Synthesis of water-in-water hydrophobically associating polyacrylamide and its application in fracturing

doi:10.16085/j.issn.1000-6613.2017-0640

Abstract

Abstract: a water-in-water hydrophobically associating polyacrylamide was synthesized using acrylamide,2-acrylamido-2-methyl propane sulfonic acid and erucylamide propyl hydroxy sulfobetaine as raw materials by dispersion polymerization in salt solution. The obtained polymer was characterized by means of FTIR and TG. The basic properties,micro-properties,and macroscopic properties of the OWPAM emulsion were also investigated. The results showed that the obtained emulsion had high yields,better averaged particle size,and better stability with erucic acid CAB of 4.0% viscosity average molecular weight of 2.43×10⁶g/mol,and OWPAM emusion critical associating concentration(CAC)0.32%. At room temperature,flow velocity of 10.0m/s and concentration of 0.10%,the OWPAM solution drag agent was 72%,The viscosity of 0.5% OWPAM solution could be increased up to 160mPa·s with TR-1 concentration of 1.0%. The fracturing fluid had good heat resistance,shear resistance,viscoelastic,and suspended sand. The new fracturing fluid could completely break in 2h when APS concentration was 0.05%.

Key words: dispersion polymerization, polyacrylamide, hydrophobic association, volume fracturing, fracturing fluid

摘要： 以丙烯酰胺、2-丙烯酰胺-2-甲基丙磺酸和芥酸酰胺羟丙基磺基甜菜碱为原料，采用水分散聚合方式合成出水包水型疏水缔合聚丙烯酰胺增稠剂，通过FTIR和TG对增稠剂的结构及热解质量进行了测试。分析了OWPAM乳液增稠剂的基本性能及水溶液的微观和宏观性能，结果表明，在单体芥酸CAB用量为4.0%时，乳液的产率、平均粒径、表观黏度和稳定性达到最优，黏均分子量为2.43×10⁶g/mol；OWPAM乳液的临界胶束缔合浓度（CAC）值为0.32%，当浓度大于CAC值后水溶液体系内的缔合形式以分子间缔合为主，OWPAM乳液在0.1%、流速10m/s时减阻率为72%。助黏剂TR-1质量分数为1.0%时可将0.5%水溶液黏度增加至160mPa·s，复配成的压裂液具有较好耐温耐剪切性、黏弹性和悬砂性，在APS质量分数为0.05%时，测试时间为2h压裂液可以完全破胶，能够达到压裂液的使用标准。

关键词: 分散聚合, 聚丙烯酰胺, 疏水缔合, 体积压裂, 压裂液

CLC Number:

TQ423.4

ZHANG Fengsan, SHEN Yiding, WU Jinqiao, YUAN Min, SUN Xiao. Synthesis of water-in-water hydrophobically associating polyacrylamide and its application in fracturing[J]. Chemical Industry and Engineering Progress, 2017, 36(08): 3058-3065.

张锋三, 沈一丁, 吴金桥, 原敏, 孙晓. 水包水型疏水缔合聚丙烯酰胺增稠剂的合成及在压裂中的应用[J]. 化工进展, 2017, 36(08): 3058-3065.

