小尺寸功能化的掺锆二氧化硅/聚砜杂化膜及性能研究
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摘要
油田采出水经过常规方法(自然沉降、絮凝、介质过滤等)处理后,水质还不能达到油田回注要求,因此我们需要对油田采出水进行深度处理。杂化膜能够有效的去除水中粒径在100微米以下的油和杂质。但是,现有的杂化膜所使用的填充材料不能够很好地与聚合物链键合,且粒子之间也容易团聚。从而限制了杂化膜性能的进一步提高。因此,研究分散性好、容易和聚合物链相互作用的填充材料具有重要意义。
本文采用填充具有低表面能的亲水性粒子的方法,增强其与高分子聚合物基体的相容性,使其在高分子膜基体中均匀分散并维持稳定的尺寸,从而实现了对杂化膜的亲水性和抗压实性能改性。
首先制备出具有较强亲水性和较低表面能的小尺寸功能化掺锆SiO_2粒子(SZP粒子),并将其添加到聚砜膜中制备出SZP/PSF无机-有机杂化膜。确定了SZP/PSF杂化膜的适宜制备条件:PSF的浓度13.5wt.%,PEG400的添加量10wt.%,SZP粒子的添加量是PSF的10wt.%;制备过程中间歇超声,每隔10min超声10min,空气中预蒸发时间20s,凝胶水浴温度25℃。
SEM图像可以看出,SZP/PSF杂化膜呈不对称结构,并且SZP粒子均匀地分散在膜表面、膜骨架以及膜孔道表面。纯水通量测试实验表明SZP/PSF杂化膜的亲水性能、抗压实性能提高。
在0.10Mpa压力下,10wt.%SZP/PSF杂化膜处理含油量和固体悬浮物含量分别为20mg/L、35mg/L的采出水,膜过滤后的采出水中的油含量和固体悬浮物含量分别为0.98mg/L,14 mg/L,符合油田回注标准。
本文研究了SZP粒子的结构、SZP粒子与PSF高聚物链之间的键合作用和采出水与SZP/PSF杂化膜表面及膜孔道的相互作用规律,为杂化膜理论的深入研究打下了基础。
Oilfield produced water can not meet the requirement for reinjection after former processes such as gravity sedimentation, flocculation and filtration. So oilfield produced water need to be further treated. Hybrid membranes filtration could remove oil and impurity substance below 100μm in oilfield produced water. However, not only the bonding effect between filling materials in hybrid membranes and polymer chain is not better but also filling materials in hybrid membranes are easy to agglomerate. So the comprehensive property of hybrid membranes could not been further improved. So it is significant to develop the filling materials with better dispersive and better bonding effect with polymer chain.
In the paper, filled particles with lower surface energy and better hydrophilic property were added into high polymer, which improves the compatibility between filled particles and the high polymer. So filled particles can disperse uniformly in the high polymer and keep stable small size,which realizes the improvement of the hydrophilic and anti-compression property of filled membrane.
Functional Zr-doped silicas with small-size (SZP particles) with stronger hydrophilic property and lower surface energy were prepared and were added into the porous of polysulfone (PSF) into SZP/PSF hybrid membranes. The fitting preparation conditions of SZP/PSF hybrid membranes were: the PSF concentration 13.5wt. %, the PEG400 concentration 16%, the ratio of SZY particles/PSF 10wt.%, intermittent ultrasound, the evaporating time 20s, the coagulation bath temperature 25℃.
SEM micrographs show that SZP/PSF hybrid membranes are the asymmetry structure and SZP particles disperse uniformly on the surface of membrane and in the membrane. The permeation flux tests of pure water show that the hydrophilic and anti-compression property of SZP/PSF hybrid membranes have been improved.
The permeation flux tests of oilfield produced water(oil concentration and solid suspended matter concentration are less than 20 and 35mg/L, respectively)were carried out under operating pressure of 0.10MPa. The results reveal that oil concentration and solid suspended matter concentration of treated oilfield produced water are less than 0.98 and 14 mg/L respectively, which meet the requirement for reinjection.
Finally, the structures of SZP particles, the bonding function between SZP particles and polymer chain of PSF were studied. And the interaction mechanism between oilfield produced water and the surface and pore channels of SZP/PSF hybrid membranes was further researched. Above these are the foundations of hybrid membrane theories.
本文采用填充具有低表面能的亲水性粒子的方法,增强其与高分子聚合物基体的相容性,使其在高分子膜基体中均匀分散并维持稳定的尺寸,从而实现了对杂化膜的亲水性和抗压实性能改性。
首先制备出具有较强亲水性和较低表面能的小尺寸功能化掺锆SiO_2粒子(SZP粒子),并将其添加到聚砜膜中制备出SZP/PSF无机-有机杂化膜。确定了SZP/PSF杂化膜的适宜制备条件:PSF的浓度13.5wt.%,PEG400的添加量10wt.%,SZP粒子的添加量是PSF的10wt.%;制备过程中间歇超声,每隔10min超声10min,空气中预蒸发时间20s,凝胶水浴温度25℃。
SEM图像可以看出,SZP/PSF杂化膜呈不对称结构,并且SZP粒子均匀地分散在膜表面、膜骨架以及膜孔道表面。纯水通量测试实验表明SZP/PSF杂化膜的亲水性能、抗压实性能提高。
在0.10Mpa压力下,10wt.%SZP/PSF杂化膜处理含油量和固体悬浮物含量分别为20mg/L、35mg/L的采出水,膜过滤后的采出水中的油含量和固体悬浮物含量分别为0.98mg/L,14 mg/L,符合油田回注标准。
本文研究了SZP粒子的结构、SZP粒子与PSF高聚物链之间的键合作用和采出水与SZP/PSF杂化膜表面及膜孔道的相互作用规律,为杂化膜理论的深入研究打下了基础。
Oilfield produced water can not meet the requirement for reinjection after former processes such as gravity sedimentation, flocculation and filtration. So oilfield produced water need to be further treated. Hybrid membranes filtration could remove oil and impurity substance below 100μm in oilfield produced water. However, not only the bonding effect between filling materials in hybrid membranes and polymer chain is not better but also filling materials in hybrid membranes are easy to agglomerate. So the comprehensive property of hybrid membranes could not been further improved. So it is significant to develop the filling materials with better dispersive and better bonding effect with polymer chain.
