摘要
Gemini表面活性剂因其在纺织、材料、生物、农业、洗涤、化工、石油等领域的应用而受到人们的重视。在能源日益短缺的情况下,只有进一步提高采收率才能使有限的石油资源得到充分利用,而表面活性剂驱被认为是化学驱的一种最有效的驱油方式之一。由于Gemini表面活性剂跟传统表面活性剂相比具有较低的临界胶束浓度和更好的表面活性,还兼有聚合物和传统表面活性剂两种驱替剂的性能,因此在三次采油领域具有很大的应用潜力。
本文对Gemini表面活性剂进行了较系统的综述,设计合成了Gemini表面活性剂,对其性能进行了表征,主要研究工作如下：
1、合成了两个系列的Gemini表面活性剂,通过元素分析、红外光谱、核磁共振等方法对其结构进行了鉴定。并对其溶液的表面张力、界面张力、临界胶束浓度(CMC)、接触角等进行了测试。
2、由于Gemini表面活性剂价格昂贵,一般是与传统的表面活性剂复配使用的。根据表面活性剂的复配原理,将各种类型的表面活性剂进行复配,通过复配筛选出性能优越的复配体系。对复配体系进行了界面张力、表面张力、接触角等测试以及抗盐、耐温性能的评价。
3、利用真实砂岩微观模型对合成的Gemini表面活性剂进行室内模拟驱油实验,通过常规水驱油实验和不同的表面活性剂驱油实验的模拟,可以看出表面活性剂的驱油效率明显较水驱油有所提高,同时也进一步验证了表面活性剂的驱油机理。
Gemini surfactant has become an important research subject because of its great significance in textile, material, biology, agriculture, washing, chemical industry and oil. With the growing shortage of energy, only further improvement in the recovery efficiency can make the limited oil resources be fully utilized, while surfactant flooding is considered as one of the most effective chemical flooding. Compared with the conventional surfactant, Gemini surfactant has lower critical micelle concentration and higher surface activity, together with the displacement agent performance of both the polymer and conventional surfactant. Therefore, it has great potential in the field of tertiary recovery.
In this dissertation, Gemini surfactant was systematically reviewed and its properties were characterized, the mainly completed task is as follows:
1. Two series of Gemini surfactants were synthesized, its structure was identified by elemental analysis, IR and 1H NMR. Its surface tension, interfacial tension, critical micelle concentration (CMC) and contact angle were also tested.
2. Owing to the expensive price of Gemini surfactant, it is generally used together with traditional surfactant. According to the surfactant formulating principle, mixing various types of surfactants up can help to select the superior performance mixture system. A series of tests for the mixture systems were implemented, such as surface tension, interfacial tension, contact angle, salt resistance and temperature resistance.
3. The oil displacement efficiency of surfactant is significantly improved compared with the water flooding, meanwhile, the surfactant oil-displacement mechanism was further validated after adopting the authentic micro-model to test the synthetic Gemini surfactant in the laboratory simulation of oil displacement experiment.
引文
[1]杨承志.化学驱提高石油采收率[M].修订版.北京：石油工业出版社,2007：44-49
[2]Li X. P., Yu L., Ji Y. Q., et al. New type flooding systems in enhanced oil recovery[J]. Chin. Chem. Lett.,2009,20:1251-1254
[3]Zheng W. H., Ma X. L., Song H. F., et al. Study and application of the combination technique of secondary oil recovery with tertiary oil recovery in low permeability reservoirs[J]. Shiyou Dizhi Yu Gongcheng,2007,21(5):69-72
[4]Babadagli T.. Evaluation of EOR methods for heavy-oil recovery in naturally fractured reservoirs[J]. J. Petro. Scien. Engin.,2003,37(1-2):25-37
[5]Claudia F. P.. Safety assessment on polyethylene gloycols(PEGs) and their derivatives as used in cosmetic products[J]. Toxicology,2005,214(1-2):1-38
[6]Dennis J. M., Torsten H., Wolfgang G. Phase inversion of W/O emulsions by adding hydrophilic surfactant-a technique for making cosmetics products[J]. Coll. and Sur. A: Physicochem. and Engin. Aspec.,2001,183-185(15):681-688
[7]Haitsma J. J., Lachmann U., Lachmann B.. Exogenous surfactant as a drug delivery agent[J]. Advan. Drug deliv. Revi.,2001,47(2-3):197-207
[8]Liu H. X.. Application of surfactants in pharmaceutical preparation[J]. Xibei Yaoxue Zazhi,2005,20(6):282-284.
