H-Zr-MCM-48的合成及其正庚烷异构性能
|
摘要
通过水热法成功合成了锆掺杂的MCM-48(Zr-MCM-48)介孔材料,并用离子交换制得H-Zr-MCM-48催化剂。采用X射线衍射(XRD)、透射电镜(TEM)、氮气吸附-脱附等测试手段对样品进行表征。结果表明,所合成的Zr-MCM-48及H-Zr-MCM-48仍保持立方有序介孔结构,H-Zr-MCM-48催化剂的酸性及催化稳定性均有所提高。在正庚烷异构化探针反应中,同等反应条件(锆/硅摩尔比为0.02、反应温度为260℃、反应时间为130min)下,与Zr-MCM-48相比,H-Zr-MCM-48对正庚烷异构化反应的催化性能更好,转化率和选择性分别达到44.6%和94.5%。相对较高的多支链异庚烷产物比例表明,所合成的H-Zr-MCM-48催化剂对于烷烃异构化有良好的应用潜力。
Zirconium incorporated MCM-48 mesoporous materials were synthesized by hydrothermal method.And the H-Zr-MCM-48 catalyst was prepared by ion exchanging method.The sample was characterized by various methods including X-ray diffraction,transmission electron microscope,N_2 adsorption-desorption,and catalytically evaluated by n-heptane isomerization.These results reveal that the synthesized Zr-MCM-48 and H-Zr-MCM-48 still maintain a cubic ordered mesoporous structure.The acidity and stability of the H-Zr-MCM-48 catalyst is also enhanced.H-Zr-MCM-48 exhibits excellent catalytic performance in n-heptane isomerization. Under the same reaction conditions,compared with Zr-MCM-48,the conversion and the selectivity in H-Zr-MCM-48 system are 44.6% and 94.5%,respectively,with molar ratio of Zr to Si of 0.02,the reaction temperature of 260℃and the reaction time of 130 min.The high selectivity of multi-branched i-heptane products indicates that the synthesized H-Zr-MCM-48 catalyst has good application potential in alkane isomerization.
Zirconium incorporated MCM-48 mesoporous materials were synthesized by hydrothermal method.And the H-Zr-MCM-48 catalyst was prepared by ion exchanging method.The sample was characterized by various methods including X-ray diffraction,transmission electron microscope,N_2 adsorption-desorption,and catalytically evaluated by n-heptane isomerization.These results reveal that the synthesized Zr-MCM-48 and H-Zr-MCM-48 still maintain a cubic ordered mesoporous structure.The acidity and stability of the H-Zr-MCM-48 catalyst is also enhanced.H-Zr-MCM-48 exhibits excellent catalytic performance in n-heptane isomerization. Under the same reaction conditions,compared with Zr-MCM-48,the conversion and the selectivity in H-Zr-MCM-48 system are 44.6% and 94.5%,respectively,with molar ratio of Zr to Si of 0.02,the reaction temperature of 260℃and the reaction time of 130 min.The high selectivity of multi-branched i-heptane products indicates that the synthesized H-Zr-MCM-48 catalyst has good application potential in alkane isomerization.
引文
[1]JIANG T S,ZHAO Q,ZHOU X P,et al.Synthesis of ordered cubic mesoporous ZrMCM-48 molecular sieve with aid of fluoride ions[J].Colloids and Surfaces A:Physicochemical and Engineering Aspects,2011,384(1-3):513-518.
[2]NARKHEDE V S,TONI A D,GIES H,et al.Au/TiO2catalysts encapsulated in the mesopores of siliceous MCM-48-Reproducible synthesis,structural characterization and activity for CO oxidation[J].Microporous and Mesoporous Materials,2009,118(1-3):52-60.
[3]HADJIIVANOVV K,TSONCHEVA T,DIMITROV M,et al.Characterization of Cu/MCM-41 and Cu/MCM-48mesoporous catalysts by FTIR spectroscopy of adsorbed CO[J].Applied Catalysis Genera1,2003,241(1-2):331-340.
[4]ZHAO D,RODRIGUEZ A,DIMITRIJEVIC N M,et al.Synthesis,structural characterization,and photocatalytic performance of mesoporous W-MCM-48[J].Journal of Physical Chemistry C,2010,114(37):15728-15734.
[5]GOMEZ S,GARCES L,VILLEGAS J,et al.Synthesis and characterization of TM-MCM-48(TM=Mn,V,Cr)and their catalytic activity in the oxidation of styrene[J].Journal of Catalysis,2005,233(1):60-67.
[6]WANG L,ZHANG J,CHEN F,et al.Fluorideinduced reduction of CTAB template amount for the formation of MCM-48 mesoporous molecular sieve[J].Journal of Physical Chemistry C,2007,111(37):13648-13651.
