方法存在多种不适合大规模应用的缺点,目前使用最广泛的还是化学药剂破乳,即破乳剂破乳脱水。
本文首先开发了一种确定原油乳状液最佳破乳温度的新方法——粘度降法。并用正交实验法对其准确性进行了验证。重点研究了将无机纳米微粒运用于聚合物破乳剂中以提高破乳剂的破乳脱水性能,主要使用直接分散法、表面接枝法和原位生成法将纳米微粒结合于聚合物破乳剂中得到含纳米结构的纳米复合破乳剂。实验结果表明,使用原位法将纳米二氧化硅与破乳剂TA1031结合而获得的复合破乳剂性能最好,它是在纳米级氧化物的生成过程中用有机高分子破乳剂将无机纳米氧化物包覆或者接枝,得到含有纳米结构的复合破乳剂。在实验室研究中该复合破乳剂可以使破乳脱水的时间加快30分钟左右,脱水率也可以提高20%～30%左右,脱出水很清,油水界面齐。
原位法合成的纳米复合破乳剂的现场药剂试验表明:处理孤东东四联注聚和油田采出液,在处理量增加,加药量仍是250kg/d时,外输油含水基本小于10%;达到孤东采油厂的规定指标。在东一联使用时,在井排来液条件相同的情况下和在外输水含油量相同时,纳米破乳剂的使用量仅为原有机高分子破乳剂的30%左右,减少破乳剂用量近70%;在孤四联游离水预分水器的试验中,未加纳米预脱水剂前,出水含油在2000mg/L以上。纳米预脱水剂加量在300mg/L时,作用时间20分钟,预分水器水出口水中含油130mg/l。
另外还通过电镜、红外、拉曼和核磁共振等多种现代分析手段对所合成的纳米复合破乳剂进行表征分析,分析了纳米复合破乳剂的形成机理和破乳剂机理。
The petroleum was one of the most important energy sources all over the world. The petroleum was exploited and formed emulsion included different amount water, which could not be directly applied and processed. It was necessary to separate the water completely from the petroleum emulsion before transporting or refining them. The method of demulsification included physical method and chemical method. Because the physical method was awkward to widespread industrializing application, the chemical agents(demulsifier) was used widely to separate the water completely from emulsion.
A new method to confirm proper demulsifing temperature of crude oil emulsion by viscometric drop method was developed and was certified by Orthogonal experimental design. Apply inorganic nano-particle on polyether demulsifier to improve the demulsification performance of the original polyether demulsifier. Make nano-particle integrate with polyether demulsifier to form nano-composite demulsifier by direct dispersion method, surface graft method and In-situ synthesis method. The test result showed that the demulsification performance of the nano-composite demulsifier synthesized by In-situ synthesis method was the best. The nano-oxides were coated or cross linked by the macromolecule polyether demulsifier and the composite demulsifier was got. Experiment Testing showed that the ratio of demulsification would be improved 20% to 30% and the time of demulification and dewatering would be greatly shorten about 30 min with regular oil/water interface and clear separated water.
The demulsification performance of the composite demulsifier synthesized by in-situ synthesis method in the field was very good. In Gudong Dongsilian when the treatment amount of emulsion increased but the dosage of composite demulsifier still was 250kg/d, water content in transported crude oil was <10% and meet the specification of Gudong Oil Production Plant. In Gudong Dongyilian when the condition of emulsion and oil content in transported water held the line, the dosage of composite demulsifier only was 30% of the dosage of organic macromolecule demulsifier, the reduction rates was about 70%. The test of dissociative water prolapsus implement in Gusilian showed that the oil content in transported water was above 2000mg/L before adding nano-composite demulsifier, when the dosage of nano-composite demulsifier was 300mg/L and treating time was 20min, the oil content in water flow from prolapsus implement was 130mg/L.
The nano-composite demulsifier was charactered by FTIR, SEM, RAMAN and ~1H-NMR. The formation mechanism and demulsiflcation mechanism of nano-composite demulsifier were analyzed.
