Chemical Industry and Engineering Progress ›› 2023, Vol. 42 ›› Issue (8): 4398-4413.DOI: 10.16085/j.issn.1000-6613.2022-1754
• Resources and environmental engineering • Previous Articles Next Articles
WU Ya1,2(), ZHAO Dan1, FANG Rongmiao1, LI Jingyao1, CHANG Nana1, DU Chunbao1, WANG Wenzhen1,2(), SHI Jun1()
Received:
2022-09-20
Revised:
2023-01-19
Online:
2023-09-19
Published:
2023-08-15
Contact:
WANG Wenzhen, SHI Jun
吴亚1,2(), 赵丹1, 方荣苗1, 李婧瑶1, 常娜娜1, 杜春保1, 王文珍1,2(), 史俊1()
通讯作者:
王文珍,史俊
作者简介:
吴亚(1979—),女,博士,教授,研究方向为提高油田水质。E-mail:wuya@xsyu.edu.cn。
基金资助:
CLC Number:
WU Ya, ZHAO Dan, FANG Rongmiao, LI Jingyao, CHANG Nana, DU Chunbao, WANG Wenzhen, SHI Jun. Research progress on highly efficient demulsifiers for complex crude oil emulsions and their applications[J]. Chemical Industry and Engineering Progress, 2023, 42(8): 4398-4413.
吴亚, 赵丹, 方荣苗, 李婧瑶, 常娜娜, 杜春保, 王文珍, 史俊. 用于复杂原油乳液的高效破乳剂开发及应用研究进展[J]. 化工进展, 2023, 42(8): 4398-4413.
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破乳剂 | 适用油水体系类型 | DE/% | 最佳破乳环境 | 优点 | 缺点 |
---|---|---|---|---|---|
BP系列[ | 胜利油田 | 90以上 | 50℃,3h | 脱水效果好 | 对分子量和破乳温度要求高,否则破乳效果不明显,对环境污染较大 |
AP系列[ | 渤海油田、东海油田 | 90 | 1.25%的水分散体系破乳剂用量25mg/L | 对海洋原油具有脱水速度快、油水界面齐、脱出水清 | |
SD破乳剂[ | 塔河油田重质原油 | 89 | 破乳剂用量100mg/L,温度为70℃ | — | |
DS-06/DL11正反破乳剂复配[ | 呼和浩特炼油厂含油污泥 | 95 | 180mg/L,30∶10复配 | 专一性强,工业应用效果明显 | |
DS-1复配型[ | 大庆油田北二联合站高机械杂质含量污油 | 97 | 4.5h,50℃ | — |
破乳剂 | 适用油水体系类型 | DE/% | 最佳破乳环境 | 优点 | 缺点 |
---|---|---|---|---|---|
BP系列[ | 胜利油田 | 90以上 | 50℃,3h | 脱水效果好 | 对分子量和破乳温度要求高,否则破乳效果不明显,对环境污染较大 |
AP系列[ | 渤海油田、东海油田 | 90 | 1.25%的水分散体系破乳剂用量25mg/L | 对海洋原油具有脱水速度快、油水界面齐、脱出水清 | |
SD破乳剂[ | 塔河油田重质原油 | 89 | 破乳剂用量100mg/L,温度为70℃ | — | |
DS-06/DL11正反破乳剂复配[ | 呼和浩特炼油厂含油污泥 | 95 | 180mg/L,30∶10复配 | 专一性强,工业应用效果明显 | |
