负载型反相破乳剂的合成及性能研究

发布时间：2019-03-05 09:29

【摘要】：三元复合驱采油技术较普通水驱提高采收率达20个百分点以上,对保持我国主力油田后期的稳产起到了重要作用,同时也产生了三元复合驱采出水水质复杂、相态稳定,油水分离难度大的难题。三元复合驱采出水处理是矿场油田开发和保护生态环境面临的重要课题,成为了三元复合驱技术推广的瓶颈之一。三元复合驱采出水处理在国内外尚无成熟的技术可供参考,而破乳脱稳是处理三元复合驱采出水首要解决的问题。近些年破乳剂的研究有了长足的进展,但适合三元复合驱采出水破乳的高效破乳剂有待研发。因此,本文提出了针对三元复合驱O/W型采出水破乳与吸附协同作用的破乳剂分子设计新思路。采用表面枝接聚合法将预先制备的聚醚聚季铵盐(PPA)反相破乳剂分子键合到比表面积大、多孔性的水合二氧化硅(SiO_2·n H2O、水合二氧化硅)表面,制备负载型聚醚聚季铵盐反相破乳剂。通过单因素条件实验考察了反应温度、反应时间、反应原料用量、催化剂用量等条件对合成中间产物与最终产品转化率的影响,并进一步优化了合成工艺。通过SEM和BET对水合二氧化硅的微观结构和孔结构进行表征,并通过FTIR、1H-NMR、SEM和XPS对合成产物进行了表征。采用单一型PPA反相破乳剂进行破乳试验,考察了季铵盐与甲基醚的配比(亲水亲油性)、破乳剂用量、破乳温度、破乳时间等因素对破乳效果的影响,并对PPA反相破乳剂与其他商用破乳剂的破乳性能进行了比较。试验结果表明,在n(环氧醚):n(甲基醚)=3:1,PPA投加量50 mg L-1,破乳温度30 oC,破乳时间60 min条件下,PPA反相破乳剂的破乳率可达85.48%。采用PPA反相破乳剂破乳后油水分层,易于分离。采用单一型吸附剂MPS-SiO_2吸附处理含油污水,在含油浓度500 mg L-1,吸附剂投加量1.5 g L-1,吸附时间60 min,吸附温度30 oC时,MPS-SiO_2吸附除油率为46.8%。采用负载型反相破乳剂SiO_2@PPA破乳-吸附处理含油污水,在含油浓度500mg L-1,吸附剂投加量1.5 g L-1,吸附时间60 min,吸附温度30 oC时,负载型反相破乳剂SiO_2@PPA的除油率为91.6%,载体粒子吸附容量达301 mg g-1,是颗粒活性炭(GAC)吸附容量的6倍。研究结果表明,负载型破乳剂SiO_2@PPA载体粒子具有多孔隙结构,粒径小、比表面积大的特点,使得SiO_2@PPA兼具破乳与吸附功能,负载型反相破乳剂SiO_2@PPA通过破乳与吸附协同作用,可以适用于三元复合驱采出水破乳处理。负载型破乳剂SiO_2@PPA载体粒子吸附油滴的动力学试验表明,其吸附过程符合伪二级动力学方程;在等温吸附中,Langmuir等温吸附模型比Freundlich等温吸附模型更能合理描述SiO_2@PPA载体粒子对油滴的吸附行为;热力学研究表明,该吸附过程ΔG0且ΔH0,说明SiO_2@PPA载体粒子对油滴吸附是一个自发的、吸热的过程。
[Abstract]:ASP flooding technology improves oil recovery by more than 20 percentage points compared with common water flooding, which plays an important role in maintaining stable production in the later stage of the main oil field in China. At the same time, it also produces complex water quality and stable phase state of produced water in ASP flooding. The difficult problem of oil-water separation. The treatment of produced water from ASP flooding is an important subject in oilfield development and protection of ecological environment, which has become one of the bottlenecks in the popularization of ASP flooding technology. There is no mature technology for treatment of produced water in ASP flooding at home and abroad, and demulsification is the first problem to be solved in the treatment of produced water in ASP flooding. The research on demulsifier has made great progress in recent years, but the high efficiency demulsifier suitable for ASP flooding water demulsifier needs to be researched and developed. Therefore, a new idea of demulsifier molecular design for the synergistic action of demulsification and adsorption of O / W type produced water by ternary composite flooding is proposed in this paper. The pre-prepared polyether polyquaternary ammonium salt (PPA) inverse demulsifier molecule was bonded to the surface of hydrated silica (SiO_ 2 路n H 2O, hydrated silica) with large specific surface area and porous surface area by surface grafting polymerization. The reverse demulsifier of supported polyether polyquaternary ammonium salt was prepared. The effects of reaction temperature, reaction time, amount of raw material and catalyst on the conversion of intermediate product and final product were investigated by single factor experiment, and the synthesis process was further optimized. The microstructure and pore structure of hydrated silica were characterized by SEM and BET, and the synthesized products were characterized by FTIR,1H-NMR,SEM and XPS. The demulsifying effect of quaternary ammonium salt and methyl ether, the amount of demulsifier, demulsification temperature, demulsification time and so on, were investigated by demulsifying test of single type PPA inverse demulsifier, and the effects of the ratio of quaternary ammonium salt and methyl ether on demulsification were investigated. The demulsifying properties of PPA reverse demulsifier were compared with other commercial demulsifiers. The experimental results show that the demulsifying rate of PPA reverse demulsifier can reach 85.48% under the conditions of n (epoxy ether): n (methyl ether) = 3 mg / L, PPA dosage 50 mg / L / L, demulsification temperature 30 oC, / demulsification time 60 min. It is easy to separate oil and water after demulsification with PPA reverse demulsifier. A single adsorbent MPS-SiO_2 was used to treat oily wastewater. When the concentration of oil was 500 mg / L, the dosage of adsorbent was 1.5g / L, and the adsorption time was 60 min, / L, the adsorption temperature was 30 oC. The oil absorption and removal rate of MPS-SiO_2 was 46.8%. The oily wastewater was treated with SiO_2@PPA demulsifier and adsorption. When the concentration of oil was 500mg / L, the dosage of adsorbent was 1.5g / L and the adsorption time was 60 min, the adsorption temperature was 30 oC. The oil removal rate of the supported inverse demulsifier SiO_2@PPA was 91.6%, and the adsorption capacity of the carrier particles reached 301 mg / g / g, which was 6 times higher than that of the granular activated carbon (GAC). The results show that the supported demulsifier SiO_2@PPA carrier particles have the characteristics of porous structure, small particle size and large specific surface area, which makes SiO_2@PPA have both demulsification and adsorption functions. Supported inverse demulsifier SiO_2@PPA can be applied to demulsification treatment of produced water by ternary compound flooding through synergistic action of demulsification and adsorption. The kinetic test of oil droplets adsorbed on SiO_2@PPA carrier shows that the adsorption process accords with pseudo-second-order kinetic equation. In isothermal adsorption, Langmuir isothermal adsorption model is more reasonable than Freundlich isothermal adsorption model to describe the adsorption behavior of SiO_2@PPA carrier particles to oil droplets. Thermodynamic studies show that the adsorption process 螖 G _ 0 and 螖 H _ 0 indicate that the adsorption of oil droplets by SiO_2@PPA carrier particles is a spontaneous and endothermic process.
【学位授予单位】：中国矿业大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TE39

【参考文献】