劣质重油胶体稳定性及对热反应性能的影响研究
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摘要
本研究考察了轻组分、大分子聚合物和表面活性剂对委内瑞拉重油粘度和胶体稳定性的影响,并对热反应条件下体系的传热状况、反应生焦状况、产物分布和组份变化进行了研究和探讨。研究表明,轻组分循环对委内瑞拉重油流动性有一定程度的改善作用。在重油中加入柴油或蜡油组分的质量分数<1%时,降粘效果相差不大;加入量>1%时,柴油组分的降粘幅度远大于蜡油组分。在重油中加入柴油组分,油样胶体稳定性下降,加入蜡油组分能改善油样胶体稳定性。不论加入柴油组分还是蜡油组分,热反应过程的传热情况都会有一定的改善;加入柴油组分能促进生焦,使生焦诱导期缩短,产物中常压渣油的生焦前驱物含量减少;加入蜡油组分能抑制生焦,使生焦诱导期延长,产物中常压渣油的生焦前驱物含量增加。
在合成的降粘剂中,SMA(苯乙烯-马来酸酐-丙烯酸十八醇酯三元共聚物)对重油有较好的降粘效果,SMA不论与柴油组分还是蜡油组分复配,均能改善油样的胶体稳定性,且SMA与柴油组分复配效果比与蜡油组分复配效果好。实验表明,SMA能抑制生焦,使生焦诱导期延长;SMA与柴油组分复配添加进行热反应时,常压渣油中饱和分和芳香分含量减少,生焦前驱物含量明显增加;与蜡油组分复配进行热反应时,常压渣油中饱和分和芳香分的含量增加,生焦前驱物含量明显减少。
SDBS(十二烷基苯磺酸钠)能改善重油的胶体稳定性,并能改善热反应过程的传热情况。但加入SDBS会促进生焦,使生焦诱导期缩短。SDBS与柴油组分复配添加进行热反应时,生焦率下降,生焦诱导期延长,常压渣油中生焦前驱物含量有明显增加。与蜡油组分复配添加进行热反应时,生焦率略有增加,常压渣油中饱和分含量明显减少,芳香分含量明显增加。
The impact of light distillate, macromolecular polymers and surfactant on the viscosity and stability colloid of Venezuelan heavy oil was studied and researched the heat transfer, formation of coke, product distribution and component changes of the thermal reaction. The flowability was improved when adding light distillate into Venezuelan heavy oil. The viscosity reducing affects little difference when adding mass fraction of diesel or wax <1%; when addition > 1%, diesel is better than wax. The stability colloid was improved by adding wax and broke by adding diesel.Whether to add diesel or wax, the heat transfer of thermal reaction was improved; Adding diesel can promote the formation of coke, shortened the coke induction period,reduce the coke precursor of atmospheric residue. Adding wax is quite the reverse.
SMA (styrene-maleic anhydride-octadecyl acrylate terpolymer) has the best effects on the viscosity reduction of heavy oil. The stability colloid was improved regardless of SMA blends with diesel or wax, and SMA blends with diesel reduced viscosity steeper then wax. Experiments show that the formation of coke was restrained and the coke induction period was lengthening when adding SMA. The saturated hydrocarbon and aromatics of asphalt decreased and the coke precursor of atmospheric residue increased when SMA mixture with diesel added in heavy oil. SMA mixture with wax is quite the reverse.
The stability colloid of heavy oil and the heat transfer of thermal reaction were improved when adding SDBS (sodium dodecyl benzene sulfonate). But the formation of coke was promoted and the coke induction period wae shortened at the same time. SDBS mixture with diesel added in heavy oil played a part in decreasing the formation of coke, lengthening the coke induction period, and increasing the coke precursor of atmospheric residue. SDBS mixture with wax is quite the reverse.
