聚合物胶稳定性影响因素的研究
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摘要
本文研究的聚合物凝胶是以分子间交联为主、分子内交联为辅的具有三维网络结构的弱交联体系。其形成和性能(特别是稳定性)主要受聚合物性质、交联剂类型和交联方式、水中盐度、活性杂质、pn值、温度等多方面因素的制约。
从研究聚合物凝胶体系稳定性出发本文主要开展了以下工作;(1)从聚合物类型(PHPAM、AP-P4和KYPAM-2)、分子量、水解度方面研究了聚合物凝胶体系的成胶性能,实验结果表明,KYPAM-2在60℃、80℃下与乙酸铬交联剂、70℃和90℃下与有机酚醛交联剂形成的凝胶体系30天粘度保留率85%—94%,而AP-P4聚合物在相同条件下形成的凝胶体系30天粘度保留率80%—90%;中、低水解度(15-25%)聚合物形成的凝胶稳定性较好(30天粘度保留率9036-94%)。(2)对乙酸铬、柠檬酸铝、有机酚醛FQ和Cr~(3+)+FQ复合交联体系进行了研究,实验结果表明,在合适的交联剂类型及浓度下,聚合物浓度1000-3000mg/L范围内能够形成成胶时间1-7天可调,强度1000-9000mPa.s,90天粘度保留率均在80%以上的凝胶体系,有机酚醛交联体系耐温抗盐(100℃,70000mg/L)能力比乙酸铬、柠檬酸铝(80℃,50000mg/L)强。(3)通过对加成及缩合反应的控制,改进了活性酚醛树脂,得到了RF交联剂,并考察了不同浓度下RF与KYPAM-2、盐度、pH值和温度的成胶性能,实验结果表明,RF成胶性能比有机酚醛提高,90天粘度保留率可达85%以上。(4)选取了具有一定代表性的四种油田注入水,在水质分析资料基础上进行了聚合物凝胶体系与油田注入水的适应性研究。馆陶水水质良好,除氧后,当KYPAM-2浓度为3000mg/L,聚合物/乙酸铬比值分别为5;1、8;1、10;1的体系60℃和70℃下3个月粘度保留率均在80%以上;吉林新立油田注入水中Fe~(2+)、Fe~(3+)、含氧较低,TGB、SRB含量较高,并含有Br~-、I~-等微量元素,实验结果表明,注入水含Br~-、I~-时,乙酸铬交联剂成胶性能极差,甚至不成胶,柠檬酸铝和有机酚醛成胶性能良好,采用柠檬酸铝交联剂,注入水除氧、杀菌后,当KYPAM-2浓度为2000mg/L,聚合物/柠檬酸铝比值分别为5;1、8;1、10;1的体系60℃下3个月粘度保留率可达80%以上;南阳双河双联注入水中活性杂质主要是H_2S,RF交联剂成胶性能良好,选用KYPAM-2和AP-P4聚合物及RF交联剂,当聚合物浓度为3000mg/L,RF浓度分别为0.6%、0.8%的体系3个月粘度保留率80℃下82%左右,90℃下75%左右;大港南部油田注入水总矿化度较高,活性杂质成分复杂,乙酸铬、柠檬酸铝交联体系不能成胶,RF交联剂成胶性能良好,当KYPAM-2浓度为2000-3000 mg/L,RF浓度为0.6-0.8%的体系3个月粘度保留率80℃下可达80%以上,90℃下可达72%以上。
研究结果表明;PHPAM、AP-P4和KYPAM-2聚合物中KYPAM-2耐温抗盐性更好,适应范围更广;改进的RF交联剂具有更高的耐温抗盐性,能够进一步提高聚合物的耐温抗盐性;油田注入水中活性杂质对凝胶性能影响很大,通过相应处理后,凝胶性能可得到进一步提高。本文的研究结果具有一定现场指导意义和实际应用价值。
The polymer gel studied in this paper is three-dimensional network structure of the weak crosslinking system which is intermolecular crosslinking mainly and is supplemented intramolecular crosslinking.The formation and properties(especially stability)of the polymer gel are constrained mainly by the polymer nature、crosslinker type and crosslinked pattern、water saltness、active impurities、pH、temperature and other factors.
