聚合物微凝胶制备及在油气田中的应用

潘江浩; 贾文峰; 盛家平

doi:10.12358/j.issn.1001-5620.2021.05.001

聚合物微凝胶制备及在油气田中的应用

doi: 10.12358/j.issn.1001-5620.2021.05.001

潘江浩^{1, 2,},
贾文峰^1, ,,
盛家平¹

1.
中国石油大学（北京）非常规油气科学技术研究院, 北京102249
2.
中国石化石油工程技术研究院, 北京100101

基金项目: 国家重大科技专项课题“彭水地区高效钻井及压裂工程工艺技术优化技术”（2016ZX05061-010）；国家重大科技专项“海相碳酸盐岩超深油气井关键工程技术”（2017ZX05005-005）

详细信息

作者简介:
潘江浩，现在主要从事油气田开发方面的研究。电话 18511318399 ；E-mail：791731634@qq.com

通讯作者:
贾文峰，副研究员，研究方向为压裂酸化及提高采收率用流体与材料研究。E-mail：jiawf@iccas.ac.cn

中图分类号: TE254.4
计量
- 文章访问数: 664
- HTML全文浏览量: 368
- PDF下载量: 82
- 被引次数: 0
出版历程
- 收稿日期: 2021-06-08
- 刊出日期: 2021-09-30

Preparation and application progress of polymer microgel in oil and gas field

PAN Jianghao^{1, 2
,},
JIA Wenfeng^{1
, ,},
SHENG Jiaping¹

1.
Unconventional Petroleum Research Institute, China University of Petroleum (Beijing), Beijing 102249
2.
Sinopec Research Institute of Petroleum Engineering, Beijing 100101

摘要

摘要: 聚合物微凝胶是一种聚合物交联网络颗粒，又称聚合物微球。聚合物微球凭借自身优良的耐温、耐盐性和特殊的构型，在油气田开发中应用。随油藏环境越来越恶劣，对聚合物微球的性能也提出了新的要求，研究高性能且稳定的功能型聚合物微球变得愈发重要。笔者综述了聚合物微球的主要制备方法，包括反相乳液聚合法、反相微乳液聚合法、反相悬浮聚合法和分散聚合法，对比了不同制备方法的优缺点。综述了聚合物微球在深部调驱、油田荧光示踪剂和钻井液降滤失方面的应用，介绍了不同微球的功能机理，比较了不同类型调驱用聚合物微球的性能特点，对比了不同荧光聚合物微球的荧光特性。目前针对功能型微球的研究较少，应从构型考虑微球的制备，研发具有特殊功能的微球。为后续功能型聚合物制备和油气田开发应用的研究指明了方向。
- 钻井液 /
- 聚合物微球 /
- 调驱 /
- 荧光特性
Abstract: Polymer microgel , also known as microspheres,a kind of polymer cross-linked network particles, have been widely used in oilfield development in recent years due to their excellent temperature and salt resistance and special configuration. As the reservoir environment becomes more and more severe, new requirements are put forward for the performance of polymer microsgels. So it is necessary to make the high performance and stable polymer microgels. In this paper, the preparation of polymer microgels were reviewed, including inverse emulsion polymerization, inverse microemulsion polymerization, inverse suspension polymerization and dispersion polymerization. The applications of polymer microgels in deep control and displacement, oilfield tracer and fluid loss control in drilling fluid were summarized. The different mechanism of microgels used in profile control is discussed. The properties of different fluorescent polymer microgels were compared. In order to solve the problems of polymer microspheres, such as few reports on functional polymer microspheres, it is necessary to deepen the research on the configuration of microspheres. And the preparation and application of functional polymers in oil and gas field development was pointed out.
- Drilling fluid /
- Polymer microsphere /
- Profile control /
- Fluorescence characteristic

HTML全文

图 1 低弹微球溶胀前(a)和溶胀后(b)的环扫电镜图像^[25]

下载: 全尺寸图片幻灯片

图 2 聚合物链水解并发生二次交联^[29]

下载: 全尺寸图片幻灯片

图 3 核壳纳米微球的合成^[30]