DS-1复配型[ | 大庆油田北二联合站高机械杂质含量污油 | 97 | 4.5h,50℃ | — |
生物质破乳剂原料 | 生物质破乳剂 | 适用乳液类型 | DE/% | 最佳破乳环境 | 优点 | 缺点 |
---|---|---|---|---|---|---|
花青素[ | PC9015 | 渤海油田老化油乳液 | 84.6 | 70℃,2h,100mg/L | 脱水性能好,实用性较强,适用于海上平台的原油和老化油破乳,以天然多酚为原料,更为经济、绿色 油水界面清晰,无挂壁,取代了用于制备常规石油衍生的壬基酚表面活性剂 | 挂壁严重 |
表没食子儿茶素没食子酸酯[ | EGA603 | 渤海油田老化原油乳液 | 94.3 | 70℃,100min,100mg/L | 挂壁较轻 | |
单宁酸[ | TAPA9920 | 南海油田老化油乳液 | 97.9 | 70℃,40min,100mg/L | 合成困难 | |
腰果酚[ | DECA | 阿拉伯重质原油 | 100 | 60℃,40min,100mg/L | 合成困难,尚在实验室阶段 | |
木质素[ | 木质素和二氧化硅的高效膜 | O/W体系 | 98.6 | 与滤纸表面完全接触。一旦有色油被完全过滤掉,分离过程就算作结束 | 效果明显,分离简单 | |
荷叶[ | HLLF | 长庆油田 | 88.17 | 1000mg/L在70℃下持续90min | 油水界面清晰,水质清亮 | 适用范围较窄,DEMLOCS较其他相似产品剂量颇高 |
稻壳[ | RHC | W/O体系 | 96.99 | 600mg/L,70℃,80min | 具有较宽的pH范围和良好的耐盐性 | 适用范围较窄,DEMLOCS较其他相似产品剂量颇高 |
椰子提取物 | DEMLOCS | 老化油乳液 | 88 | 45℃,24h,2000mg/L | 温度适宜,水热法合成步骤简单 |
生物质破乳剂原料 | 生物质破乳剂 | 适用乳液类型 | DE/% | 最佳破乳环境 | 优点 | 缺点 |
---|---|---|---|---|---|---|
花青素[ | PC9015 | 渤海油田老化油乳液 | 84.6 | 70℃,2h,100mg/L | 脱水性能好,实用性较强,适用于海上平台的原油和老化油破乳,以天然多酚为原料,更为经济、绿色 油水界面清晰,无挂壁,取代了用于制备常规石油衍生的壬基酚表面活性剂 | 挂壁严重 |
表没食子儿茶素没食子酸酯[ | EGA603 | 渤海油田老化原油乳液 | 94.3 | 70℃,100min,100mg/L | 挂壁较轻 | |
单宁酸[ | TAPA9920 | 南海油田老化油乳液 | 97.9 | 70℃,40min,100mg/L | 合成困难 | |
腰果酚[ | DECA | 阿拉伯重质原油 | 100 | 60℃,40min,100mg/L | 合成困难,尚在实验室阶段 | |
木质素[ | 木质素和二氧化硅的高效膜 | O/W体系 | 98.6 | 与滤纸表面完全接触。一旦有色油被完全过滤掉,分离过程就算作结束 | 效果明显,分离简单 | |
荷叶[ | HLLF | 长庆油田 | 88.17 | 1000mg/L在70℃下持续90min | 油水界面清晰,水质清亮 | 适用范围较窄,DEMLOCS较其他相似产品剂量颇高 |
稻壳[ | RHC | W/O体系 | 96.99 | 600mg/L,70℃,80min | 具有较宽的pH范围和良好的耐盐性 | 适用范围较窄,DEMLOCS较其他相似产品剂量颇高 |
椰子提取物 | DEMLOCS | 老化油乳液 | 88 | 45℃,24h,2000mg/L | 温度适宜,水热法合成步骤简单 |
性能 | 离子液体 | 传统破乳剂(表面活性剂) |
---|---|---|
