双功能金属纳米晶/水合肼体系催化稠油原位裂解加氢降黏改质
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摘要
催化裂解加氢技术在高温条件下使稠油大分子催化裂解,并通过加氢提高产物的氢/碳比,从而降低稠油黏度,提高产物轻质化程度。采用液相还原法制备了Ni、Pd及Ni-Pd合金纳米晶催化剂,并采用水合肼(N_2H_4·H_2O)作为供氢剂,对南堡油田稠油进行催化裂解加氢降黏研究。利用永磁旋转搅拌高压釜模拟地层条件,通过正交实验确定了最佳反应条件并利用HSC Chemistry软件分析了供氢剂的热力学性质,在最佳反应条件下进行对比实验。结果表明:金属纳米晶可促进稠油大分子裂解并使供氢剂分解释氢,其中钯纳米晶/水合肼体系对稠油的降黏效果最好。与原油样品相比,改质后油样重质组分质量分数减少8.34百分点,降黏率达到91.3%。根据文献对稠油黏度降低的可能机理进行了简要分析。改质后的稠油黏度显著降低,可为稠油有效开采提高采收率提供理论参考。
Catalytic hydrocracking technology enable long chain macromolecule in heavy oils cracking at high temperatures, and thus results in higher H/C atomic ratio, less viscosity and more light products. In this work, Ni, Pd and Ni-Pd alloy metal nanocrystal catalysts were prepared through one-pot wet chemical route, and hydrazine hydrate(N_2H_4·H_2O) was used as hydrogen donor to study in-situ viscosity reduction of Nanpu heavy oil by hydrocracking method. The stratum conditions were simulated by a high pressure autoclave with a magnetic stirrer, and the optimal reaction conditions were investigated by the orthogonal test method. In addition, thermodynamic properties of the hydrogen donor were also analyzed with the HSC chemistry software, and comparison experiments were performed under the optimal reaction conditions. Experimental results indicate that metal nanocrystals can enhance catalytic cracking reactions of macromolecules in the heavy oil and also promote hydrogen donor to release hydrogen. It is found that Pd nanocrystals/hydrazine hydrate system exhibits the best heavy oil viscosity reduction performance. After catalytic hydrogenation, the mass fraction of heavy components decreased by 8.34 percentage point, and the viscosity reduction rate can be up to 91.3%. Possible viscosity reduction mechanisms were also analyzed based on literature review. The viscosity of heavy oils after hydrotreating can be significantly reduced, and the proposed method can provide theoretical guidance for heavy oil enhanced oil recovery development.
Catalytic hydrocracking technology enable long chain macromolecule in heavy oils cracking at high temperatures, and thus results in higher H/C atomic ratio, less viscosity and more light products. In this work, Ni, Pd and Ni-Pd alloy metal nanocrystal catalysts were prepared through one-pot wet chemical route, and hydrazine hydrate(N_2H_4·H_2O) was used as hydrogen donor to study in-situ viscosity reduction of Nanpu heavy oil by hydrocracking method. The stratum conditions were simulated by a high pressure autoclave with a magnetic stirrer, and the optimal reaction conditions were investigated by the orthogonal test method. In addition, thermodynamic properties of the hydrogen donor were also analyzed with the HSC chemistry software, and comparison experiments were performed under the optimal reaction conditions. Experimental results indicate that metal nanocrystals can enhance catalytic cracking reactions of macromolecules in the heavy oil and also promote hydrogen donor to release hydrogen. It is found that Pd nanocrystals/hydrazine hydrate system exhibits the best heavy oil viscosity reduction performance. After catalytic hydrogenation, the mass fraction of heavy components decreased by 8.34 percentage point, and the viscosity reduction rate can be up to 91.3%. Possible viscosity reduction mechanisms were also analyzed based on literature review. The viscosity of heavy oils after hydrotreating can be significantly reduced, and the proposed method can provide theoretical guidance for heavy oil enhanced oil recovery development.
引文
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[12] 李伟,朱建华,齐建华.纳米Ni催化剂在超稠油水热裂解降黏中的应用研究[J].燃料化学学报,2007,35(2):176-180.(LI Wei,ZHU Jianhua,QI Jianhua.Application of nano-nickel catalyst in the viscosity reduction of Liaohe extra-heavy oil by aquathermolysis[J].Journal of Fuel Chemistry and Technology,2007,35(2):176-180.)