Research from the stability of the polymer gel system,this paper carried out the following tasks;(1)The gelling performance of the polymer gel system is studied from the polymer type(PHPAM,AP-P4 and KYPAM-2),the molecular weight and degree of the hydrolysis,experimental results show that 30 days viscosity retention rate of the gel systems formed by KYPAM-2 in 60℃and 80℃with chromium acetate crosslinker,in 70℃and 90℃with the organic phenolic crosslinker is between 85% and 94%,and under the same conditions 30 days viscosity retention rate of the gel systems formed by AP-P4 is between 80% and 90%; the polymer gel formed by low degree of hydrolysis(15-25%)had good stability(30 days viscosity retention rate is between 90% and 94 %).(2)The chromium acetate、aluminum citrate、organic phenolic FQ and Cr~(3+)+FQ compound crosslinking system are Studied,experimental results show that in suitable type and concentration of crosslinker, when polymer concentration is in the range of 1000-3000mg/L,the gel systems which have 1-7 days adjustable gelling time,strength 1000-9000mPa.s,90 days viscosity retention rate at over 80% can be formed,temperature and salt-resistant capacity of the organic phenolic crosslinldng system(100℃,70000mg/L)is stronger than chromium acetate、aluminum citrate (80℃,50000rag/L).(3)Through controlling on the addition reaction and the condensation reaction,the active phenolic resin crosslinker has been improved,and the RF crosslinker is obtained.Under the different concentrations,the gelling performance of RF with KYPAM-2, salinity,pH and temperature is taken into consideration,experimental results show that the gelling performance of the RF is better than organic phenolic,90 days viscosity retention rate can achieve 85%.(4)Selecting four good representative oilfield induced water,and the adaptability between polymer gel system and oilfield induced water is studied on the basis of the water quality analysis data.Guantao water has good quality,after deaeration,under the 60℃and 70℃three months viscosity retention rate of the systems when concentration of KYPAM-2 is 3000rag/L,polymer / chromium acetate ratio respectively is 5;1,8;1,10;1 is above 80%.In the Jilin Xinli Oilfield induced water the content of Fe~(2+),Fe~(3+),oxygen is low, TGB and SRB have higher levels,and containing Br~-,I~- and other trace elements, experimental results show that in the induced water with Br~-,I~-,gelling performance of the chromium acetate crosslinker is very poor,or even no gelling,aluminum citrate and organic phenolic crosslinking system have good gelling performance,using aluminum citrate erosslinker,after deaeration、sterilization with induced water,under 60℃three months viscosity retention rate of the systems when concentration of KYPAM-2 is 2000mg/L, polymer / aluminum citrate ratio respectively is 5;1,8;1,10;1 can achieve above 80%.The main active impuritiy in Nanyang Shuanghe Shuangliang induced water is H_2S,gelling performance of the RF crosslinker is well,selecting KYPAM-2 and AP-P4 polymer and RF crosslinker,when the polymer concentration is 3000mg/L and RF concentrations respectively is 0.6%,0.8%,under 80℃three months viscosity retention rate of the systems is about 82% and under 90℃is about 75%; In the induced water of the Dagang southern Oilfield,total salinity is high,and active impurities are complex,chromium acetate,aluminum citrate crosslinking system can not erosslink,gelling performance of RF crosslinker is well,when concentration of KYPAM-2 respectively is 2000、3000 mg/L,concentration of RF respectively is 0.6、0.8%,under 80℃three months viscosity retention rate of the system can achieve above 80%,and under 90℃can achieve above 72%.
The results show;among PHPAM.AP-P4 and KYPAM-2,the resistance to temperature and salt of KYPAM-2 is better than others,and it can meet a wider range; improved RF crosslinker has higher resistance to temperature and salt,can further improve the temperature and salt-resistant of polymer; the effect of active impurities in the oilfield induced water on the polymer gel is very significant,through the corresponding treatment,gel performance can be further increased.The research results of' this paper have certain-spot guidance and practical application value.