下载: 全尺寸图片幻灯片

图 4 FRGO(a)和RGO-PMSs微球(b)的合成路线^[40]

下载: 全尺寸图片幻灯片

图 5 PMSCNs微球受力形变过程^[43]

下载: 全尺寸图片幻灯片

图 6 PMSCNs微球的合成^[41]

下载: 全尺寸图片幻灯片

图 7 盐水中pH值和不同离子对P(AM-BA-RhB)微球荧光强度的影响^[46]

下载: 全尺寸图片幻灯片

表 1 不同荧光微球性能对比

单体名称	单体结构式	荧光颜色	微球适用pH值范围	特点
烯丙基罗丹明B(RhB)		红色	3～10	注入岩心后，注入压力呈波浪式前进，完成了有效封堵
8-烯丙氧基- 1, 3, 6-芘三磺酸三钠		红棕色	1～14	在90 ℃下仍保持较高的荧光强度，可保存30 d
四（4, 4′, 4′′, 4′′′ - 烯丙氧基）四苯基乙烯 (ALTPE)		蓝色	1～14	在150 ℃下保持荧光性，自然条件保存60 d

下载: 导出CSV

参考文献(56)

[1]	WANG H, LIN M, CHEN D, et al. Research on the rheological properties of cross-linked polymer microspheres with different microstructures[J]. Powder Technology, 2018, 331:310-321.
[2]	刘祥,杜荣荣,邓凯迪,等. 交联聚丙烯酰胺纳米微球的制备及性能评价[J]. 精细化工,2015,32(11):1301-1306. LIU Xiang, DU Rongrong, DENG Kaidi, et al. Preparation and performance evaluation of cross-linked polyacrylamide nanoparticles[J]. Fine Chemicals, 2015, 32(11):1301-1306.
[3]	余昊,梅雪,陈吟龙. 一种聚合物微球的合成[J]. 应用化工,2015,44(5):914-917. YU Hao, MEI Xue, CHEN Yinlong. Synthesis of a polymericparticle[J]. Applied Chemical Industry, 2015, 44(5):914-917.
[4]	穆蒙,宁学文,罗新杰,等. 刺激响应性聚合物微球的制备、性能及应用[J]. 化学进展,2020,32(7):882-894. MU Meng, NING Xuewen, LUO Xinjie, et al. Fabrications, properties, and applications of stimuli-responsive polymer microspheres[J]. Progress in Chemistry, 2020, 32(7):882-894.
[5]	YU Z S, LI Y C, SHA O, et al. Synthesis and properties of amphiprotic polyacrylamide microspheres as water shutoff and profile control[J]. Journal of Applied Polymer Science, 2016, 133(17).
[6]	邓凯迪,李谦定. 提高采收率用聚(N-羟甲基丙烯酰胺-丙烯酰胺)微球的反相微乳液聚合及其性能[J]. 材料科学与工程学报,2017,35(3):468-474. DENG Kaidi, LI Qiangding. Inverse microemulsion polymerization and performance study of poly(N-hydroxymethyl acrylamide-co-acrylamide)microspheres for EOR[J]. Journal of Materials Science and Engineering, 2017, 35(3):468-474.
[7]	HUA JIE L, YUHUAN B, RUI M, et al. High-strength metakaolin-based hollow-core microspheres as an internal curing agent for mitigation of autogenous shrinkage of well cement[J]. Construction and Building Materials, 2021, 272:121970.
[8]	陶丹阳,杜文浩,田圆芳,等. 耐温抗盐聚合物微球降滤失剂的制备与性能评价[J]. 油田化学,2020,37(3):386-390. TAO Danyang, DU Wenhao, TIAN Yuanfang, et al. Preparation and performance evaluation of temperature and salt resistant polymer microspheres for fluid loss control[J]. Oilfield Chemistry, 2020, 37(3):386-390.
[9]	魏鑫,钟宏. 反相乳液聚合的研究进展[J]. 化学与生物工程,2007(12):12-14. doi: 10.3969/j.issn.1672-5425.2007.12.004 WEI Xin, ZHONG Hong. Research progress of inverse emulsion polymerization[J]. Chemistry & Bioengineering, 2007(12):12-14. doi: 10.3969/j.issn.1672-5425.2007.12.004
[10]	张海波,陈岚岚,杨艳平,等. 聚丙烯酰胺的合成及应用研究进展[J]. 高分子材料科学与工程,2016,32(8):177-181. ZHANG Haibo, CHEN Lanlan, YANG Yanping, et al. Research progress on synthesis and application of polyacrylamide[J]. Polymer Materials Science and Engineering, 2016, 32(8):177-181.
