煤负载Fe/Mo催化剂在煤/油加氢共炼中的应用
|
摘要
以一种褐煤为载体,钼酸铵、硫酸亚铁、硫化钠为原料,采用浸渍法制备了以Fe/Mo为活性组分的煤负载催化剂,并在500mL高压釜内进行煤-油加氢共炼评价。通过XRD、XPS、BET、SEM-EDS等表征手段对催化剂和反应后固体残渣进行表征,考察了第2金属Fe的加入和Fe/Mo的浸渍顺序对催化剂催化性能的影响。结果表明,催化剂中加入第2金属组分Fe可以促进煤转化。在制备Fe/Mo双金属催化剂时,先浸渍FeS得到的催化剂中Mo金属在煤载体表面的分布更加均匀,反应后固体残渣表面Mo的相对含量最高,煤转化率达到79.12%。
A kind of lignite as support was impregnated with aqueous solution of ammonium molybdate,ferrous sulfate and sodium sulfide,to prepare coal supported Fe/Mo catalysts.The activity of catalysts was evaluated in a 500 mL autoclave.The influences of the addition of Fe component and the impregnation sequence of Fe/Mo components on the catalytic performance were investigated.XRD,XPS,BET and SEM-EDS were used for the characterization of catalysts and solid residuals.Results show the enhancement of the conversion of coal is relevant with the adding Fe component to a coal supported Mo catalyst.The Mo species are more uniformly distributed on the surface of coal support after the first step of impregnation of FeS,resulting in a higher relative content of Mo on the surface than bulk phase and the conversion of coal of 79.12%.
A kind of lignite as support was impregnated with aqueous solution of ammonium molybdate,ferrous sulfate and sodium sulfide,to prepare coal supported Fe/Mo catalysts.The activity of catalysts was evaluated in a 500 mL autoclave.The influences of the addition of Fe component and the impregnation sequence of Fe/Mo components on the catalytic performance were investigated.XRD,XPS,BET and SEM-EDS were used for the characterization of catalysts and solid residuals.Results show the enhancement of the conversion of coal is relevant with the adding Fe component to a coal supported Mo catalyst.The Mo species are more uniformly distributed on the surface of coal support after the first step of impregnation of FeS,resulting in a higher relative content of Mo on the surface than bulk phase and the conversion of coal of 79.12%.
引文
[1]鄢红兵,李琳,成金华.低油价背景下的国际石油贸易格局与中国对策[J].中国石油大学学报(社会科学版),2017,33(2):1-6.(YAN Hongbing,LI Lin,CHENG Jinhua.Countermeasures adopted by China for international oil trade pattern in low oil price[J].Journal of China University of Petroleum(Edition of Social Sciences),2017,33(2):1-6.)
[2]田春荣.2015年中国石油进出口状况分析[J].国际石油经济,2016,24(3):44-53.(TIAN Chunrong.China’s oil imports and exports in 2015[J].International Petroleum Economics,2016,24(3):44-53.)
[3]许友好,何鸣元.重油在加工过程中的碳氢优化分布及有效利用的探索[J].石油学报(石油加工),2017,33(1):1-7.(XU Youhao,HE Mingyuan.Explorations of optimization and highly effective usage of carbon&hydrogen in upgrading of heavy oil[J].Acta Petrolei Sinica(Petroleum Processing Section),2017,33(1):1-7)
[4]宋洪柱.中国煤炭资源分布特征与勘查开发前景研究[D].北京:中国地质大学,2013.
[5]李志强,景晓霞,刘晓,等.褐煤的热处理及其提质煤在CO2气氛中的热解气化行为[J].煤炭学报,2015,40(2):463-469.(LI Zhiqiang,JING Xiaoxia,LIU Xiao,et al.Thermal pretreatment of lignite and the pyrolysis and gasification properties of upgrading coal in CO2[J].Journal of China Coal Society,2015,40(2):463-469.)
[6]周峤.雾霾天气的成因[J].中国人口资源与环境,2015,(增刊1):211-212.(ZHOU Qiao.Cause of the haze weather[J].China Population,Resources and Environment,2015,(Supple 1):211-212.)
