双十二烷基甲基甜菜碱的合成及中试研究
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摘要
碱-表面活性剂-聚合物(ASP)三元复合驱是适合我国大多数油田的一项三次采油技术,可以使采收率在水驱的基础上进一步提高15-20%,但近年来的矿场实验表明,碱的使用可引起多价离子沉淀、岩石矿物溶蚀等副作用,严重的可能导致油井报废。为此近年来三次采油向无碱化方向发展。然而ASP三元复合驱中使用的表面活性剂在无碱条件下大多无效,因此需要开发新型表面活性剂以适应无碱二元复合驱。双十二烷基甲基甜菜碱(diC12甜菜碱)已被证明是优良的无碱驱油用表面活性剂,但采用传统的氯乙酸合成工艺叔胺转化率只能达到70%左右。为此本文试图通过系统的研究以揭示转化率偏低的原因并提出改进措施,在此基础上进行中试放大实验。
本文首先研究了diC12甜菜碱产品中游离叔胺和活性物含量的测定方法,以便监测叔胺转化率。结果表明,可以通过盐酸-异丙醇直接滴定测定产品中游离叔胺含量,在此基础上可用两相滴定法测定产品中活性物含量。合成diC12甜菜碱过程中,由于反应温度高(100℃左右),氯乙酸的水解不可避免。采用高效液相色谱法可以测定水解产物羟基乙酸和残存氯乙酸的含量。分析表明,实际反应体系反应6h后氯乙酸即已消耗殆尽,其中仅70%左右转变成甜菜碱,而氯乙酸的最终水解率达到27%左右。合成diC12甜菜碱的反应是非均相反应,加快搅拌速率和添加乳化剂都可以改善反应体系的非均质性,从而提高叔胺转化率。在其它反应条件相同的情况下,提高搅拌速度和添加乳化剂可使叔胺转化率提高7%左右,但最终转化率都只能达到80%左右。显然提高叔胺转化率的关键是保证体系中有足够的氯乙酸并防止其水解。提高氯乙酸/叔胺摩尔比可以提高转化率,例如氯乙酸/叔胺摩尔=1.8时,转化率可达到86%,但生产成本和浪费过大。控制氯乙酸/叔胺摩尔比=1.1,NaOH/氯乙酸摩尔比=1.1,在反应6h后一次性补加20%的氯乙酸和相应的氢氧化钠,再反应4h,氯乙酸/叔胺总摩尔比不超过1.3,可使叔胺最终转化率提高到85%左右。
在上述优化工艺条件下用0.5 M3反应釜进行了两次中试,叔胺转化率分别达到85.6%和84.4%,平均85%,产品活性物含量达到64%左右,表明中试工艺条件稳定可靠。用中试获得的diC12甜菜碱为主表面活性剂配制的无碱驱油剂具有优良的性能,45℃下在0.05%~0.3%活性物浓度范围内能使大庆原油/地层水界面张力降至10-3mN/m数量级,天然岩芯驱油实验在水驱基础上平均提高采收率17.8%,达到大庆无碱驱油剂的技术指标。
Alkali-surfactant-polymer (ASP) flooding is one of enhanced oil recovery techniques suitable for most of Chinese oilfields by which the recovery can be increased by 15-20% on the basis of water flooding. However, resent field experiments show that the use of alkali gives rise to some side effects, such as precipitation of the multivalent ions, erosion of rocks and materials, which more severely may results in destroying of oil wells. Thus alkali-free SP flooding becomes more attractive than ASP flooding in China. Unfortunately, surfactants effective in ASP flooding are usually ineffective in the absence of alkali and new surfactants need to be designed. It has been reported that didodecylmethylcarboxybetaine (diC_(12)B), synthesized by reacting tertiary amine with chloroactic acid in the presence of sodium hydroxide, is a good surfactant effective in alkali-free SP flooding. The conversion of the tertiary amine, however, is difficult to exceed 70%. This paper will focus on analyzing the reasons why the conversion of tertiary amine is so low and testing the measures which can be used to improve the recovery. After that production of diC_(12)B in pilot plant scale will be tested.
