CoMo/MgO催化剂的制备及其对4,6-二甲基二苯并噻吩的加氢脱硫性能
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摘要
以高比表面积的纳米氧化镁(MgO)为载体,分别以四硫代钼酸铵、钼酸铵为Mo源,采用浸渍法制备了MgO负载的催化剂CoMo/MgO-S和CoMo/MgO-O;并对硫化后的催化剂进行了N_2吸附-脱附、XPS、TEM等系列表征;以4,6-二甲基二苯并噻吩(4,6-DMDBT)为模型化合物,考察了CoMo/MgO-S和CoMo/MgO-O的加氢脱硫活性。结果表明:与CoMo/MgO-O催化剂相比,CoMo/MgO-S具有比表面积大、Mo物种的硫化程度高、活性相堆垛层数多等特点;以CoMo/MgO-S为催化剂,4,6-DMDBT的转化率为70.8%,分别高于CoMo/γ-Al_2O_3-O和CoMo/MgO-O催化剂的59.8%和52.3%;进一步消除传质的影响,得到CoMo/MgO-S催化剂的催化转化频率(TOF)为2.2 h~(-1),优于CoMo/MgO-O催化剂。
The CoMo/MgO-S and CoMo/MgO-O catalysts were prepared by impregnation method using ammonium tetrathiomolybdate and ammonium molybdate as Mo precursor, respectively. The sulfided catalysts were characterized by multiple methods, including N_2 adsorption-desorption, XPS and TEM. The catalytic performance of the catalysts was evaluated by using the hydrodesulfurization of 4,6-dimethyldibenzothiophene(4,6-DMDBT). Results show that CoMo/MgO-S catalyst has larger specific surface area, higher degree of sulfurization, and more stacking layers than those of CoMo/MgO-O catalyst. Thus, the CoMo/MgO-S catalyst exhibits much higher hydrodesulfurization(HDS) activity(70.8%) in the HDS of the 4,6-DMDBT than CoMo/γ-Al_2O_3-O(59.8%) and CoMo/MgO-O catalysts(52.3%). After solving the mass transfer limitations, the obtained turnover frequency(TOF) value over the CoMo/MgO-S catalyst is 2.2 h~(-1), much higher than that over the CoMo/MgO-O catalyst.
The CoMo/MgO-S and CoMo/MgO-O catalysts were prepared by impregnation method using ammonium tetrathiomolybdate and ammonium molybdate as Mo precursor, respectively. The sulfided catalysts were characterized by multiple methods, including N_2 adsorption-desorption, XPS and TEM. The catalytic performance of the catalysts was evaluated by using the hydrodesulfurization of 4,6-dimethyldibenzothiophene(4,6-DMDBT). Results show that CoMo/MgO-S catalyst has larger specific surface area, higher degree of sulfurization, and more stacking layers than those of CoMo/MgO-O catalyst. Thus, the CoMo/MgO-S catalyst exhibits much higher hydrodesulfurization(HDS) activity(70.8%) in the HDS of the 4,6-DMDBT than CoMo/γ-Al_2O_3-O(59.8%) and CoMo/MgO-O catalysts(52.3%). After solving the mass transfer limitations, the obtained turnover frequency(TOF) value over the CoMo/MgO-S catalyst is 2.2 h~(-1), much higher than that over the CoMo/MgO-O catalyst.
引文
[1]安高军,周同娜,柴永明,等.轻质油品非加氢脱硫技术[J].化学进展,2007,19(9):1331-1344.(ANGaojun,ZHOU Tongna,CHAI Yongming,et al.Nonhydesulfurization technologies of light oil[J].Progress in Chemistry,2007,19(9):1331-1344.)
[2]SRIVASTAVA V C.An evaluation of desulfurization technologies for sulfur removal from liquid fuels[J].RSC Advances,2012,2(1):759-783.
[3]中国国家标准化管理委员会.车用柴油:GB 19147-2013[S].北京:中国标准出版社,2016.
[4]CHIANELLI R R,DAAGE M,LEDOUX M J.Fundamental studies of transition-metal sulfide catalytic materials[J].Advances in Catalysis,1994,40(1):177-232.
[5]张舜光,王欣,杨红健,等.CA和EDTA对Co-Mo-P/TiO2-γ-Al2O3选择性加氢脱硫催化剂性能的影响[J].石油学报(石油加工),2011,27(2):316-321.(ZHANG Shunguang,WANG Xin,YANGHongjian,et al.Effect of CA and EDTA on catalytic performance of Co-Mo-P/TiO2-γ-A12O3 selective hydrodesulfurization catalysts[J].Acta Petrolei Sinica(Petroleum Processing Section),2011,27(2):316-321.)