从研究聚合物凝胶体系稳定性出发本文主要开展了以下工作;(1)从聚合物类型(PHPAM、AP-P4和KYPAM-2)、分子量、水解度方面研究了聚合物凝胶体系的成胶性能,实验结果表明,KYPAM-2在60℃、80℃下与乙酸铬交联剂、70℃和90℃下与有机酚醛交联剂形成的凝胶体系30天粘度保留率85%—94%,而AP-P4聚合物在相同条件下形成的凝胶体系30天粘度保留率80%—90%;中、低水解度(15-25%)聚合物形成的凝胶稳定性较好(30天粘度保留率9036-94%)。(2)对乙酸铬、柠檬酸铝、有机酚醛FQ和Cr~(3+)+FQ复合交联体系进行了研究,实验结果表明,在合适的交联剂类型及浓度下,聚合物浓度1000-3000mg/L范围内能够形成成胶时间1-7天可调,强度1000-9000mPa.s,90天粘度保留率均在80%以上的凝胶体系,有机酚醛交联体系耐温抗盐(100℃,70000mg/L)能力比乙酸铬、柠檬酸铝(80℃,50000mg/L)强。(3)通过对加成及缩合反应的控制,改进了活性酚醛树脂,得到了RF交联剂,并考察了不同浓度下RF与KYPAM-2、盐度、pH值和温度的成胶性能,实验结果表明,RF成胶性能比有机酚醛提高,90天粘度保留率可达85%以上。(4)选取了具有一定代表性的四种油田注入水,在水质分析资料基础上进行了聚合物凝胶体系与油田注入水的适应性研究。馆陶水水质良好,除氧后,当KYPAM-2浓度为3000mg/L,聚合物/乙酸铬比值分别为5;1、8;1、10;1的体系60℃和70℃下3个月粘度保留率均在80%以上;吉林新立油田注入水中Fe~(2+)、Fe~(3+)、含氧较低,TGB、SRB含量较高,并含有Br~-、I~-等微量元素,实验结果表明,注入水含Br~-、I~-时,乙酸铬交联剂成胶性能极差,甚至不成胶,柠檬酸铝和有机酚醛成胶性能良好,采用柠檬酸铝交联剂,注入水除氧、杀菌后,当KYPAM-2浓度为2000mg/L,聚合物/柠檬酸铝比值分别为5;1、8;1、10;1的体系60℃下3个月粘度保留率可达80%以上;南阳双河双联注入水中活性杂质主要是H_2S,RF交联剂成胶性能良好,选用KYPAM-2和AP-P4聚合物及RF交联剂,当聚合物浓度为3000mg/L,RF浓度分别为0.6%、0.8%的体系3个月粘度保留率80℃下82%左右,90℃下75%左右;大港南部油田注入水总矿化度较高,活性杂质成分复杂,乙酸铬、柠檬酸铝交联体系不能成胶,RF交联剂成胶性能良好,当KYPAM-2浓度为2000-3000 mg/L,RF浓度为0.6-0.8%的体系3个月粘度保留率80℃下可达80%以上,90℃下可达72%以上。
研究结果表明;PHPAM、AP-P4和KYPAM-2聚合物中KYPAM-2耐温抗盐性更好,适应范围更广;改进的RF交联剂具有更高的耐温抗盐性,能够进一步提高聚合物的耐温抗盐性;油田注入水中活性杂质对凝胶性能影响很大,通过相应处理后,凝胶性能可得到进一步提高。本文的研究结果具有一定现场指导意义和实际应用价值。
The polymer gel studied in this paper is three-dimensional network structure of the weak crosslinking system which is intermolecular crosslinking mainly and is supplemented intramolecular crosslinking.The formation and properties(especially stability)of the polymer gel are constrained mainly by the polymer nature、crosslinker type and crosslinked pattern、water saltness、active impurities、pH、temperature and other factors.