在合成的降粘剂中,SMA(苯乙烯-马来酸酐-丙烯酸十八醇酯三元共聚物)对重油有较好的降粘效果,SMA不论与柴油组分还是蜡油组分复配,均能改善油样的胶体稳定性,且SMA与柴油组分复配效果比与蜡油组分复配效果好。实验表明,SMA能抑制生焦,使生焦诱导期延长;SMA与柴油组分复配添加进行热反应时,常压渣油中饱和分和芳香分含量减少,生焦前驱物含量明显增加;与蜡油组分复配进行热反应时,常压渣油中饱和分和芳香分的含量增加,生焦前驱物含量明显减少。
SDBS(十二烷基苯磺酸钠)能改善重油的胶体稳定性,并能改善热反应过程的传热情况。但加入SDBS会促进生焦,使生焦诱导期缩短。SDBS与柴油组分复配添加进行热反应时,生焦率下降,生焦诱导期延长,常压渣油中生焦前驱物含量有明显增加。与蜡油组分复配添加进行热反应时,生焦率略有增加,常压渣油中饱和分含量明显减少,芳香分含量明显增加。
The impact of light distillate, macromolecular polymers and surfactant on the viscosity and stability colloid of Venezuelan heavy oil was studied and researched the heat transfer, formation of coke, product distribution and component changes of the thermal reaction. The flowability was improved when adding light distillate into Venezuelan heavy oil. The viscosity reducing affects little difference when adding mass fraction of diesel or wax <1%; when addition > 1%, diesel is better than wax. The stability colloid was improved by adding wax and broke by adding diesel.Whether to add diesel or wax, the heat transfer of thermal reaction was improved; Adding diesel can promote the formation of coke, shortened the coke induction period,reduce the coke precursor of atmospheric residue. Adding wax is quite the reverse.
SMA (styrene-maleic anhydride-octadecyl acrylate terpolymer) has the best effects on the viscosity reduction of heavy oil. The stability colloid was improved regardless of SMA blends with diesel or wax, and SMA blends with diesel reduced viscosity steeper then wax. Experiments show that the formation of coke was restrained and the coke induction period was lengthening when adding SMA. The saturated hydrocarbon and aromatics of asphalt decreased and the coke precursor of atmospheric residue increased when SMA mixture with diesel added in heavy oil. SMA mixture with wax is quite the reverse.
The stability colloid of heavy oil and the heat transfer of thermal reaction were improved when adding SDBS (sodium dodecyl benzene sulfonate). But the formation of coke was promoted and the coke induction period wae shortened at the same time. SDBS mixture with diesel added in heavy oil played a part in decreasing the formation of coke, lengthening the coke induction period, and increasing the coke precursor of atmospheric residue. SDBS mixture with wax is quite the reverse.
引文
[1]于连东.世界稠油资源的分布及其开采技术的现状与展望[J].特种油气藏,2002,8(2):98～103
[2]阙国和主编.石油组成与转化化学[M].中国石油大学出版社,2008
[3]吴本芳,郭金波.稠油油溶性降粘剂研究进展概况[J].油气储运,2003,22(2):1～6
[4]程亮,邹长军,杨林,等.稠油化学组成对其粘度影响的灰熵分析[J].石油化工高等学校学报,2006,19(3):6～10