[6]TANG T,ZHANG L,FU W,et al.Design and synthesis of metal sulfide catalysts supported on zeolite nanofiber bundles with unprecedented hydrodesulfurization activities[J].Journal of the American Chemical Society,2013,135(31):11437-11440.
[7]庞文琴,于龙.Mo-ZSM-5型分子筛合成与结构研究[J].石油学报(石油加工),1989,5(2):18-22.(PANG Wenqin,YU Long.Study on the synthesis and structure of Mo-ZSM-5type molecular sieves[J].Acta Petrolei Sinica(Petroleum Processing Section),1989,5(2):18-22.)
[8]张海荣,李哲,黄伟.Mo源对Mo-ZSM-5分子筛粒径、Mo元素引入分子筛骨架的影响[J].石油学报(石油加工),2008,24(增刊1):350-354.(ZHANG Hairong,LI Zhe,HUANG Wei.The influence of Mo source on Mo-ZSM-5zeolite particle size and the introduction of Mo into zeolite skeletion[J].Acta Petrolei Sinica(Petroleum Processing Section),2008,24(S1):350-354.)
[9]商红岩,徐永强,刘晨光.炭负载Co-Mo催化剂的二苯并噻吩加氢脱硫性能研究[J].石油大学学报:自然科学版,2004,28(2):103-107.(SHANG Hongyan,XUYongqiang,LIU Chenguang.Hydrodesulfurization properties of dibenzuothiphene over carbon-supported Co-Mo catalysts[J].Journal of the University of Petroleum(Edition of Natural Science),2004,28(2):103-107.)
[10]HU J,ZHANG Z,WANG F,et al.A controllable synthesis of nitrogen-doped mesoporous carbon supported MoS2 catalysts for hydrodesulfurization of thiophene[J].RSC Advances,2016,6(5):101544-101551.
[11]FURIMSKY E,MASSOTH F E.Deactivation of hydroprocessing catalysts[J].Catalysis Today,1999,52(4):381-495.
[12]YAHIRO H,MURAWAKI K,SAIKI K,et al.Study on the supported Cu-based catalysts for the lowtemperature water-gas shift reaction[J].Catalysis Today,2007,126(3):436-440.
[13]李俊平,刘民,郭新闻,等.氧化镁改性微米TS-1催化丙烯环氧化[J].石油学报(石油加工),2012,28(3):388-392.(LI Junping,LIU Min,GUO Xinwen,et al.Propylene oxidation over MgO modified micro TS-1[J].Acta Petrolei Sinica(Petroleum Processing Section),2012,28(3):388-392.)
[14]KLICPERA T,ZDRAIL M.Preparation of highactivity MgO-supported Co-Mo and Ni-Mo sulfide hydrodesulfurization catalysts[J].Journal of Catalysis,2002,206(2):314-320.
[15]KALUA L,GULKOVD,VT Z,et al.Highactivity MgO-supported CoMo hydrodesulfurization catalysts prepared by non-aqueous impregnation[J].Applied Catalysis B:Environmental,2015,162(7):430-436.
[16]ZDRAIL M.MgO-supported Mo,CoMo and NiMo sulfide hydrotreating catalysts[J].Catalysis Today,2003,86(1):151-171.
[17]ZHANG L,FU W,XIANG M,et al.MgO nanosheet assemblies supported CoMo catalyst with high activity in hydrodesulfurization of dibenzothiophene[J].Industrial&Engineering Chemistry Research,2015,54(21):5580-5588.
[18]NIKULSHIN P A,MINAEV P P,MOZHAEV A V,et al.Investigation of co-effect of 12-tungstophosphoric heteropolyacid,nickel citrate and carbon-coated alumina in preparation of NiW catalysts for HDS,HYD and HDN reactions[J].Applied Catalysis B:Environmental,2015,176-177(1):374-384.
[19]SHAN S,YUAN P,HAN W,et al.Supported NiWcatalysts with tunable size and morphology of active phases for highly selective hydrodesulfurization of fluid catalytic cracking naphtha[J].Journal of Catalysis,2015,330(10):288-301.
[20]LAI W,SONG W,PANG L,et al.The effect of starch addition on combustion synthesis of NiMo-Al2O3catalysts for hydrodesulfurization[J].Journal of Catalysis,2013,303(13):80-91.
[21]NIKULSHIN P A,ISHUTENKO D I,MOZHAEV AA,et al.Effects of composition and morphology of active phase of CoMo/Al2O3 catalysts prepared using Co2Mo10-heteropolyacid and chelating agents on their catalytic properties in HDS and HYD reactions[J].Journal of Catalysis,2014,312(2):152-169.
[22]PEA L,VALENCIA D,KLIMOVA T.CoMo/SBA-15catalysts prepared with EDTA and citric acid and their performance in hydrodesulfurization of dibenzothiophene[J].Applied Catalysis B:Environmental,2014,147(8):879-887.
