油田封隔器用遇水/遇油膨胀橡胶制备与性能研究
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摘要
随着工业的发展,人们对石油的需求量日益增多,油田钻井漏失情况日益严重,在此背景下,新型的油田用堵漏防渗材料——遇水膨胀和遇油自膨胀封隔器,已成为研究应用的热点方向。遇水膨胀和遇油膨胀橡胶是自封隔器的核心材料,它具有优良弹性和吸水或吸油膨胀性能。考虑到成本以及工艺因素,工业上一般将橡胶基体和吸水树脂(SAR)或吸油树脂(OAR)进行物理共混来制备遇水或遇油膨胀橡胶,所合成的吸水或吸油树脂、橡胶基体的选择以及树脂与基体材料的相容性对共混材料的膨胀和封压性能有着重要的影响。本文的主要研究内容如下:
本文以SAR、炭黑、白炭黑、聚乙二醇、硅烷偶联剂KH-570以及各种橡胶助剂与丁腈橡胶(NBR)机械共混制备遇水膨胀橡胶(WSR),并以此材料制备WSR自膨胀封隔器,研究了SAR用量、炭黑/白炭黑用量比、聚乙二醇用量以及硅烷偶联剂KH-570用量对WSR的力学性能和吸水膨胀性能的影响,利用SEM对WSR进行了微观结构分析,并对封隔器的径向膨胀率和耐压差性能进行了测试。结果表明:白炭黑和聚乙二醇可以明显提高WSR的吸水速率,KH-570可以降低WSR的流失率;封隔器的径向膨胀率5天达到110%,耐压差高达23.6MPa,可以初步满足油田使用要求。
以甲基丙烯酸十八酯(SMA)、丙烯酸丁酯(BA)、苯乙烯(St)为共聚单体,二乙烯苯( DVB)为交联剂,过氧化苯甲酰( BPO)作引发剂,三氯甲烷(CHCl_3)为致孔剂以及聚乙烯醇(PVA)为分散剂,采用悬浮聚合法制备出致孔性高吸油树脂。研究了水油比、分散剂用量、引发剂用量、交联剂用量、致孔剂用量以及单体配比对高吸油树脂吸油性能的影响。实验表明,合成高吸油树脂的适宜工艺条件:水油比为3:1,w(DVB)=1.2%,w(BPO)=1.0%, w(PVA)=1%,w(CHCl_3)=35%, m(SMA):m(BA):m(St)=33:67:12,合成的高吸油树脂吸四氯化碳、甲苯、柴油的倍率分别为11.2 g/g、18.8 g/g、27.4 g/g。
以OAR、炭黑、石油树脂以及其他橡胶助剂等与丁苯橡胶(SBR)物理共混制备遇油膨胀橡胶(OSR),并以此材料制备OSR自膨胀封隔器,研究了OAR用量、炭黑用量、石油树脂用量等对OSR力学性能和吸油膨胀倍率的影响,利用SEM对OSR进行了微观结构分析,并对封隔器的径向膨胀率和封压性能进行了测试。结果表明:随着OAR用量的增加,OSR的吸油膨胀倍率显著增加,但力学性能明显降低;石油树脂有助于改善OSR的相容性,提高OSR的力学性能和吸油膨胀倍率;封隔器的径向膨胀率6天可达80%,耐压差高达27.6 MPa,可以初步满足油田使用要求。
With the development of industry, the demand of petroleum is greatly increased, which leads to the oil spills condition becomes more and more serious, as a result, the research of new impervious materials, water or oil swelling rubber self-swollen packer, become a burgeoning field. The main material of the packer is water swelling rubber(WSR)or oil swelling rubber(OSR), which is a new function sealed material with high elasticity and water or oil swollen property. Considering the costs and technological factors in industry, WSR or OSR is always prepared by the way of mixing the supper absorb resin (SAR) or oil absorb resin (OAR) and the rubber together based on physical blending method, and the absorbent capability of the resin, the mechanical of the rubber as well as the compatibility between the resin and the rubber have a great influence on the application of the swelling material. The main design work is as follows:
In the thesis, WSR was prepared by NBR, SAR, carbon black (CB), white carbon black (WCB), polyethylene glycol (PEG), silane coupling agent KH-570, and all other addition agents blended, moreover, the self-swollen packer was prepared by WSR. The effects of the mass of SAR, CB, WCB, PEG, silane coupling agent on the mechanical and swelling capabilities of WSR were separately studied. In addition, the microcosmic structure was studied by SEM. What's more, the radial expansion rate and pressure resistance property of the packer was investigated. The results showed that the swelling speed of WSR was greatly accelerated with the help of WCB and PEG, the mass lose rate of WSR was reduced under the influence of KH-570. In addition, the radial expansion rate of the WSR packer achieved to 110% in 5 days, and the pressure resistance of the parker reached to 23.6 MPa, which could meet the requirement of used for oilfield.