[7]商思玉,凌开成,王建平,等.神府煤与胜利减压渣油共处理反应特性的研究[J].燃料化学学报,2005,33(1):47-52.(SHANG Siyu,LING Kaicheng,WANG Jianping,et al.Reaction characteristics of co-processing of Shenfu coal and Shengli vacuum residue[J].Journal of Fuel Chemistry and Technology,2005,33(1):47-52.)
[8]刘华.提高煤直接液化催化剂活性的研究进展及展望[J].洁净煤技术,2016,22(4):105-111.(LIU Hua.Improvement of catalysts activity for direct coal liquefaction[J].Clean Coal Technology,2016,22(4):105-111.)
[9]LASTRA B,ROBERTO G A,MOINELO S R.Novel mo-containing organometallic compounds as dispersed catalysts for liquefaction and hydropyrolysis of coals[J].Energy&Fuels,1997,11(2):411-415.
[10]LI Y,MA F,SU X,et al.Synthesis and catalysis of oleic acid-coated Fe3O4 nanocrystals for direct coal liquefaction[J].Catalysis Communications,2012,26(35):231-234.
[11]SUZUKI T,YAMADA H,SEARS P L,et al.Hydrogenation and hydrogenolysis of coal model compounds by using finely dispersed catalysts[J].Energy&Fuels,1989,3(6):707-713.
[12]蒋中山,黄传峰,李慧慧,等.多功能负载型α-FeOOH催化剂在煤-油共炼中的应用[J].石油学报(石油加工),2017,33(1):144-149.(JIANG Zhongshan,HUANG Chuanfeng,LI Huihui,et al.The application of multifunction supportedα-FeOOH catalysts in coal-oil co-processing[J].Acta Petrolei Sinica(Petroleum Processing Section),2017,33(1):144-149.)
[13]WANG Z,SHUI H,ZHANG D,et al.A comparison of FeS,FeS+S and solid superacid catalytic properties for coal hydro-liquefaction[J].Fuel,2007,86(5-6):835-842.
[14]ZHANG S,LIU D,DENG W,et al.A review of slurry-phase hydrocracking heavy oil technology[J].Energy&Fuels,2007,21(6):3057-3062.
[15]管翠诗,王宗贤,郭爱军,等.悬浮床加氢裂化水溶性催化剂的筛选与表征[J].燃料化学学报,2003,31(5):434-438.(GUAN Cuishi,WANG Zongxian,GUO Aijun,et al.Study on slurry catalyst for Kalamayi residue hydrocracking[J].Journal of Fuel Chemistry and Technology,2003,31(5):434-438.)
[16]邹纲明,凌开成,李香兰.烟煤和低温煤焦油共处理反应及机理的研究[J].燃料化学学报,1996,24(5):447-451.(ZOU Gangming,LING Kaicheng,LI Xianglan.Study on reaction and mechanism in coprocessing of Yanzhou coal and tar[J].Journal of Fuel Chemistry and Technology,1996,24(5):447-451.)
[17]LIU Chenguang,ZHOU Jiashun,QUE Guohe,et al.Hydrocracking of Gudao residue with dispersed-phase Mo catalyst[J].Fuel,1994,73(9):1544-1550.
[18]刘东,张继昌,赵英男,等.渣油悬浮床加氢分散型Mo催化剂硫化程度的XPS分析[J].石油学报(石油加工),2007,23(5):33-37.(LIU Dong,ZHANG Jichang,ZHAO Yingnan,et al.XPS study on the sulfurization of dispersed Mo catalyst for slurry-bed hydroprocessing of residue[J].Acta Petrolei Sinica(Petroleum Processing Section),2007,23(5):33-37.)
[2]田春荣.2015年中国石油进出口状况分析[J].国际石油经济,2016,24(3):44-53.(TIAN Chunrong.China’s oil imports and exports in 2015[J].International Petroleum Economics,2016,24(3):44-53.)
[3]许友好,何鸣元.重油在加工过程中的碳氢优化分布及有效利用的探索[J].石油学报(石油加工),2017,33(1):1-7.(XU Youhao,HE Mingyuan.Explorations of optimization and highly effective usage of carbon&hydrogen in upgrading of heavy oil[J].Acta Petrolei Sinica(Petroleum Processing Section),2017,33(1):1-7)
[4]宋洪柱.中国煤炭资源分布特征与勘查开发前景研究[D].北京:中国地质大学,2013.