To detect the conversion of tertiary amine new efficient methods to determine the amounts of both free tertiary amine and diC_(12)B was first developed. The results show that by controlling suitable end point the contents of free tertiary amine in synthesized product can be measured by direct titration with standard hydrochloric acid-in-isopropanol solution and on this basis the content of active matter can be determined by two-phase titration method. It is found that the hydrolysis of chloroactic acid is unavoidable at synthesizing temperature (ca.100°C) and the hydrolysis product, glycolic acid, and the residual chloroactic acid in reaction system can be quantitatively determined by HPLC. The results show that after 6 hours of reaction the chloroactic acid in reaction system exhausted, and only 70% of the total chloroactic acid was converted to target product, with the rest, approximately 27% of the total chloroactic acid, was hydrolyzed. The reaction system is not isotropic but a heterogeneous oil-water mixed system. Increasing stirring speed and adding emulsifies are found to be beneficial to the enhancement of conversion, but it is still difficult to made the total conversion to exceed 80%. Obviously the key to improve the conversion of the tertiary amine is to ensure sufficient chloroactic acid in the reaction system and prevent them from hydrolyzing. Increasing initial chloroactic acid/tertiary amine molar ratio can improve the conversion of tertiary amine, for example, by increasing the molar ratio to 1.8, a conversion of 86% can be achieved. This method, however, is not economically efficient. It is found that with an initial chloroactic acid /tertiary amine molar ration of 1.1, NaOH/ chloroactic acid molar ration of 1.1, by adding 20% extra chloroactic acid and corresponding NaOH after 6 hours of reaction at 100°C and continue to react for 4h, a total conversion of 85% can be achieved, while the total chloroactic acid/ /tertiary amine molar ratio is not beyond 1.3.
The production tests in pilot plant scale were carried out using a reactor of approximately 0.5 M~3. A conversion of 85.6% and 84.4% were achieved respectively in two tests, indicating that the technology and related reaction conditions in synthesizing diC_(12)B are stable and reliable. As a key surfactant, the diC_(12)B produced in the pilot plant scale production was formulated to an oil displacements agent used for SP flooding. With this formulation the lab examinations show that the Daqing crude oil/water interfacial tension can be reduced to an magnitude of 10-3 mN/m in a total surfactant concentration range of 0.01~0.3%wt.% at 45°C without adding any alkaline chemicals or salts, and an average tertiary oil recovery, 17.8%, was achieved in oil displacement tests with natural cores.
本文首先研究了diC12甜菜碱产品中游离叔胺和活性物含量的测定方法,以便监测叔胺转化率。结果表明,可以通过盐酸-异丙醇直接滴定测定产品中游离叔胺含量,在此基础上可用两相滴定法测定产品中活性物含量。合成diC12甜菜碱过程中,由于反应温度高(100℃左右),氯乙酸的水解不可避免。采用高效液相色谱法可以测定水解产物羟基乙酸和残存氯乙酸的含量。分析表明,实际反应体系反应6h后氯乙酸即已消耗殆尽,其中仅70%左右转变成甜菜碱,而氯乙酸的最终水解率达到27%左右。合成diC12甜菜碱的反应是非均相反应,加快搅拌速率和添加乳化剂都可以改善反应体系的非均质性,从而提高叔胺转化率。在其它反应条件相同的情况下,提高搅拌速度和添加乳化剂可使叔胺转化率提高7%左右,但最终转化率都只能达到80%左右。显然提高叔胺转化率的关键是保证体系中有足够的氯乙酸并防止其水解。提高氯乙酸/叔胺摩尔比可以提高转化率,例如氯乙酸/叔胺摩尔=1.8时,转化率可达到86%,但生产成本和浪费过大。控制氯乙酸/叔胺摩尔比=1.1,NaOH/氯乙酸摩尔比=1.1,在反应6h后一次性补加20%的氯乙酸和相应的氢氧化钠,再反应4h,氯乙酸/叔胺总摩尔比不超过1.3,可使叔胺最终转化率提高到85%左右。
在上述优化工艺条件下用0.5 M3反应釜进行了两次中试,叔胺转化率分别达到85.6%和84.4%,平均85%,产品活性物含量达到64%左右,表明中试工艺条件稳定可靠。用中试获得的diC12甜菜碱为主表面活性剂配制的无碱驱油剂具有优良的性能,45℃下在0.05%~0.3%活性物浓度范围内能使大庆原油/地层水界面张力降至10-3mN/m数量级,天然岩芯驱油实验在水驱基础上平均提高采收率17.8%,达到大庆无碱驱油剂的技术指标。