[9]Dong Y. F., Liu W. X., Jiang X. M.. Progress of application of surfactant in papermaking industry[J]. ZhongGuo ZaoZhi,2009,28(5):68-73
[10]Gu X. D.. Application of surfactant AS in industrial decolorization[J]. Huaxue Gongchengshi,2006,20(4):69-70
[11]Matar O. K., Lawrence C. J.. The effect of surfactant on the flow of a thin liquid film over a spinning disc[J]. Chem. Engin. Scien.,2006,61(4):1074-1091
[12]Ma J. Z., Hu J.. Application and development of surfactant in leather industry[J]. ZhongGuo PiGe,2007,36(5):56-59
[13]Li D. C., Wang J. L., Ren S. G., et al. Application of surfactant in leather-making process[J]. ZhongGuo PiGe,2006,35(17):35-37
[14]Marcela P. C., Ana M. R., Carmen A. C., et al. Effect of preservatives, tween 20, model salad dressings[J]. J. LWT-Food Sci. and Tech.,2009,42(8):1428-1434
[15]Weng Y. M., Chen M. J.. Sorbic anhydride as antimycotic additive in polyethylene food packaging films[J]. J. LWT-Food Sci. and Tech.,1997,30(5):485-487
[16]Horiie, Takafumi. Application of surfactants to rubbers and plastics[J]. Kinosei Kaimen Kasseizai,2000,224-234
[17]Li D. C., Ma J. J., Cao Y. X., et al. Application of surfactants in ceramic industry[J]. Riyong Huaxue Gongye,2005,35(5):309-313
[18]Ho C. C., Lee K. C., Yeap E. B.. The effect of electrolytes, pH and surfactant on the adsorption of natural rubber latex on tin tailings slimes[J]. Coll. Surf. A:Physicochem. Engin. Aspec.,1993,81:83-91
[19]Zhang J. X., Yang J. G., Chen X. G., et al. Application of surfactant in coal preparation industry[J]. Meitan Jishu,2004,23(10):67-68
[20]Serreau L., Beauvais M., Heitz C., et al. Adsorption and onset of lubrication by a double-chained cationic surfactant on silica surfaces[J]. J. Coll. Inter. Scien.,2009,332(2): 382-388
[21]Ahn C. K., Kim Y. M., Park J. M.. Soil washing using various nonionic surfactants and their recovery by selective adsorption with activated carbon[J]. J. Hazar. Mater.,2008, 154(1-3):153-160
[22]Li Y. G., Chen B. L., Chen Z. M., et al. Surfactant Effects on the affinity of plant cuticles with organic pollutants [J]. J. Agric. Food Chem.,2009,57(9):3681-3688
[23]Devinsky F., Pisarcik M., Lacko I.. Hydrodynamic size of DNA/cationic gemini surfactant complex as a function of surfactant structure [J]. Gener. Physi. and Bioph., 2009,28(2):160-167
[24]Zhao X. F., Shang Y. Z., Liu H. H., et al. Complexation of DNA with cationic gemini surfactant in aqueous solution[J]. J. Coll. and Inter. Scien.,2007,314:478-483
[25]Wettig S. D., Badea I., Donkuru M., et al. Structural and transfection properties of amine-substituted gemini surfactant-based nanopaticles[J]. J. Gene Medic.,2007,9:
649-658