本文首先开发了一种确定原油乳状液最佳破乳温度的新方法——粘度降法。并用正交实验法对其准确性进行了验证。重点研究了将无机纳米微粒运用于聚合物破乳剂中以提高破乳剂的破乳脱水性能,主要使用直接分散法、表面接枝法和原位生成法将纳米微粒结合于聚合物破乳剂中得到含纳米结构的纳米复合破乳剂。实验结果表明,使用原位法将纳米二氧化硅与破乳剂TA1031结合而获得的复合破乳剂性能最好,它是在纳米级氧化物的生成过程中用有机高分子破乳剂将无机纳米氧化物包覆或者接枝,得到含有纳米结构的复合破乳剂。在实验室研究中该复合破乳剂可以使破乳脱水的时间加快30分钟左右,脱水率也可以提高20%～30%左右,脱出水很清,油水界面齐。
原位法合成的纳米复合破乳剂的现场药剂试验表明:处理孤东东四联注聚和油田采出液,在处理量增加,加药量仍是250kg/d时,外输油含水基本小于10%;达到孤东采油厂的规定指标。在东一联使用时,在井排来液条件相同的情况下和在外输水含油量相同时,纳米破乳剂的使用量仅为原有机高分子破乳剂的30%左右,减少破乳剂用量近70%;在孤四联游离水预分水器的试验中,未加纳米预脱水剂前,出水含油在2000mg/L以上。纳米预脱水剂加量在300mg/L时,作用时间20分钟,预分水器水出口水中含油130mg/l。
另外还通过电镜、红外、拉曼和核磁共振等多种现代分析手段对所合成的纳米复合破乳剂进行表征分析,分析了纳米复合破乳剂的形成机理和破乳剂机理。
The petroleum was one of the most important energy sources all over the world. The petroleum was exploited and formed emulsion included different amount water, which could not be directly applied and processed. It was necessary to separate the water completely from the petroleum emulsion before transporting or refining them. The method of demulsification included physical method and chemical method. Because the physical method was awkward to widespread industrializing application, the chemical agents(demulsifier) was used widely to separate the water completely from emulsion.
A new method to confirm proper demulsifing temperature of crude oil emulsion by viscometric drop method was developed and was certified by Orthogonal experimental design. Apply inorganic nano-particle on polyether demulsifier to improve the demulsification performance of the original polyether demulsifier. Make nano-particle integrate with polyether demulsifier to form nano-composite demulsifier by direct dispersion method, surface graft method and In-situ synthesis method. The test result showed that the demulsification performance of the nano-composite demulsifier synthesized by In-situ synthesis method was the best. The nano-oxides were coated or cross linked by the macromolecule polyether demulsifier and the composite demulsifier was got. Experiment Testing showed that the ratio of demulsification would be improved 20% to 30% and the time of demulification and dewatering would be greatly shorten about 30 min with regular oil/water interface and clear separated water.
The demulsification performance of the composite demulsifier synthesized by in-situ synthesis method in the field was very good. In Gudong Dongsilian when the treatment amount of emulsion increased but the dosage of composite demulsifier still was 250kg/d, water content in transported crude oil was <10% and meet the specification of Gudong Oil Production Plant. In Gudong Dongyilian when the condition of emulsion and oil content in transported water held the line, the dosage of composite demulsifier only was 30% of the dosage of organic macromolecule demulsifier, the reduction rates was about 70%. The test of dissociative water prolapsus implement in Gusilian showed that the oil content in transported water was above 2000mg/L before adding nano-composite demulsifier, when the dosage of nano-composite demulsifier was 300mg/L and treating time was 20min, the oil content in water flow from prolapsus implement was 130mg/L.
The nano-composite demulsifier was charactered by FTIR, SEM, RAMAN and ~1H-NMR. The formation mechanism and demulsiflcation mechanism of nano-composite demulsifier were analyzed.
引文
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