Mo_2N/Zr-MCM-41新型催化剂的制备、表征及其麻疯树油加氢脱氧的催化性能
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摘要
采用水热法合成载体MCM-41与不同初始n(Si)/n(Zr)的Zr-MCM-41,由(NH_4)_6Mo_7O_(24)与载体经过共浸渍、高温焙烧、氨气程序升温氮化制备了Mo_2N/Zr-MCM-41新型加氢脱氧催化剂。采用XRD、BET、XPS、TEM以及吡啶红外等手段对催化剂进行了表征,并采用高压反应釜评价了不同n(Si)/n(Zr)的Mo_2N/Zr-MCM-41催化麻疯树油加氢脱氧反应的性能。结果表明,Zr改性后的载体与纯硅MCM-41同样具有良好的孔道结构,且L酸、B酸酸值提高。Mo_2N作为活性组分体现出了优异的加氢脱氧性能,在反应温度350℃、氢气分压3.0 MPa条件下催化的产品油组成主要为直链烷烃与芳香族化合物,占产品组分的90%(质量分数)以上;不同n(Si)/n(Zr)的新型催化剂脱氧率可高达100%;芳香族化合物含量高于直链烷烃,最高可占组成的72.09%(质量分数),主要以单环、双环芳香烃为主,碳链长度分布在C_(8-16);直链烷烃碳链长度分布在C_(8-17)。通过Mo_2N/Zr-MCM-41催化后的麻疯树油经分馏处理后可制备生物燃料。
MCM-41 and Zr-MCM-41 with different initial n(Si)/n(Zr)ratios were synthesized by hydrothermal method.Mo_2N/Zr-MCM-41 hydrodeoxygenation catalysts were prepared by(NH_4)_6Mo_7O_(24)carrier co-impregnation,calaination,temperature programing and nitridation,and characterized by XRD,XPS,TEMand Py-FTIR methods.The catalytic performance of Mo_2N/Zr-MCM-41 in hydrodeoxygenation of Jatropha curcas oil was evaluated in a high pressure reactor.The results indicate that Zr modified carrier has the same pore structure as pure silicon MCM-41,and the value of L acid and B acid increases.As the active component,the Mo_2N has an excellent HDO performance.Under the reaction temperature of 350℃and the hydrogen pressure of 3.0 MPa,the catalyzed product oil is mainly composed of straight chain alkanes and aromatic compounds,accounting for more than 90% of the product components.The deoxygenation rates of the newcatalysts with different n(Si)/n(Zr)ratios are all above 98%,and the content of aromatic compounds is higher than that of straight chain alkanes,which accounts for 72.09%of the total composition.The aromatic compounds are mainly single ring and bicyclic aromatic hydrocarbons with the length of carbon chain of C_(8-16).After the leprosy oils catalyzed by Mo_2N/Zr-MCM-41 are fractionated,it can be prepared to be biofuels.
MCM-41 and Zr-MCM-41 with different initial n(Si)/n(Zr)ratios were synthesized by hydrothermal method.Mo_2N/Zr-MCM-41 hydrodeoxygenation catalysts were prepared by(NH_4)_6Mo_7O_(24)carrier co-impregnation,calaination,temperature programing and nitridation,and characterized by XRD,XPS,TEMand Py-FTIR methods.The catalytic performance of Mo_2N/Zr-MCM-41 in hydrodeoxygenation of Jatropha curcas oil was evaluated in a high pressure reactor.The results indicate that Zr modified carrier has the same pore structure as pure silicon MCM-41,and the value of L acid and B acid increases.As the active component,the Mo_2N has an excellent HDO performance.Under the reaction temperature of 350℃and the hydrogen pressure of 3.0 MPa,the catalyzed product oil is mainly composed of straight chain alkanes and aromatic compounds,accounting for more than 90% of the product components.The deoxygenation rates of the newcatalysts with different n(Si)/n(Zr)ratios are all above 98%,and the content of aromatic compounds is higher than that of straight chain alkanes,which accounts for 72.09%of the total composition.The aromatic compounds are mainly single ring and bicyclic aromatic hydrocarbons with the length of carbon chain of C_(8-16).After the leprosy oils catalyzed by Mo_2N/Zr-MCM-41 are fractionated,it can be prepared to be biofuels.
引文
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[23]QIAN Z,ZHOU X,LI Y,LI M,JIANG T,YIN H,CHANG S. Effect of the thermal and hydrothermal treatment on textural properties of Zr-M CM-41 mesoporous molecular sieve[J]. Appl Surf Sci,2009,255(12):6397-6403.