[26]Bombelli C., Faggioli F., Luciani P., et al. Efficient transfection of DNA by liposomes formulated with cationic Gemini amphiphiles[J]. J. Med. Chem.,2005,48(16): 5378-5382
[27]Robertson B., Henry L. H.. Principles of surfactant replacement[J]. Bioch. Biophy. Acta-Molec. Basis Disea.,1998,1408(2-3):346-361
[28]Liu Z. Y., Lu X. F., Tang C.. Research on application of new type gemini surfactants in tertiary recovery[J]. Shiyou Huagong Yingyong,2009,28(7):8-10
[29]陆大年.表面活性剂化学及纺织助剂[M].第一版.北京：中国纺织出版社,2009：1-4
[30]Li F., Li K. B., Li Q. S.. Gemini surfactants and their structure, function and application[J]. Huagong Shikan,2008,22(7):46-49
[31]Zhou M., Liu H. L., Yang H. F., et al. Spontaneous crystallization at the air-water interface:an unusual feature of Gemini surfactant with a rigid spacer[J]. Langmuir, 2006(22):10877-10879
[32]Menger F. M., Galloway A. L., Chlebowski M. E.. Surface tension of aqueous amphiphiles[J]. Langmuir,2005,21,9010-9012
[33]Wang J., Luan L. H., Yang X. Z., et al. Synthesis and surface activity of cationic gemini surfactants[J]. Jingxi Huagong,2009,26(1):14-17
[34]Zhang S. Z., Ma X. M., Xing Y. C.. Synthesis and characterization of a new kind of Gemini surfactant[J]. Yingyong Huagong,2008,37(4):396-398
[35]Ma B. L., Jiang H. L., Shi L. Y.. Synthesis and properties of Gemini surfactants [J]. Yingyong Huagong,2009,38(4):559-562
[36]Kabir D., Mohammad S., Parvaiz A., et al. Solubilization capabilities of mixtures of cationic Gemini surfactant with conventional cationic, nonionic, and anionic surfactants towards polycyclic aromatic hydrocarbons [J]. J. Hazar. Mater.,2009,167(1-3):575-581
[37]Zhong Y., Liu C. F., Bian J. P.. Preparation and phase behavior of microemulsion of gemini surfactant[J]. Huaxue Shijie,2009,50(8):457-459
[38]Santanna V. C., Curbelo F. D. S., CastroDantas T. N., et al. Microemulsion flooding for enhanced oil recovery[J]. J. Petro. Scien. Engin.,2009,66(3-4):117-120
[39]Downs H. H., Hoover P. D.. Enhanced oil recovery by wettability alteration[J]. Oil-Field Chem.,1989:577-595
[40]Hammond P. S., Evren U.. Spontaneous and forced imbibition of aqueous wettability altering surfactant solution into an initially oil-wet capillary[J]. Langmuir,2009,25(21): 12591-12603
[41]Chen F. S., Zhang L. M.. Advances in oil recovery enhanced by high temperature steam foam flooding[J]. Jingxi Shiyou Huagong,2008,25(1):76-80
[42]Zhao J. Y.. Studies on the development of tertiary recovery wastewater[J]. Huagong Keji Shichang,2008,31(3):22-25
[43]Zhang W. F.. Application of surfactant in disinfection and antiseptic field[J]. Riyong Huaxue Gongye,2004,34(2):108-110
[44]Han M., Ji G. D., Ni J. R.. Washing of field weathered crude oil contaminated soil with an envioronmentally compatible surfactant, alkyl polyglucoside[J]. Chemosphere,2009, 76(5):579-586