[23]KLIMOVA T E,VALENCIA D,MENDOZA-NIETO J A,et al.Behavior of NiMo/SBA-15catalysts prepared with citric acid in simultaneous hydrodesulfurization of dibenzothiophene and 4,6-dimethyldibenzothiophene[J].Journal of Catalysis,2013,304(11):29-46.
[24]NINH T K T,LAURENTI D,LECLERC E,et al.Support effect for CoMoS and CoNiMoS hydrodesulfurization catalysts prepared by controlled method[J].Applied Catalysis A:General,2014,487(19):210-218.
[25]SHI J,WANG Y,YANG W,et al.Recent advances of pore system construction in zeolite-catalyzed chemical industry processes[J].Chemical Society Reviews,2016,47(6):8877-8903.
[26]柴永明,南军,相春娥,等.以硫化态前驱物制备的NiMoS/γ-Al2O3催化剂表面活性相HRTEM研究[J].石油学报(石油加工),2007,23(3):20-26.(CHAIYongming,NAN Jun,XIANG Chune,et al.Investigation of active phase of NiMoS/γ-Al2O3prepared by thiosalt as precursor through HRTEM[J].Acta Petrolei Sinica(Petroleum Processing Section),2007,23(3):20-26.)
[27]DAAGE M,CHIANELLI R R.Structure-function relations in molydenum sulfide catalysts:The“rimedge”model[J].Journal of Catalysis,1994,149(2):414-427.
[28]ZHANG L,DAI Q,FU W,et al.CoMo catalyst on zeolite TS-1nanorod assemblies with high activity in the hydrodesulfurization of 4,6-dimethyldibenzothiophene[J].Journal of Catalysis,2018,359(3):130-142.
[2]SRIVASTAVA V C.An evaluation of desulfurization technologies for sulfur removal from liquid fuels[J].RSC Advances,2012,2(1):759-783.
[3]中国国家标准化管理委员会.车用柴油:GB 19147-2013[S].北京:中国标准出版社,2016.
[4]CHIANELLI R R,DAAGE M,LEDOUX M J.Fundamental studies of transition-metal sulfide catalytic materials[J].Advances in Catalysis,1994,40(1):177-232.
[5]张舜光,王欣,杨红健,等.CA和EDTA对Co-Mo-P/TiO2-γ-Al2O3选择性加氢脱硫催化剂性能的影响[J].石油学报(石油加工),2011,27(2):316-321.(ZHANG Shunguang,WANG Xin,YANGHongjian,et al.Effect of CA and EDTA on catalytic performance of Co-Mo-P/TiO2-γ-A12O3 selective hydrodesulfurization catalysts[J].Acta Petrolei Sinica(Petroleum Processing Section),2011,27(2):316-321.)
[6]TANG T,ZHANG L,FU W,et al.Design and synthesis of metal sulfide catalysts supported on zeolite nanofiber bundles with unprecedented hydrodesulfurization activities[J].Journal of the American Chemical Society,2013,135(31):11437-11440.
[7]庞文琴,于龙.Mo-ZSM-5型分子筛合成与结构研究[J].石油学报(石油加工),1989,5(2):18-22.(PANG Wenqin,YU Long.Study on the synthesis and structure of Mo-ZSM-5type molecular sieves[J].Acta Petrolei Sinica(Petroleum Processing Section),1989,5(2):18-22.)
[8]张海荣,李哲,黄伟.Mo源对Mo-ZSM-5分子筛粒径、Mo元素引入分子筛骨架的影响[J].石油学报(石油加工),2008,24(增刊1):350-354.(ZHANG Hairong,LI Zhe,HUANG Wei.The influence of Mo source on Mo-ZSM-5zeolite particle size and the introduction of Mo into zeolite skeletion[J].Acta Petrolei Sinica(Petroleum Processing Section),2008,24(S1):350-354.)
[9]商红岩,徐永强,刘晨光.炭负载Co-Mo催化剂的二苯并噻吩加氢脱硫性能研究[J].石油大学学报:自然科学版,2004,28(2):103-107.(SHANG Hongyan,XUYongqiang,LIU Chenguang.Hydrodesulfurization properties of dibenzuothiphene over carbon-supported Co-Mo catalysts[J].Journal of the University of Petroleum(Edition of Natural Science),2004,28(2):103-107.)
[10]HU J,ZHANG Z,WANG F,et al.A controllable synthesis of nitrogen-doped mesoporous carbon supported MoS2 catalysts for hydrodesulfurization of thiophene[J].RSC Advances,2016,6(5):101544-101551.