[11]	李光辉,未九森,李晓丹,等. 聚(苯乙烯-丙烯酰胺)核壳型微球破胶剂的制备与缓释效果[J]. 油田化学,2020,37(2):208-211. LI Guanghui, WEI Jiusen, LI Xiaodan, et al. Preparation and sustained release of poly (styrene-acrylamide) core-shell microsphere breaker[J]. Oilfield Chemistry, 2020, 37(2):208-211.
[12]	宗进旗,王敏,王斌,等. 绿色环保型微球的合成及性能评价[J]. 精细石油化工进展,2021,22(1):41-45. doi: 10.3969/j.issn.1009-8348.2021.01.011 ZONG Jinqi, WANG Min, WANG Bin, et al. Synthesis and performance evaluation of green microspheres[J]. Advances in Fine Petrochemicals, 2021, 22(1):41-45. doi: 10.3969/j.issn.1009-8348.2021.01.011
[13]	戴姗姗,寇子敏,刘艳,等. SiO₂/聚丙烯酰胺核壳复合材料的制备研究[J]. 化工新型材料,2018,46(6):135-139. DAI Shanshan, KOU Zimin, LIU Yan, et al. Research on Preparation of Nano-SiO₂/Polyacrylamide core-shell composite[J]. New Chemical Materials, 2018, 46(6):135-139.
[14]	欧明. 核壳型聚丙烯酰胺共聚物微球调剖剂的制备与评价[D]. 中国石油大学(华东), 2018. OU Ming. Preparation and properties of core-shell polyacrylamide copolymer microsphere profile control agent[D]. China University of Petroleum (East China), 2018.
[15]	LIU L, GOU S H, FANG S W, et al. Organic-inorganic microspheres of temperature-controlled size for profile control[J]. Journal of Molecular Liquids, 2020, 317:113993.
[16]	季一辉,赵雄虎,李外,等. 微乳液聚合在钻井液中的研究进展[J]. 应用化工,2014,43(9):1683-1687. JI Yihui, ZHAO Xionghu, LI Wai, et al. Microemulsion polymerization and its application in drilling fluid.[J]. Applied Chemical Industry, 2014, 43(9):1683-1687.
[17]	路建萍,沈燕宾,王佳,等. 纳米微球技术在油田领域的研究进展及应用[J]. 应用化工,2020,49(3):768-772. doi: 10.3969/j.issn.1671-3206.2020.03.052 LU Jianping, SHEN Yanbin, WANG Jia, et al. Research progress and application of nanosphere technology in oilfield[J]. Applied Chemical Industry, 2020, 49(3):768-772. doi: 10.3969/j.issn.1671-3206.2020.03.052
[18]	王建莉,王金良,周晓楠,等. 乳液聚合在油田开发应用中的研究进展[J]. 石油化工,2013,42(2):243-247. doi: 10.3969/j.issn.1000-8144.2013.02.020 WANG Jianli, WANG Jinliang, ZHOU Xiaonan, et al. Progresses in research of emulsion polymerization for oilfield exploitation[J]. Petrochemical Technology, 2013, 42(2):243-247. doi: 10.3969/j.issn.1000-8144.2013.02.020
[19]	夏燕敏,宋晓芳,于志省,等. 聚丙烯酰胺微球的制备方法及其在油田调剖封堵中应用的研究进展[J]. 石油化工,2014,43(6):729-734. doi: 10.3969/j.issn.1000-8144.2014.06.020 XIA Yanmin, SONG Xiaofang, YU Zhixing, et al. Progresses in preparation of polyacrylamide microspheres and their application to profile control and water plugging in oilfields[J]. Petrochemical Technology, 2014, 43(6):729-734. doi: 10.3969/j.issn.1000-8144.2014.06.020
[20]	康万利,周博博,杨红斌,等. 油田调驱用聚合物微球的研究进展[J]. 高分子材料科学与工程,2020,36(9):173-180. KANG Wanli, ZHOU Bobo, YANG Hongbin, et al. Comprehensive review of polymer microspheres for oil field conformance control and flooding[J]. Polymer Materials Science & Engineering, 2020, 36(9):173-180.
[21]	LI J B, NIU L W, WU W X, et al. The reservoir adaptability and oil displacement mechanism of polymer microspheres[J]. Polymers, 2020, 12(4).
