劣质渣油性质对受热生焦趋势影响的研究
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摘要
以四种劣质渣油为原料,研究组成性质对其热转化过程初期生焦特性的影响。结果表明,不同油样生焦诱导期受温度改变的影响程度可以用敏感度参数衡量,生焦诱导期越短的油样,敏感度参数越大,反应温度升高其生焦诱导期降低率越大。相同反应条件下,劣质渣油的生焦特性取决于其自身的基本性质,且各个性质对其生焦特性的影响程度不一。残炭、灰分、分子量、沥青质沉淀点和稳定性参数与其生焦诱导期相关性较强,其中,沥青质沉淀点和稳定性参数均反映的是油样胶体稳定性的突出影响。劣质渣油自身的胶体稳定性与其生焦密切相关,胶体稳定性越差的渣油,越容易生焦,油样的生焦过程是热反应过程中胶体体系逐渐被破坏的过程。
Using 4 inferior residual oils as raw materials,the effect of feedstock properties on the characteristics of coke formation during initial thermal conversion process was studied. The results show that the influence for coke induction period of different oils affected by temperature can be measured with the sensitivity parameters.The shorter the coke induction period of the residue,the bigger the sensitivity parameter. The coke induction period has a higher decrease rate with the reaction temperature rising. The coke formation property generally depends on feedstock's basic properties,and the influence of various properties of inferior residual oils on coke formation is different under the same reaction conditions. Carbon residue, ash, relative molecular mass,asphaltene precipitation onset point and stability parameter have strong correlations with the coke induction period,especially for the colloidal stability of oil reflected by asphaltene precipitation onset point and stability parameter. The colloidal stability of the inferior residual oils is related to the coke formation characteristics. The worse the stability of the residue,the more likely the coke is to form. The coke forming process is a gradual destruction of the colloid system during thermal reaction.
Using 4 inferior residual oils as raw materials,the effect of feedstock properties on the characteristics of coke formation during initial thermal conversion process was studied. The results show that the influence for coke induction period of different oils affected by temperature can be measured with the sensitivity parameters.The shorter the coke induction period of the residue,the bigger the sensitivity parameter. The coke induction period has a higher decrease rate with the reaction temperature rising. The coke formation property generally depends on feedstock's basic properties,and the influence of various properties of inferior residual oils on coke formation is different under the same reaction conditions. Carbon residue, ash, relative molecular mass,asphaltene precipitation onset point and stability parameter have strong correlations with the coke induction period,especially for the colloidal stability of oil reflected by asphaltene precipitation onset point and stability parameter. The colloidal stability of the inferior residual oils is related to the coke formation characteristics. The worse the stability of the residue,the more likely the coke is to form. The coke forming process is a gradual destruction of the colloid system during thermal reaction.
引文
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[9]郭爱军,张宏玉,于道永,王宗贤.热重法考察渣油及其亚组分的焦化性能[J].石油炼制与化工,2002,33(7):49-53.(GUO Ai-jun,ZHANG Hong-yu,YU Dao-yong,WANG Zong-xian.Coking performance of residue and its four groups by thermogravimetric analysis[J].Pet Process Petrochem,2002,33(7):49-53.)
[10]王宗贤,张宏玉,郭爱军,阙国和.渣油中沥青质的缔合状况与热生焦趋势研究[J].石油学报(石油加工),2000,16(4):60-64.(WANG Zong-xian,ZHANG Hong-yu,GUO Ai-jun,QUE Guo-he.A study of association of asphaltene molecules in vacuum residues[J].Acta Pet Sin(Pet Process Sect),2000,16(4):60-64.)
[11]郭爱军,张艳琦,刘贺,王宗贤.重金属对重油热转化过程生焦特性的影响[J].燃料化学学报,2013,41(6):686-690.(GUO Ai-jun,ZHANG Yan-qi,LIU He,WANG Zong-xian.Effect of heavy metals on characteristics of coke formation during thermal conversion of heavy oils[J].J Fuel Chem Technol,2013,41(6):686-690.)
[12]郭爱军,王宗贤,张会军,王治卿.减压渣油掺炼工业供氢剂缓和热转化的基础研究[J].燃料化学学报,2007,35(6):667-672.(GUO Ai-jun,WANG Zong-xian,ZHANG Hui-jun,WANG Zhi-qing.Fundamental study on mild thermal cracking of vacuum residue with industrial hydrogen donors[J].J Fuel Chem Technol,2007,35(6):667-672.)
[13]张龙力,杨国华,张庆轩,杨普江,阙国和.渣油胶体稳定性与热反应生焦性能的关系[J].石油化工高等学校学报,2005,18(1):4-6.(ZHANG Long-li,YANG Guo-hua,ZHANG Qing-xuan,YANG Pu-jiang,QUE Guo-he.The relationship between the colloidal stability and thermal reaction characteristics of residues[J].J Petrochem Univ,2005,18(1):4-6.)
[14]王继乾.添加物对渣油热反应生焦的影响及作用机理研究[D].青岛:中国石油大学,2007.(WANG Ji-qian.Effect of additives on coke formation and its mechanism during residue thermal reaction[D].Qingdao:China University of Petroleum,2007.)