In the paper, filled particles with lower surface energy and better hydrophilic property were added into high polymer, which improves the compatibility between filled particles and the high polymer. So filled particles can disperse uniformly in the high polymer and keep stable small size,which realizes the improvement of the hydrophilic and anti-compression property of filled membrane.
Functional Zr-doped silicas with small-size (SZP particles) with stronger hydrophilic property and lower surface energy were prepared and were added into the porous of polysulfone (PSF) into SZP/PSF hybrid membranes. The fitting preparation conditions of SZP/PSF hybrid membranes were: the PSF concentration 13.5wt. %, the PEG400 concentration 16%, the ratio of SZY particles/PSF 10wt.%, intermittent ultrasound, the evaporating time 20s, the coagulation bath temperature 25℃.
SEM micrographs show that SZP/PSF hybrid membranes are the asymmetry structure and SZP particles disperse uniformly on the surface of membrane and in the membrane. The permeation flux tests of pure water show that the hydrophilic and anti-compression property of SZP/PSF hybrid membranes have been improved.
The permeation flux tests of oilfield produced water(oil concentration and solid suspended matter concentration are less than 20 and 35mg/L, respectively)were carried out under operating pressure of 0.10MPa. The results reveal that oil concentration and solid suspended matter concentration of treated oilfield produced water are less than 0.98 and 14 mg/L respectively, which meet the requirement for reinjection.
Finally, the structures of SZP particles, the bonding function between SZP particles and polymer chain of PSF were studied. And the interaction mechanism between oilfield produced water and the surface and pore channels of SZP/PSF hybrid membranes was further researched. Above these are the foundations of hybrid membrane theories.
引文
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[8] Jeffrey M,Yanwei C,Robert H D,Crossflow microfiltration of oily water,J. Membr. Sci.,1997,129(2):221~235
[9] Yang Y N,Zhang H X,Wang P,et al.,The influence of nano-sized TiO2 fillers on the morphologies and properties of PSF UF membrane,J. Membr. Sci.,2007,288(1-2):231~238
[10]朱愉洁,文晨,朱华章等,聚偏氟乙烯/TiO2杂化膜的结构与性能研究,天津工业大学学报,2008,27 (3):65~67
[11] Yang Y N,Zhang H X,Wang P,et al.,The influence of nano-sized TiO2 fillers on the morphologies and properties of PSF UF membrane,J. Membr. Sci.,2007,288(1-2):231~238
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[13]姜云鹏,王榕树,纳米SiO2/PVA杂化超滤膜的制备及性能研究,高分子材料科学与工程,2002,18(5):177~180
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[15]刘晓娟,彭跃莲,纪树兰,一种新的制备有机-无机杂化膜的方法,膜科学与技术,2008,28(1):46~48
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[17]曲云,张裕卿,具有耐污染性的SiO2/聚砜共混膜的研究,工业水处理,2006,26(7):26~29
[18] Zhang Q,Miller J M,ZrO2/SiO2 Mixed Oxides as Catalysts for Alcohol Dehydration,Appl. Catal.,A:General,2001,209(1-2):1~6
[19]张新荣,杨平等,附载型杂化光催化剂TiO2·Al2O3/beads降解有机磷农药, 2001,14(2):36~40
[20]迟亚武,梁东白,罗洪原等,在超细催化剂CuO/ZnO/SiO2上CO2加氢合成甲醇的优化研究,1997,1(2):41~46
[21] Thomas C L,Catalytic Process and Proven Catalytic,Academic Press,New York,1970,67~89
[22] Hamamoto Y,Mitsutani A,Kogyo Kagaku Zasshi,1964,127(1):67~68
[23]陈永礼,宋代磊,王润霞等,磷钨酸铝盐催化合成十二烷基磷酸单酯,工业催化, 2009,17(6):1008~1143
[24]杨水金,李臻,童文龙等,TiO2负载磷钨杂多酸催化剂催化合成缩醛(酮),精细化工,2005,22(11):842~852
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[26]姚超,高国生,林西平等,硅烷偶联剂对纳米二氧化钛表面改性的研究,无机材料学报,2006,21(2):317~318
[27]冯猛,赵春贵,巩方玲等,氨基硅烷偶联剂对蒙脱石的修饰改性研究,化学学报,2004,62(1):83~87
[28]杜高翔,纳米沉淀二氧化硅的硅烷偶联剂原位表面改性,功能材料,2008,39(1):2072~2074
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[31]徐伟平,黄锐,聚合物/无机纳米粒子杂化材料的研究进展,中国塑料, 1997,11(5):15~22
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[33]姚雪丽,马晓燕,陈芳等,SiO2/氰酸酯纳米杂化材料的力学性能和热性能,杂化材料学报,2006,23(2):54~55
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