[13] WU Chuan,LEI Guanglun,YAO Chuanjin,et al.Mechanism for reducing the viscosity of extra-heavy oil by aquathermolysis with an amphiphilic catalyst[J].Journal of Fuel Chemistry and Technology,2010,38(6):684-690.
[14] CHEN Yanling,WANG Yuanqing,WU Chuan,et al.Laboratory experiments and field tests of an amphiphilic metallic chelate for catalytic aquathermolysis of heavy oil[J].Energy & Fuels,2008,22(3):1502-1508.
[15] 秦文龙,苏碧云,蒲春生.稠油井下改质降黏开采中高效催化剂的应用[J].石油学报(石油加工),2009,25(6):772-776.(QIN Wenlong,SU Biyun,PU Chunsheng.Application of high efficiency catalyst in downhole upgrading heavy oil[J].Acta Petrolei Sinica (Petroleum Processing Section),2009,25(6):772-776.)
[16] 周明辉,孙文杰,李克文.纳米催化剂辅助超稠油氧化改质实验研究[J].中国科学:技术科学,2017,47(2):197-203.(ZHOU Minghui,SUN Wenjie,LI Kewen.Experimental research of nano catalyst assisted oxidization upgrading of super heavy oil[J].Scientia Sinaca:Technologica,2017,47(2):197-203.)
[17] 石岩松,赵法军.应用于稠油降粘改质中的超分散纳米催化剂的研究进展与前景展望[J].当代化工,2015,44(12):2805-2810.(SHI Yansong,ZHAO Fajun.Research progress and development prospect of ultradispersed catalysts for heavy oil upgrading[J].Contemporary Chemical Industry,2015,44(12):2805-2810.)
[18] LI Chun,WANG Tao,CHU Wei,et al.Synthesis of octahedral,truncated octahedral,and cubic Rh2Ni nanocrystals and their structure-activity relationship for the decomposition of hydrazine in aqueous solution to hydrogen[J].Nanoscale,2016,8(13):7043-7055.
[19] TONG Dongge,CHU Wei,WU Ping,et al.Honeycomb-like Co-B amorphous alloy catalysts assembled by a solution plasma process show enhanced catalytic hydrolysis activity for hydrogen generation[J].RSC Advances,2012,2(6):2369-2376.
[20] TONG Dongge,ZENG Xiaoli,CHU Wei,et al.Preparation of monodispersed cobalt boron-spherical nanoparticles and their behavior during the catalytic decomposition of hydrous hydrazine[J].Materials Research Bulletin,2010,45(4):442-447.
[21] VARIN R A,BIDABADI A S.Nanostructured complex hydride systems for hydrogen generation[J].Energy,2015,3(1):121-143.
[22] POLANSKI J,BARTCZAK P,AMBROZKIEWCZ W,et al.Ni-supported Pd nanoparticles with Ca promoter:A new catalyst for low-temperature ammonia cracking[J].Plos One,2015,10(8):1-14.
[23] LAN Jian,WANG Kai,YUAN Qiang,et al.Composition-controllable synthesis of defect-rich PtPdCu nanoalloy with hollow cavity as superior electrocatalyst for alcohol oxidation[J].Materials Chemistry Frontiers,2017,1(6):1217-1222.
[24] 黄娟,李本高,秦冰,等.塔河稠油催化降黏机理研究[J].石油炼制与化工,2014,45(5):16-20.(HUANG Juan,LI Bengao,QIN Bing,et al.Study on viscosity reduction mechanism of the heavy oil by catalytic aquathermolysis[J].Petroleum Processing and Petrochemicals,2014,45(5):16-20.)
[25] 林世雄.石油炼制工程[M].北京:石油工业出版社,2000.
[26] LI Jian,CHEN Yanling,LIU Hua,et al.Influences on the aquathermolysis of heavy oil catalyzed by two different catalytic ions:Cu2+ and Fe3+[J].Energy & Fuels,2013,27(5):2555-2562.In-Situ Viscosity Reduction for Heavy Oil Through Catalytic Hydrocracking With Bifunctional Metal Nanocrystals/Hydrazine Hydrate SystemLI Yanping ZHANG Hui CUI Yingxian LI Chenyu LI Jianhu WU XiBifunctional Ni,Pd and Ni-Pd alloy nanocrystals/hydrazine hydrate system was used in the viscosity reduction and upgrading process of Nanpu heavy oil by in-situ catalytic cracking.Metal nanocrystals have dual functions,i.e.promoting macromolecule catalytic cracking reactions in heavy oil and help hydrogen donor to release hydrogen through catalytical reactions.Pd nanocrystals/hydrazine hydrate system exhibited the best viscosity reduction performance for heavy oil.The mass fraction of heavy components of the upgraded oil could decrease 8.34%,and the viscosity reduction rate could be up to 91.3%.The proposed bifunctional system can be used for heavy oil enhanced oil recovery development.
