NiH/Hβ催化剂的制备及催化正己烷异构化性能
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摘要
采用浸渍还原法制备了一种新型镍氢化物/分子筛(NiH/Hβ)烷烃异构化催化剂,考察了催化剂制备条件及反应条件对其催化正己烷异构化性能的影响。结果发现,当活性组分质量分数为0.5%,反应温度为300℃,反应压力为2.0MPa,氢/油摩尔比为4.0及质量空速为1.0h~(-1)时,NiH/Hβ催化剂催化正己烷异构化活性最优,正己烷的转化率为83.0%,异构烷烃的选择性与收率分别达到78.6%、65.2%。根据实验结果,提出了NiH/Hβ催化剂催化正己烷异构化反应机理,证明NiH金属活性中心具有良好的加氢/脱氢功能。
A novel NiH/Hβcatalyst for n-alkanes isomerization was prepared by impregnation method.Effects of catalyst preparation conditions and reaction conditions on the catalytic performance of catalyst in n-hexane isomerization were investigated.It is found that when the mass fraction of NiH is 0.5%,reaction temperature is 300 ℃,reaction pressure is 2.0 MPa,H_2 to n-hexane molar ratio is 4.0 and MHSV is 1.0h~(-1),the corresponding catalyst shows the best catalytic activity.The maximum conversion of n-hexane reaches 83.0%,while the selectivity and yield of isohexane obtain up to 78.6% and 65.2%,respectively.Based on the above results,the reaction mechanism of n-hexane isomerization was proposed.It is suggested that Ni-H species acting as metal active sites exhibit promising hydrogenation/dehydrogenation performance.
A novel NiH/Hβcatalyst for n-alkanes isomerization was prepared by impregnation method.Effects of catalyst preparation conditions and reaction conditions on the catalytic performance of catalyst in n-hexane isomerization were investigated.It is found that when the mass fraction of NiH is 0.5%,reaction temperature is 300 ℃,reaction pressure is 2.0 MPa,H_2 to n-hexane molar ratio is 4.0 and MHSV is 1.0h~(-1),the corresponding catalyst shows the best catalytic activity.The maximum conversion of n-hexane reaches 83.0%,while the selectivity and yield of isohexane obtain up to 78.6% and 65.2%,respectively.Based on the above results,the reaction mechanism of n-hexane isomerization was proposed.It is suggested that Ni-H species acting as metal active sites exhibit promising hydrogenation/dehydrogenation performance.
引文
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[3]李瑞峰,宋华,李峰,等.烷烃异构化的研究进展[J].辽宁化工,2006,35(8):494-500.(LI Ruifeng,SONGHua,LI Feng,et al.Advances in research on alkane isomerization[J].Liaoning Chemical Industry,2006,35(8):494-500.)
[4]KUCHAR P J,GILLESPIE R D.Developments in isomerization[J].Hydrocarbon Engineering,1999,50(3):35.
[5]JAO R M,LEU L J,CHANG J R.Effects of catalyst preparation and pretreatment on light naphtha isomerization over mordenite-supported Pt catalysts:Optimal reduction temperature for pure feed and for sulfur-containing feed[J].Applied Catalysis A:General,1996,135:301-316.
[6]SPIELBAUER D,MEKHEMER G A H,ZAKI M I,et al.Acidity of sulfated zirconia as studied by FTIRspectroscopy of adsorbed CO and NH3 as probe molecules[J].Catalysis Letters,1996,40(1/2):71-79.
[7]VIJAY S,WOLF E E.A highly active and stable platinum-modified sulfated zirconia catalyst:1.Preparation and activity for n-pentane isomerization[J].Applied Catalysis A:General,2004,264(1):117-124.
[8]ARATA K,MATSUHASHI H,HINO M,et al.Synthesis of solid superacids and their activities for reactions of alkanes[J].Catalysis Today,2003,81(1):17-30.
[9]MASALSKA A,GRZECHOWIAK J R,JAROSZEWSKA K.Effect of metal-support interactions in Ni/ZSM-5+Al2O3catalysts on the transformation of n-paraffins[J].Topic in Catalysis,2013,56(11):981-994.
[10]OHNO T,LI Z,SAKAI N,SAKAGAMI H,et al.Heptane isomerization over molybdenum oxides obtained by H2 reduction of HxMoO3 with different hydrogen contents[J].Applied Catalysis A:General,2010,389(1):52-59.
[11]乐传俊.钌氢配合物合成及其催化氢转移反应研究[D].大连:大连理工大学,2006.
[12]COLLMAN J P,ROPER W R.Preparation and oxidative addition reactions of a monomeric ruthenium(0)complex[J].J Am Chem Soc,1965,87(17):4008-4009.
[13]LEVISON J J,ROBINSON S D.Triarylphosphite complexes of cobalt,nickel,platinum and rhodium[J].Inorganic Synthesis,1972:105-112.
[14]KRUCK T,PRASCH A.Synthesis und struktur der tetrakis(trifluorophosphine)-metalldihydride und metallate(Ⅱ)von eisen,ruthenium und osmium[J].Zeitschrift Fur Anorganische und Allgemeine Chemie,1969,371:1-22.
[15]KAESZ H D,KNOX S A R,KOEPKE J W,et al.Synthesis of metal carbonyl hydrides from metal carbonyls and hydrogen at atmospheric pressure[J].Journal of the Chemical Society D:Chemical Communications,1971,(10):477.
[16]COTTON F A.Inorganic Syntheses[M].Massachusetts:Massachusetts Institute of Technology,1972:106-112.
[17]LIU H,MENG X,ZHANG R,et al.Reaction performance and disappearance kinetics of n-pentane isomerization catalyzed by chloroaluminate ionic liquid[J].Catalysis Communications,2010,12(3):180-183.
[18]WAN G F,DUAN AJ,ZHANG Y,et al.Hydrodesulfurization of fluidized catalytic cracking diesel oil over NiW/AMB catalysts containing H-type-zeolite in situ synthesized from kaolin material[J].Energy Fuel,2009,23:3846-3852.
[19]MACHT J,CARR R T,IGLESIA E.Consequences of acid strength for isomerization and elimination catalysis on solid acids[J].J Am Chem Soc,2009,131:6554-6565.
[20]GAUW F J M M,GRONDELLE J,SANTEN R A.The intrinsic kinetics of n-hexane hydroisomerization catalyzed by platinum-loaded solid-acid catalysts[J].JCatal,2002,206:295-304.
[21]KONDO J N,YANG S,ZHU Q,et al.In situ infrared study of n-heptane isomerization over Pt/H-beta zeolites[J].J Catal,2007,248:53-59.
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