[22]	ZHAO W Y, NI J, HOU G G, et al. Research on optimal blocking limits and injection parameter optimization of polymer microsphere conformance control[J]. Acs Omega, 2021, 6(12):8297-8307. doi: 10.1021/acsomega.1c00009
[23]	蒲万芬,赵帅,王亮亮,等. 聚合物微球粒径与喉道匹配性研究[J]. 油气地质与采收率,2018,25(4):100-105. PU Wanfen, ZHAO Shuai, WANG Liangliang, et al. Investigation into the matching between the size of polymer microspheres and pore throats[J]. Petroleum Geology and Recovery Efficiency, 2018, 25(4):100-105.
[24]	LI J J, LIU Y Z, NA Z, et al. Investigation on the adaptability of the polymer microspheres for fluid flow diversion in porous media[J]. Journal of Dispersion Science and Technology, 2014, 35(1):120-129. doi: 10.1080/01932691.2013.769111
[25]	YANG H B, SHAO S, ZHU T Y, et al. Shear resistance performance of low elastic polymer microspheres used for conformance control treatment[J]. Journal of Industrial and Engineering Chemistry, 2019, 79:295-306. doi: 10.1016/j.jiec.2019.07.005
[26]	LIN M Q, ZHAO Q, DANG S M, et al. Temperature resistance of AM/AMPS/NVP copolymer microspheres[J]. Iranian Polymer Journal, 2020, 29(5):445-453. doi: 10.1007/s13726-020-00809-5
[27]	DU D J, PU W F, JIN F Y, et al. Experimental investigation on plugging and transport characteristics of Pore-Scale microspheres in heterogeneous porous media for enhanced oil recovery[J]. Journal of Dispersion Science and Technology, 2021, 42(8):1152-1162. doi: 10.1080/01932691.2020.1729796
[28]	赵田红,彭国峰,郭淑凤,等. AMPS/AM的合成及其性能测试[J]. 西南石油学院学报,2006(4):82-84. ZHAO Tianhong, PENG Guofeng, GUO Shufeng, et al. Synthesis and property Test of AMPS/AM[J]. Journal of Southwest Petroleum University(Science & Technology Edition), 2006(4):82-84.
[29]	WANG Z Y, LIN M Q, XIANG Y Q, et al. Zr-induced thermostable polymeric nanospheres with double-cross-linked architectures for oil recovery[J]. Energy & Fuels, 2019, 33(10):10356-10364.
[30]	ZHANG L Y, ABBASPOURRAD A, PARSA S, et al. Core-shell nanohydrogels with programmable swelling for conformance control in porous media[J]. Acs Applied Materials & Interfaces, 2020, 12(30):34217-34225.
[31]	潘凤英,乔孟占,董彦龙,等. 核壳结构功能聚合物微球的评价与应用[J]. 石油化工,2021,50(2):163-167. doi: 10.3969/j.issn.1000-8144.2021.02.010 PAN Fengying, QIAO Mengzhan, DONG Yanlong, et al. Characterization and evaluation of functional polymer microspheres with core-shell structure[J]. Petrochemical Technology, 2021, 50(2):163-167. doi: 10.3969/j.issn.1000-8144.2021.02.010
[32]	王磊,薛蓉,赵云鹏,等. 核壳型聚丙烯酰胺纳米微球的制备及其性能[J]. 精细化工,2018,35(3):517-524. WANG Lei, XUE Rong, ZHAO Yunpeng, et al. Preparation and performance of polyacrylamide nano-microspheres with core-shell structure[J]. Fine Chemicals, 2018, 35(3):517-524.
[33]	CAO Z H, CHEN Q, CHEN H N, et al. Preparation of polymeric/inorganic nanocomposite particles in miniemulsions: I. Particle formation mechanism in systems stabilized with sodium dodecyl sulfate[J]. Colloids and Surfaces a-Physicochemical and Engineering Aspects, 2017, 516:199-210.
