高含盐采油污水处理与回用技术研究
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摘要
开发高含盐采油污水处理及回用技术有利于降低海上油田和许多陆上油田的采油成本、提高原油采收率、减少原油开采对周边环境的污染。
本文通过室内模拟实验、理论推导、现场实验及应用开展了高含盐采油污水处理及回用技术研究,主要内容及结论如下:
1)利用动态胶体稳定仪、四通道电化学工作站及冷场发射电镜等检测仪器,研究了高含盐采油污水的油水乳化、腐蚀、结垢特性。结果表明,高含盐采油污水中的乳化油含量受溶解盐的种类及含量影响,高价金属离子的存在会降低油水乳状液双电层结构对油水乳状液稳定性的影响,导致油水乳状液稳定性降低;而有结垢趋势的采油污水,油水乳状液稳定性会增加;温度升高,高含盐采油污水的腐蚀性增加;有结垢趋势的采油污水,温度升高,其电化学腐蚀会受到抑制;溶解氧含量增加,会加剧采油污水的腐蚀性;结垢型高含盐采油污水析出的污垢中会夹带大量可溶解盐垢,因此结垢情况会比理论推导情况严重。
2)通过分子设计,以十二叔胺、二甲胺、乙二胺等为原料制得了以具有星状结构的聚季铵盐(SPQA)和具有枝网结构的部分交联聚季铵盐(CPQA)为主要成分的聚季铵盐反相破乳剂,聚合反应时间、各组分的配比、使用量、破乳沉降时间等因素对反相破乳剂的处理效果均有影响。反相破乳剂加量15mg/L,除油率可达97.6%,
3)利用激光粒度仪等仪器对聚季铵盐反相破乳剂的作用机理进行了探讨。结果表明,聚季铵盐反相破乳剂可以在添加1~2min内促进乳化油滴的聚集、聚并,其破乳机理在于兼具电性中和、替换、吸附架桥等多重作用。
4)通过水质、油品、腐蚀产物和工艺特点分析,开发的缓蚀杀菌技术、反相破乳技术可控制高含盐采油污水H2S、CO2、溶解盐和SRB菌引起的复杂腐蚀,系统腐蚀率<0.02mm/a,可确保海上稠油高含盐油田外排水油含量<25mg/L,稀油油田外排水油含量<20mg/L。
5)研究表明,马来酸酐共聚物与有机磷酸复配阻垢剂加量10mg/L,即可控制海水、高含盐污水混注的结垢问题,阻垢率>93%,可安全回注。
The development of water treatment and reuse technology for high-salinity oilfield produced water is highly beneficial to the reduction of the production cost, the improvement of the oil recovery and the decrease of the surrounding environment pollution in the exploration and production of offshore oilfields as well as many onshore oilfields.
In this work the high-salinity oilfield produced-water treatment and reuse technology was investigated via the approach of lab simulation experiment, theoretical deduction, and field trial. The main contents and results obtained are as follows:
1) Taking the advantage of the advanced detection equipments such as dynamic colloidal stability analysis, this thesis investigated the oil-in-water(o/w) emulsion, corrosion and scaling tendency of the high-salinity oilfield produced water. The results show that: the content of the emulsified oil in high-salinity oilfield produced water was influenced by the type and content of the dissolved salts. The presence of the multi-charged ions will decrease the influence brought by the double electrical layers, which will decrease the stability of the o/w emulsion. While for the oilfield produced water with scaling tendency, the stability of the o/w emulsion will be improved. With the rise of the temperature, the corrosion rate of the high-salinity oilfield produced water will be increased. As for the oilfield produced water with scaling tendency, the rise of temperature will inhibit the electrochemical corrosion. The presence of the dissolved oxygen will dramatically enhance the corrosion of the oilfield produced water. Since the precipitated scales contain a significant amount of dissolvable salts, more scale from the high-salinity oilfield produced water is expected than the theoretical prediction.
2) Based on the molecular design, dodecydimethylamine, dimethylamine and ethylenediamine were used as starting materials to prepare the star-like polymer of quaternary ammonium salt ( SPQA) and partially crosslinked polyquaternary ammonium. They were used as the main ingredients for the prototype polyquaternary ammonium reverse demulsifier. The examination of the holding time during the synthesis, the ratio of ingredients, the dosage of the chemicals and the sedimentation time on the demulsifier performance indicates that all four factors influence the performance of the reverse demulsifier. The oil removal rate can reach as high as 97.6% by dosing 15mg/L of demulsifier.
3) Analytical equipments such as laser particle size analyzer were used to study the demulsification mechanism and the results show that the reverse demulsifier can enable the emulsion droplets aggregate and flocculate within 1-2 mins, thus the demulsification mechanism is attributed to its multiple functionalities of charge neutralization, substitution and adsorption bridging.
4)By analyzing the water quality, oil quality, corrosion products and characteristics of the technology, the developed technology of the corrosion and bacteria inhibitor and reverse demulsifier can cope with the complex corrosion brought by the H2S, CO2, dissolved salt and SRB bacteria,and attaining a corrosion rate less than 0.02 mm/a, can control the sewage discharge at OIW<25mg/L in the marine heavy oil exploitation,and <20mg/L in the lubrication oil exploitation.
5)The simulated experiments shows that with the 10mg/L dosage of the complex formulation of maleic anhydride copolymer and organic phosphoric acid, the scale inhibiting efficiency of the mixed injection of the sea water and the high-salinity oilfield produced water can be >93%, safe for reuse.