[11]FURIMSKY E,MASSOTH F E.Deactivation of hydroprocessing catalysts[J].Catalysis Today,1999,52(4):381-495.
[12]YAHIRO H,MURAWAKI K,SAIKI K,et al.Study on the supported Cu-based catalysts for the lowtemperature water-gas shift reaction[J].Catalysis Today,2007,126(3):436-440.
[13]李俊平,刘民,郭新闻,等.氧化镁改性微米TS-1催化丙烯环氧化[J].石油学报(石油加工),2012,28(3):388-392.(LI Junping,LIU Min,GUO Xinwen,et al.Propylene oxidation over MgO modified micro TS-1[J].Acta Petrolei Sinica(Petroleum Processing Section),2012,28(3):388-392.)
[14]KLICPERA T,ZDRAIL M.Preparation of highactivity MgO-supported Co-Mo and Ni-Mo sulfide hydrodesulfurization catalysts[J].Journal of Catalysis,2002,206(2):314-320.
[15]KALUA L,GULKOVD,VT Z,et al.Highactivity MgO-supported CoMo hydrodesulfurization catalysts prepared by non-aqueous impregnation[J].Applied Catalysis B:Environmental,2015,162(7):430-436.
[16]ZDRAIL M.MgO-supported Mo,CoMo and NiMo sulfide hydrotreating catalysts[J].Catalysis Today,2003,86(1):151-171.
[17]ZHANG L,FU W,XIANG M,et al.MgO nanosheet assemblies supported CoMo catalyst with high activity in hydrodesulfurization of dibenzothiophene[J].Industrial&Engineering Chemistry Research,2015,54(21):5580-5588.
[18]NIKULSHIN P A,MINAEV P P,MOZHAEV A V,et al.Investigation of co-effect of 12-tungstophosphoric heteropolyacid,nickel citrate and carbon-coated alumina in preparation of NiW catalysts for HDS,HYD and HDN reactions[J].Applied Catalysis B:Environmental,2015,176-177(1):374-384.
[19]SHAN S,YUAN P,HAN W,et al.Supported NiWcatalysts with tunable size and morphology of active phases for highly selective hydrodesulfurization of fluid catalytic cracking naphtha[J].Journal of Catalysis,2015,330(10):288-301.
[20]LAI W,SONG W,PANG L,et al.The effect of starch addition on combustion synthesis of NiMo-Al2O3catalysts for hydrodesulfurization[J].Journal of Catalysis,2013,303(13):80-91.
[21]NIKULSHIN P A,ISHUTENKO D I,MOZHAEV AA,et al.Effects of composition and morphology of active phase of CoMo/Al2O3 catalysts prepared using Co2Mo10-heteropolyacid and chelating agents on their catalytic properties in HDS and HYD reactions[J].Journal of Catalysis,2014,312(2):152-169.
[22]PEA L,VALENCIA D,KLIMOVA T.CoMo/SBA-15catalysts prepared with EDTA and citric acid and their performance in hydrodesulfurization of dibenzothiophene[J].Applied Catalysis B:Environmental,2014,147(8):879-887.
[23]KLIMOVA T E,VALENCIA D,MENDOZA-NIETO J A,et al.Behavior of NiMo/SBA-15catalysts prepared with citric acid in simultaneous hydrodesulfurization of dibenzothiophene and 4,6-dimethyldibenzothiophene[J].Journal of Catalysis,2013,304(11):29-46.
[24]NINH T K T,LAURENTI D,LECLERC E,et al.Support effect for CoMoS and CoNiMoS hydrodesulfurization catalysts prepared by controlled method[J].Applied Catalysis A:General,2014,487(19):210-218.
[25]SHI J,WANG Y,YANG W,et al.Recent advances of pore system construction in zeolite-catalyzed chemical industry processes[J].Chemical Society Reviews,2016,47(6):8877-8903.
[26]柴永明,南军,相春娥,等.以硫化态前驱物制备的NiMoS/γ-Al2O3催化剂表面活性相HRTEM研究[J].石油学报(石油加工),2007,23(3):20-26.(CHAIYongming,NAN Jun,XIANG Chune,et al.Investigation of active phase of NiMoS/γ-Al2O3prepared by thiosalt as precursor through HRTEM[J].Acta Petrolei Sinica(Petroleum Processing Section),2007,23(3):20-26.)
[27]DAAGE M,CHIANELLI R R.Structure-function relations in molydenum sulfide catalysts:The“rimedge”model[J].Journal of Catalysis,1994,149(2):414-427.
[28]ZHANG L,DAI Q,FU W,et al.CoMo catalyst on zeolite TS-1nanorod assemblies with high activity in the hydrodesulfurization of 4,6-dimethyldibenzothiophene[J].Journal of Catalysis,2018,359(3):130-142.