Kelland Malcolm A, Ghosh Radhakanta, Undheim Audun, Dirdal Erik G, Ajiro Hiroharu
Department of Chemistry, Bioscience and Environmental Engineering, Faculty of Science and Technology, University of Stavanger, N-4036 Stavanger, Norway.
Division of Material Science, Graduate School of Science and Technology, Nara Institute of Science and Technology, 8916-5 Takayama-cho, Ikoma, Nara 630-0192, Japan.
ACS Omega. 2022 Sep 27;7(40):35686-35693. doi: 10.1021/acsomega.2c03644. eCollection 2022 Oct 11.
The deployment of kinetic hydrate inhibitors (KHIs) is a chemical method for the prevention of gas hydrate plugging in gas, condensate, and oil production flow lines. Polymers made using the monomer -vinylcaprolactam (VCap) are one of the most common KHI classes. Alternative classes of polymers containing caprolactam groups are rare. Here, we present a study on oxyvinylenelactam polymers and copolymers with pendant piperidone or caprolactam groups. Low-molecular-weight homo- and copolymers were obtained. The nonrotating vinylene groups impart rigidity to the polymer backbone. Poly(oxyvinylenecaprolactam) (POVCap) was insoluble in water, but poly(oxyvinylenepiperidone) (POVPip) and OVPip:OVCap copolymers with 60+ mol % OVPip were soluble with low cloud points. KHI screening tests were carried out using the slow constant cooling method in steel rocking cells. POVPip was water soluble with no cloud point up to 95 °C but showed a poor KHI performance. In contrast, OVPip:OVCap copolymers with about 60-70 mol % OVPip were also water soluble and showed a reasonable KHI performance, better than that of poly(-vinylpyrrolidone) but not as good as that of poly(-vinylcaprolactam). Surprisingly, several additives known to be good synergists for VCap-based polymers showed negligible synergy or were antagonistic with the 62:38 OVPip:OVCap copolymer with regard to lowering the onset temperature of hydrate formation. However, a blend with hexabutylguanidinium chloride showed a strong effect to delay the onset of rapid hydrate formation.
动力学水合物抑制剂(KHI)的部署是一种防止天然气、凝析油和石油生产流线中气体水合物堵塞的化学方法。使用单体乙烯基己内酰胺(VCap)制成的聚合物是最常见的KHI类别之一。含己内酰胺基团的其他聚合物类别很少见。在此,我们展示了一项关于带有侧基哌啶酮或己内酰胺基团的氧化乙烯基内酰胺聚合物和共聚物的研究。获得了低分子量的均聚物和共聚物。非旋转的亚乙烯基赋予聚合物主链刚性。聚(氧化乙烯基己内酰胺)(POVCap)不溶于水,但聚(氧化乙烯基哌啶酮)(POVPip)和含60摩尔%以上POVPip的OVPip:OVCap共聚物在低浊点下可溶。使用钢摇瓶中的缓慢恒定冷却方法进行了KHI筛选测试。POVPip在高达95°C时可溶于水且无浊点,但表现出较差的KHI性能。相比之下,含约60 - 70摩尔%POVPip的OVPip:OVCap共聚物也可溶于水,并表现出合理的KHI性能,优于聚(乙烯基吡咯烷酮),但不如聚(乙烯基己内酰胺)。令人惊讶的是,几种已知对基于VCap的聚合物有良好协同作用的添加剂,在降低水合物形成起始温度方面,与62:38的OVPip:OVCap共聚物显示出可忽略不计的协同作用或具有拮抗作用。然而,与六丁基氯化铵的共混物显示出强烈的效果,可延迟快速水合物形成起始时间。