甲基噻吩在HY分子筛上的吸附、脱附及转化行为
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摘要
由NH4Y分子筛制备了HY分子筛,运用N2吸附、NH3-TPD和Py-FTIR等手段表征HY分子筛的物化性能;采用智能重量分析仪(IGA)方法研究了甲基噻吩(2-甲基噻吩、3-甲基噻吩)在HY分子筛上的吸附-脱附行为;采用程序升温脱附-质谱(TPD-MS)联用手段研究了甲基噻吩在HY分子筛上的转化行为。结果表明,在200℃下2-甲基噻吩和3-甲基噻吩在HY分子筛中的强B酸上发生强化学吸附作用,与B酸结合后生成了甲基噻吩的碳正离子结构进而发生了歧化反应、脱烷基反应以及裂化反应;与2-甲基噻吩不同的是,3-甲基噻吩与HY通过一定的氢转移反应生成了3-甲基四氢噻吩,且200℃吸附条件下3-甲基噻吩比2-甲基噻吩更容易发生裂化反应。
HY zeolite obtained from NH4 Y was characterized by N2 physisorption,NH3-TPD,and in-situ Py-FTIR. The adsorption,desorption,and conversion of methylthiophene on the HY zeolite was investigated by using the intelligent gravimetric analysis( IGA) and temperature programmed desorption-mass spectrum( TPDM S). The results indicated that 2-methylthiophene and 3-methylthiophene are strongly chemisorbed on the strong Brnsted acid sites of HY zeolite,which promote the disproportionation,dealkylation and cracking reactions at200 ℃. Compared with 2-methylthiophene, 3-methylthiophene is prone to crack and form 3-methyltetrahydrothiophene via the hydrogen transfer reactions.
HY zeolite obtained from NH4 Y was characterized by N2 physisorption,NH3-TPD,and in-situ Py-FTIR. The adsorption,desorption,and conversion of methylthiophene on the HY zeolite was investigated by using the intelligent gravimetric analysis( IGA) and temperature programmed desorption-mass spectrum( TPDM S). The results indicated that 2-methylthiophene and 3-methylthiophene are strongly chemisorbed on the strong Brnsted acid sites of HY zeolite,which promote the disproportionation,dealkylation and cracking reactions at200 ℃. Compared with 2-methylthiophene, 3-methylthiophene is prone to crack and form 3-methyltetrahydrothiophene via the hydrogen transfer reactions.
引文
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[13]吴群英,达志坚,朱玉霞,宋海涛.噻吩类硫化物在催化裂化过程中转化规律的研究[J].石油炼制与化工,2012,43(12):29-34.(WU Qun-ying,DA Zhi-jian,ZHU Yu-xia,SONG Hai-tao.Research on the conversion of thiophene derivatives under catalytic cracking conditions[J].Pet Process Petrochem,2012,43(12):29-34.)
[14]SARRIA F,MARIE O,SAUSSEY J,DATURI M.Infrared evidence of three distinct acidic hydroxyls in defect-free HY faujasite[J].J Phys Chem B,2005,109(5):1660-1662.
[15]李宣文,佘励勤,刘兴云.La HY表面与Na OH的作用及酸性表面性质研究[J].催化学报,1983,4(1):43-50.(LI Xuan-wen,SHE Li-qin,LIU Xing-yun.Studies on the interaction between Na OH and acidic sites on La HY surface and the nature of acidic surface of La HY[J].Chin J Catal,1983,4(1):43-50.)
[16]庞新梅,李春义,山红红,郑俊生,杨朝合,张建芳,李树本.硫化物在FCC催化剂上的裂化脱硫研究[J].石油大学学报:自然科学版,2003,27(1):95-98.(PANG Xin-mei,LI Chun-yi,SHAN Hong-hong,ZHENG Jun-sheng,YANG Chao-he,ZHANG Jian-fang,LI Shu-ben.Crackingdesulfurization of sulfur compounds on FCC catalyst[J].J Univ Petrol(Nat Sci Edi),2003,27(1):95-98.)
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[18]LAPPAS A A,VALLA J A,VASALOS I A,KUEHLER C,FRANCIS J,CONNOR P,GUDDE N J.The effect of catalyst properties on the in situ reduction of sulfur in FCC gasoline[J].Appl Catal A:Gen,2004,262(1):31-41.
