中低温煤焦油加氢转化路径
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摘要
以中低温煤焦油<360℃的馏分油为原料,Ni-Mo/γ-Al2O3为催化剂,在小型固定床单管加氢反应器上进行加氢实验。在压力13 MPa、空速0.4 h-1、氢油体积比1 700∶1和反应温度370℃工艺条件下进行催化加氢反应,通过对原料油和加氢产物的GC-MS的检测结果分析,确定了酚类、萘类、联苯类和菲类化合物的加氢转化路径,得到煤焦油馏分油中主要化合物的加氢反应网络。
The hydrogenation experiment was carried out in a small-scale single tube fixed bed reactor with mid-low-temperature coal tar distillates below 360 ℃ as raw material. The commercial catalyst( Ni-Mo/γ-Al2 O3) was used as the main catalysts. Hydrogenation was carried out under conditions of pressure13 MPa,liquid hourly space velocity 0. 4 h-1,hydrogen to oil volume ratio 1 700∶1,and temperatures 370 ℃,respectively. By analyzing the GC-MS data of hydrogenated products and raw oil,the hydrogenation conversion pathway of phenols,naphthalene,biphenyls and phenanthrene compounds were determined.Hydrogenation reaction network of main compounds in coal tar distillate oil was obtained.
The hydrogenation experiment was carried out in a small-scale single tube fixed bed reactor with mid-low-temperature coal tar distillates below 360 ℃ as raw material. The commercial catalyst( Ni-Mo/γ-Al2 O3) was used as the main catalysts. Hydrogenation was carried out under conditions of pressure13 MPa,liquid hourly space velocity 0. 4 h-1,hydrogen to oil volume ratio 1 700∶1,and temperatures 370 ℃,respectively. By analyzing the GC-MS data of hydrogenated products and raw oil,the hydrogenation conversion pathway of phenols,naphthalene,biphenyls and phenanthrene compounds were determined.Hydrogenation reaction network of main compounds in coal tar distillate oil was obtained.
引文
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[3]徐春霞.煤焦油的性质与加工利用[J].洁净煤技术,2013,19(5):63-67.Xu Chunxia.Characteristics and processing utilization of coal tar[J].Clean Coal Technology,2013,19(5):63-67.
[4]赵璞,裴贤丰,王之正.中低温煤焦油加工利用现状研究[J].煤质技术,2016,(6):11-16.Zhao Pu,Pei Xianfeng,Wang Zhizheng.Study on the present situation of medium/low temperature coal tar processing and utilization[J].Coal Quality Technology,2016,(6):11-16.
[5]刘芳,王林,杨卫兰,等.中低温煤焦油深加工技术及市场前景分析[J].现代化工,2012,32(7):7-11.Liu Fang,Wang Lin,Yang Weilan,et al.Study on deep processing technology of medium and low temperature coal tar and analysis of its market prospect[J].Modern Chemical Industry,2012,32(7):7-11.
[6]张兴刚.低油价时代煤焦油加氢路线如何选择[J].中国石油和化工,2016,(1):34-37.
[7]Tang W,Fang M.L,Wang H.Y,et al.Mild hydrotreatment of low temperature coal tar distillate:product composition[J].Chemical Engineering Journal,2014,236(2):529-537.
[8]王洪岩.淮南煤多联产焦油催化加氢试验研究[D].杭州:浙江大学,2013.Wang Hongyan.Studies for hydroprocessing on coal tar from polygeneration system in Huainan[D].Hangzhou:Zhejiang University,2013.
[9]许人军,胡薇月,崔文岗,等.煤焦油加氢脱氧精制研究进展[J].广州化工,2016,44(15):39-42.Xu Renjun,Hu Weiyue,Cui Wengang,et al.Research progress on carl tar hydrodeoxygenation[J].Guangzhou Chemical Industry,2016,44(15):39-42.
[10]佟瑞利.煤基液体产物的组成分析与芳烃组分催化加氢研究[D].北京:中国矿业大学,2016.Tong Ruili.Composition analysis of coal based liquid and its aromatics catalytic hydrogenation[D].Beijing:China University of Mining Technology,2016.
[11]Korre S C,Klein M T,Quann R J.Polynuclear aromatic hydrocarbons hydrogenationⅠ.Experimental reaction pathways and kinetics[J].Industrial Engineering Chemistry Research,1995,34(1):101-117.
[12]Korre S C,Klein M T,Quann R J.Hydrocracking of polynuclear aromatic hydrocarbons.Development of rate laws through inhibition studies[J].Industrial Engineering Chemistry Research,1997,36(6):2041-2050.
[13]刘成运.多环芳烃的选择性催化加氢研究[D].大连:大连理工大学,2013.Liu Chengyun.Selective catalytic hydrogenation of polycyclic aromatic hydrocarbons[D].Dalia:Dalian University of Technology,2013.
[14]Yamadaya S,Oba M,Miki Y.Hydrocracking of tetralin on supported nickel-tungsten catalysts[J].Bulletin of the Chemical Society of Japan,1977,50(1):79-82.
[15]袁履冰,丁勇.苯系芳烃共振能的计算[J].辽宁师范大学学报(自然科学版),1987,(2):60-63.Yuan Lubing,Ding Yong.The caculation of resonace energy for benzoid hydrocarbons[J].Journal of Liaoning Normal University(Natural Science Edition),1987,(2):60-63.
[16]张全信,刘希尧.多环芳烃的加氢裂化[J].工业催化,2001,9(2):10-16.Zhang Quanxin,Liu Xiyao.Hydrocracking of polycyclic aromatic hydrocarbons[J].Industrial Catalysis,2001,9(2):10-16.
[17]Haynes W H,Parcher J F,Heimer N E.Hydrocracking polycyclic hydrocarbons over a dual-functional zeolite(faujasite)-based catalyst[J].Industrial Engineering Chemistry Process Design Development,1983,22(3):401-409.