改性羧甲基淀粉降滤失剂的合成及评价
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摘要
随着目前钻井过程中复杂情况的增加和对钻井环境保护要求的提高,降滤失剂等钻井液添加剂,面临高温、高矿化度及环保性能等方面的挑战。本文以羧甲基淀粉CMS为合成基体,在过硫酸钾和亚硫酸钠氧化还原体系的引发下,以接枝非离子单体AM和阴离子单体AMPS,合成了改性羧甲基淀粉共聚物。并使用Design-Expert软件进行数据分析,通过响应面法确定了最佳聚合条件为:CMS的取代度为0.29,AM/AMPS摩尔比为3:1,单体与羧甲基淀粉加量比0.38:1,反应温度为65℃,引发剂加量为0.22g/L。并采用物理改性的方法,即将共聚物与成膜剂按质量比2:1进行复配,制备得到性能更加优良的改性羧甲基淀粉降滤失剂。
室内评价结果表明,该降滤失剂在淡水基浆和盐水基浆中均有很好的降滤失能力。在降滤失剂加量为1%时,在淡水基浆老化前后API降滤失率分别达到81.3%、82.1%;在降滤失剂加量为2%时,盐水基浆、饱和盐水基浆及海水基浆中老化前后API降滤失率分别达到90.5%、91.9%、90.8%、90%、93.3%、93%。该降滤失剂还具有优良的耐温抗盐能力,抗高温可达150℃,抗NaCl至饱和,抗钙侵达2.5%,降滤失效果也优于与常用降滤失剂OCL、CMS,同时,新型降滤失剂可生物降解,毒性低,对环境影响小。
With the increasing of complex situations in the process of drilling, Filtration reducing agents have to face the challenges of high temperature, high salinity and environmental protection. The graft copolymer intermedium which used potassium peroxodisulfate and sodium sulfite as the initiator system was prepared by carboxymethyl starch(CMS) and 2-acrylamide-2-methyl propanesulfonic acid (AMPS) and acrylamide (AM). Operation conditions were optimized with the Design-Expert 8.0 software, The optimum reaction conditions were that the degree of substitution of CMS was 0.29, the molar ration of AM:AMPS was 3:1, the mass ratio of monomer and CMS was 0.38:1, reaction temperature 65℃, reaction time 2h, pH value 7.0. The modified carboxymethyl starch as filtration control agent was formulated with the graft copolymer and film forming agent at the mass ratio of 1:2.
Laboratory experiments were done on the evaluated of the new type of filtration control agent, which showed that it has very good abilities of depressing the filter loss at both fresh mud and salty mud. With the additive of 1% filtration control agent, the API filter loss rate of pre and post aging could be controlled at 81.3% and 82.1% at the fresh mud. At salty mud, saturated salty mud and sea water mud, the API filter loss rate of pre and post aging could be controlled at 90.5%, 91.9%, 90.8%, 90%, 93.3%, 93%. The agent also has very good abilities of saturated brine, 2.5% calcium and 150℃temperature-resistant. Compared with filtration control agent OCL and CMS, and the ratio of performance and cost is relatively high. The environmental protection of experiment results showed that the new agent was degradable and will not pollute the environment.
室内评价结果表明,该降滤失剂在淡水基浆和盐水基浆中均有很好的降滤失能力。在降滤失剂加量为1%时,在淡水基浆老化前后API降滤失率分别达到81.3%、82.1%;在降滤失剂加量为2%时,盐水基浆、饱和盐水基浆及海水基浆中老化前后API降滤失率分别达到90.5%、91.9%、90.8%、90%、93.3%、93%。该降滤失剂还具有优良的耐温抗盐能力,抗高温可达150℃,抗NaCl至饱和,抗钙侵达2.5%,降滤失效果也优于与常用降滤失剂OCL、CMS,同时,新型降滤失剂可生物降解,毒性低,对环境影响小。
With the increasing of complex situations in the process of drilling, Filtration reducing agents have to face the challenges of high temperature, high salinity and environmental protection. The graft copolymer intermedium which used potassium peroxodisulfate and sodium sulfite as the initiator system was prepared by carboxymethyl starch(CMS) and 2-acrylamide-2-methyl propanesulfonic acid (AMPS) and acrylamide (AM). Operation conditions were optimized with the Design-Expert 8.0 software, The optimum reaction conditions were that the degree of substitution of CMS was 0.29, the molar ration of AM:AMPS was 3:1, the mass ratio of monomer and CMS was 0.38:1, reaction temperature 65℃, reaction time 2h, pH value 7.0. The modified carboxymethyl starch as filtration control agent was formulated with the graft copolymer and film forming agent at the mass ratio of 1:2.