[19]CAN F,TRAVERT A,RUAUX V,GILSON J P,MAUGF,HU R,WORMSBECHER R F.FCC gasoline sulfur reduction additives:M echanism and active sites[J].J Catal,2007,249(1):79-92.
[20]LEFLAIVE P,LEMBERTON J L,PROT G,MIRGAINB C,CARRIATB J Y,COLINB J M.On the origin of sulfur impurities in fluid catalytic cracking gasoline-Reactivity of thiophene derivatives and of their possible precursors under FCC conditions[J].Appl Catal A:Gen,2002,227(1):201-215.
[21]唐津莲,许友好,徐莉,汪燮卿.庚烯与H2S在酸性催化剂上的反应机理II.噻吩类化合物生成机理[J].石油学报(石油加工),2008,24(3):243-250.(TANG Jin-lian,XU You-hao,XU Li,WANG Xie-qing.Reaction mechanism of heptene and H2S on acid catalyst II.Formation mechanism of thiophenic compounds[J].Acta Pet Sin(Pet Process Sect),2008,24(3):243-250.)
[2]山红红,李春义,赵博艺,杜峰,杨朝和,张建芳.FCC汽油中硫分布和催化脱硫研究[J].石油大学学报(自然科学版),2001,25(6):78-80.(SHAN Hong-hong,LI Chun-yi,ZHAO Bo-yi,DU Feng,YANG Chao-he,ZHANG Jian-fang.Study on distribution of sulfur compounds in FCC gasoline and catalytic desulfuration[J].J Univ Petrol(Nat Sci Edi),2001,25(6):78-80.)
[3]殷长龙,夏道宏.催化裂化汽油中类型硫含量分布[J].燃料化学学报,2001,29(3):256-258.(YIN Chang-long,XIA Dao-hong.Distribution of sulfur compounds in the full-range FCC and RFCC gasoline[J].J Fuel Chem Technol,2001,29(3):256-258.)
[4]WANG J,XU F,XIE W,MEI Z,ZHANG Q,CAI J,CAI W.The enhanced adsorption of dibenzothiophene onto cerium/nickel-exchanged zeolite Y[J].J Hazard M ater,2009,163(2/3):538-543.
[5]BABICH I V,MOULIJN J A.Science and technology of novel processes for deep desulfurization of oil refinery streams:A review[J].Fuel,2003,82(6):607-631.
[6]YANG R T,HERMAMDEZ-MALDONADO A J,YANG F H.Desulfufization of transportation fuels with zeolites under ambient conaitions[J].Science,2003,301(4):79-81.
[7]董世伟,秦玉才,阮艳军,王源,于文广,张磊,范跃超,宋丽娟.改性Y型分子筛对FCC汽油脱硫性能的研究[J].燃料化学学报,2013,41(3):341-346.(DONG Shi-wei,QIN Yu-cai,RUAN Yan-jun,WANG Yuan,YU Wen-guang,ZHANG Lei,FAN Yue-chao,SONG Li-juan.Performance of adsorptive desulfurization for FCC gasoline over modified Y zeolites[J].J Fuel Chem Technol,2013,41(3):341-346.)
[8]王旺银,潘明雪,秦玉才,王凌涛,宋丽娟.Cu(I)Y分子筛表面酸性对其吸附脱硫性能的影响[J].物理化学学报,2011,27(5):1176-1180.(WANG Wang-yin,PAN Ming-xue,QIN Yu-cai,WANG Ling-tao,SONG Li-juan.Effects of surface acidity on the adsorption desulfurization of Cu(I)Y zeolites[J].Acta Phys-Chim Sin,2011,27(5):1176-1180.)
[9]秦玉才,高雄厚,裴婷婷,郑兰歌,王琳,莫周胜,宋丽娟.噻吩在稀土离子改性Y型分子筛上吸附与催化转化研究[J].燃料化学学报,2013,41(7):889-896.(QIN Yu-cai,GAO Xiong-hou,PEI Ting-ting,ZHENG Lan-ge,WANG Lin,MO Zhou-sheng,SONG Li-juan.Adsorption and catalytic conversion of thiophene on Y-type zeolites modified w ith rare-earth metal ions[J].J Fuel Chem Technol,2013,41(7):889-896.)