[45]Bunton C. A., Robinson J., Schaak J., et al. Catalysis of nucleophilic substitutions by micelles of dicationic detergents[J]. Org. Chem.,1971,36(16):2346-2350
[46]Zhu Y. P., Masuyama A., Kobata Y. Preparation and surface active properties of amphipathic compounds with two sulfate groups and two lipophilic alkyl chains[J]. J. Am. Chem. Soc.,1990,67(7):459-463
[47]Menger F.M., Littan C.A.. Gemini surfactants:synthesis and properties[J]. J. Am. Chem. Soc.,1991,113:1451-1452
[48]Menger F.M., Littau C.A.. Gemini surfactants:A new class of self-assembling molecules[J]. J. Am. Chem. Soc,1993,115(22):10083-10090
[49]Rosen M. J.. Gemini a new generation of surfactants [J]. Chem. Tech.,1993,23(3): 30-33
[50]Zana R., Levy H., Papoutsi D., et al. Micellization of two tiquaternary ammonium surfactants in aqueous solution[J]. Langmuir,1995,11:3694-3698
[51]王可为.非离子Gemini表面活性剂的合成及性能表征[D].大连：大连理工大学,2003
[52]郑宝江.驱油用阴离子Gemini表面活性剂的制备及性能表征[D].天津：天津大学, 2005
[53]高进锋,刘世恩.Gemini稠油乳化降黏剂GMS-1的合成及应用性能[J].油田化学,2008,25(1)：13-16
[54]张永明,朱红,夏建华,等.磺酸盐型Gemini表面活性剂的合成及在三次采油中的应用研究[J].北京交通大学学报,2007,31(3)：100-104
[55]Mingqi A., Xu G. Y., Zhu Y. Y., et al. Synthesis and properties of ionic liquid-type Gemini imidazolium surfactants[J]. J. Coll. and Inter. Scien.2008,326:490-495
[56]姚同玉,刘福海,刘卫东.季铵盐型表面活性剂的驱油机理研究[J].西南石油学院学报,2003,25(6)：43-45
[57]蒋平,张贵才,葛际江,等.润湿反转机理的研究进展[J].西安石油大学学报(自然科学版),2007,22(6)：78-84
[58]刘卫东.低渗透油田润湿反转降压增注技术及应用[J].辽宁工程技术大学学报(自然科学版),2009,28：146-149
[59]李秀红,杨桦,陈喜田,等.润湿反转提高压裂液返排技术在吉林油田新119区块的应用[J].钻采工艺,2004,27(6)：51-53
[60]俞稼镛,宋万超,李之平,等.化学复合驱基础及进展[M].北京：中国石化出版社,2002：72-74
[61]岳湘安,王尤福,王克亮.提高石油采收率基础[M].第一版.北京：石油工业出版社：1-7
[62]Chhetri A. B., Watts K. C., Rahman M. S., et al. Soapnut extract as a natural surfactant for enhanced oil recovery[J]. Energy Sources, Part A:Recovery, Utilization, and Environmental Effects,2009,31(20),1893-1903
[1]Khan I. A., Mohammad R., Alam M. S., et al. Surface properties and mixed micellization of cationic Gemini surfactants with ethyleneamines[J]. J. Chem. Engin. Data,2010,55(1): 370-380
[2]Banno T., Toshima K., Kawada K., et al. Synthesis and properties of Gemini-type cationic surfactants containing carbonate linkages in the linker moiety directed toward green and sustainable chemistry[J]. J. Surf. Deter.,2009,12:249-259
[3]常建华,董绮功.波谱原理及解析[M].第二版.北京：科学出版社,2005：59-118
[4]李艳红,王升宝,常丽萍.表(界)面张力测定方法的研究[J].日用化学工业,2007,37(2)：102—106
[5]Karagianni M., Avranas A.. The effect of deaeration on the surface tension of water and some other liquids[J]. Coll. Surf. A:Physicochem. Engin. Aspec.,2009,335(1-3), 168-173
[6]尹东霞,马沛生,夏淑倩.液体表面张力测定方法的研究进展[J].科技通报,2007,23(3)：424-433