界面张力 | 表面活性离子液体可以将界面张力降低到10-2mN/m,有必要提高离子液体的表面活性,并注意界面张力与盐度的协同作用 | 可以降低IFT达到10-4~10-3mN/m,显示了它们在油水分离应用中的有效性 |
黏度 | 离子液体的黏度可以通过支化的变化来调节 | 在水溶液中,它们无法产生更高的黏度 |
稳定性 | 离子液体高温下是稳定的,可以长时间储存而不会分解 | 表面活性剂在高温下不稳定 |
毒性 | 离子液体毒性较小且环保 | 部分烷基酚表面活性剂毒性大,无法达到降解要求 |
可回收性 | 回收离子液体的方法有很多种,如液液萃取、蒸馏、吸附、结晶、力场分离和膜分离等[ | 不可回收 |
性能 | 离子液体 | 传统破乳剂(表面活性剂) |
---|---|---|
界面张力 | 表面活性离子液体可以将界面张力降低到10-2mN/m,有必要提高离子液体的表面活性,并注意界面张力与盐度的协同作用 | 可以降低IFT达到10-4~10-3mN/m,显示了它们在油水分离应用中的有效性 |
黏度 | 离子液体的黏度可以通过支化的变化来调节 | 在水溶液中,它们无法产生更高的黏度 |
稳定性 | 离子液体高温下是稳定的,可以长时间储存而不会分解 | 表面活性剂在高温下不稳定 |
毒性 | 离子液体毒性较小且环保 | 部分烷基酚表面活性剂毒性大,无法达到降解要求 |
可回收性 | 回收离子液体的方法有很多种,如液液萃取、蒸馏、吸附、结晶、力场分离和膜分离等[ | 不可回收 |
离子液体 | 阳离子 | 阴离子 | 乳液 类型 | 剂量/mg·L-1 | DE/% | 界面张力 降低 | 结论 |
---|---|---|---|---|---|---|---|
C n mim NTf2(n=10、12、14) | 咪唑啉 | 双(三氟甲基 磺酰基)亚胺 | SW/O | 100~3500 | 93.6~100 | 77~95 | 对于亲水性离子液体,增加离子液体的剂量和烷基阳离子链长度导致聚集并导致破乳不良以及增加IFT[ |
C n mim PF6(n=10、12、14) | 六氟磷酸 | 500~3500 | 71.25~86.25 | 54~81 | |||
C n mim Cl(n=10、12、14) | 氯离子 | 500~3500 | 76.25~93.75 | 64~80 | |||
三阳离子液体 | |||||||
TNPy | 氨基吡啶 | 溴离子 | W/O | 250~1000 | 100 | 24 | 研究了烷基链长度、破乳剂剂量和RSN值对破乳活性的影响。结果表明,与含有十六烷基链的TCPyILs相比,壬基和十四烷基链的TCPyILs具有更好和更高的破乳效率。TNPy和TTPyIL对W/O(50/50、30/70和10/90,v/v)的破乳效率即使在低浓度下也达到100%[ |
TTPy | |||||||
W/O | 250~1000 | 100 | 26.5 | ||||
TCPy | |||||||
W/O | 500 | 100 | 26 | ||||
绿色环保的ILs | |||||||
海藻基 | 铵 | 溴离子 | SW/O | 1000 | 100 | — | BH-ALG和BN-ALG都表现出良好的降低界面张力的能力。在这两种PIL中,BH-ALG的表面活性高于BN-ALG,这可能是由于与BN-ALG相比,其烷基链更长,因此具有更高的疏水性[ |
松香酸(AA) | 咪唑 | 碘离子 | SW/O | 250~1000 | 100 | — | 在原油与盐水体积比为90∶10时,两种AILs的脱水率均达到100%,这可以称为由于存在聚乙二酸酯环而增加其疏水性[ |
废弃塑料[ | 铵 | 氯离子 | W/O | 1000 | 94 | 34.5 | PET废物的糖酵解产生BHET,其与氯化亚砜反应形成BCET,然后与HEOD和DOAD进行季铵化,分别形成相应的两亲性GIL、HEOD-IL和DOAD-IL。HEOD-IL的CMC低于DOAD-IL,两种两亲性GIL中烷基链的存在有助于它们在连续相中的扩散,以取代刚性沥青质薄膜 |
