硫磺改性沥青H_2S释放机理及抑制剂研究进展
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摘要
硫磺改性沥青是一种铺砌公路的新型材料,该材料在高温拌合过程中产生的H_2S是限制其使用的重要原因。本文对国内外硫磺沥青拌合过程中H_2S的释放机理,以及自由基抑制剂、强氧化性抑制剂、碱性抑制剂、温拌抑制剂的抑制效果进行了探讨。现有抑制剂存在价格昂贵、抑制效果差、影响路用性能、使用受限等问题。在此基础上,课题组初步研究了以煤化工行业中采用湿式氧化技术脱除H_2S产生的低品质硫磺为原料改性沥青的新技术,结果表明,与纯硫磺相比,经过处理的低品质硫磺与沥青拌合过程中H_2S释放量减少了2502.2μg/g,与基质沥青相比,改性沥青软化点、延度和冻融劈裂强度分别增加了11.6℃、7.45cm和10%,针入度降低了30.1dmm,混合料动稳定度提高一倍。因此,低品质硫磺可作为改性沥青的优质原料。
Sulfur modified asphalt is a new material of paving road. However, the sulfur and asphalt mixtures have not realized a wide paving application due to H2 S emission during mixing process at high temperature. The release mechanism of H2 S and the inhibitory effects of four kinds of inhibitors including free radical inhibitors, strong oxidative inhibitors, alkaline inhibitors and warmmix inhibitors were discussed. Existing inhibitors have problems such as high price, poor suppression effect, affecting road performance, and limited use. Based on this, our research group conducted a preliminary study on the process of using the lowquality sulfur from H2 S removal by wet oxidation technology in the coal chemical industry as raw material to modify asphalt.Compared with pure sulfur, the H2 S emission during the mixing process of low-quality sulfur and asphalt reduced by 2502.2μg/g.Compared with the matrix asphalt, the softening point, ductility and freeze-thaw cleavage strength of the asphalt modified by the lowquality sulfur increased by 11.6℃, 7.45 cm and 10%, respectively, the penetration degree reduced by 30.1mm, and the dynamic stability of the mixture was doubled. Therefore, the low-quality sulfur can be used as a high-quality raw material for modified asphalt.
Sulfur modified asphalt is a new material of paving road. However, the sulfur and asphalt mixtures have not realized a wide paving application due to H2 S emission during mixing process at high temperature. The release mechanism of H2 S and the inhibitory effects of four kinds of inhibitors including free radical inhibitors, strong oxidative inhibitors, alkaline inhibitors and warmmix inhibitors were discussed. Existing inhibitors have problems such as high price, poor suppression effect, affecting road performance, and limited use. Based on this, our research group conducted a preliminary study on the process of using the lowquality sulfur from H2 S removal by wet oxidation technology in the coal chemical industry as raw material to modify asphalt.Compared with pure sulfur, the H2 S emission during the mixing process of low-quality sulfur and asphalt reduced by 2502.2μg/g.Compared with the matrix asphalt, the softening point, ductility and freeze-thaw cleavage strength of the asphalt modified by the lowquality sulfur increased by 11.6℃, 7.45 cm and 10%, respectively, the penetration degree reduced by 30.1mm, and the dynamic stability of the mixture was doubled. Therefore, the low-quality sulfur can be used as a high-quality raw material for modified asphalt.
引文
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[38]陈保莲,范思远,张静,等.温拌硫磺沥青混合料及其制备方法[P].CN:106630766A,2017.
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[40]李国强,李珍珍,石玉良,等.HPF焦化脱硫废液资源化处理技术开发[J].工业水处理,2013,33(9):10-15.
[41]何建平,李辉.炼焦化学产品回收技术[M].北京:冶金工业出版社,2006.
[2]Benzowitz J,Boe E S.Effect of sulfur upon some of the properties of asphalt[C]//ASTM Proceeding,1938,38:539-547.
[3]Syroezhko A M,Begak O Y,Fedorov V V,et al.Modification of paving asphalts with sulfur[J].Russ J Appl Chem,2003,76(3):491-496.
[4]Jacques C,David S,Gordon M C,et al.Asphalt Mixtures Modified with sulphur pellets,impact on pavement thickness[J].Road Mater Pavement,2010,11(sup1):459-485.
[5]Yen T F,Chilingarian G V.Asphaltenes and asphalts,2[M].Volume 40B.Dev Petrol SIC,2000:515-530.
[6]徐世法,贾璐.新型硫磺改性沥青混合料性能评价与应用关键技术[M].北京:人民交通出版社,2015.
[7]Saylak D,Gallaway B M,Ahmad H.Beneficial use of sulfur in sulfur-asphalt,pavements[M]//West J R.New Uses of Sulfur.Adv Chem Ser,1975,140:102-129.
[8]Boduszynski M M.Chemistry of asphalt[C]//Am Chem Soc,Washington D.C,1981:119.