本文通过室内模拟实验、理论推导、现场实验及应用开展了高含盐采油污水处理及回用技术研究,主要内容及结论如下:
1)利用动态胶体稳定仪、四通道电化学工作站及冷场发射电镜等检测仪器,研究了高含盐采油污水的油水乳化、腐蚀、结垢特性。结果表明,高含盐采油污水中的乳化油含量受溶解盐的种类及含量影响,高价金属离子的存在会降低油水乳状液双电层结构对油水乳状液稳定性的影响,导致油水乳状液稳定性降低;而有结垢趋势的采油污水,油水乳状液稳定性会增加;温度升高,高含盐采油污水的腐蚀性增加;有结垢趋势的采油污水,温度升高,其电化学腐蚀会受到抑制;溶解氧含量增加,会加剧采油污水的腐蚀性;结垢型高含盐采油污水析出的污垢中会夹带大量可溶解盐垢,因此结垢情况会比理论推导情况严重。
2)通过分子设计,以十二叔胺、二甲胺、乙二胺等为原料制得了以具有星状结构的聚季铵盐(SPQA)和具有枝网结构的部分交联聚季铵盐(CPQA)为主要成分的聚季铵盐反相破乳剂,聚合反应时间、各组分的配比、使用量、破乳沉降时间等因素对反相破乳剂的处理效果均有影响。反相破乳剂加量15mg/L,除油率可达97.6%,
3)利用激光粒度仪等仪器对聚季铵盐反相破乳剂的作用机理进行了探讨。结果表明,聚季铵盐反相破乳剂可以在添加1~2min内促进乳化油滴的聚集、聚并,其破乳机理在于兼具电性中和、替换、吸附架桥等多重作用。
4)通过水质、油品、腐蚀产物和工艺特点分析,开发的缓蚀杀菌技术、反相破乳技术可控制高含盐采油污水H2S、CO2、溶解盐和SRB菌引起的复杂腐蚀,系统腐蚀率<0.02mm/a,可确保海上稠油高含盐油田外排水油含量<25mg/L,稀油油田外排水油含量<20mg/L。
5)研究表明,马来酸酐共聚物与有机磷酸复配阻垢剂加量10mg/L,即可控制海水、高含盐污水混注的结垢问题,阻垢率>93%,可安全回注。
The development of water treatment and reuse technology for high-salinity oilfield produced water is highly beneficial to the reduction of the production cost, the improvement of the oil recovery and the decrease of the surrounding environment pollution in the exploration and production of offshore oilfields as well as many onshore oilfields.
In this work the high-salinity oilfield produced-water treatment and reuse technology was investigated via the approach of lab simulation experiment, theoretical deduction, and field trial. The main contents and results obtained are as follows:
1) Taking the advantage of the advanced detection equipments such as dynamic colloidal stability analysis, this thesis investigated the oil-in-water(o/w) emulsion, corrosion and scaling tendency of the high-salinity oilfield produced water. The results show that: the content of the emulsified oil in high-salinity oilfield produced water was influenced by the type and content of the dissolved salts. The presence of the multi-charged ions will decrease the influence brought by the double electrical layers, which will decrease the stability of the o/w emulsion. While for the oilfield produced water with scaling tendency, the stability of the o/w emulsion will be improved. With the rise of the temperature, the corrosion rate of the high-salinity oilfield produced water will be increased. As for the oilfield produced water with scaling tendency, the rise of temperature will inhibit the electrochemical corrosion. The presence of the dissolved oxygen will dramatically enhance the corrosion of the oilfield produced water. Since the precipitated scales contain a significant amount of dissolvable salts, more scale from the high-salinity oilfield produced water is expected than the theoretical prediction.
2) Based on the molecular design, dodecydimethylamine, dimethylamine and ethylenediamine were used as starting materials to prepare the star-like polymer of quaternary ammonium salt ( SPQA) and partially crosslinked polyquaternary ammonium. They were used as the main ingredients for the prototype polyquaternary ammonium reverse demulsifier. The examination of the holding time during the synthesis, the ratio of ingredients, the dosage of the chemicals and the sedimentation time on the demulsifier performance indicates that all four factors influence the performance of the reverse demulsifier. The oil removal rate can reach as high as 97.6% by dosing 15mg/L of demulsifier.
3) Analytical equipments such as laser particle size analyzer were used to study the demulsification mechanism and the results show that the reverse demulsifier can enable the emulsion droplets aggregate and flocculate within 1-2 mins, thus the demulsification mechanism is attributed to its multiple functionalities of charge neutralization, substitution and adsorption bridging.
4)By analyzing the water quality, oil quality, corrosion products and characteristics of the technology, the developed technology of the corrosion and bacteria inhibitor and reverse demulsifier can cope with the complex corrosion brought by the H2S, CO2, dissolved salt and SRB bacteria,and attaining a corrosion rate less than 0.02 mm/a, can control the sewage discharge at OIW<25mg/L in the marine heavy oil exploitation,and <20mg/L in the lubrication oil exploitation.
5)The simulated experiments shows that with the 10mg/L dosage of the complex formulation of maleic anhydride copolymer and organic phosphoric acid, the scale inhibiting efficiency of the mixed injection of the sea water and the high-salinity oilfield produced water can be >93%, safe for reuse.
引文
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