聚离子液体修饰的磁性纳米复合材料 | |||||||
乙烯基咪唑 | 溴离子 | W/O | 1000 | 99.9±0.3 | 18±0.1 | 对于W/O乳液,1000μg/L的破乳剂,在70℃下2h后获得了(99.9±0.3)%的破乳效率。破乳后,破乳剂的界面张力从(20.0±0.1)mN/m降低到(1.9±0.1)mN/m,证明了其破乳率高。第一次破乳循环后,通破乳剂过外部磁铁从容器中取出,并重新用于下一个破乳循环。重复使用4个循环后,其破乳效率达到89%[ |
离子液体 | 阳离子 | 阴离子 | 乳液 类型 | 剂量/mg·L-1 | DE/% | 界面张力 降低 | 结论 |
---|---|---|---|---|---|---|---|
C n mim NTf2(n=10、12、14) | 咪唑啉 | 双(三氟甲基 磺酰基)亚胺 | SW/O | 100~3500 | 93.6~100 | 77~95 | 对于亲水性离子液体,增加离子液体的剂量和烷基阳离子链长度导致聚集并导致破乳不良以及增加IFT[ |
C n mim PF6(n=10、12、14) | 六氟磷酸 | 500~3500 | 71.25~86.25 | 54~81 | |||
C n mim Cl(n=10、12、14) | 氯离子 | 500~3500 | 76.25~93.75 | 64~80 | |||
三阳离子液体 | |||||||
TNPy | 氨基吡啶 | 溴离子 | W/O | 250~1000 | 100 | 24 | 研究了烷基链长度、破乳剂剂量和RSN值对破乳活性的影响。结果表明,与含有十六烷基链的TCPyILs相比,壬基和十四烷基链的TCPyILs具有更好和更高的破乳效率。TNPy和TTPyIL对W/O(50/50、30/70和10/90,v/v)的破乳效率即使在低浓度下也达到100%[ |
TTPy | |||||||
W/O | 250~1000 | 100 | 26.5 | ||||
TCPy | |||||||
W/O | 500 | 100 | 26 | ||||
绿色环保的ILs | |||||||
海藻基 | 铵 | 溴离子 | SW/O | 1000 | 100 | — | BH-ALG和BN-ALG都表现出良好的降低界面张力的能力。在这两种PIL中,BH-ALG的表面活性高于BN-ALG,这可能是由于与BN-ALG相比,其烷基链更长,因此具有更高的疏水性[ |
松香酸(AA) | 咪唑 | 碘离子 | SW/O | 250~1000 | 100 | — | 在原油与盐水体积比为90∶10时,两种AILs的脱水率均达到100%,这可以称为由于存在聚乙二酸酯环而增加其疏水性[ |
废弃塑料[ | 铵 | 氯离子 | W/O | 1000 | 94 | 34.5 | PET废物的糖酵解产生BHET,其与氯化亚砜反应形成BCET,然后与HEOD和DOAD进行季铵化,分别形成相应的两亲性GIL、HEOD-IL和DOAD-IL。HEOD-IL的CMC低于DOAD-IL,两种两亲性GIL中烷基链的存在有助于它们在连续相中的扩散,以取代刚性沥青质薄膜 |
聚离子液体修饰的磁性纳米复合材料 | |||||||
乙烯基咪唑 | 溴离子 | W/O | 1000 | 99.9±0.3 | 18±0.1 | 对于W/O乳液,1000μg/L的破乳剂,在70℃下2h后获得了(99.9±0.3)%的破乳效率。破乳后,破乳剂的界面张力从(20.0±0.1)mN/m降低到(1.9±0.1)mN/m,证明了其破乳率高。第一次破乳循环后,通破乳剂过外部磁铁从容器中取出,并重新用于下一个破乳循环。重复使用4个循环后,其破乳效率达到89%[ |
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