[7]Souckova M., Klomfar J., Patek J.. Measurement and correlation of the surface tension-temperature relation for methanol. J. Chem. Eng. Data 2008,53:2233-2236
[8]Jaroslav K., Monika S., Jaroslav P.. Surface tension measurement for four 1-alkyl-3-methylimidazolium-based ionic liquids with hexafluorophosphate anion[J]. J. Chem. Engin. Data,2009,54:1389-1394
[9]郝子洋,杜凤沛.最大气泡压力法测表面张力实验数据处理的改进[J].大学化学,23(6)：34-36
[10]Contreras P., Olteanu M.. Interfacial tension measurement by the rotating meniscus[J]. Coll. Surf. A:Physicochem. Engin. Aspec.,2000,170(1):45-50
[11]Josefina V. T., Jesus G. F.. Spinning drop method:from young-laplace to vonnegut[J]. Coll. Surf. A:Physicochem. Engin. Aspec.,2007,302(1-3):549-552
[12]Zhang X. C., Jackson J. K., Burt H. M.. Determination of surfactant critical micelle concentration by a novel fluorescence depolarization technique[J]. J. Bioch. Bioph. Methods,1996,31(3-4):145-150
[13]Romain R., Michel V., Helena A., et al. Drop impact on soft surfaces:beyond the static contact angles[J]. Langmuir,2010,26(7):4873-4879
[14]张玉亭,吕彤.胶体与界面化学[M].北京：中国纺织出版社,2008：147-158
[1]谭中良,韩冬,杨普华.孪连表面活性剂的性质和三次采油中的应用前景[J].油田化学,2003,20(2)：187-191
[2]赵田红,郑国华,李少庆,等.三次采油用表面活性剂的研究现状与趋势[J].化学工程师,2005,1(1)：33-34
[3]Zhao J. X., Liu J. Y., Jiang R.. Interaction between anionic and cationic gemini surfactants at air/water interface and in aqueous bulk solution[J]. Coll. Surfa. A:physicochem. Engin. Aspects,2009,350:141-146
[4]Tsubone K.. The interaction of an anionic gemini surfactant with conventional anionic surfactants[J]. J. Coll. Interf. Scien.,2003,261:524-528
[5]Zhou W. J., Zhu L. Z.. Enhanced soil flushing of phenanthrene by anionic-nonionic mixed surfactant[J]. Water Resear.,2008,42(1-2):101-108
[6]Mahmoodi N. M., Asefi D., Arami M.. Effect of nonionic co-surfactants on corrosion inhibition effect of cationic gemini surfactant[J]. Colloids and Surfaces A:Physicochem. Eng. Aspects,2009,12:1-20
[7]Singh K., Maranggoni D. G.. Synergistic interactions in the mixed micelles of cationic gemini with zwitterionic surfactants:The pH and spacer effect[J]. J. Coll. Interf. Scien., 2007,315:620-626
[8]王世荣,李祥高,刘东志,等.表面活性剂化学[M].第一版.北京：化学工业出版社,2005：203-212
[9]Azum N., Naqvi A. Z., Akram M.. Mixing behavior of conventional and Gemini cationic surfactants[J]. J. of Dispe. Scien. Tech.,2008,29(5):711-717
[10]Shang Y. Z., Zhang Q., Liu H. L., et al. Properties of the mixed aqueous solutions of gemini surfactant and conventional surfactant[J]. Huadong Ligong Daxue Xuebao,2004, 30(4):419-424
[11]Ye Z. B., Zhang F. X., Han L. J., et al. The effect of temperature on the interfacial, tension between crude oil and gemini surfactant solution[J]. Coll. Surf. A:Physicochem. Engin. Aspec.,2008,322:138-141