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[25]王威燕,杨运泉,罗和安,杨彦松,胡韬,刘文英,何兵,钦柏豪.复合载体TiO2-Al2O3的制备及其对Ni-Mo-S负载型催化剂加氢脱氧性能的影响[J].燃料化学学报,2011,39(12):924-929.(WANG Wei-yan,YANG Yun-quan,LUO He-an,YANG Yan-song,HU Tao,LIU Wen-ying,HE Bing,QING Bai-hao. Preparation of TiO2-Al2O3composite support and its performance in catalystic hydrodeoxygenation[J]. J Fuel Chem Technol,2011,39(12):924-929.)
[26]任行涛.烷烃加氢异构化分子筛催化剂的研究[D].天津:南开大学,2005.(REN Hang-tao. Study on hydrosiomerization of molecular sieve catalysts for alkanes[D]. Tianjin:Nankai University,2005.)
[27]LI Z,GAO L,ZHENG S. Investigation of the dispersion of MoO3,onto the support of mesoporous silica MCM-41[J]. Appl Cataly A:Gen,2002,236(1):163-171.
[28]肖进兵,罗有训,罗根祥,孙兆林,辛勤,李灿.氧化铝负载氮化钼的表面性质及加氢脱氢性能[J].催化学报,2001,22(6):571-574.(XIAO Jin-bing,LUO You-xin,LUO Gen-xiang,SUN Zhao-lin,XIN Qin,LI Can. Surface properties and hydrogenation/dehydrogenation performance of alumina-supported molybdenum nitride[J]. Chin J Catal,2001,22(6):571-574.)
[29]刘振林,孟明,伏义路,姜明,胡天斗,谢亚宁,刘涛.γ-Mo2N和分子筛负载的钼氮化物的结构表征[J].物理化学学报,2001,17(7):631-635.(LIU Zheng-lin,MENG Ming,FU Yi-lu,JIANG Ming,HU Tian-dou,XIE Ya-ning,LIU Tao. Structure characterization ofγ-Mo2N and M o nitrides supported on zeolites[J]. Acta Phys-Chim Sin,2001,17(7):631-635.)
[30]HADA K,MASATOSHI NAGAI A,OMI S. Characterization and HDS activity of cobalt molybdenum nitrides[J]. J Phys Chem B,2001,105(19):217-219.
[31]NAGATA T,KOBLMLLER G,BIERWAGEN O,GALLINAT C S,SPECK J S. Surface structure and chemical states of a-plane and cplane InN films[J]. Appl Phy Lett,2009,95(13):132104-132104-3.
[32]NAGAI M,JUMPEI TAKADA A,OMI S. XPS study of nitrided molybdena/titania catalyst for the hydrodesulfurization of dibenzothiophene[J]. J Phy Chem B,1999,103(46):10180-10188.
[33]刘维桥,刘杰,赵琳,孙桂大,吴义志,张金媛. Mo2N催化剂的研究进展[J].抚顺石油学院学报,2003,23(3):18-21.(LIU Wei-qiao,LIU Jie,ZHAO Lin,SUN Gui-da,WU Yi-zhi,ZHANG Jin-yuan. Advance on study of Mo2N catalyst[J]. J Fushun Pet Inst,2003,23(3):18-21.)
[34]罗楠,曹阳,李进,郭威,赵子为. Ni2P/Zr-M CM-41催化剂的制备及其对麻疯树油加氢脱氧的催化性能[J].燃料化学学报,2016,44(1):76-83.(LUO Nan,CAO Yang,LI Jin,GUO Wei,ZHAO Zi-wei. Preparation of Ni2P/Zr-M CM-41 catalyst and its performance in the hydrodeoxygenation of Jatropha curcas oil[J]. J Fuel Chem Technol,2016,44(1):76-83.)
[35]杨树武,徐江. SiO2负载的氮化钼催化剂的合成与表征[J].催化学报,1998,V19(2):125-129.(YANG Shu-wu,XU Jiang. Synthesis and characterization of SiO2supported molybdenum nitride hydrodenitro genation catalysts[J]. Chin J Catal,1998,V19(2):125-129.)
[2]WANG Y,TAO H,LIU K,WU J,FANG Y. From biomass to advanced bio-fuel by catalytic pyrolysis/hydro-processing:Hydrodeoxygenation of bio-oil derived from biomass catalytic pyrolysis[J]. Bioresour Technol,2012,108(108):280-284.
[3]HUBER G W,IBORRA S,CORMA A. Synthesis of transportation fuels from biomass:Chemistry,catalysts,and engineering[J]. Chem Rev,2006,106(9):4044-4098.
[4]YANG Y,LUO H,TONG G,SMITH K J,TYE C T. Hydrodeoxygenation of phenolic model compounds over MoS2catalysts w ith different structures[J]. Chin J Chem Eng,2008,16(5):733-739.
