道路沥青抗老化性能及其改性的研究
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摘要
本论文通过热处理法降低原料渣油的蜡含量,并调制出基质沥青-YH沥青,将它与两种沥青TH和SH沥青作对比,重点考察老化时间和温度对沥青组成及性质的影响。并利用元素组成、1H-NMR及XPS等多种分析手段,对TH、SH沥青老化前后的结构及特征官能团进行了表征,在以上研究的基础上对沥青的老化机理进行了初步探讨。另外,本论文通过SBS改性的方法提高了YH沥青的各项性能,特别是抗老化性能。
随老化时间的延长、老化温度的升高,沥青四组分的变化趋势为:饱和分基本不变,芳香分和胶质明显减少,沥青质明显增加。老化过程中,沥青的针入度呈指数衰减,软化点线性增加,延度减小但并未呈现明显的线性关系,沥青的胶体不稳定指数逐渐增加。试验结果表明沥青老化为一级动力学反应。
沥青老化前后结构参数的变化表明,沥青的组成和结构对其老化性能有较大影响,沥青各组分结构上的不连续性导致其抗老化性能较差,同时老化过程中发生了芳香环系的缩合反应。通过XPS分析可以看出,沥青老化过程中,伴随有羰基和亚砜官能团的生成。通过对沥青老化机理的探讨,发现沥青的老化是一个缓慢的自氧化过程,氧化反应符合自由基反应历程。
通过考察SBS剂量及稳定剂用量对改性沥青性能的影响,可以得出,适合自制YH沥青的SBS用量为4.0%-5.0%;适合YH沥青的稳定剂用量为0.15%-0.25%。通过对沥青改性前后性能及组成的分析,可以看出,改性剂的掺入引起了沥青组分的重新分配;稳定剂对SBS改性沥青的相容稳定性具有很好的改善作用。
The vacuum residue was dewaxed by thermal treatment to form the basic asphalt-YH. YH, TH and SH asphalts were taken as testing samples to ivestigate their group fractions and chemical\physical properties. The changes of special functional group and molecular structure of TH and SH asphalts during thermal aging were investigated by a series of analysises, such as elemental analysis, 1H-NMR and XPS. On the basis of above studies, the aging mechanism of asphalt was preliminary studied. The performance of the asphalt was markedly improved by the effective addition of SBS, especially its anti-aging property.
The trend of the group fractions was, when asphalt aged, saturates essentially constant, aromatics and resins decreased, whereas asphaltene increased evidently. Meanwhile, the results about properties were as follows: penetration decreased in term of index, softening point increased linearly, lower ductility and colloid instable index increased. The results showed that the aging of paving asphalt was attributed to first order reaction.
The molecular structural change in aging proved that, the composition and structure of paving asphalt had large influence on the aging performance of paving asphalt, the structural discontinuity of asphalt components led to the poor of the aging resistant performance of asphalt. The condensation reaction of aromatic ring was occurred. Functional groups such as carbonyl and sulfoxide formed during aging of asphalt. The aging reaction was on radical reaction mechanism.
The effect of the modifier and stabilizer quantity on the properties of modified asphalt was analyzed. The optimal dosage of modifier was 4.0%-5.0% and that of stabilizer was 0.15%-0.25%. A comprehensive evaluation of performance and composition was made in this thesis. It was found that the change of the group fractions due to modifier dosage, the stabilizer improved miscible stability of SBS modified asphalt.