A super oil absorb resin(OAR) based on suspension copolymerization was synthesised, with stearoyl methacrylate(SMA), butylacrylate(BA) and styrene(St) as functional monomers, polyvinyl alcohol(PVA) as dispersing agent, benzoyl peroxide as initiator, divinylbenzene(DVB) as cross-linking agent and chloroform as porogenic agent. The effect of water/oil ratio, dispersing agent, initiator, cross-linking agent, porogenic agent, comonomer ratio on the swelling property of OSR were studied. It showed that the preferable condition were water/oil ratio was 3:1, w(DVB)=1.2% ,w(BPO)=1.0%, w(PVA)=1%,w(CHCl_3)=35%, m(SMA):m(BA):m(St)= 33:67:12. The absorbent capability of OAR in phenixin,toluene,diesel oil was 11.2 g/g, 18.8 g/g, 27.4 g/g, respectively. Otherwise, the TG analysis showed that the OAR excellent thermal stability.
OSR was prepared by SBR, OAR, CB, petroleum resin, and all other addition agents blended, and then, the self-swelling packer was made from OSR. The effects of the contain of OAR, CB, petroleum resin on the mechanical and swelling capabilities of OSR were separately studied. Moreover, the microcosmic structure was studied by SEM. The results showed that with the increasement of OAR, the oil absorbent capability of OSR was ameliorated but the mechanical was reduced, and when mixed with the petroleum resin, the compatibility of OSR was improved, as well as the mechanical and swelling capabilities. In addition, the radial expansion rate of the OSR packer could achieve to 80% in 6 days, and the pressure resistance of the parker could reach up to 27.6 MPa, which could meet the requirement of used for oilfield.
本文以SAR、炭黑、白炭黑、聚乙二醇、硅烷偶联剂KH-570以及各种橡胶助剂与丁腈橡胶(NBR)机械共混制备遇水膨胀橡胶(WSR),并以此材料制备WSR自膨胀封隔器,研究了SAR用量、炭黑/白炭黑用量比、聚乙二醇用量以及硅烷偶联剂KH-570用量对WSR的力学性能和吸水膨胀性能的影响,利用SEM对WSR进行了微观结构分析,并对封隔器的径向膨胀率和耐压差性能进行了测试。结果表明:白炭黑和聚乙二醇可以明显提高WSR的吸水速率,KH-570可以降低WSR的流失率;封隔器的径向膨胀率5天达到110%,耐压差高达23.6MPa,可以初步满足油田使用要求。
以甲基丙烯酸十八酯(SMA)、丙烯酸丁酯(BA)、苯乙烯(St)为共聚单体,二乙烯苯( DVB)为交联剂,过氧化苯甲酰( BPO)作引发剂,三氯甲烷(CHCl_3)为致孔剂以及聚乙烯醇(PVA)为分散剂,采用悬浮聚合法制备出致孔性高吸油树脂。研究了水油比、分散剂用量、引发剂用量、交联剂用量、致孔剂用量以及单体配比对高吸油树脂吸油性能的影响。实验表明,合成高吸油树脂的适宜工艺条件:水油比为3:1,w(DVB)=1.2%,w(BPO)=1.0%, w(PVA)=1%,w(CHCl_3)=35%, m(SMA):m(BA):m(St)=33:67:12,合成的高吸油树脂吸四氯化碳、甲苯、柴油的倍率分别为11.2 g/g、18.8 g/g、27.4 g/g。
以OAR、炭黑、石油树脂以及其他橡胶助剂等与丁苯橡胶(SBR)物理共混制备遇油膨胀橡胶(OSR),并以此材料制备OSR自膨胀封隔器,研究了OAR用量、炭黑用量、石油树脂用量等对OSR力学性能和吸油膨胀倍率的影响,利用SEM对OSR进行了微观结构分析,并对封隔器的径向膨胀率和封压性能进行了测试。结果表明:随着OAR用量的增加,OSR的吸油膨胀倍率显著增加,但力学性能明显降低;石油树脂有助于改善OSR的相容性,提高OSR的力学性能和吸油膨胀倍率;封隔器的径向膨胀率6天可达80%,耐压差高达27.6 MPa,可以初步满足油田使用要求。
With the development of industry, the demand of petroleum is greatly increased, which leads to the oil spills condition becomes more and more serious, as a result, the research of new impervious materials, water or oil swelling rubber self-swollen packer, become a burgeoning field. The main material of the packer is water swelling rubber(WSR)or oil swelling rubber(OSR), which is a new function sealed material with high elasticity and water or oil swollen property. Considering the costs and technological factors in industry, WSR or OSR is always prepared by the way of mixing the supper absorb resin (SAR) or oil absorb resin (OAR) and the rubber together based on physical blending method, and the absorbent capability of the resin, the mechanical of the rubber as well as the compatibility between the resin and the rubber have a great influence on the application of the swelling material. The main design work is as follows:
In the thesis, WSR was prepared by NBR, SAR, carbon black (CB), white carbon black (WCB), polyethylene glycol (PEG), silane coupling agent KH-570, and all other addition agents blended, moreover, the self-swollen packer was prepared by WSR. The effects of the mass of SAR, CB, WCB, PEG, silane coupling agent on the mechanical and swelling capabilities of WSR were separately studied. In addition, the microcosmic structure was studied by SEM. What's more, the radial expansion rate and pressure resistance property of the packer was investigated. The results showed that the swelling speed of WSR was greatly accelerated with the help of WCB and PEG, the mass lose rate of WSR was reduced under the influence of KH-570. In addition, the radial expansion rate of the WSR packer achieved to 110% in 5 days, and the pressure resistance of the parker reached to 23.6 MPa, which could meet the requirement of used for oilfield.
A super oil absorb resin(OAR) based on suspension copolymerization was synthesised, with stearoyl methacrylate(SMA), butylacrylate(BA) and styrene(St) as functional monomers, polyvinyl alcohol(PVA) as dispersing agent, benzoyl peroxide as initiator, divinylbenzene(DVB) as cross-linking agent and chloroform as porogenic agent. The effect of water/oil ratio, dispersing agent, initiator, cross-linking agent, porogenic agent, comonomer ratio on the swelling property of OSR were studied. It showed that the preferable condition were water/oil ratio was 3:1, w(DVB)=1.2% ,w(BPO)=1.0%, w(PVA)=1%,w(CHCl_3)=35%, m(SMA):m(BA):m(St)= 33:67:12. The absorbent capability of OAR in phenixin,toluene,diesel oil was 11.2 g/g, 18.8 g/g, 27.4 g/g, respectively. Otherwise, the TG analysis showed that the OAR excellent thermal stability.
OSR was prepared by SBR, OAR, CB, petroleum resin, and all other addition agents blended, and then, the self-swelling packer was made from OSR. The effects of the contain of OAR, CB, petroleum resin on the mechanical and swelling capabilities of OSR were separately studied. Moreover, the microcosmic structure was studied by SEM. The results showed that with the increasement of OAR, the oil absorbent capability of OSR was ameliorated but the mechanical was reduced, and when mixed with the petroleum resin, the compatibility of OSR was improved, as well as the mechanical and swelling capabilities. In addition, the radial expansion rate of the OSR packer could achieve to 80% in 6 days, and the pressure resistance of the parker could reach up to 27.6 MPa, which could meet the requirement of used for oilfield.
引文
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