磺酸盐型聚丙烯酰胺研究
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摘要
部分水解聚丙烯酰胺(HPAM)在我国油田聚合物驱中广泛应用,取得了良好的经济和社会效益,但HPAM耐温、抗盐能力较差,不能适用于高温、高盐储层,使其应用范围受到了一定的限制。针对高温高盐油藏对驱油聚合物的要求,设计了丙烯酰胺与四种含磺酸基单体的共聚,优选出一种增粘性能最好的共聚物,采用正交试验法确定了聚合反应的最佳条件,并考察了反应时间、温度、单体加量、单体配比、引发剂加量及烘干温度等条件对聚合物水溶液粘度的影响,优选出磺酸盐型聚丙烯酰胺SPAM;采用红外光谱对SPAM进行了结构表征,用乌式粘度计测定了SPAM的特性粘数,求出了SPAM的粘均相对分子质量为515万;对SPAM的性能进行了综合评价,SPAM在较高温度下不易分解,具有良好的热稳定性,SPAM水溶液性能研究表明,相对于丙烯酰胺均聚物,SPAM水溶液具有良好的溶解、增粘、耐温、抗盐及抗剪切性能,可以满足高温高盐油藏对驱油聚合物的基本要求。为了提高SPAM的相对分子质量,室内用不同交联剂对SPAM进行了适度交联,优选出苯酚/甲醛交联剂体系,采用此交联剂体系的粘度大幅度提高,在60℃下SPAM浓度为500mg·L-1时体系的粘度为172mPa·s,且具有良好的流变性。探讨了磺酸盐型聚丙烯酰胺SPAM分子结构对其耐温抗盐性能的影响,磺酸基团的强阴离子性赋予SPAM优良的耐温与抗盐性能,为磺酸盐型聚丙烯酰胺在聚合物驱中的应用提供了依据和重要的参考数据。
Partially hydrolyzed polyacrylamide (HPAM) is widely used in polymer flooding and got a good economic and social benefit. Due to its poor temperature and salt tolerance, HPAM is not suitable to be used in high-temperature and high-salinity reservoir. In allusion to the characteristics of high-temperature and high-salinity resevior, polymerization of AM and 4 monomers with sulfonic acid group was carried respectively. And the polymer with best viscosity was chosen. Orthogonal test was carried to determine the optimal condition of polymerization. Effects of time, temperature, monomer concentration, monomer compound, the amount of initiator and drying temperature on the polymer’s viscosity were investigated. The Sulfonated polyacrylamide (SPAM) was composed under those conditions. IR spectrums of HPAM and SPAM can explain their structures. Limiting viscosity of SPAM was tested by viscometer, and then its molecular weight was calculated as 5.15×106. Compare to HPAM, the excellent solubility, thickening property, temperature and salt tolerance of SPAM were indicated by experiments. SPAM can satisfy the requirements of high-temperature and high-salinity reservoir. To improve the molecular weight of SPAM, crosslinking of SPAM and different cross Linkers were taken and the proper cross linker was selected. When the polymer addition was 500mg·L-1 and phenol/formaldehyde crosslinker concentration was 1000mg·L-1, the viscosity of crosslinking system increased greatly and reached to 172mPa·s at 60℃with a good rheology. Effect of sulfonated polymer’s structure on its temperature and salt tolerance approved that, the incorporation of the sulfer acid radial in polymer backbone of HPAM results in excellent properties of the copolymers such as improved resistance to temperature and improved salt tolerance. The research provides foundation and important reference database for the application of sulfonated polyacrymides in polymerflooding.