随老化时间的延长、老化温度的升高,沥青四组分的变化趋势为:饱和分基本不变,芳香分和胶质明显减少,沥青质明显增加。老化过程中,沥青的针入度呈指数衰减,软化点线性增加,延度减小但并未呈现明显的线性关系,沥青的胶体不稳定指数逐渐增加。试验结果表明沥青老化为一级动力学反应。
沥青老化前后结构参数的变化表明,沥青的组成和结构对其老化性能有较大影响,沥青各组分结构上的不连续性导致其抗老化性能较差,同时老化过程中发生了芳香环系的缩合反应。通过XPS分析可以看出,沥青老化过程中,伴随有羰基和亚砜官能团的生成。通过对沥青老化机理的探讨,发现沥青的老化是一个缓慢的自氧化过程,氧化反应符合自由基反应历程。
通过考察SBS剂量及稳定剂用量对改性沥青性能的影响,可以得出,适合自制YH沥青的SBS用量为4.0%-5.0%;适合YH沥青的稳定剂用量为0.15%-0.25%。通过对沥青改性前后性能及组成的分析,可以看出,改性剂的掺入引起了沥青组分的重新分配;稳定剂对SBS改性沥青的相容稳定性具有很好的改善作用。
The vacuum residue was dewaxed by thermal treatment to form the basic asphalt-YH. YH, TH and SH asphalts were taken as testing samples to ivestigate their group fractions and chemical\physical properties. The changes of special functional group and molecular structure of TH and SH asphalts during thermal aging were investigated by a series of analysises, such as elemental analysis, 1H-NMR and XPS. On the basis of above studies, the aging mechanism of asphalt was preliminary studied. The performance of the asphalt was markedly improved by the effective addition of SBS, especially its anti-aging property.
The trend of the group fractions was, when asphalt aged, saturates essentially constant, aromatics and resins decreased, whereas asphaltene increased evidently. Meanwhile, the results about properties were as follows: penetration decreased in term of index, softening point increased linearly, lower ductility and colloid instable index increased. The results showed that the aging of paving asphalt was attributed to first order reaction.
The molecular structural change in aging proved that, the composition and structure of paving asphalt had large influence on the aging performance of paving asphalt, the structural discontinuity of asphalt components led to the poor of the aging resistant performance of asphalt. The condensation reaction of aromatic ring was occurred. Functional groups such as carbonyl and sulfoxide formed during aging of asphalt. The aging reaction was on radical reaction mechanism.
The effect of the modifier and stabilizer quantity on the properties of modified asphalt was analyzed. The optimal dosage of modifier was 4.0%-5.0% and that of stabilizer was 0.15%-0.25%. A comprehensive evaluation of performance and composition was made in this thesis. It was found that the change of the group fractions due to modifier dosage, the stabilizer improved miscible stability of SBS modified asphalt.
引文
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[2]黄伟祈.用溶剂脱沥青方法从中东和吐哈减压渣油中生产高等级道路沥青[J].石油沥青,1996;10(4):38-45
[3]白文茹.改进道路沥青质量的探讨[J].石油炼制,1993;24(3):23-27
[4] Whteoak O. Handbook of shell asphalts [M]. London:Shell Bitumen UK,1991
[5]郭金敏,王小召,汪建立.国内改性沥青的研究与使用[J].建筑技术开发,2005;32(3):48-50
[6]冯敏哿,李志军,宁爱民.道路石油沥青蜡对沥青性质的影响[J].石油沥青,1999,(133):1-23