[7]JIANG T S,CHENG J L,LIU W P,et al.Sulfuric acid functional zirconium(or aluminum)incorporated mesoporous MCM-48solid acid catalysts for alkylation of phenol with tert-butyl alcohol[J].Journal of Solid State Chemistry,2014,218(2):71-80.
[8]JIANG T S,WUO D L,SONG J N,et al.Synthesis and characterization of mesoporous ZrMCM-48molecular sieves with good thermal and hydrothermal stability[J].Powder Technology,2011,207(1-3):422-427.
[9]GU G N,WANG X Q,SUN J W et al.Controlled synthesis of mesoporous silicas MCM-48and MCM-41by using mixed templates[J].Chinese J Inorg Chem,2010,26(1):13-16.
[10]ZHAO Q,ZHOU X,JI M,et al.Stability and textural properties of cobalt incorporated MCM-48 mesoporous molecular sieve[J].Applied Surface Science,2011,257(7):2436-2442.
[11]ZHANG Y H.Synthesis,characterization and catalytic activity of Fe(V)-MCM-48[J].Journal of Functional Materials,2013,44(1):157-160.
[12]LEE J S,KIM D,CHOI B,et al.Hydrogen-rich gas production from ethanol steam-reforming reaction using NiZr-loaded MCM-48catalysts at mild temperature[J].International Journal of Energy Research,2013,37(14):1896-1907.
[13]SAKTHIVEL A,HIJAZI A K,HUI Y Y,et al.Heterogenization of a manganese(II)acetonitrile complex on AlMCM-41and AlMCM-48molecular sieves by ion exchange[J].Journal of Materials Chemistry,2005,15(41):4441-4445.
[14]WU H Y,ZHANG X L,CHEN X,et al.Preparation,characterization and catalytic properties of MCM-48supported tungstophosphoric acid mesoporous materials for green synthesis of benzoic acid[J].Journal of Solid State Chemistry,2014,211(5):51-57.
[15]JIANG T,CHENG J,LIU W,et al.Sulfuric acid functional zirconium(or aluminum)incorporated mesoporous MCM-48solid acid catalysts for alkylation of phenol with tert-butyl alcohol[J].Journal of Solid State Chemistry,2014,218(2):71-80.
[16]SAKTHIVEL A,BADAMALI S K,SELVAM P.para-Selective tert-butylation of phenol over mesoporous H-AlMCM-41[J].Microporous&Mesoporous Materials,2000,39(3):457-463.
[17]ZHAN W,GUO Y,WANG Y,et al.Synthesis of lanthanum-doped MCM-48 molecular sieves and its catalytic performance for the oxidation of styrene[J].Journal of Physical Chemistry B,2007,111(42):12103-12110.
[18]JIA J,ZHAO Q,MA Y,et al.Synthesis and catalytic property of SO2-4/ZrMCM-48 and H-ZrMCM-48[J].Nanotechnology&Precision Engineering,2013,11(5):396-401.
[19]黄国维,李承烈,刘凡.烃类异构化[M].北京:中国石化出版社,1992:55-89.
[20]SIE S T.Acid-catalyzed cracking of paraffinic hydrocarbons.1.Discussion of existing mechanisms and proposal of a new mechanism[J].Industrial&Engineering Chemistry Research,2002,31(8):1881-1889.
[21]袁剑,张波,汤明慧,等.ZrO2/MCM-41催化的苯乙酮氢转移反应[J].高校化学工程学报,2013,27(5):818-824.(YUAN Jian,ZHANG Bo,TANG Minghui,et al.ZrO2/MCM-41 catalyzed hydrogen transfer of acetophenone[J].Journal of Chemical Engineering of Chinese Universities,2013,5(27):818-824.
[22]BLOMSMA E,MARTENS J A,JAXOBS P A.Mechanisms of heptane isomerization on bifunctional Pd/H-Beta zeolites[J].Journal of Catalysis,1996,159(2):323-331.
[23]POPE T D,KRIZ J F,MONNIER J,et al.A study of catalyst formulations for isomerization of C7 hydrocarbons[J].Applied Catalysis A:General,2002,233(1-2):45-62.
[24]BOGDAN V I,KOKLIN A E,POKUSAEVA Y A,et al.The transformation of n-alkanes on H-forms of zeolites under supercritical conditions[J].Russian Journal of Physical Chemistry B,2010,4(7):1085-1091.
[25]CALEMMA V,PERATELLO S,PEREGO C.Hydroisomerization and hydrocracking of long chain n-alkanes on Pt/amorphous SiO2-Al2O3 catalyst[J].Applied Catalysis A General,2000,190(1-2):207-218.