[34]	HUANG X B, LV K H, SUN J S, et al. Enhancement of thermal stability of drilling fluid using laponite nanoparticles under extreme temperature conditions[J]. Materials Letters, 2019, 248:146-149. doi: 10.1016/j.matlet.2019.04.005
[35]	KUMAR R S, SHARMA T. Stability and rheological properties of nanofluids stabilized by SiO₂ nanoparticles and SiO₂-TiO₂ nanocomposites for oilfield applications[J]. Colloids and Surfaces a-Physicochemical and Engineering Aspects, 2018, 539:171-183.
[36]	BEE S L, ABDULLAH M A A, BEE S T, et al. Polymer nanocomposites based on silylated-montmorillonite: A review[J]. Progress in Polymer Science, 2018, 85:57-82. doi: 10.1016/j.progpolymsci.2018.07.003
[37]	CAO J, SONG T, WANG X J, et al. Studies on the rheological properties of amphiphilic nanosilica and a partially hydrolyzed polyacrylamide hybrid for enhanced oil recovery[J]. Chemical Engineering Science, 2019, 206:146-155. doi: 10.1016/j.ces.2019.05.034
[38]	DAI C L, HUANG Y P, LYU X Y, et al. Solid-like film formed by nano-silica self-assembly at oil-water interface[J]. Chemical Engineering Science, 2019, 195:51-61. doi: 10.1016/j.ces.2018.11.042
[39]	GONG L X, PEI Y B, HAN Q Y, et al. Polymer grafted reduced graphene oxide sheets for improving stress transfer in polymer composites[J]. Composites Science and Technology, 2016, 134:144-152. doi: 10.1016/j.compscitech.2016.08.014
[40]	DU D J, PU W F, ZHANG S, et al. Preparation and migration study of graphene oxide-grafted polymeric microspheres: EOR implications[J]. Journal of Petroleum Science and Engineering, 2020:192.
[41]	TANG X C, KANG W L, ZHOU B B, et al. Characteristics of composite microspheres for in-depth profile control in oilfields and the effects of polymerizable silica nanoparticles[J]. Powder Technology, 2020, 359:205-215. doi: 10.1016/j.powtec.2019.09.070
[42]	TANG X C, YANG H B, GAO Y B, et al. Preparation of a micron-size silica-reinforced polymer microsphere and evaluation of its properties as a plugging agent[J]. Colloids and Surfaces a-Physicochemical and Engineering Aspects, 2018, 547:8-18.
[43]	TANG X C, ZHOU B B, CHEN C, et al. Regulation of polymerizable modification degree of nano-SiO₂ and the effects on performance of composite microsphere for conformance control[J]. Colloids and Surfaces a-Physicochemical and Engineering Aspects, 2020, 548:124100.
[44]	JI J Q, ZHAO J Q, KE Y C. Synthesis and characterization of poly(AM-SSS-AMPS)/O-MMT nanocomposite microspheres with tailored nanomechanical properties[J]. Colloids and Surfaces a-Physicochemical and Engineering Aspects, 2019:583.
[45]	巩锦程,季岩峰,王彦玲,等. 油田调驱用聚合微球的构效关系及应用进展[J]. 精细化工,2021,38(7):1342-1354. GONG Jincheng, JI Yanfeng, WANG Yanling, et al. Structure-activity relationship and application progress of polymer microspheres for profile control and flooding in oilfield[J]. Fine Chemicals, 2021, 38(7):1342-1354.