Alkali-surfactant-polymer (ASP) flooding is one of enhanced oil recovery techniques suitable for most of Chinese oilfields by which the recovery can be increased by 15-20% on the basis of water flooding. However, resent field experiments show that the use of alkali gives rise to some side effects, such as precipitation of the multivalent ions, erosion of rocks and materials, which more severely may results in destroying of oil wells. Thus alkali-free SP flooding becomes more attractive than ASP flooding in China. Unfortunately, surfactants effective in ASP flooding are usually ineffective in the absence of alkali and new surfactants need to be designed. It has been reported that didodecylmethylcarboxybetaine (diC_(12)B), synthesized by reacting tertiary amine with chloroactic acid in the presence of sodium hydroxide, is a good surfactant effective in alkali-free SP flooding. The conversion of the tertiary amine, however, is difficult to exceed 70%. This paper will focus on analyzing the reasons why the conversion of tertiary amine is so low and testing the measures which can be used to improve the recovery. After that production of diC_(12)B in pilot plant scale will be tested.
To detect the conversion of tertiary amine new efficient methods to determine the amounts of both free tertiary amine and diC_(12)B was first developed. The results show that by controlling suitable end point the contents of free tertiary amine in synthesized product can be measured by direct titration with standard hydrochloric acid-in-isopropanol solution and on this basis the content of active matter can be determined by two-phase titration method. It is found that the hydrolysis of chloroactic acid is unavoidable at synthesizing temperature (ca.100°C) and the hydrolysis product, glycolic acid, and the residual chloroactic acid in reaction system can be quantitatively determined by HPLC. The results show that after 6 hours of reaction the chloroactic acid in reaction system exhausted, and only 70% of the total chloroactic acid was converted to target product, with the rest, approximately 27% of the total chloroactic acid, was hydrolyzed. The reaction system is not isotropic but a heterogeneous oil-water mixed system. Increasing stirring speed and adding emulsifies are found to be beneficial to the enhancement of conversion, but it is still difficult to made the total conversion to exceed 80%. Obviously the key to improve the conversion of the tertiary amine is to ensure sufficient chloroactic acid in the reaction system and prevent them from hydrolyzing. Increasing initial chloroactic acid/tertiary amine molar ratio can improve the conversion of tertiary amine, for example, by increasing the molar ratio to 1.8, a conversion of 86% can be achieved. This method, however, is not economically efficient. It is found that with an initial chloroactic acid /tertiary amine molar ration of 1.1, NaOH/ chloroactic acid molar ration of 1.1, by adding 20% extra chloroactic acid and corresponding NaOH after 6 hours of reaction at 100°C and continue to react for 4h, a total conversion of 85% can be achieved, while the total chloroactic acid/ /tertiary amine molar ratio is not beyond 1.3.
The production tests in pilot plant scale were carried out using a reactor of approximately 0.5 M~3. A conversion of 85.6% and 84.4% were achieved respectively in two tests, indicating that the technology and related reaction conditions in synthesizing diC_(12)B are stable and reliable. As a key surfactant, the diC_(12)B produced in the pilot plant scale production was formulated to an oil displacements agent used for SP flooding. With this formulation the lab examinations show that the Daqing crude oil/water interfacial tension can be reduced to an magnitude of 10-3 mN/m in a total surfactant concentration range of 0.01~0.3%wt.% at 45°C without adding any alkaline chemicals or salts, and an average tertiary oil recovery, 17.8%, was achieved in oil displacement tests with natural cores.
引文
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