Laboratory experiments were done on the evaluated of the new type of filtration control agent, which showed that it has very good abilities of depressing the filter loss at both fresh mud and salty mud. With the additive of 1% filtration control agent, the API filter loss rate of pre and post aging could be controlled at 81.3% and 82.1% at the fresh mud. At salty mud, saturated salty mud and sea water mud, the API filter loss rate of pre and post aging could be controlled at 90.5%, 91.9%, 90.8%, 90%, 93.3%, 93%. The agent also has very good abilities of saturated brine, 2.5% calcium and 150℃temperature-resistant. Compared with filtration control agent OCL and CMS, and the ratio of performance and cost is relatively high. The environmental protection of experiment results showed that the new agent was degradable and will not pollute the environment.
引文
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[10]王中华.钻井液用丙烯酰胺/2-丙烯酰胺基,2-甲基丙磺酸三元共聚物PAMS的合成[J].油田化学,2000,17(1):6-9
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[14]杨小华.AOIAS/AM/AA共聚物钻井液降滤失剂的合成[J].精细与专用化学品,2007,15(19):22-24
[15]李占国,蔡素君,潘宏涛.钻井液用抗盐降滤失剂MPA-99的研究与应用[J].钻井液与完井液,2008,20(3):24-26
[16]马贵平,喻发全,苏亚明.AA/AM/AMPS超浓反相乳液聚合合成钻井液降滤失剂的研究[J].油田化学,2006,23(1):1-4
[17]刘雨晴,孙金生,王书琪,等.抗高温抗盐阳离子降滤失剂CHSP-I的合成及其应用[J].油田化学,1996,13(1):21-24
[18]刘盈,刘雨晴.新型阳离子抗高温降滤失剂CAP的研制与室内评价[J].油田化学,1996,13(4):294-298
[19]沈丽.新型阳离子聚合物NCP的合成及应用[J].钻井液与完井液,2006, 23(3):54-56
[20]马涛,张贵才.阳离子表面活性剂在国内油田中的应用简介[J].精细石油化工,2004,(5):58-60
[21]郑海洪,李建波,罗庆英,等.钻井液用两性离子聚合物降滤失剂的研究[J].天然气勘探与开发,2009,32(3):59-62
[22]王艳新,陈艳玲,宋俊庭.Hofmann法制备新型两性离子AM-AMPS共聚物降滤失剂[J].地质科技情报,2008,27(4):107-110
[23]贺爱民,杨海,耿波,等.AEDMAC/AM/AA两性共聚物降滤失剂的合成与性能[J].精细石油化工进展,2002,3(12):12-14
[24]孙绍春,邹长军.三元共聚物降滤失剂在无侵害钻井液中的作用[J].钻井液与完井液,2008,25(1):15-17
[25]王中华,杨小华.水溶性纤维素类钻井液处理剂制备与应用进展[J].应用科技,2009,17(9):15-18
[26]朱刚卉.高性能聚阴离子纤维素处理剂的研制[J].石油钻探技术,2005,33(3) :36-38
[27]谭业邦,张黎明,李卓美.纤维素接枝共聚物CGAD的泥浆性能研究[J].油田化学,1999,16(4):291-294
[28]王岩,何静,路婷.纤维素接枝共聚研究[J].精细与专用化学品,2004,12(16):18-21
[29]张黎明,尹向春,李卓美.羧甲基纤维素接枝AM/DMDAAC共聚物作为泥浆处理剂的性能[J].油田化学,1999,16(2):102-105
[30]杨艳丽,李仲谨,王征帆.水基钻井液用改性玉米淀粉降滤失剂的合成[J].油田化学,2006,23(3):198-200
[31]刘祥,李谦定,于红江.羧丙基淀粉的合成及其在钻井液中的应用[J].钻井液与完井液,2000,17(6):5-7
[32]周玲革,赵红静.CSJ复合离子型改性淀粉降滤失剂的研制[J].江汉石油学院学报,2004,26(3):81-82
[33]刘祥,吕伟,李谦定.高粘度复合变性淀粉的流变性与降滤失性能[J].钻井液与完井液,2006,23(6):1-4
[34]姜翠玉,于维钊,张春晓.高取代度阳离子淀粉的合成及其降滤失性能[J].应用化学,2002,23(4):424-428
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