春风减渣改质塔河减渣制取60~#道路沥青效果
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摘要
塔河减渣(THVR)直接生产合格道路沥青存在技术瓶颈。本文用调和工艺,以塔河减渣为基质沥青,在荆门油浆、荆门抽出油及春风减渣3种不同种类的调和组分中优选出新疆春风减渣(CFVR)为优质软组分,对THVR改质制备60~#道路沥青的效果进行考察,建立基于正庚烷沥青质含量的沥青热老化动力学模型,并对改质前后沥青四组分进行平均分子结构表征。结果表明:与THVR相比,CFVR热老化性能及低温性能较好,但感温性能较差,添加40%CFVR的调和沥青TH-CF-40可满足道路石油沥青60~#标准。TH-CF-40老化速率较小,老化反应活化能Ea为102.00kJ/mol,较THVR为高;其饱和分链长为14.44,较THVR短;芳香分、胶质及沥青质芳碳率fA分别为0.29、0.42、0.46,芳环与环烷环之比RA/RN分别为1.24、2.65、2.93,平均侧链长度L分别为6.78、6.09、5.40,均向CFVR趋近,从而使得调和沥青的抗热老化性能及低温延展性有所提高。采用该工艺有助于减少塔河减渣焦化处理量,提高塔河减渣的利用水平,研究结果为拓展春风优质沥青的更高效利用提供理论指导,具有学术意义和应用前景。
There are technical bottlenecks in producing qualified road asphalt using Tahe vacuum residue oil(THVR). In present work, THVR, used as a matrix asphalt, was blended with Chunfeng vacuum residue oil(CFVR) as an added component which was selected from 3 different kinds of blending components including FCC slurry oil, furfural extract oil and CFVR. The preparation of 60~# road asphalt based on THVR was investigated; thermal aging kinetics model of the resulting asphalt was established based on the contents of insoluble asphalt component in heptane; and the average molecular structures of four components contained in asphalt before and after modification were characterized. The results showed that the thermal aging and low temperature performance of CFVR was better while temperature sensitivity was worse compared with THVR,and blending asphalt TH-CF-40 containing 40% CFVR could meet the standard of 60~# Road Petroleum Asphalt. Compared to THVR, TH-CF-40 had the lower aging rate and higher activation energy of aging reaction of 102.00 kJ/mol. Average chain length L of the saturate was 14.44, which was shorter than THVR. The aromatic carbon rates fA of aromatic, resin and asphaltene were 0.29, 0.42 and 0.46, respectively. The ratios of aromatic ring to naphthenic ring RA/RN were 1.24, 2.65 and 2.93; and the average chain lengths L were 6.78, 6.09 and 5.40. The results indicated that the molecularstructure was close to CFVR, therefore, leading to the improved anti-aging performance and low-temperature ductility of blending asphalt. Such processing technology can help reduce the throughput of THVR involved in coking process. Furthermore, the research results can improve the utilization level of THVR and provide theoretical guidance for expanding the efficient use of CFVR, as a result, indicating academic significance and application foreground.
There are technical bottlenecks in producing qualified road asphalt using Tahe vacuum residue oil(THVR). In present work, THVR, used as a matrix asphalt, was blended with Chunfeng vacuum residue oil(CFVR) as an added component which was selected from 3 different kinds of blending components including FCC slurry oil, furfural extract oil and CFVR. The preparation of 60~# road asphalt based on THVR was investigated; thermal aging kinetics model of the resulting asphalt was established based on the contents of insoluble asphalt component in heptane; and the average molecular structures of four components contained in asphalt before and after modification were characterized. The results showed that the thermal aging and low temperature performance of CFVR was better while temperature sensitivity was worse compared with THVR,and blending asphalt TH-CF-40 containing 40% CFVR could meet the standard of 60~# Road Petroleum Asphalt. Compared to THVR, TH-CF-40 had the lower aging rate and higher activation energy of aging reaction of 102.00 kJ/mol. Average chain length L of the saturate was 14.44, which was shorter than THVR. The aromatic carbon rates fA of aromatic, resin and asphaltene were 0.29, 0.42 and 0.46, respectively. The ratios of aromatic ring to naphthenic ring RA/RN were 1.24, 2.65 and 2.93; and the average chain lengths L were 6.78, 6.09 and 5.40. The results indicated that the molecularstructure was close to CFVR, therefore, leading to the improved anti-aging performance and low-temperature ductility of blending asphalt. Such processing technology can help reduce the throughput of THVR involved in coking process. Furthermore, the research results can improve the utilization level of THVR and provide theoretical guidance for expanding the efficient use of CFVR, as a result, indicating academic significance and application foreground.