[5]SENOL O·I,VILJAVA T R,KRAUSE A O I. Hydrodeoxygenation of aliphatic esters on sulphided NiM o/γ-Al2O3,and CoMo/γ-Al2O3,catalyst:The effect of w ater[J]. Catal Today,2005,106(1):186-189.
[6]COUMANS A E,HENSEN E J M. A model compound(methyl oleate,oleic acid,triolein)study of triglycerides hydrodeoxygenation over alumina-supported NiM o sulfide[J]. Appl Catal B:Environ,2017,201:290-301.
[7]WANG W,LI L,TAN S,Wu K,ZHU G,LIU Y,XU Y,YANG Y. Preparation of NiS2//M oS2,catalysts by two-step hydrothermal method and their enhanced activity for hydrodeoxygenation of p-cresol[J]. Fuel,2016,179:1-9.
[8]WAWRZETZ A,PENG B, HRABAR A, JENTYS A,LEMONIDOU A A, LERCHER J A. Towards understanding the bifunctional hydrodeoxygenation and aqueous phase reforming of glycerol[J]. J Catal,2010,269(2):411-420.
[9]LEE E H,PARK R S,KIM H,PARK S H,JUNG S C,JEON J K,KIM S C,PARK T K. Hydrodeoxygenation of guaiacol over Pt loaded zeolitic materials[J]. J Ind Eng Chem,2016,37:18-21.
[10]DWIATMOKO A A,ZHOU L,KIM I,CHOI J W,SUH D J,HA J M. Hydrodeoxygenation of lignin-derived monomers and lignocellulose pyrolysis oil on the carbon-supported Ru catalysts[J]. Catal Today,2016,265:192-198.
[11]MONNIER J,SULIMMA H,DALAI A,CARAVAGGIO G. Hydrodeoxygenation of oleic acid and canola oil over alumina-supported metal nitrides[J]. Appl Catal A:Gen,2010,382(2):176-180.
[12]GHAMPSON I T,SEP'U LVEDA C,GARCIA R,FREDERICK B G,WHEELER M C,ESCALONA N,DESISTO W J. Guaiacol transformation over unsupported molybdenum-based nitride catalysts[J]. Appl Catal A:Gen,2012,413(4):78-84.
[13]TOBA M,ABE Y,KURAMOCHI H,OSAKO M,MOCHIZUKI T,YOSHIMURA Y. Hydrodeoxygenation of waste vegetable oil over sulfide catalysts[J]. Catal Today,2011,164(1):533-537.
[14]STINNER C,TANG Z,HAOUAS M,WEBER T,PRINS R. Preparation and 31P NMR characterization of nickel phosphides on silica[J].J Catal,2002,208(2):456-466.
[15]BLASCO T,CORMA A,NAVARRO M T,PARIENTE J P. Synthesis,characterization,and catalytic activity of Ti-MCM-41 structures[J].Cheminform,2010,27(3):65-74.
[16]XU J,CHU W,LUO S. Synthesis and characterization of mesoporous V-MCM-41 molecular sieves with good hydrothermal and thermal stability[J]. J M ol Catal A:Chem,2006,256(1):48-56.
[17]ZIOLEK M,NOWAK I,KILOS B,SOBCZAK I,DECYK P,TREJDA M,VOLTA J C. Template synthesis and characterisation of MCM-41 mesoporous molecular sieves containing various transition metal elements-TM E(Cu,Fe,Nb,V,M o)[J]. J Phy Chem Solids,2004,65(2):571-581.
[18]LIM S,CIUPARU D,YANG Y,DU G,PFEFFERLE L D,HALLER G L. Improved synthesis of highly ordered Co-MCM-41[J].M icroporous M esoporous M ater,2007,101(1):200-206.
[19]LAHA S C,MUKHERJEE P,SAINKAR S R,KUMAR R. Cerium containing MCM-41-Type mesoporous materials and their acidic and redox catalytic properties[J]. J Catal,2002,207(2):213-223.
[20]CHEN L F,WANG J A,NOREA L E,AGUILAR J,NAVARRETE J,SALAS P,MONTOYA J A,ANGEL P D. Synthesis and physicochemical properties of Zr-M CM-41 mesoporous molecular sieves and Pt/H 3 PW 12 O 40/Zr-M CM-41 catalysts[J]. J Solid State Chem,2007,180(10):2958-2972.
[21]JIANG T S,ZHAO Q,YIN H B. Synthesis and characterization of Ni-mesoporous molecular sieves with high stability[J]. Inorg Mater,2007,43(1):30-34.
[22]DONG Z,YE F,ZHANG H. Mesoporous structure stability of zirconium-doped mesoporous silica at elevated temperature[J]. Mater Lett,2009,63(27):2343-2345.