[2] 李传,王继乾,隋李涛,等.委内瑞拉稠油沥青质的XPS研究[J].石油学报(石油加工),2013,29(3):459-463.(LI Chuan,WANG Jiqian,SUI Litao,et al.Study on XPS of Venezuela heavy oil asphaltene[J].Acta Petrolei Sinica (Petroleum Processing Section),2013,29(3):459-463.)
[3] 李晨,苏路,李秋叶,等.稠油催化降黏技术开发研究进展[J].化学研究,2015,26(3):323-330.(LI Chen,SU Lu,LI Qiuye,et al.The development of viscosity reduction of heavy oil by catalytic techniques[J].Chemical Research,2015,26(3):323-330.)
[4] 席笑迎,张玉明,高士秋,等.渣油流化床催化裂解与积炭气化燃烧催化剂再生[J].石油学报(石油加工),2016,32(2):254-262.(XI Xiaoying,ZHANG Yuming,GAO Shiqiu,et al.Fluid catalytic cracking of petroleum residue and regeneration of spent catalyst by coke gasification and combustion[J].Acta Petrolei Sinica (Petroleum Processing Section),2016,32(2):254-262.)
[5] 邓刘扬,唐晓东,李晶晶,等.稠油地面催化改质降黏技术的研究进展[J].石油化工,2016,45(2):237-243.(DENG Liuyang,TANG Xiaodong,LI Jingjing,et al.Progresses in surface catalytic upgrading and viscosity reduction of heavy oil[J].Petrochemical Technology,2016,45(2):237-243.)
[6] CLARK P D,CLARK R A,HYNE J B,et al.Studies on the effect of metal species on oil sands undergoing steam treatments[J].AOSTRA Journal of Research,1990,53(6):53-64.
[7] MOHAMMAD A,MAMORA D.Insitu upgrading of heavy oil under steam injection with tetralin and catalyst[C]//Newfoundland:Society of Petroleum Engineers,2008.
[8] 吴川,陈艳玲,王颖,等.有机酸盐与甲苯协同作用超稠油催化降粘研究[J].石油天然气学报,2007,29(3):267-269.(WU Chuan,CHEN Yanling,WANG Ying,et al.Synergism of organic-acid salt and toluene for viscosity reduction of ultra-heavy oil[J].Journal of Oil and Gas Technology,2007,29(3):267-269.)
[9] 樊泽霞,赵福麟,王杰祥,等.超稠油供氢水热裂解改质降黏研究[J].燃料化学学报,2006,34(3):315-318.(FAN Zexia,ZHAO Fulin,WANG Jiexiang,et al.Upgrading and viscosity reduction of super heavy oil by aquathermolysis with hydrogen donor[J].Journal of Fuel Chemistry and Technology,2006,34(3):315-318.)
[10] 李博.辽河油田催化供氢稠油改质的实验[J].大庆石油学院学报,2005,28(4):24-26.(LI Bo.Experiments of in-situ upgarding heavy oil by means of catalyst and hydrogen donor[J].Journal of Daqing Petroleum Institute,2005,28(4):24-26.)
[11] 吴信朋,李燕,宋林花.稠油开采中降粘技术研究进展[J].广东化工,2016,43(4):50-53.(WU Xinpeng,LI Yan,SONG Linhua.Advances in viscosity-reducing methed and techniques for heavy oil recovery[J].Guangdong Chemical Industry,2016,43(4):50-53.)
[12] 李伟,朱建华,齐建华.纳米Ni催化剂在超稠油水热裂解降黏中的应用研究[J].燃料化学学报,2007,35(2):176-180.(LI Wei,ZHU Jianhua,QI Jianhua.Application of nano-nickel catalyst in the viscosity reduction of Liaohe extra-heavy oil by aquathermolysis[J].Journal of Fuel Chemistry and Technology,2007,35(2):176-180.)
[13] WU Chuan,LEI Guanglun,YAO Chuanjin,et al.Mechanism for reducing the viscosity of extra-heavy oil by aquathermolysis with an amphiphilic catalyst[J].Journal of Fuel Chemistry and Technology,2010,38(6):684-690.