[5]Peng Luo,Yongan Gu.effects of asphaltene content on the heavy oil viscosity at different temperatures [J].Fuel,2007,86:1069～1078
[6]Farouq Ali SM.Heavy oil-evermore mobile [J].Journal of Petroleum Science and Engineering,2003,37:5～9
[7]孙慧,张付生.稠油化学降粘研究进展[J].精细与专用化学品,2005,13(23):16～20
[8]敬加强,罗平亚,朱毅飞.原油组成对其粘度影响的灰色关联分析[J].油气田地面工程,2000,19 (6):12～13
[9]柳荣伟,陈侠玲,周宁.稠油降粘技术及降粘机理研究进展[J].精细石油化工进展,2008,9(4):20～25
[10]李四红.渣油降粘技术[J].当代化工,2009,38(2):138～140
[11]张凤英,李建波,诸林,等.稠油油溶性降粘剂研究进展[J].特种油气藏,2006,13(2):1～4
[12]刘春天,刘永建,程显彪.稠油水裂解反应动力学研究[J].石油与天然气化工, 2004,33 (4):281～283
[13]范晓娟,王霞,陈玉祥,等.稠油化学降粘方法研究进展[J].化工时刊,2007,21(3):46～49
[14]尉小明,刘喜林,王卫东,等.稠油降粘方法概述[J].精细石油化工,2002,45(5):45～48
[15]常运兴,张新军.稠油油溶性降粘剂降粘机理研究[J].油气田地面工程,2006,25(4):8～9
[16]吴本芳,杨允明,沈木贤.SL的合成及降黏性能研究[J].油田化学,2003,20(1):78～82
[17]陈艳玲,胡江,张巧莲.垦西特稠油化学降粘机理的研究[J].地球科学-中国地质大学学报,1998,23(6):605～609
[18]张付生,王彪.复合型原油降凝降粘剂EMS的研制[J].油田化学,1995,12(2):117～120
[19]王大喜,陈秋芬,赵玉玲,等.油溶性降粘剂作用机理的密度泛函计算[J].石油学报,2005,21(6):40～45
[20]Kan MP.Rheological properties of heavy oils and heavy oil emulsions [J].Energy sources,1996,18:385～391
[21] Ala B.Bazyleva,MD.Anwarul Hasan.Bitumen and Heavy Oil Rheological Properties: Reconciliation with Viscosity Measurements [J].Journal of Chemical & Engineering Data,2009,35:1～6
[22]赵素惠,王永清,赵田红.稠油化学降粘法概述[J].化工时刊,2005,19(8):64～66
[23]周风山,吴瑾光.稠油化学降粘技术研究进展[J].油田化学,2002,18 (3):268～272
[24]周风山,吴瑾光.稠油的类乳化复合降黏作用机理[J].油田化学,2002,19 (4):312～315
[25]舒福昌,史茂勇,向兴金.聚合物作为稠油降粘剂的实验研究[J].应用化工,2007,36(6):575～577
[26] Siddhartha Seth, Brian F. Towler.Diachronic viscosity increase in waxy crude oils [J].Journal of Petroleum Science and Engineering, 2004, 43: 13～23
[27]李炯.流动改进剂在原油长输管道的应用研究[J].油田化学,1987,4(2):146～155
[28]吴本芳,张敏涛.复配型特稠原油降粘剂研究[J].洛阳师范学院学报,2003,02:45～49
[29]罗艳托,朱建华,张世杰.石油焦灰分与原料性质的关系分析[J].石油大学学报,2005,20(3):116～118
[30]李新学,林瑞森.延迟焦化循环油组成的估算及其对生焦率的影响[J].石油炼制化工,1999,30(9):6～8
[31]王宗贤,郭爱军,阙国和.辽河渣油热转化和加氢裂化过程中生焦行为的研究[J].燃料化学学报,1998,26(4): 326～333
[32]Spiecker P. Matthew, Gawrys Keith L, Kilpatrick Peter K.Aggregation and solubility behavior of asphaltenes and their subfractions[J].Journal of Colloid and Interface Science, 2003,V267(1):178～193
[33]Amy Hinkle, Eun-Jae Shin, Matthew W. Liberatore, Andrew M. Herring, Mike Batzle.Correlating the chemical and physical properties of a set of heavy oils from around the world [J].Fuel, 2008,87:3065～3070
[34]杨天华,张娟利,张吉仁,等.延迟焦化装置炉管结焦原因分析及对策探讨[J].天然气与石油,2006,24(6):43～45
[35]梁朝林,沈本贤,吴世逵.焦化反应温度、循环比对焦化产物分布的影响[J].茂名学院学报,2008,18(6):1～4
[36]郭爱军,王宗贤,阙国和.饱和烃促进渣油热反应初期生焦的考察[J].燃料化学学报,2001,29(5):408～412