[9]Nellensteyn F J.Relation of the micelle to the medium in asphalt[J].Inst Petrol Technol,1928,14:134-138.
[10]Al-Ansary M,Masad E,Strickland D.Sulphur sustainable applications:initial field monitoring and performance of shell thiopave trial road in qatar[C]//Proc Annu Gas Process Symp,2010:121-130.
[11]Wiewiorowski T K,Parthasarathy A,Slaten B L.Molten sulfur chemistry.V.Kinetics of chemical equilibration in pure liquid sulfur[J].J Phys Chem,1968,72(6):1890-1892.
[12]钱鹏.路面材料硫磺沥青改性剂的研制[D].南京:东南大学,2009:27-45.
[13]Kennepohl G J,Miller L J.Sulfur-asphalt binder technology for pavements[M]//New Uses of SulfurⅡ.Adv Chem Ser,1978,165:113.
[14]Petrossi U,Bocca P L,Pacor P.Reactions and technological propertier of sulfur-treated asphalt[J].Ind Eng Chem Prod Res Dev,1972,11(2):214-219.
[15]Qarles Van Ufford J J,Vlugter J C.Schwefel und Bitumen II Brennst[J].Chemistry,1965,16:7.
[16]Kennepohl G J,Miller L J.Sulfur-asphalt binder technology for pavements[J].Adv Chem,2009,165(7):113-134.
[17]Lee D.Modification of asphalt and asphalt paving mixtures by sulfur additives[J].Ind Eng Chem Prod Res Dev,1975,14(3):171-177.
[18]刘植昌,凌立成,乔文明,刘朗.添加硫沥青球不熔化机理的研究[J].中国科学院山西煤炭化学研究所,1998,28(2):10-14.
[19]杨锡武,熊世银,角述兵,刘克.硫磺改性沥青混合料性能及机理研究[J].湖南科技大学学报,2009,(9):61-67.
[20]De Filippis P,Giavarini C,Santarelli M L.Sulphurextended asphalt:reaction kinetics of H2S evolution[J].Fuel,1998,77(5):459-463.
[21]朱玛莉.硫磺性性沥青的研究[D].南京:东南大学,2012:15-17.
[22]周彬,封志鹏,肖雪春,等.新型硫磺温拌剂的制备研究[J].公路交通科技(应用技术版),2015,(2):88-91.
[23]孙敏,辛星,渠广镇.Thiopave沥青混合料性能评价[J].石油沥青,2011,25(6):19-24.
[24]金鸣林,杨俊和,史美仁,等.道路沥青的硫化反应[J].煤炭转化,2001,24(4):87-91.
[25]汪灿.硫磺改性沥青的性能研究[D].南京:东南大学,2014.
[26]钱鹏,乔海滨,马全红.改性硫磺颗粒的制备及其改性沥青路用性能[J].东南大学学报(自然科学版),2009,39(3):592-597.
[27]司中向.聚合物硫磺改性沥青性能测试与评价[J].石油沥青,2015,(4):52-55.
[28]张庆新,张珑瑛.一种硫磺改性混合料配方及其施工工艺[P].CN:1690126A,2005.
[29]张予东,张建州,李宾杰,等.阻燃抑烟剂锡酸锌和羟基锡酸锌的研究进展[J].河南化工,2007,24(7):1-4.
[30]程明,金佑成,车淳万.温拌沥青及其制备方法[P].CN:102321373 B,2013.
[31]Gawel I.The selection of additives reducing the evolution of gaseous effluents during the preparation of sulfurbitumen mixes[C]//Int Conf Cat Adsorpt Env Prot,Szklarska Poreba,Poland,1994.
[32]Gladkikh V A,Korolev E V.Suppressing the hydrogen sulfide and sulfur dioxide emission from sulfurbituminous concrete[J].Adv Mater Res,2014,1040:387-392.
[33]Deme I.Sulphur pellet comprizing H2S-supperssant[P].CA:02548142,2005.
[34]Muller J M A F,Touzard B.Decreasing H2S emission in bitumen/Sulphur mixtures[P].GB:137633A,1984.
[35]Alama K,Blasiak I,Dojka M.Badania emisji gazowych zwiazkow siarki z mieszanek siarkowo-asfaltowych[J].Prace Insfytutu Badawczego Drog i Mosto'w(Warsaw),1981,3:105.
[36]Ashtekar S,Narayanan S.Bituminous composition[P].WO:2012004199 A1,2012.
[37]张广磊.硫磺温拌改性沥青技术应用研究[D].济南:山东大学,2016.
[38]陈保莲,范思远,张静,等.温拌硫磺沥青混合料及其制备方法[P].CN:106630766A,2017.
[39]Colange J,Strickland D.Process for manufacturing asphalt[P].US:8557034,2013.
[40]李国强,李珍珍,石玉良,等.HPF焦化脱硫废液资源化处理技术开发[J].工业水处理,2013,33(9):10-15.
[41]何建平,李辉.炼焦化学产品回收技术[M].北京:冶金工业出版社,2006.