[14] CHEN Yanling,WANG Yuanqing,WU Chuan,et al.Laboratory experiments and field tests of an amphiphilic metallic chelate for catalytic aquathermolysis of heavy oil[J].Energy & Fuels,2008,22(3):1502-1508.
[15] 秦文龙,苏碧云,蒲春生.稠油井下改质降黏开采中高效催化剂的应用[J].石油学报(石油加工),2009,25(6):772-776.(QIN Wenlong,SU Biyun,PU Chunsheng.Application of high efficiency catalyst in downhole upgrading heavy oil[J].Acta Petrolei Sinica (Petroleum Processing Section),2009,25(6):772-776.)
[16] 周明辉,孙文杰,李克文.纳米催化剂辅助超稠油氧化改质实验研究[J].中国科学:技术科学,2017,47(2):197-203.(ZHOU Minghui,SUN Wenjie,LI Kewen.Experimental research of nano catalyst assisted oxidization upgrading of super heavy oil[J].Scientia Sinaca:Technologica,2017,47(2):197-203.)
[17] 石岩松,赵法军.应用于稠油降粘改质中的超分散纳米催化剂的研究进展与前景展望[J].当代化工,2015,44(12):2805-2810.(SHI Yansong,ZHAO Fajun.Research progress and development prospect of ultradispersed catalysts for heavy oil upgrading[J].Contemporary Chemical Industry,2015,44(12):2805-2810.)
[18] LI Chun,WANG Tao,CHU Wei,et al.Synthesis of octahedral,truncated octahedral,and cubic Rh2Ni nanocrystals and their structure-activity relationship for the decomposition of hydrazine in aqueous solution to hydrogen[J].Nanoscale,2016,8(13):7043-7055.
[19] TONG Dongge,CHU Wei,WU Ping,et al.Honeycomb-like Co-B amorphous alloy catalysts assembled by a solution plasma process show enhanced catalytic hydrolysis activity for hydrogen generation[J].RSC Advances,2012,2(6):2369-2376.
[20] TONG Dongge,ZENG Xiaoli,CHU Wei,et al.Preparation of monodispersed cobalt boron-spherical nanoparticles and their behavior during the catalytic decomposition of hydrous hydrazine[J].Materials Research Bulletin,2010,45(4):442-447.
[21] VARIN R A,BIDABADI A S.Nanostructured complex hydride systems for hydrogen generation[J].Energy,2015,3(1):121-143.
[22] POLANSKI J,BARTCZAK P,AMBROZKIEWCZ W,et al.Ni-supported Pd nanoparticles with Ca promoter:A new catalyst for low-temperature ammonia cracking[J].Plos One,2015,10(8):1-14.
[23] LAN Jian,WANG Kai,YUAN Qiang,et al.Composition-controllable synthesis of defect-rich PtPdCu nanoalloy with hollow cavity as superior electrocatalyst for alcohol oxidation[J].Materials Chemistry Frontiers,2017,1(6):1217-1222.
[24] 黄娟,李本高,秦冰,等.塔河稠油催化降黏机理研究[J].石油炼制与化工,2014,45(5):16-20.(HUANG Juan,LI Bengao,QIN Bing,et al.Study on viscosity reduction mechanism of the heavy oil by catalytic aquathermolysis[J].Petroleum Processing and Petrochemicals,2014,45(5):16-20.)
[25] 林世雄.石油炼制工程[M].北京:石油工业出版社,2000.
[26] LI Jian,CHEN Yanling,LIU Hua,et al.Influences on the aquathermolysis of heavy oil catalyzed by two different catalytic ions:Cu2+ and Fe3+[J].Energy & Fuels,2013,27(5):2555-2562.In-Situ Viscosity Reduction for Heavy Oil Through Catalytic Hydrocracking With Bifunctional Metal Nanocrystals/Hydrazine Hydrate SystemLI Yanping ZHANG Hui CUI Yingxian LI Chenyu LI Jianhu WU XiBifunctional Ni,Pd and Ni-Pd alloy nanocrystals/hydrazine hydrate system was used in the viscosity reduction and upgrading process of Nanpu heavy oil by in-situ catalytic cracking.Metal nanocrystals have dual functions,i.e.promoting macromolecule catalytic cracking reactions in heavy oil and help hydrogen donor to release hydrogen through catalytical reactions.Pd nanocrystals/hydrazine hydrate system exhibited the best viscosity reduction performance for heavy oil.The mass fraction of heavy components of the upgraded oil could decrease 8.34%,and the viscosity reduction rate could be up to 91.3%.The proposed bifunctional system can be used for heavy oil enhanced oil recovery development.
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