[37]黎元生.提高延迟焦化液收的专利方法[J].石油化工动态,1999,7(6): 50～52
[38] Gong Jing-Song, Fu Wei-Biao, Zhong Bei-Jing.A study on the pyrolysis of asphalt [J].Fuel, 2003, 82:49～52
[39]Xianghai Meng , Chunming Xu, Jinsen Gao, Li Li.Studies on catalytic pyrolysis of heavy oils: Reaction behaviors and mechanistic pathways [J].Applied Catalysis A: General, 2005, 294:168～176
[40]田书红,章琦.减压渣油掺炼高芳烃油焦化反应的研究[J].茂名学院学报,2002,12(3):35～38
[41]孟科全,唐晓东,邹雯蚊,等.稠油降粘技术研究进展[J].天然气与石油,2009,27(3):30～34
[42]宋新红,王冠,李侠.提高稠油集输系统效率的措施及认识[J].国外油田工程,2003,19(4):65～67
[43]陈秋芬,王大喜,刘然冰.油溶性稠油降粘剂研究进展[J].石油钻采工艺,2004,26(2):45～48
[44]Wilburn, Bruse E. Heilman, William J.Methacrylate pour point depressants and compositions [P].US Patent 4844829,1989
[45]Gilles Meunier,Rene Brouard,Paul Maldonado.Polymeric additives usable for inhibition of the deposit of paraffin in crude oils[P].UK:2160536,1985,10:24～26
[46]王霞辉,李季,张秀莲,等.塔河油田油溶性降粘剂的合成及室内评价[J].化学工程与装备,2009,3:65～67
[47]祝明华,姜红金,贺星耀.原油降凝降粘剂HC在稠油生产井中的应用[J].油田化学,1998,15(1):28～30
[48]张凤英,李建波,诸林,等.稠油油溶性降粘剂MASM的合成及室内评价[J].精细石油化工进展,2005,6(12):5～7
[49]金发扬,蒲万芬,任兆刚,等.SZ36-1稠油油溶性降粘剂JN-1的合成及评价[J].精细石油化工进展,2005,6(11):16～17
[50] Andre′L.C. Machado, Elizabete F. Lucas, Gaspar Gonza′lez.Poly (ethylene-co-vinyl acetate) (EVA) as wax inhibitor of a Brazilian crude oil: oil viscosity, pour point and phase behavior of organic solutions [J] .Journal of Petroleum Science and Engineering, 2001, 32:159～165
[51]黄志宇,杨林,王兵,等.丙烯酸酯-苯乙烯-马来酸酐三元聚合物油溶性降粘剂的研究[J].吉林化工学院学报,2003,20(4):25～27
[52]吴国云,浦琳,曾顺鹏,等.稠油降粘剂SMA的合成及性能评价[J].石油天然气学报(江汉石油学院学报),2008,30(2):343～345
[53]王云峰,张春光,侯万国,等.表面活性剂及其在油气田中的应用[M].石油工业出版社,1995:2～30
[54]杜巧云,葛虹.表面活性剂基础及应用[M] .中国石化出版社,1996:32～65
[55]陈玉祥,王霞,潘成松,等.表面活性剂在稠油降粘中的应用[J].重庆科技学院学报(自然科学版),2009,11(1):48～51
[56]Yousef Al-Roomi, Reena George, Ahmed Elgibaly, Ali Elkamel .Use of a novel surfactant for improving the transportability/transportation of heavy/viscous crude oils[J].Journal of Petroleum Science and Engineering, 2004,42:235～243
[57]B. Lu, X. Li, L. E. Scriven, H. T. Davis,Y. Talmon,and J. L. Zakin.Effect of Chemical Structure on Viscoelasticity andExtensional Viscosity of Drag-Reducing CationicSurfactant Solutions [J].Langmuir, 1998, 14:8～16
[58]Yunying Qi, Jacques L. Zakin . Chemical and Rheological Characterization ofDrag-Reducing Cationic Surfactant Systems [J].Ind. Eng. Chem. Res, 2002,41:6326～6336
[59]李传,崔敏,王继乾,等.表面活性剂对渣油沥青质体系分散性质的影响[J].应用化学,2008,25(1):85～89
[2]阙国和主编.石油组成与转化化学[M].中国石油大学出版社,2008
[3]吴本芳,郭金波.稠油油溶性降粘剂研究进展概况[J].油气储运,2003,22(2):1～6