[15]周迎梅.沥青质分散剂对渣油热反应生焦的影响及其作用机理[D].青岛:中国石油大学,2007.(ZHOU Ying-mei.Effect of asphaltene dispersants on coke formation and its mechanism during residue[D].Qingdao:China University of Petroleum,2007.)
[2]丁巍,陈畅,赵德智,宋官龙,李鑫宇.渣油分离方法的研究进展[J].化工进展,2015,34(2):549-553.(DING Wei,CHEN Chang,ZHAO De-zhi,SONG Guan-long,LI Xin-yu.Progress and prospect of separation of residuum[J].Chem Ind Eng Prog,2015,34(2):549-553.)
[3]钟英竹,靳爱民.渣油加工技术现状及发展趋势[J].石油学报(石油加工),2015,31(2):436-443.(ZHONG Ying-zhu,JIN Ai-min.Present situation and progresses of residue processing technology[J].Acta Pet Sin(Pet Process Sect),2015,31(2):436-443.)
[4]瞿国华,黄大智,梁文杰.延迟焦化在我国石油加工中的地位和前景[J].石油学报(石油加工),2005,21(3):47-53.(QU Guo-hua,HUANG Da-zhi,LIANG Wen-jie.Role and prospects of delayed coking in china's petroleum proessing[J].Acta Pet Sin(Pet Process Sect),2005,21(3):47-53.)
[5]梁文杰.重质油化学[M].青岛:中国石油大学出版社,2000.(LIANG Wen-jie.The Chemistry of Heavy Oil[M].Qingdao:China University of Petroleum Press,2000.)
[6]YEN T F.The colloidal aspects of a macrostructure of petroleum asphalt[J].Fuel Sci Technol Int,1992,10(4/6):723-733.
[7]WIEHE I A.A phase-separation kinetic model for coke formation[J].Ind Eng Chem Res,1993,32(11):2447-2454.
[8]王宗贤,何岩,郭爱军,张宏玉,阙国和.辽河和孤岛渣油供氢能力与生焦趋势[J].燃料化学学报,1999,27(3):251-255.(WANG Zong-xian,HE Yan,GUO Ai-jun,ZHANG Hong-yu,QUE Guo-he.Study on hydrogen-donating ability of vacuum residues and their sub-fractions[J].J Fuel Chem Technol,1999,27(3):251-255.)
[9]郭爱军,张宏玉,于道永,王宗贤.热重法考察渣油及其亚组分的焦化性能[J].石油炼制与化工,2002,33(7):49-53.(GUO Ai-jun,ZHANG Hong-yu,YU Dao-yong,WANG Zong-xian.Coking performance of residue and its four groups by thermogravimetric analysis[J].Pet Process Petrochem,2002,33(7):49-53.)
[10]王宗贤,张宏玉,郭爱军,阙国和.渣油中沥青质的缔合状况与热生焦趋势研究[J].石油学报(石油加工),2000,16(4):60-64.(WANG Zong-xian,ZHANG Hong-yu,GUO Ai-jun,QUE Guo-he.A study of association of asphaltene molecules in vacuum residues[J].Acta Pet Sin(Pet Process Sect),2000,16(4):60-64.)
[11]郭爱军,张艳琦,刘贺,王宗贤.重金属对重油热转化过程生焦特性的影响[J].燃料化学学报,2013,41(6):686-690.(GUO Ai-jun,ZHANG Yan-qi,LIU He,WANG Zong-xian.Effect of heavy metals on characteristics of coke formation during thermal conversion of heavy oils[J].J Fuel Chem Technol,2013,41(6):686-690.)
[12]郭爱军,王宗贤,张会军,王治卿.减压渣油掺炼工业供氢剂缓和热转化的基础研究[J].燃料化学学报,2007,35(6):667-672.(GUO Ai-jun,WANG Zong-xian,ZHANG Hui-jun,WANG Zhi-qing.Fundamental study on mild thermal cracking of vacuum residue with industrial hydrogen donors[J].J Fuel Chem Technol,2007,35(6):667-672.)
[13]张龙力,杨国华,张庆轩,杨普江,阙国和.渣油胶体稳定性与热反应生焦性能的关系[J].石油化工高等学校学报,2005,18(1):4-6.(ZHANG Long-li,YANG Guo-hua,ZHANG Qing-xuan,YANG Pu-jiang,QUE Guo-he.The relationship between the colloidal stability and thermal reaction characteristics of residues[J].J Petrochem Univ,2005,18(1):4-6.)
[14]王继乾.添加物对渣油热反应生焦的影响及作用机理研究[D].青岛:中国石油大学,2007.(WANG Ji-qian.Effect of additives on coke formation and its mechanism during residue thermal reaction[D].Qingdao:China University of Petroleum,2007.)
[15]周迎梅.沥青质分散剂对渣油热反应生焦的影响及其作用机理[D].青岛:中国石油大学,2007.(ZHOU Ying-mei.Effect of asphaltene dispersants on coke formation and its mechanism during residue[D].Qingdao:China University of Petroleum,2007.)