剑麻纤维素合成多级孔SAPO-11分子筛及其临氢异构化性能
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摘要
用酸碱处理的剑麻纤维素作为模板剂,采用一步水热法合成多级孔SAPO-11分子筛。对合成分子筛的形貌、孔结构和酸类型进行表征;以正十二烷作为原料,考察Pt负载量为0.5%(质量分数)的SAPO-11分子筛的异构化反应性能。结果表明:利用酸碱处理后的剑麻纤维素合成的多级孔SAPO-11分子筛具有较大的BET比表面积,分子筛中有明显的介孔产生,分子筛孔道内B酸和L酸的比值增加,在正十二烷的临氢异构化反应中表现出更为优异的催化性能。在反应温度为320℃,反应空速为2.0 h-1,反应压力为2 MPa,氢与油体积比为200:1条件下正十二烷转化率为95.36%时,异构烃收率为69.36%。
The hierarchical pore SAPO-11 molecular sieves were synthesized by a conventional one-step hydrothermally method with acid-base treatment sisal fibers.The morphology,pore structure properties and acid types of the hierarchical pore SAPO-11 molecular sieves were investigated.The catalytic hydroisomerization performance of hierarchical pore SAPO-11 catalysts with 0.5%Pt loading was evaluated with n-dodecane as a material.The results indicate that the sample synthesized by adding sisal fiber treated with acid and alkali has a greater specific surface area and a mesoporous structure,and increases a ratio of B acid to L acid in the SAPO-11 molecular sieve pore.The SAPO-11 catalyst sample exhibits the excellent catalytic performance in the n-dodecane hydroisomerization.The n-dodecane conversion rate is 95.36%,and the isomer yield is 69.36% at the reaction temperature of 320 oC,reaction space velocity of 2.0 h~(-1),reaction pressure of 2 MPa,and hydrogen and oil volume ratio of 200:1.
The hierarchical pore SAPO-11 molecular sieves were synthesized by a conventional one-step hydrothermally method with acid-base treatment sisal fibers.The morphology,pore structure properties and acid types of the hierarchical pore SAPO-11 molecular sieves were investigated.The catalytic hydroisomerization performance of hierarchical pore SAPO-11 catalysts with 0.5%Pt loading was evaluated with n-dodecane as a material.The results indicate that the sample synthesized by adding sisal fiber treated with acid and alkali has a greater specific surface area and a mesoporous structure,and increases a ratio of B acid to L acid in the SAPO-11 molecular sieve pore.The SAPO-11 catalyst sample exhibits the excellent catalytic performance in the n-dodecane hydroisomerization.The n-dodecane conversion rate is 95.36%,and the isomer yield is 69.36% at the reaction temperature of 320 oC,reaction space velocity of 2.0 h~(-1),reaction pressure of 2 MPa,and hydrogen and oil volume ratio of 200:1.
引文
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[3]YANG X,LU T,CHEN C,et al.Synthesis of hierarchical AIPO-n molecular sieves templated by saccharides[J].Micropor Mesopor Mater,2011,144(1/3):176-182.
[4]FAN Y,XIAO H,SHI G,et al.Alkylphosphonic acid and small amine-templated synthesis of hierarchical silicoaluminophosphate molecular sieves with high isomerization selectivity to dibranched paraffins[J].J Catal,2012,285(1):251-259.
[5]汪哲明,阎子峰.SAPO-11分子筛的合成[J].燃料化学学报,2003,31(4):360-366.WANG Zheming,YAN Zifeng.J Fuel Chem Technol(in Chinese),2003,31(4):360-366.
[6]章毅鹏,廖建和,桂红星.剑麻纤维及其复合材料的研究进展[J].热带农业科学,2007,27(5):53-58.ZHANG Yipeng,LIAO Jianhe,GUI Hongxing.Chin J Trop Agric(in Chinese),2007,27(5):53-58.
[7]廖双泉,马凤国,邵自强,等.不同预处理对剑麻纤维组分和结构的影响[J].纤维素科学与技术,2002,10(2):37-40.LIAO Shuangquan,MA Fengguo,SHAO Ziqiang,et al.J Cellul Sci Technol(in Chinese),2002,10(2):37-40.
[8]李肖建,刘红霞,韦春,等.剑麻纤维素微晶的制备与表征[J].高分子材料科学与工程,2012,28(8):160-166.LI Xiaojian,LIU Hongxia,WEI Chun,et al.Polym Mater Sci Eng(in Chinese),2012,28(8):160-166.
[9]OH S Y,YOO D H,SHIN Y,et al.FTIR analysis of cellulose treated with sodiumhydroxide and carbon dioxide[J].Carbohydr Res,2005,340:417-428.
[10]YANG S M,LIN J Y,GUO D H,et al.1-Butene isomerization over aluminophosphate molecular sieves and zeolites[J].Appl Catal A,1999,181(1):113-122.
[11]WALENDZIEWSKI J,PNIAK B.Synthesis,physicochemical properties and hydroisomerization activity of SAPO-11 based catalysts[J].Appl Catal A,2003,250(1):39-47.
[12]MARTERNS J A,PARTON R,UYTTERHOEVEN L,et al.Selective conversion of decane into branched isomers:a comparison of platinum/ZSM-22,platinum/ZSM-5 and platinum/USY zeolite catalysts[J].Appl Catal,1991,76(1):95-116.
[13]EMEIS A C.Determination of integrated molar extinction coefficients for infrared absorption bands of pyridine adsorbed on solid acid catalysts[J].J Catal,1993,141(2):347-354.
[14]刘平,任杰,孙予罕.合成条件对SAPO-11分子筛骨架Si分布的影响[J].石油学报(石油加工),2008,24(4):388-393.LIU Ping,REN Jie,SUN Yuhan.Acta Petrol Sin(in Chinese),2008,24(4):388-393.
[15]张胜振,陈胜利,董鹏,等.小晶粒SAPO-11分子筛的合成及其催化异构化性能[J].催化学报,2007,28(10):857-864.ZHANG Shengzhen,CHEN Shengli,DONG Peng,et al.Chin J Catal(in Chinese),2007,28(10):857-864.
[16]SARAH C Larsen.Nanocrystalline zeolites and zeolite strutures:Synthesis,characterization and application[J].J Phys Chem C,2007,111(50):18464-18474.
[17]CLAUDE M C,MARTENS J A.Monomethyl branching of long n-alkane in the range from decane to tetracosane on Pt/HZSM-22Bi-function catalyst[J].J Catal,2000,190(1):39-48.
[18]YANG X,LU T,CHEN C,et al.Synthesis of hierarchical AIPO-n molecular sieves templated by saccharides[J].Micropor Mesopor Mater,2011,144(1/3):176-182.