[26]KARTHIKEYAN D,ATCHUDAN R,SIVAKUMAR R,et al.Effect of metal content on the activity and product selectivity of n-decane hydroisomerization over Ni-Pd/HY zeolite[J].Chinese Journal of Catalysis,2016,37(11):1907-1917.
[27]汪颖军,李长海,谷春旭,等.正庚烷在分子筛负载杂多酸催化剂上的异构化石油学报[J].石油学报(石油加工),2008,24(3):298-305.(WANG Yingjun,LI Changhai,GU Chunxu,et al.Isomerization of heptane over molecular sieve supported heteropolyacid catalysts[J].Acta Petrolei Sinica(Petroleum Processing Section),2008,24(3):298-305.
[28]YANG Y H,HU S Q,LIU D P,et al.Highly selective1-heptene isomerization over vanadium grafted mesoporous molecular sieve catalysts[J].Chemical Engineering Journal,2010,165(3):916-923.
[29]HERNANDEZ-PEREZ F,RODRIGUEZ-HERNANDEZ A,ALEMAN-VAZQUEZ L O,et al.Binder effect on the catalytic activity of MoO3 bulk catalyst reduced by H2for n-heptane hydroisomerization[J].Fuel,2014,117(1):463-469.
[30]石洋,董鹏飞,宋华.Pt含量及活化温度对固体超强酸催化剂异构化性能的影响[J].高等学校化学学报,2011,32(2):355-360.(SHI Yang,DONG Pengfei,SONG Hua.Effect of Pt content and activation temperature on isomerization of solid superacid catalysts[J].Chemical Journal of Chinese Universities,2011,32(2):355-360.
[2]NARKHEDE V S,TONI A D,GIES H,et al.Au/TiO2catalysts encapsulated in the mesopores of siliceous MCM-48-Reproducible synthesis,structural characterization and activity for CO oxidation[J].Microporous and Mesoporous Materials,2009,118(1-3):52-60.
[3]HADJIIVANOVV K,TSONCHEVA T,DIMITROV M,et al.Characterization of Cu/MCM-41 and Cu/MCM-48mesoporous catalysts by FTIR spectroscopy of adsorbed CO[J].Applied Catalysis Genera1,2003,241(1-2):331-340.
[4]ZHAO D,RODRIGUEZ A,DIMITRIJEVIC N M,et al.Synthesis,structural characterization,and photocatalytic performance of mesoporous W-MCM-48[J].Journal of Physical Chemistry C,2010,114(37):15728-15734.
[5]GOMEZ S,GARCES L,VILLEGAS J,et al.Synthesis and characterization of TM-MCM-48(TM=Mn,V,Cr)and their catalytic activity in the oxidation of styrene[J].Journal of Catalysis,2005,233(1):60-67.
[6]WANG L,ZHANG J,CHEN F,et al.Fluorideinduced reduction of CTAB template amount for the formation of MCM-48 mesoporous molecular sieve[J].Journal of Physical Chemistry C,2007,111(37):13648-13651.
[7]JIANG T S,CHENG J L,LIU W P,et al.Sulfuric acid functional zirconium(or aluminum)incorporated mesoporous MCM-48solid acid catalysts for alkylation of phenol with tert-butyl alcohol[J].Journal of Solid State Chemistry,2014,218(2):71-80.
[8]JIANG T S,WUO D L,SONG J N,et al.Synthesis and characterization of mesoporous ZrMCM-48molecular sieves with good thermal and hydrothermal stability[J].Powder Technology,2011,207(1-3):422-427.
[9]GU G N,WANG X Q,SUN J W et al.Controlled synthesis of mesoporous silicas MCM-48and MCM-41by using mixed templates[J].Chinese J Inorg Chem,2010,26(1):13-16.
[10]ZHAO Q,ZHOU X,JI M,et al.Stability and textural properties of cobalt incorporated MCM-48 mesoporous molecular sieve[J].Applied Surface Science,2011,257(7):2436-2442.
[11]ZHANG Y H.Synthesis,characterization and catalytic activity of Fe(V)-MCM-48[J].Journal of Functional Materials,2013,44(1):157-160.
[12]LEE J S,KIM D,CHOI B,et al.Hydrogen-rich gas production from ethanol steam-reforming reaction using NiZr-loaded MCM-48catalysts at mild temperature[J].International Journal of Energy Research,2013,37(14):1896-1907.
[13]SAKTHIVEL A,HIJAZI A K,HUI Y Y,et al.Heterogenization of a manganese(II)acetonitrile complex on AlMCM-41and AlMCM-48molecular sieves by ion exchange[J].Journal of Materials Chemistry,2005,15(41):4441-4445.