Partially hydrolyzed polyacrylamide (HPAM) is widely used in polymer flooding and got a good economic and social benefit. Due to its poor temperature and salt tolerance, HPAM is not suitable to be used in high-temperature and high-salinity reservoir. In allusion to the characteristics of high-temperature and high-salinity resevior, polymerization of AM and 4 monomers with sulfonic acid group was carried respectively. And the polymer with best viscosity was chosen. Orthogonal test was carried to determine the optimal condition of polymerization. Effects of time, temperature, monomer concentration, monomer compound, the amount of initiator and drying temperature on the polymer’s viscosity were investigated. The Sulfonated polyacrylamide (SPAM) was composed under those conditions. IR spectrums of HPAM and SPAM can explain their structures. Limiting viscosity of SPAM was tested by viscometer, and then its molecular weight was calculated as 5.15×106. Compare to HPAM, the excellent solubility, thickening property, temperature and salt tolerance of SPAM were indicated by experiments. SPAM can satisfy the requirements of high-temperature and high-salinity reservoir. To improve the molecular weight of SPAM, crosslinking of SPAM and different cross Linkers were taken and the proper cross linker was selected. When the polymer addition was 500mg·L-1 and phenol/formaldehyde crosslinker concentration was 1000mg·L-1, the viscosity of crosslinking system increased greatly and reached to 172mPa·s at 60℃with a good rheology. Effect of sulfonated polymer’s structure on its temperature and salt tolerance approved that, the incorporation of the sulfer acid radial in polymer backbone of HPAM results in excellent properties of the copolymers such as improved resistance to temperature and improved salt tolerance. The research provides foundation and important reference database for the application of sulfonated polyacrymides in polymerflooding.
引文
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[19]李季,吕茂森,荆建红.驱油用耐温抗盐三元共聚物ZYS性能评价[J].油田化学.1999,16(3):258-260
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[21]陈哲,杨旭明,王琪.SPS/P(AM-DMDAAC)分子复合型驱油剂的研究[J].高分子材料科学与工程.1998,14(4):128-l30,135
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[23]魏莹璐.新型水溶性聚合物溶液性能研究[D].北京:北京科技大学,2004
[34] Kulkami R.A, Gundiah S. Solution Behavior of Hydrolysed Polyacrylamides in 0.12M NaCl [J]. Makrol Chem, 1984, 185: 957-96
[25] Lee LT, Lecouriter J, Chaureteau G. Oil Chemistry, 1989, 224
[26]丁伟.丙烯酰胺类聚合物合成及性能研究[D].黑龙江大庆:大庆石油学院,2005
[27]刘平德.三次采油用新型耐温、抗盐聚合物的研究[D].北京:中国石油勘探开发研究院,2003
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[29]张健,李健,罗平亚.疏水化羟甲基纤维素的水溶性质[M].四川南充:油气藏地质及开发工程国家重点实验室第二次国际学术会议,1999
[30]武玉民,于跃芹,秦大伟,等.SAMPS/NVP/AM/SAA四元共聚物的制备与表征[J].青岛科技大学学报.2003,24(4):283-286
[31] Ilipoulous Magny B, Lafuma F, lliopoulous I. Polymer,1992,33: 31-51
[32]罗开富,叶林,黄荣华.疏水缔合水溶性聚合物的溶液性质[J].油田化学.1999,16(3):286-290
[33]吕静兰,顾民,李伟,等.甲基丙烯磺酸钠-N,N-二甲基丙烯酰胺-丙烯酰胺耐温抗盐共聚物性能的研究[J].石油化工.2005,34(6):573-577
[34]杨凤艳,刘昆元,韩淑珍.反相悬浮法合成超高分子量AM/AA/AMPS及盐的共聚物[J].北京化工大学学报(自然科学版).2003,30(2):5-9
[35] Schutz D N, Kaldas J J, Maurer J J, et al. Copolymers of Acrylamide and Surfactant Macromonomers: Synthesis and Solution Properties [J]. Polymer, 1987, 28: 2110
[36] Siddiq M, Tam K C Jenkins R D. Dissolution Behavior of Model Alkali-soluble Emulsion Polymers: Effects of Molecular Weight and Ionic Strength [J]. Colloid Polymer Science,1999,277: 1172
[37]樊剑.耐温耐盐驱油用聚合物的研究[D].北京:中国石油勘探开发科学研究院.2003
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