[4]程亮,邹长军,杨林,等.稠油化学组成对其粘度影响的灰熵分析[J].石油化工高等学校学报,2006,19(3):6～10
[5]Peng Luo,Yongan Gu.effects of asphaltene content on the heavy oil viscosity at different temperatures [J].Fuel,2007,86:1069～1078
[6]Farouq Ali SM.Heavy oil-evermore mobile [J].Journal of Petroleum Science and Engineering,2003,37:5～9
[7]孙慧,张付生.稠油化学降粘研究进展[J].精细与专用化学品,2005,13(23):16～20
[8]敬加强,罗平亚,朱毅飞.原油组成对其粘度影响的灰色关联分析[J].油气田地面工程,2000,19 (6):12～13
[9]柳荣伟,陈侠玲,周宁.稠油降粘技术及降粘机理研究进展[J].精细石油化工进展,2008,9(4):20～25
[10]李四红.渣油降粘技术[J].当代化工,2009,38(2):138～140
[11]张凤英,李建波,诸林,等.稠油油溶性降粘剂研究进展[J].特种油气藏,2006,13(2):1～4
[12]刘春天,刘永建,程显彪.稠油水裂解反应动力学研究[J].石油与天然气化工, 2004,33 (4):281～283
[13]范晓娟,王霞,陈玉祥,等.稠油化学降粘方法研究进展[J].化工时刊,2007,21(3):46～49
[14]尉小明,刘喜林,王卫东,等.稠油降粘方法概述[J].精细石油化工,2002,45(5):45～48
[15]常运兴,张新军.稠油油溶性降粘剂降粘机理研究[J].油气田地面工程,2006,25(4):8～9
[16]吴本芳,杨允明,沈木贤.SL的合成及降黏性能研究[J].油田化学,2003,20(1):78～82
[17]陈艳玲,胡江,张巧莲.垦西特稠油化学降粘机理的研究[J].地球科学-中国地质大学学报,1998,23(6):605～609
[18]张付生,王彪.复合型原油降凝降粘剂EMS的研制[J].油田化学,1995,12(2):117～120
[19]王大喜,陈秋芬,赵玉玲,等.油溶性降粘剂作用机理的密度泛函计算[J].石油学报,2005,21(6):40～45
[20]Kan MP.Rheological properties of heavy oils and heavy oil emulsions [J].Energy sources,1996,18:385～391
[21] Ala B.Bazyleva,MD.Anwarul Hasan.Bitumen and Heavy Oil Rheological Properties: Reconciliation with Viscosity Measurements [J].Journal of Chemical & Engineering Data,2009,35:1～6
[22]赵素惠,王永清,赵田红.稠油化学降粘法概述[J].化工时刊,2005,19(8):64～66
[23]周风山,吴瑾光.稠油化学降粘技术研究进展[J].油田化学,2002,18 (3):268～272
[24]周风山,吴瑾光.稠油的类乳化复合降黏作用机理[J].油田化学,2002,19 (4):312～315
[25]舒福昌,史茂勇,向兴金.聚合物作为稠油降粘剂的实验研究[J].应用化工,2007,36(6):575～577
[26] Siddhartha Seth, Brian F. Towler.Diachronic viscosity increase in waxy crude oils [J].Journal of Petroleum Science and Engineering, 2004, 43: 13～23
[27]李炯.流动改进剂在原油长输管道的应用研究[J].油田化学,1987,4(2):146～155
[28]吴本芳,张敏涛.复配型特稠原油降粘剂研究[J].洛阳师范学院学报,2003,02:45～49
[29]罗艳托,朱建华,张世杰.石油焦灰分与原料性质的关系分析[J].石油大学学报,2005,20(3):116～118
[30]李新学,林瑞森.延迟焦化循环油组成的估算及其对生焦率的影响[J].石油炼制化工,1999,30(9):6～8
[31]王宗贤,郭爱军,阙国和.辽河渣油热转化和加氢裂化过程中生焦行为的研究[J].燃料化学学报,1998,26(4): 326～333
[32]Spiecker P. Matthew, Gawrys Keith L, Kilpatrick Peter K.Aggregation and solubility behavior of asphaltenes and their subfractions[J].Journal of Colloid and Interface Science, 2003,V267(1):178～193
[33]Amy Hinkle, Eun-Jae Shin, Matthew W. Liberatore, Andrew M. Herring, Mike Batzle.Correlating the chemical and physical properties of a set of heavy oils from around the world [J].Fuel, 2008,87:3065～3070
[34]杨天华,张娟利,张吉仁,等.延迟焦化装置炉管结焦原因分析及对策探讨[J].天然气与石油,2006,24(6):43～45