引文
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[9]ZHANGF,YUJY.AstudyontheagingkineticsofPPAmodified asphalt[J].PetroleumScience&Technology.2010,28(13):1338-1344.
[10]董喜贵,雷群芳,俞庆森.石油沥青质的NMR测定及其模型分子推测[J].燃料化学学报, 2004, 32(6):668-672.DongXigui,LEIQunfang,YUQingsen.NMRdeterminationof petroleumasphaltenesandtheirmodelmoleculesevaluation[J].Journal of Fuel Chemistry and Technology, 2004, 32(6):668-672.
[11]REN W, YANG C, SHAN H. Characterization of average molecular structure of heavy oil fractions by 1H nuclear magnetic resonance and X-raydiffraction[J].ChinaPetroleumProcessing&Petrochemical Technology, 2011, 13(3):1-7.
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[14]HALEYGA.Molecularandunitsheetweightsofasphaltfractions separated by gel permeation chromatography[J]. Analytical Chemistry,1971, 43(3):371-375.
[15]梁文杰,阙国和,陈月珠.我国原油减压渣油的化学组成与结构Ⅱ.减压渣油及其各组分的平均结构[J].石油学报(石油加工),1991, 7(4):1-7.LIANG Wenjie, QUE Guohe, CHEN Yuezhu. Chemical composition andstructureofvacuumresiduesofChinesecrudesⅡ.Average structureofvacuumresiduesandtheirfractions[J].ActaPetrolei Sinica(Petroleum Processing Section), 1991,7(4):1-7.
[16]陈月珠,袁红,梁文杰,等.我国几种原油中减压馏分的化学组成与结构的研究[J].石油炼制与化工, 1991(2):60-66.CHENYuezhu,YUANHong,LIANGWenjie,etal.Studyon chemicalcompositionandstructureofvacuumdistillatesofthree Chinese crudes[J]. Petroleum Processing and Petrochemicals, 1991(2):60-66.
[17]郭爱军,任志惠,田凌燕,等.红外光谱法研究重质油分子的轻度热转化[J].燃料化学学报, 2007, 35(2):169-175.GUOAijun,RENZhihui,TIANLingyan,etal.Characterizationof molecularchangeofheavyoilundermildthermalprocessingusing FT-IRspectroscopy[J].JournalofFuelChemistryandTechnology,2007, 35(2):169-175.
[2]张艳梅,赵广辉,卢竟蔓,等.催化裂化油浆高值化利用技术研究现状[J].化工进展, 2016, 35(3):754-757.ZHANGYanmei,ZHAOGuanghui,LUJingman,etal.Current situationofhighervalueapplicationofFCCslurry[J].Chemical Industry and Engineering Progress, 2016, 35(3):754-757.
[3]左兰娇.催化裂化油浆改质道路沥青抗热老化性能研究[D].武汉:武汉工程大学, 2009.ZUOLanjiao.Studyonthermalagingresistanceofroadasphalt modifiedbyFCCslurryoil[D].Wuhan:WuhanInstituteof Technology, 2009.
[4]李耀伟.催化裂化油浆改善沥青品质的优化研究[D].青岛:山东科技大学, 2006.LIYaowei.Theoilthickliquidofcatalyticcrackingimprovesthe optimizationresearchofbitumenquality[D].Qingdao:Shandong University of Science and Technology, 2006.