[1]Xiong W., Lei Q., Gao S. S., et al. Pseudo threshold pressure gradient to flow for low permeability reservoirs[J]. Petro. Explo. Develo.,2009,36(2):232-236
[2]高辉.特低渗透砂岩储层微观孔隙结构与渗流机理研究[D].西安：西北大学,2009
[3]孙焕泉,曹刚,杨勇,等.低渗透油田提高采收率技术[J].胜利油田有限公司,87-128
[4]郭沫贞,肖林鹏,张生兵,等.低渗透砂岩油层相对渗透率曲线特征、影响因素及其对开发的影响[J].沉积学报,2008,26(3)：445-451
[5]赵冰,顾晓敏,邓海蓉.超前注水技术改善低渗透油田开发机理的研究[J].石油化工应用,2009,28(1)：39-40
[6]Ralph S.. Enhanced oil recovery:Definitions, fundamentals, applications, and research frontiers[J]. Physic. Chem. The Earth,1981, (13-14):447-460
[7]Michael E. P., James P. M., Stephanie R. M.. Carbon dioxide enhanced oil recovery injection operations technologies [J]. Energ. Proced.,2009,1(1):3141-3148
[8]Schaffie M., Ranjbar M.. Geochemical alteration of crude oils during thermal recovery processes[J]. J. Petro. Scien. Engin.,2000,26(1-4):57-65
[9]Dong M. Z., Ma S. Z., Liu Q.. Enhanced heavy oil recovery through interfacial instability: A study of chemical flooding for Brintnell heavy oil[J]. Fuel,2009,88(6):1049-1056
[10]Sen R.. Biotechnology in petroleum recovery:The microbial EOR[J]. Progr. In Energ. Combu. Scien.,2008,34(6):714-724
[11]Almalik M. S., Attia A. M., Jang L. K.. Effects of alkaline flooding on the recovery of safaniya crude oil of Saudi Arabia[J]. J. Petro. Scien. Engin.,1997,17(3-4):367-372
[12]Jing G. L., Wang X. Y., Han C. J.. The effect of oilfield polymer-flooding wastewater on anion-exchange membrance performance[J]. Desal.,2008,220(1-3):386-393
[13]Zhao Z. K., Li Z. S., Qiao W. H., et al. Dynamic interfacial behavior between crude oil and octylmethylnaphthalene sulfonate surfactant flooding systems[J]. Coll. Surf. A: Physicochem. Engin. Aspec.,2005,259(1-3):71-80
[14]Wang H. Y., Cao X. L., Zhang J. C., et al. Development and application of dilute surfactant-polymer flooding system for Shengli oilfield[J]. J. Petro. Scien. Engin.,2009, 65(1-2):45-50
[15]Carrero E., Queipo N. V., Pintos S., et al. Global sensitivity analysis of Alkali-Surfactant-Polymer enhanced oil recovery processes[J]. J. Petro. Scien. Engin., 2007,58(1-2):30-42
[16]Li G. Z., Mu J. H., Li Y., et al. An experimental study on alkaline/surfactant/polymer flooding systems using nature mixed carboxylate[J]. Coll. Surf. A:Physicochem. Engin. Aspec.,2000,173(1-3):219-229
[17]Stefan I., Wu Y.F., Patrick S., et al. New surfactant classes for enhanced oil recovery and their tertiary oil recovery potential[J]. J. Petro. Scien. and Engin.,2010,71:23-29
[18]赵阳,曲志浩,陈蓉.真实砂岩微观模型活性水驱油实验研究[J].西北地质,1999,32(2)：30-34
[19]孔令荣,曲志浩,万发宝,等.砂岩微观孔隙模型两相驱替实验[J].石油勘探与开发,1991,18(4)：79-85
[20]刘林玉,王震亮,高潮.真实砂岩微观模型在鄂尔多斯盆地泾川地区长8砂岩微观非均质性研究中的应用[J].地学前缘,2008,15(1)：80-84
[21]赵阳,曲志浩,刘震.裂缝水驱油机理的真实砂岩微观模型实验研究[J].石油勘探与开发,2002,29(1)：116-119