[5]李志强,景晓霞,刘晓,等.褐煤的热处理及其提质煤在CO2气氛中的热解气化行为[J].煤炭学报,2015,40(2):463-469.(LI Zhiqiang,JING Xiaoxia,LIU Xiao,et al.Thermal pretreatment of lignite and the pyrolysis and gasification properties of upgrading coal in CO2[J].Journal of China Coal Society,2015,40(2):463-469.)
[6]周峤.雾霾天气的成因[J].中国人口资源与环境,2015,(增刊1):211-212.(ZHOU Qiao.Cause of the haze weather[J].China Population,Resources and Environment,2015,(Supple 1):211-212.)
[7]商思玉,凌开成,王建平,等.神府煤与胜利减压渣油共处理反应特性的研究[J].燃料化学学报,2005,33(1):47-52.(SHANG Siyu,LING Kaicheng,WANG Jianping,et al.Reaction characteristics of co-processing of Shenfu coal and Shengli vacuum residue[J].Journal of Fuel Chemistry and Technology,2005,33(1):47-52.)
[8]刘华.提高煤直接液化催化剂活性的研究进展及展望[J].洁净煤技术,2016,22(4):105-111.(LIU Hua.Improvement of catalysts activity for direct coal liquefaction[J].Clean Coal Technology,2016,22(4):105-111.)
[9]LASTRA B,ROBERTO G A,MOINELO S R.Novel mo-containing organometallic compounds as dispersed catalysts for liquefaction and hydropyrolysis of coals[J].Energy&Fuels,1997,11(2):411-415.
[10]LI Y,MA F,SU X,et al.Synthesis and catalysis of oleic acid-coated Fe3O4 nanocrystals for direct coal liquefaction[J].Catalysis Communications,2012,26(35):231-234.
[11]SUZUKI T,YAMADA H,SEARS P L,et al.Hydrogenation and hydrogenolysis of coal model compounds by using finely dispersed catalysts[J].Energy&Fuels,1989,3(6):707-713.
[12]蒋中山,黄传峰,李慧慧,等.多功能负载型α-FeOOH催化剂在煤-油共炼中的应用[J].石油学报(石油加工),2017,33(1):144-149.(JIANG Zhongshan,HUANG Chuanfeng,LI Huihui,et al.The application of multifunction supportedα-FeOOH catalysts in coal-oil co-processing[J].Acta Petrolei Sinica(Petroleum Processing Section),2017,33(1):144-149.)
[13]WANG Z,SHUI H,ZHANG D,et al.A comparison of FeS,FeS+S and solid superacid catalytic properties for coal hydro-liquefaction[J].Fuel,2007,86(5-6):835-842.
[14]ZHANG S,LIU D,DENG W,et al.A review of slurry-phase hydrocracking heavy oil technology[J].Energy&Fuels,2007,21(6):3057-3062.
[15]管翠诗,王宗贤,郭爱军,等.悬浮床加氢裂化水溶性催化剂的筛选与表征[J].燃料化学学报,2003,31(5):434-438.(GUAN Cuishi,WANG Zongxian,GUO Aijun,et al.Study on slurry catalyst for Kalamayi residue hydrocracking[J].Journal of Fuel Chemistry and Technology,2003,31(5):434-438.)
[16]邹纲明,凌开成,李香兰.烟煤和低温煤焦油共处理反应及机理的研究[J].燃料化学学报,1996,24(5):447-451.(ZOU Gangming,LING Kaicheng,LI Xianglan.Study on reaction and mechanism in coprocessing of Yanzhou coal and tar[J].Journal of Fuel Chemistry and Technology,1996,24(5):447-451.)
[17]LIU Chenguang,ZHOU Jiashun,QUE Guohe,et al.Hydrocracking of Gudao residue with dispersed-phase Mo catalyst[J].Fuel,1994,73(9):1544-1550.
[18]刘东,张继昌,赵英男,等.渣油悬浮床加氢分散型Mo催化剂硫化程度的XPS分析[J].石油学报(石油加工),2007,23(5):33-37.(LIU Dong,ZHANG Jichang,ZHAO Yingnan,et al.XPS study on the sulfurization of dispersed Mo catalyst for slurry-bed hydroprocessing of residue[J].Acta Petrolei Sinica(Petroleum Processing Section),2007,23(5):33-37.)