[10]DUAN L,GAO X,MENG X,ZHANG H,WANG Q,QIN Y,ZHANG X,SONG L.Adsorption,Co-adsorption,and reactions of sulfur compounds,aromatics,olefins over Ce-exchanged Y zeolite[J].J Phys Chem C,2012,116(49):25748-25756.
[11]吴群英,达志坚,朱玉霞.FCC过程中噻吩类硫化物转化规律的研究进展[J].石油化工,2012,41(4):477-483.(WU Qun-ying,DA Zhi-jian,ZHU Yu-xia.Research progresses in conversion of thiophene derivatives in FCC process[J].Petrochem Technol,2012,41(4):477-483.)
[12]CORMA A,GULLBRAND P,MARTNEZ C.Gasoline sulfur removal:Kinetics of S compounds in FCC conditions[J].Stud Surf Sci Catal,2001,134:153-165.
[13]吴群英,达志坚,朱玉霞,宋海涛.噻吩类硫化物在催化裂化过程中转化规律的研究[J].石油炼制与化工,2012,43(12):29-34.(WU Qun-ying,DA Zhi-jian,ZHU Yu-xia,SONG Hai-tao.Research on the conversion of thiophene derivatives under catalytic cracking conditions[J].Pet Process Petrochem,2012,43(12):29-34.)
[14]SARRIA F,MARIE O,SAUSSEY J,DATURI M.Infrared evidence of three distinct acidic hydroxyls in defect-free HY faujasite[J].J Phys Chem B,2005,109(5):1660-1662.
[15]李宣文,佘励勤,刘兴云.La HY表面与Na OH的作用及酸性表面性质研究[J].催化学报,1983,4(1):43-50.(LI Xuan-wen,SHE Li-qin,LIU Xing-yun.Studies on the interaction between Na OH and acidic sites on La HY surface and the nature of acidic surface of La HY[J].Chin J Catal,1983,4(1):43-50.)
[16]庞新梅,李春义,山红红,郑俊生,杨朝合,张建芳,李树本.硫化物在FCC催化剂上的裂化脱硫研究[J].石油大学学报:自然科学版,2003,27(1):95-98.(PANG Xin-mei,LI Chun-yi,SHAN Hong-hong,ZHENG Jun-sheng,YANG Chao-he,ZHANG Jian-fang,LI Shu-ben.Crackingdesulfurization of sulfur compounds on FCC catalyst[J].J Univ Petrol(Nat Sci Edi),2003,27(1):95-98.)
[17]RICHARD F,BOITA T,MOREAU M,BACHMANN C,PROT G.Transformation of thiophenic compounds over HY zeolite:Study of the acid-catalyzed isomerization and disproportionation mechanisms by quantum chemical calculations[J].J M ol Catal A:Chem,2007,273(1):48-54.
[18]LAPPAS A A,VALLA J A,VASALOS I A,KUEHLER C,FRANCIS J,CONNOR P,GUDDE N J.The effect of catalyst properties on the in situ reduction of sulfur in FCC gasoline[J].Appl Catal A:Gen,2004,262(1):31-41.
[19]CAN F,TRAVERT A,RUAUX V,GILSON J P,MAUGF,HU R,WORMSBECHER R F.FCC gasoline sulfur reduction additives:M echanism and active sites[J].J Catal,2007,249(1):79-92.
[20]LEFLAIVE P,LEMBERTON J L,PROT G,MIRGAINB C,CARRIATB J Y,COLINB J M.On the origin of sulfur impurities in fluid catalytic cracking gasoline-Reactivity of thiophene derivatives and of their possible precursors under FCC conditions[J].Appl Catal A:Gen,2002,227(1):201-215.
[21]唐津莲,许友好,徐莉,汪燮卿.庚烯与H2S在酸性催化剂上的反应机理II.噻吩类化合物生成机理[J].石油学报(石油加工),2008,24(3):243-250.(TANG Jin-lian,XU You-hao,XU Li,WANG Xie-qing.Reaction mechanism of heptene and H2S on acid catalyst II.Formation mechanism of thiophenic compounds[J].Acta Pet Sin(Pet Process Sect),2008,24(3):243-250.)