[23]QIAN Z,ZHOU X,LI Y,LI M,JIANG T,YIN H,CHANG S. Effect of the thermal and hydrothermal treatment on textural properties of Zr-M CM-41 mesoporous molecular sieve[J]. Appl Surf Sci,2009,255(12):6397-6403.
[24]李福祥,张香娣,李瑞丰,谢克昌. Zr-MCM-41的合成及其表征[J].燃料化学学报,2004,32(4):471-474.(LI Fu-xiang,ZHANG Xiang-ti,LI Rui-feng,XIE Ke-chang. Synthesis and characterization of mesoporous Zr-MCM-41[J]. J Fuel Chem Technol,2004,32(4):471-474.)
[25]王威燕,杨运泉,罗和安,杨彦松,胡韬,刘文英,何兵,钦柏豪.复合载体TiO2-Al2O3的制备及其对Ni-Mo-S负载型催化剂加氢脱氧性能的影响[J].燃料化学学报,2011,39(12):924-929.(WANG Wei-yan,YANG Yun-quan,LUO He-an,YANG Yan-song,HU Tao,LIU Wen-ying,HE Bing,QING Bai-hao. Preparation of TiO2-Al2O3composite support and its performance in catalystic hydrodeoxygenation[J]. J Fuel Chem Technol,2011,39(12):924-929.)
[26]任行涛.烷烃加氢异构化分子筛催化剂的研究[D].天津:南开大学,2005.(REN Hang-tao. Study on hydrosiomerization of molecular sieve catalysts for alkanes[D]. Tianjin:Nankai University,2005.)
[27]LI Z,GAO L,ZHENG S. Investigation of the dispersion of MoO3,onto the support of mesoporous silica MCM-41[J]. Appl Cataly A:Gen,2002,236(1):163-171.
[28]肖进兵,罗有训,罗根祥,孙兆林,辛勤,李灿.氧化铝负载氮化钼的表面性质及加氢脱氢性能[J].催化学报,2001,22(6):571-574.(XIAO Jin-bing,LUO You-xin,LUO Gen-xiang,SUN Zhao-lin,XIN Qin,LI Can. Surface properties and hydrogenation/dehydrogenation performance of alumina-supported molybdenum nitride[J]. Chin J Catal,2001,22(6):571-574.)
[29]刘振林,孟明,伏义路,姜明,胡天斗,谢亚宁,刘涛.γ-Mo2N和分子筛负载的钼氮化物的结构表征[J].物理化学学报,2001,17(7):631-635.(LIU Zheng-lin,MENG Ming,FU Yi-lu,JIANG Ming,HU Tian-dou,XIE Ya-ning,LIU Tao. Structure characterization ofγ-Mo2N and M o nitrides supported on zeolites[J]. Acta Phys-Chim Sin,2001,17(7):631-635.)
[30]HADA K,MASATOSHI NAGAI A,OMI S. Characterization and HDS activity of cobalt molybdenum nitrides[J]. J Phys Chem B,2001,105(19):217-219.
[31]NAGATA T,KOBLMLLER G,BIERWAGEN O,GALLINAT C S,SPECK J S. Surface structure and chemical states of a-plane and cplane InN films[J]. Appl Phy Lett,2009,95(13):132104-132104-3.
[32]NAGAI M,JUMPEI TAKADA A,OMI S. XPS study of nitrided molybdena/titania catalyst for the hydrodesulfurization of dibenzothiophene[J]. J Phy Chem B,1999,103(46):10180-10188.
[33]刘维桥,刘杰,赵琳,孙桂大,吴义志,张金媛. Mo2N催化剂的研究进展[J].抚顺石油学院学报,2003,23(3):18-21.(LIU Wei-qiao,LIU Jie,ZHAO Lin,SUN Gui-da,WU Yi-zhi,ZHANG Jin-yuan. Advance on study of Mo2N catalyst[J]. J Fushun Pet Inst,2003,23(3):18-21.)
[34]罗楠,曹阳,李进,郭威,赵子为. Ni2P/Zr-M CM-41催化剂的制备及其对麻疯树油加氢脱氧的催化性能[J].燃料化学学报,2016,44(1):76-83.(LUO Nan,CAO Yang,LI Jin,GUO Wei,ZHAO Zi-wei. Preparation of Ni2P/Zr-M CM-41 catalyst and its performance in the hydrodeoxygenation of Jatropha curcas oil[J]. J Fuel Chem Technol,2016,44(1):76-83.)
[35]杨树武,徐江. SiO2负载的氮化钼催化剂的合成与表征[J].催化学报,1998,V19(2):125-129.(YANG Shu-wu,XU Jiang. Synthesis and characterization of SiO2supported molybdenum nitride hydrodenitro genation catalysts[J]. Chin J Catal,1998,V19(2):125-129.)