Research from the stability of the polymer gel system,this paper carried out the following tasks;(1)The gelling performance of the polymer gel system is studied from the polymer type(PHPAM,AP-P4 and KYPAM-2),the molecular weight and degree of the hydrolysis,experimental results show that 30 days viscosity retention rate of the gel systems formed by KYPAM-2 in 60℃and 80℃with chromium acetate crosslinker,in 70℃and 90℃with the organic phenolic crosslinker is between 85% and 94%,and under the same conditions 30 days viscosity retention rate of the gel systems formed by AP-P4 is between 80% and 90%; the polymer gel formed by low degree of hydrolysis(15-25%)had good stability(30 days viscosity retention rate is between 90% and 94 %).(2)The chromium acetate、aluminum citrate、organic phenolic FQ and Cr~(3+)+FQ compound crosslinking system are Studied,experimental results show that in suitable type and concentration of crosslinker, when polymer concentration is in the range of 1000-3000mg/L,the gel systems which have 1-7 days adjustable gelling time,strength 1000-9000mPa.s,90 days viscosity retention rate at over 80% can be formed,temperature and salt-resistant capacity of the organic phenolic crosslinldng system(100℃,70000mg/L)is stronger than chromium acetate、aluminum citrate (80℃,50000rag/L).(3)Through controlling on the addition reaction and the condensation reaction,the active phenolic resin crosslinker has been improved,and the RF crosslinker is obtained.Under the different concentrations,the gelling performance of RF with KYPAM-2, salinity,pH and temperature is taken into consideration,experimental results show that the gelling performance of the RF is better than organic phenolic,90 days viscosity retention rate can achieve 85%.(4)Selecting four good representative oilfield induced water,and the adaptability between polymer gel system and oilfield induced water is studied on the basis of the water quality analysis data.Guantao water has good quality,after deaeration,under the 60℃and 70℃three months viscosity retention rate of the systems when concentration of KYPAM-2 is 3000rag/L,polymer / chromium acetate ratio respectively is 5;1,8;1,10;1 is above 80%.In the Jilin Xinli Oilfield induced water the content of Fe~(2+),Fe~(3+),oxygen is low, TGB and SRB have higher levels,and containing Br~-,I~- and other trace elements, experimental results show that in the induced water with Br~-,I~-,gelling performance of the chromium acetate crosslinker is very poor,or even no gelling,aluminum citrate and organic phenolic crosslinking system have good gelling performance,using aluminum citrate erosslinker,after deaeration、sterilization with induced water,under 60℃three months viscosity retention rate of the systems when concentration of KYPAM-2 is 2000mg/L, polymer / aluminum citrate ratio respectively is 5;1,8;1,10;1 can achieve above 80%.The main active impuritiy in Nanyang Shuanghe Shuangliang induced water is H_2S,gelling performance of the RF crosslinker is well,selecting KYPAM-2 and AP-P4 polymer and RF crosslinker,when the polymer concentration is 3000mg/L and RF concentrations respectively is 0.6%,0.8%,under 80℃three months viscosity retention rate of the systems is about 82% and under 90℃is about 75%; In the induced water of the Dagang southern Oilfield,total salinity is high,and active impurities are complex,chromium acetate,aluminum citrate crosslinking system can not erosslink,gelling performance of RF crosslinker is well,when concentration of KYPAM-2 respectively is 2000、3000 mg/L,concentration of RF respectively is 0.6、0.8%,under 80℃three months viscosity retention rate of the system can achieve above 80%,and under 90℃can achieve above 72%.
The results show;among PHPAM.AP-P4 and KYPAM-2,the resistance to temperature and salt of KYPAM-2 is better than others,and it can meet a wider range; improved RF crosslinker has higher resistance to temperature and salt,can further improve the temperature and salt-resistant of polymer; the effect of active impurities in the oilfield induced water on the polymer gel is very significant,through the corresponding treatment,gel performance can be further increased.The research results of' this paper have certain-spot guidance and practical application value.
引文
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