[14]WU H Y,ZHANG X L,CHEN X,et al.Preparation,characterization and catalytic properties of MCM-48supported tungstophosphoric acid mesoporous materials for green synthesis of benzoic acid[J].Journal of Solid State Chemistry,2014,211(5):51-57.
[15]JIANG T,CHENG J,LIU W,et al.Sulfuric acid functional zirconium(or aluminum)incorporated mesoporous MCM-48solid acid catalysts for alkylation of phenol with tert-butyl alcohol[J].Journal of Solid State Chemistry,2014,218(2):71-80.
[16]SAKTHIVEL A,BADAMALI S K,SELVAM P.para-Selective tert-butylation of phenol over mesoporous H-AlMCM-41[J].Microporous&Mesoporous Materials,2000,39(3):457-463.
[17]ZHAN W,GUO Y,WANG Y,et al.Synthesis of lanthanum-doped MCM-48 molecular sieves and its catalytic performance for the oxidation of styrene[J].Journal of Physical Chemistry B,2007,111(42):12103-12110.
[18]JIA J,ZHAO Q,MA Y,et al.Synthesis and catalytic property of SO2-4/ZrMCM-48 and H-ZrMCM-48[J].Nanotechnology&Precision Engineering,2013,11(5):396-401.
[19]黄国维,李承烈,刘凡.烃类异构化[M].北京:中国石化出版社,1992:55-89.
[20]SIE S T.Acid-catalyzed cracking of paraffinic hydrocarbons.1.Discussion of existing mechanisms and proposal of a new mechanism[J].Industrial&Engineering Chemistry Research,2002,31(8):1881-1889.
[21]袁剑,张波,汤明慧,等.ZrO2/MCM-41催化的苯乙酮氢转移反应[J].高校化学工程学报,2013,27(5):818-824.(YUAN Jian,ZHANG Bo,TANG Minghui,et al.ZrO2/MCM-41 catalyzed hydrogen transfer of acetophenone[J].Journal of Chemical Engineering of Chinese Universities,2013,5(27):818-824.
[22]BLOMSMA E,MARTENS J A,JAXOBS P A.Mechanisms of heptane isomerization on bifunctional Pd/H-Beta zeolites[J].Journal of Catalysis,1996,159(2):323-331.
[23]POPE T D,KRIZ J F,MONNIER J,et al.A study of catalyst formulations for isomerization of C7 hydrocarbons[J].Applied Catalysis A:General,2002,233(1-2):45-62.
[24]BOGDAN V I,KOKLIN A E,POKUSAEVA Y A,et al.The transformation of n-alkanes on H-forms of zeolites under supercritical conditions[J].Russian Journal of Physical Chemistry B,2010,4(7):1085-1091.
[25]CALEMMA V,PERATELLO S,PEREGO C.Hydroisomerization and hydrocracking of long chain n-alkanes on Pt/amorphous SiO2-Al2O3 catalyst[J].Applied Catalysis A General,2000,190(1-2):207-218.
[26]KARTHIKEYAN D,ATCHUDAN R,SIVAKUMAR R,et al.Effect of metal content on the activity and product selectivity of n-decane hydroisomerization over Ni-Pd/HY zeolite[J].Chinese Journal of Catalysis,2016,37(11):1907-1917.
[27]汪颖军,李长海,谷春旭,等.正庚烷在分子筛负载杂多酸催化剂上的异构化石油学报[J].石油学报(石油加工),2008,24(3):298-305.(WANG Yingjun,LI Changhai,GU Chunxu,et al.Isomerization of heptane over molecular sieve supported heteropolyacid catalysts[J].Acta Petrolei Sinica(Petroleum Processing Section),2008,24(3):298-305.
[28]YANG Y H,HU S Q,LIU D P,et al.Highly selective1-heptene isomerization over vanadium grafted mesoporous molecular sieve catalysts[J].Chemical Engineering Journal,2010,165(3):916-923.
[29]HERNANDEZ-PEREZ F,RODRIGUEZ-HERNANDEZ A,ALEMAN-VAZQUEZ L O,et al.Binder effect on the catalytic activity of MoO3 bulk catalyst reduced by H2for n-heptane hydroisomerization[J].Fuel,2014,117(1):463-469.
[30]石洋,董鹏飞,宋华.Pt含量及活化温度对固体超强酸催化剂异构化性能的影响[J].高等学校化学学报,2011,32(2):355-360.(SHI Yang,DONG Pengfei,SONG Hua.Effect of Pt content and activation temperature on isomerization of solid superacid catalysts[J].Chemical Journal of Chinese Universities,2011,32(2):355-360.