[5]李国民,骆新平,欧晔,等.糠醛抽出油对道路沥青针入度影响规律探讨[J].中外能源, 2014, 19(12):83-86.LI Guomin, LUO Xinping, OU Ye, et al. A discuss on the influence of furfural extract oil on road asphalt penetration[J]. Sino-Global Energy,2014, 19(12):83-86.
[6]《沥青生产与应用技术手册》编委会.沥青生产与应用技术手册[M].北京:中国石化出版社, 2010:16-44.Handbook of asphalt production and application technology Editorial.Handbookofasphaltproductionandapplicationtechnology[M].Beijing:China Petrochemical Press, 2010:16-44.
[7]水恒福,沈本贤,高晋生.道路沥青老化动力学研究[J].华东理工大学学报, 1998(4):399-404.SHUIHengfu,SHENBenxian,GAOJinsheng.Studyontheaging kineticsofroadasphalt[J].JournalofEastChinaUniversityof Science and Technology, 1998(4):399-404.
[8]YUAN D M, KANG L, LIAO K J, et al. Aging kinetics of two kinds of road asphalt[J]. Chemical Industry&Engineering, 2008.
[9]ZHANGF,YUJY.AstudyontheagingkineticsofPPAmodified asphalt[J].PetroleumScience&Technology.2010,28(13):1338-1344.
[10]董喜贵,雷群芳,俞庆森.石油沥青质的NMR测定及其模型分子推测[J].燃料化学学报, 2004, 32(6):668-672.DongXigui,LEIQunfang,YUQingsen.NMRdeterminationof petroleumasphaltenesandtheirmodelmoleculesevaluation[J].Journal of Fuel Chemistry and Technology, 2004, 32(6):668-672.
[11]REN W, YANG C, SHAN H. Characterization of average molecular structure of heavy oil fractions by 1H nuclear magnetic resonance and X-raydiffraction[J].ChinaPetroleumProcessing&Petrochemical Technology, 2011, 13(3):1-7.
[12]DICKINSONEM.Structuralcomparisonofpetroleumfractions usingprotonand 13C-NMRspectroscopy[J].Fuel,1980,59(5):290-294.
[13]QIANSA,LICF,ZHANGPZ.Studyof structuralparameterson some petroleum aromatic fractions by 1H-NMR/IR and 13C, 1H-NMR spectroscopy[J]. Fuel, 1984, 63(2):268-273.
[14]HALEYGA.Molecularandunitsheetweightsofasphaltfractions separated by gel permeation chromatography[J]. Analytical Chemistry,1971, 43(3):371-375.
[15]梁文杰,阙国和,陈月珠.我国原油减压渣油的化学组成与结构Ⅱ.减压渣油及其各组分的平均结构[J].石油学报(石油加工),1991, 7(4):1-7.LIANG Wenjie, QUE Guohe, CHEN Yuezhu. Chemical composition andstructureofvacuumresiduesofChinesecrudesⅡ.Average structureofvacuumresiduesandtheirfractions[J].ActaPetrolei Sinica(Petroleum Processing Section), 1991,7(4):1-7.
[16]陈月珠,袁红,梁文杰,等.我国几种原油中减压馏分的化学组成与结构的研究[J].石油炼制与化工, 1991(2):60-66.CHENYuezhu,YUANHong,LIANGWenjie,etal.Studyon chemicalcompositionandstructureofvacuumdistillatesofthree Chinese crudes[J]. Petroleum Processing and Petrochemicals, 1991(2):60-66.
[17]郭爱军,任志惠,田凌燕,等.红外光谱法研究重质油分子的轻度热转化[J].燃料化学学报, 2007, 35(2):169-175.GUOAijun,RENZhihui,TIANLingyan,etal.Characterizationof molecularchangeofheavyoilundermildthermalprocessingusing FT-IRspectroscopy[J].JournalofFuelChemistryandTechnology,2007, 35(2):169-175.