References

[1] 邹才能,董大忠,王玉满,等. 中国页岩气特征、挑战及前景(一)[J]. 石油勘探与开发,2015(6):689-701. ZOU C N,DONG D Z,WANG Y M,et al. Shale gas in China:characteristics,challenges and prospects (Ⅰ)[J]. Petroleum Exploration and Development,2015(6):689-701.
[2] 张东晓,杨婷云. 页岩气开发综述[J]. 石油学报,2013,34(04):792-801. ZHANG D X,YANG T Y. An overview of shale-gas production[J]. Acta Petrolei Sinica,2013,34(04):792-801.
[3] 曹喆,柳广弟,柳庄小雪,等. 致密油地质研究现状及展望[J]. 天然气地球科学,2014(10):1499-1508. CAO Z,LIU G D,LIU ZHUANG X X,et al. research status on tight oil and its prospects[J]. Natural Gas Geoscience,2014(10):1499-1508.
[4] 邱振,李建忠,吴晓智,等. 国内外致密油勘探现状、主要地质特征及差异[J]. 岩性油气藏,2015,27(4):119-126. QIU Z,LI J Z,WU X Z,et al. Exploration status,main geologic characteristics and their differences of tight oil between America and China[J]. Lithologic Reservoirs,2015,27(4):119-126.
[5] 陈作,薛承瑾,蒋廷学,等. 页岩气井体积压裂技术在我国的应用建议[J].天然气工业,2010,30(10):30-32,116-117. CHEN Z,XUE C J,JIANG T X,et al. Proposals for the application of fracturing by stimulated reservoir volume(SRV)in shale gas wells in China[J]. Natural Gas Industry,2010,30(10):30-32,116-117.
[6] 王晓东,赵振峰,李向平,等. 鄂尔多斯长7致密砂岩储层体积压裂可行性评价[J]. 西安石油大学学报(自然科学版),2014,29(1):52-55,7. WANG X D,ZHAO Z F,LI X P,et al. Mixing water fracturing technology for tight oil reservoir in Ordos Basin[J]. Journal of Xi'an Shiyou University (Natural Science Edition),2014,29(1):52-55,7.
[7] 张华丽,周继东,杲春,等. 胍胶压裂液伤害性研究[J]. 科学技术与工程,2013,13(23):6866-6871. ZHANG H L,ZHOU J D,HAO C,et al. The damage of Guar gum fracturing fluid[J]. Science Technology and Engineering,2013,13(23):6866-6871.
[8] 王明磊.致密油储层特点与压裂液伤害的关系——以鄂尔多斯盆地三叠系延长组长7段为例[J]. 石油与天然气地质,2015,36(5):22-27. WANG M L. Relationship between characteristics of tight oil reservoirs and fracturing fluid damage:a case from Chang 7 Member of the Triassic Yanchang Fm in Ordos Basin[J]. Oil & Gas Geology,2015,36(5):22-27.
[9] GONG H H,LIU M Z,,CHEN J C,et al. Synthesis and characterization of carboxymethyl guar gum and rheological properties of its solutions[J].Carbohydrate Polymers,2012,88(3):1015-1022.
[10] 麦永发,朱宏,林建云,等. 阳离子聚丙烯酰胺的重要研究技术进展[J]. 高分子通报,2012(08):105-110. MAI Y F,ZHU H,LIN J Y,et al. Important technical progresses of cationic polyacrylamide[J]. Polymer Bulletin,2012(08):105-110.
[11] 张锋三,沈一丁,王磊,等. 聚丙烯酰胺压裂液减阻剂的合成及性能[J]. 化工进展,2016,35(11):3640-3644. ZHANG F S,SHEN Y D,WANG L,et al. Synthesis and properties of polyacrylamide drag reducer for fracturing fluid[J]. Chemical Industry and Engineering Progress,2016,35(11):3640-3644.
[12] 马悦,李小瑞,杨晓武,等.酸性有机钛交联剂的合成及在压裂液中的应用[J].精细化工,2014,31(06):34-37. MA Y,LI X R,YANG X W,et al. Synthesis and application of acidic organic titanium cross-linking agent for fracturing fluid[J]. Fine Chemicals,2014,31(06):34-37.
[13] 赵珣,万美,吴海平,等. 水分散聚合合成两性聚丙烯酰胺[J]. 精细与专用化学品,2014(1):18-22. ZHAO X,WAN M,WU H P,et al. Synthesis of amphoteric polyacrylamide via aqueous dispersion polymerization[J]. Fine and Specialty Chemicals,2014(1):18-22.
[14] 王晨,李小瑞,沈一丁,等. 离子型表面活性剂与疏水缔合聚丙烯酰胺的相互作用[J]. 功能材料,2012,43(23):3316-3321. WANG C,LI X R,SHEN Y D,et al. Interactions between ionic surfactants and hydrophobically associatingpolyacrylamide in aqueous solution[J]. Journal of Functional Materials,2012,43(23):3316-3321.
[15] 段冬海李培枝. 压裂用疏水缔合型聚丙烯酰胺稠化剂的制备与表征[J]. 西安石油大学学报(自然科学版),2010,25(6):66-68. DUAN D H,LI P Z. Preparation and characterization of hydrophobically associated polyacrylamide for the thickener of fracturing fluid[J]. Journal of Xi'an Shiyou University (Natural Science Edition),2010,25(6):66-68.
[16] 韩磊,宁荣昌,谢钢,等. 分散聚合法制备聚丙烯酰胺水包水乳液[J]. 功能高分子学报,2004(03):493-495. HAN L,NING R C,XIE G,et al. Preparation of the water-in-water emulsoin of polyacrylamide by dispersion polymerization[J]. Journal of Functional Polymer,2004(03):493-495.
[17] 李宇,陈俊耿,杨俊峰,等. 两性聚丙烯酰胺"水包水"乳液的制备[J]. 精细化工,2012,29(11):1112-1116,1136. LI Y,CHEN J G,YANG J F,et al. Preparation of amphoteric polyacrylamide "water-in-water" emulsion[J]. Fine Chemicals,2012,29(11):1112-1116,1136.
[18] 袁金颍,朱平平,唐鸿娟,等. 聚乙二醇黏均分子量的测定[J]. 高分子材料科学与工程,1999,15(4):159-160. YUAN J Y,ZHU P P,TANG H J,et al.Mesurement of average viscosimetric molecular weight of polyethylene glyco[J]. Polymer Materials Science & Engineering,1999,15(4):159-160.
[19] 陈洪,李二晓,叶仲斌. 疏水缔合聚丙烯酰胺与双子表面活性剂的相互作用[J]. 物理化学学报,2011,27(3):671-676. CHEN H,LI E X,YE Z B. Interaction of hydrophobically associating polyacrylamide with Gemini surfactant[J]. Acta Physico-Chemica Sinica,2011,27(3):671-676.
[20] ABO-SHOSHA M H,IBRAHIMA N A,ALLAMB E,et al. Preparation and characterization of polyacrylic acid/karaya gum and polyacrylic acid/tamarindseed gum adducts and utilization in textile printing[J]. Carbohydrate Polymers,2008,74(2):241-249.