[7] Weihe I.A.. A solvent-residue Phase diagram for tracking residue conversion[J]. Ind. Eng. Chem. Res.,1992;31(2):530-535
[8] Que Guohe,Liang wenjie. Thermal conversion of ShengLi residue and its constituents[J]. Fuel,1992;71:1483-1485
[9]李生华,刘晨光,梁文杰等.从石油溶液到碳质中间相Ⅰ.石油胶体溶液及其理论尝析[J].石油学报(石油加工),1995;11(1):55-60
[10]李生华,刘晨光,阙国和等.渣油热反应体系中第二液相形成与液相掺兑物的关系[J].石油学报(石油加工),1999;15(4):7-11
[11]程建,刘以红,罗运华.溶剂脱沥青生产道路沥青技术进展[J].现代化工,2000; 20(9):28-31
[12]张会成,邓文安,阙国和.胜利渣油在掺兑物下热反应体系的相态分离行为[J].燃料化学学报,1997;25(3):227-232
[13]王宗贤,阙国和,梁文杰.用微波和红外光谱研究沥青的热老化性质[J].石油沥青,1992
[14]陈平,蒋曙萍,黄晓明.老化因素对沥青性能的影响[J].交通科技,2005(2):104-106
[15]原健安,张登良.温度对胜利沥青热老化的影响[J].西安公路学院学报,1995;15(1):35-39
[16]彭一川,孙立军.不同老化方式对沥青低温性能的影响[J].南京工业大学学报,2007;29(1):81-84
[17]吕伟民,王佐民.排水性沥青路面的空隙特性[J].上海公路,1996(3):8-11
[18]杨小莉,陆婉珍.辽河原油沥青质及胶质油水界面化学性质初探[J].石油学报,1999;15(4):1-6
[19]徐鸥明,韩森,李洪军.克拉玛依重交通90#沥青及其SBS改性沥青紫外线老化研究[J].武汉理工大学学报,2007;31(1):81-83
[20]金鸣林,史美仁,冯安祖.胜利100B和韩国70道路沥青的热老化过程[J].南京化工大学学报,2001;23(1):35-39
[21]穆光照.自由基反应[M].北京:高等教育出版社,1985
[22]卢铁瑞.道路沥青结合料性能评价指标的研究[J].石油沥青,1996;10(2):14-27
[23]王翠红,王子军,黄伟祈.用SHRP手段评价国产沥青的性质[J].石油沥青,2003;17(4):10-13
[24]樊永革,樊洪.美国SHRP沥青混合料设计及主要试验方法简介[J].黑龙江交通科技,2003(10):25-26
[25]吴传海,袁玉卿,王选仓.重交通道路沥青老化规律及评价方法[J].长安大学学报,2007;27(5):35-39
[26]马濉溪.沥青老化影响因素及评价指标分析[J].山西建筑,2007;33(12):297-298
[27]王芳,袁万杰,陈忠达.沥青老化性能评价指标研究[J].公路交通技术,2005(2):57-58
[28] Ronald R.E.. California Desert Test Road-a Step Closer to Performance Based Specifications[J]. Asphalt Paving Technol.,1993;62:247-313
[29] Schmidt R.J.. Laboratory Measurement of the Durability of Paving Asphalts[J]. ASTM STP,1973(532):79-99
[30] Petersen J.C.. A Thin Film Accelerated Ageing Test for Evaluating Asphalt Oxidative Ageing,Proc.[J],Assoc. Asphalt Paving Technol.,1989;58:220-237
[31] Hamsberger P.M.,Petersen J.C.,Branthaver J.F.,Comparison of Oxidation of SHRP(Strategic Highway Research Program)Asphalts by Two Different Methods[J]. Fuel Sci. and Technol.,1993;11(1):89-121
[32]贺华,陈海峰.沥青老化性能的两种试验方法的评价[J].西部探矿工程,2006(1):249-250
[33] Wright J.R.. Determination of oxidation rates of air-blown asphalts by infrared-red spectroscopy[J]. Appl Chem,1962;12:256-266
[34] Petersen J.C.,Factors affecting the kinetics and mechanisms of asphalt oxidation and the relative effects of oxidation products on age hardening[J]. Prepr. Pap.-Am. Chem. Soc., Div.Fuel Chem.,1996,44(4):1322-1344
[35]范耀华,丁国靖,刘国祥.石油沥青抗老化性能研究[J].石油沥青,1997;11(1):1-12
[36]水恒福,沈本贤,高晋升.道路沥青老化动力学研究[J].华东理工大学学报,1998;24(4):399-404
[37]闫峰,王海彦,廖克俭.高等级道路沥青老化动力学研究[J].石油炼制与化工,2001;32(6):56-59
[38]丛玉凤,廖克俭,翟玉春.道路沥青老化动力学的研究—以软化点为参数建立沥青老化动力学模型[J].石油炼制与化工,2005;36(5):23-26
[39]杨鹏,闫峰,魏毅.辽曙沥青老化行为的研究[J].抚顺石油学院学报,2002;22(1):8-11
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