[46]	CAO M J, CAI Q, GUO G F, et al. The preparation and displacement performances of a hollow structure microsphere with swelling-deswelling properties for enhanced oil recovery (EOR)[J]. Polymer Bulletin, 2021.
[47]	胡雷雷,康万利,季岩峰,等. 丙烯酰氧基聚丙烯酰胺荧光微球的制备及性能[J]. 高分子材料科学与工程,2015,31(10):170-174. HU Leilei, KANG Wanli, JI Yanfeng, et al. Preparation and properties of acryloxypolyacrylamide fluorescent microspheres[J]. Polymer Materials Science & Engineering, 2015, 31(10):170-174.
[48]	YANG H B, HU L L, CHEN C, et al. Synthesis and plugging behavior of fluorescent polymer microspheres as a kind of conformance control agent in reservoirs[J]. Rsc Advances, 2018, 8(19):10478-10488. doi: 10.1039/C8RA00903A
[49]	石道涵,李鹏,陈义鹏,等. 丙烯酰胺共聚物纳米荧光微球的制备与性能[J]. 化学工业与工程,2021,38(5):53-58. SHI Daohan, Li Peng, CHEN Yipeng, et al. Preparation and properties of fluorescent polyacrylamide nano-spheres[J]. Chemical Industry and Engineering, 2021, 38(5):53-58.
[50]	马国锐,李丹丹,高仰刚,等. 荧光聚合物微球示踪剂的合成与性能[J]. 石油化工,2018,47(5):468-473. doi: 10.3969/j.issn.1000-8144.2018.05.012 MA Guorui, LI Dandan, GAO Yanggang, et al. Synthesis and properties of fluorescent polymer microspheres tracer[J]. Petrochemical Technology, 2018, 47(5):468-473. doi: 10.3969/j.issn.1000-8144.2018.05.012
[51]	李财富,李本高,汪燮卿. 国内水基钻井液降滤失剂研究现状[J]. 中外能源,2013,18(2):39-44. LI Caifu, LI Bengao, WANG Tiaoqing. Research status of fluid loss reducer for water-based drilling fluid in China[J]. Sino-Global Energy, 2013, 18(2):39-44.
[52]	许洁,乌效鸣,朱永宜,等. 抗240℃超高温水基钻井液室内研究[J]. 钻井液与完井液,2015,32(1):10-13. doi: 10.3969/j.issn.1001-5620.2015.01.003 XU Jie, WU Xiaoming, ZHU Yongyi, et al. Laboratory study of 240℃ ultra high temperature water based drilling fluid[J]. Drilling Fluid & Completion Fluid, 2015, 32(1):10-13. doi: 10.3969/j.issn.1001-5620.2015.01.003
[53]	尹达,吴晓花,刘锋报,等. 抗160℃超高密度柴油基钻井液体系[J]. 钻井液与完井液,2019,36(3):280-286. doi: 10.3969/j.issn.1001-5620.2019.03.003 YIN Da, WU Xiaohua, LIU Fengbao, et al. An ultra-high density diesel oil base drilling fluid for use at 160 ℃[J]. Drilling Fluid & Completion Fluid, 2019, 36(3):280-286. doi: 10.3969/j.issn.1001-5620.2019.03.003
[54]	杜文浩,宋兆辉,吴鹏伟,等. 亲水性两性离子交联聚合物微球的制备及性能[J]. 高分子材料科学与工程,2020,36(11):1-6. DU Wenhao, SONG Zhaohui, WU Pengwei, et al. Preparation and properties of hydrophilic zwitterionic crosslinked polymer microspheres[J]. Polymer Materials Science & Engineering, 2020, 36(11):1-6.
[55]	王中华. 国内钻井液处理剂研发现状与发展趋势[J]. 石油钻探技术,2016,44(3):1-8. WANG Zhonghua. Present status and trends in research and development of drilling fluid additives in China[J]. Petroleum Drilling Techniques, 2016, 44(3):1-8.
[56]	ZHONG H Y, GAO X, QIU Z S, et al. Formulation and evaluation of beta-cyclodextrin polymer microspheres for improved HTHP filtration control in water-based drilling fluids[J]. Journal of Molecular Liquids, 2020, 313:113549.