[35]梁朝林,沈本贤,吴世逵.焦化反应温度、循环比对焦化产物分布的影响[J].茂名学院学报,2008,18(6):1～4
[36]郭爱军,王宗贤,阙国和.饱和烃促进渣油热反应初期生焦的考察[J].燃料化学学报,2001,29(5):408～412
[37]黎元生.提高延迟焦化液收的专利方法[J].石油化工动态,1999,7(6): 50～52
[38] Gong Jing-Song, Fu Wei-Biao, Zhong Bei-Jing.A study on the pyrolysis of asphalt [J].Fuel, 2003, 82:49～52
[39]Xianghai Meng , Chunming Xu, Jinsen Gao, Li Li.Studies on catalytic pyrolysis of heavy oils: Reaction behaviors and mechanistic pathways [J].Applied Catalysis A: General, 2005, 294:168～176
[40]田书红,章琦.减压渣油掺炼高芳烃油焦化反应的研究[J].茂名学院学报,2002,12(3):35～38
[41]孟科全,唐晓东,邹雯蚊,等.稠油降粘技术研究进展[J].天然气与石油,2009,27(3):30～34
[42]宋新红,王冠,李侠.提高稠油集输系统效率的措施及认识[J].国外油田工程,2003,19(4):65～67
[43]陈秋芬,王大喜,刘然冰.油溶性稠油降粘剂研究进展[J].石油钻采工艺,2004,26(2):45～48
[44]Wilburn, Bruse E. Heilman, William J.Methacrylate pour point depressants and compositions [P].US Patent 4844829,1989
[45]Gilles Meunier,Rene Brouard,Paul Maldonado.Polymeric additives usable for inhibition of the deposit of paraffin in crude oils[P].UK:2160536,1985,10:24～26
[46]王霞辉,李季,张秀莲,等.塔河油田油溶性降粘剂的合成及室内评价[J].化学工程与装备,2009,3:65～67
[47]祝明华,姜红金,贺星耀.原油降凝降粘剂HC在稠油生产井中的应用[J].油田化学,1998,15(1):28～30
[48]张凤英,李建波,诸林,等.稠油油溶性降粘剂MASM的合成及室内评价[J].精细石油化工进展,2005,6(12):5～7
[49]金发扬,蒲万芬,任兆刚,等.SZ36-1稠油油溶性降粘剂JN-1的合成及评价[J].精细石油化工进展,2005,6(11):16～17
[50] Andre′L.C. Machado, Elizabete F. Lucas, Gaspar Gonza′lez.Poly (ethylene-co-vinyl acetate) (EVA) as wax inhibitor of a Brazilian crude oil: oil viscosity, pour point and phase behavior of organic solutions [J] .Journal of Petroleum Science and Engineering, 2001, 32:159～165
[51]黄志宇,杨林,王兵,等.丙烯酸酯-苯乙烯-马来酸酐三元聚合物油溶性降粘剂的研究[J].吉林化工学院学报,2003,20(4):25～27
[52]吴国云,浦琳,曾顺鹏,等.稠油降粘剂SMA的合成及性能评价[J].石油天然气学报(江汉石油学院学报),2008,30(2):343～345
[53]王云峰,张春光,侯万国,等.表面活性剂及其在油气田中的应用[M].石油工业出版社,1995:2～30
[54]杜巧云,葛虹.表面活性剂基础及应用[M] .中国石化出版社,1996:32～65
[55]陈玉祥,王霞,潘成松,等.表面活性剂在稠油降粘中的应用[J].重庆科技学院学报(自然科学版),2009,11(1):48～51
[56]Yousef Al-Roomi, Reena George, Ahmed Elgibaly, Ali Elkamel .Use of a novel surfactant for improving the transportability/transportation of heavy/viscous crude oils[J].Journal of Petroleum Science and Engineering, 2004,42:235～243
[57]B. Lu, X. Li, L. E. Scriven, H. T. Davis,Y. Talmon,and J. L. Zakin.Effect of Chemical Structure on Viscoelasticity andExtensional Viscosity of Drag-Reducing CationicSurfactant Solutions [J].Langmuir, 1998, 14:8～16
[58]Yunying Qi, Jacques L. Zakin . Chemical and Rheological Characterization ofDrag-Reducing Cationic Surfactant Systems [J].Ind. Eng. Chem. Res, 2002,41:6326～6336
[59]李传,崔敏,王继乾,等.表面活性剂对渣油沥青质体系分散性质的影响[J].应用化学,2008,25(1):85～89