Sn/MgAl LDO的制备、表征及其催化性能研究
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摘要
通过焙烧浸渍重构制得含Sn的镁铝层状双氢氧化物,经焙烧制得负载Sn的复合金属氧化物Sn/MgAl LDO,利用X射线衍射(XRD)、扫描电镜(SEM)、N2吸附-脱附等技术对其结构进行了表征。研究了其对苯乙烯环氧化制环氧苯乙烷反应的催化性能。考察了Sn含量、载体镁铝比例、焙烧温度对样品催化性能的影响,结果表明,当Sn掺杂量为2wt%,镁铝比为5∶1,焙烧温度为400℃时的Sn(2)/LDO(5)-400对苯乙烯环氧化制环氧苯乙烷具有比较好的催化活性。70℃,0.015 mol苯乙烯,0.075 mol 30wt%H2O2,20 mL乙腈,10 mL乙醇和3 g催化剂,反应6 h时,苯乙烯的转化率达到95.37%,环氧苯乙烷选择性达到97.23%,循环使用4次后催化剂对苯乙烯的转化率仍能达到91.26%,环氧苯乙烷选择性为94.89%。
Sn-doped Mg-Al layered double oxides were acquired by the calcination at 400 ℃ of the corresponding Sn-doped Mg-Al hydrotalcite which was prepared by wetness impregnation.The structural information of Sn/LDO catalysts was characterized using XRD,SEM and nitrogen-adsorption/desorption techniques.Their catalytic activities were studied by epoxidation of styrene.The influences of the doping amount of Sn,mole ratio of Mg-Al and calcined temperature were investigated.The regeneration performance of catalysts was also studied.The results indicate that Sn loading of 2 wt%,Mg∶Al of 5∶1,calcined at 400 ℃,Sn(2)/LDO(5)-400 shows much a higher activity in synthesis of styrene epoxide.Under the reaction conditions with 0.015 mol styrene,0.075 mol 30 wt% H_2O_2,20 mL acetonitrile,10 mL ethanol,3 g catalyst,reacting at 70 ℃ for 6 h,the conversion of styrene is 95.37%,the selectivity to styrene epoxide can reach 97.23%.In a set of reuse experiments,there is almost no reduction of the catalytic activity.
Sn-doped Mg-Al layered double oxides were acquired by the calcination at 400 ℃ of the corresponding Sn-doped Mg-Al hydrotalcite which was prepared by wetness impregnation.The structural information of Sn/LDO catalysts was characterized using XRD,SEM and nitrogen-adsorption/desorption techniques.Their catalytic activities were studied by epoxidation of styrene.The influences of the doping amount of Sn,mole ratio of Mg-Al and calcined temperature were investigated.The regeneration performance of catalysts was also studied.The results indicate that Sn loading of 2 wt%,Mg∶Al of 5∶1,calcined at 400 ℃,Sn(2)/LDO(5)-400 shows much a higher activity in synthesis of styrene epoxide.Under the reaction conditions with 0.015 mol styrene,0.075 mol 30 wt% H_2O_2,20 mL acetonitrile,10 mL ethanol,3 g catalyst,reacting at 70 ℃ for 6 h,the conversion of styrene is 95.37%,the selectivity to styrene epoxide can reach 97.23%.In a set of reuse experiments,there is almost no reduction of the catalytic activity.
引文
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[2]Chen Y H,Tetsuya Y,Katsutoshi I.Photosensitization of carbazole derivatives in cationic polymerization with a novel sensitivity to near-UV light[J].J.Polym.Sci.Part A:Polym.Chem.,2000,38(1):90-100.
[3]王伟,肖国民.1-甲基-3-苯基哌嗪的合成[J].精细化工,2004,21(9):711-713.
[4]吕绍洁,徐成华,陈义均,等.溴醇法合成环氧苯乙烷的研究[J].合成化学,2000,8(1):71-74.
[5]李海明,丁云,石春杰,等.双氧水作用下的芳香基烯烃氧化[J].化学试剂,2015,37(12):1077-1079.
[6]孙琪,詹明坤.H2O2为氧源Li/Mg O催化苯乙烯环氧化[J].辽宁师范大学学报(自然科学版),2013,36(3):365-368.
[7]王晓丽,陈星,杨刚,等.枝状钴配合物的合成及其对苯乙烯环氧化的催化性能[J].南京工业大学学报(自然科学版),2014,36(1):23-27.
[8]白向向,沈健.W-SBA-15催化环氧化苯乙烯合成环氧苯乙烷[J].精细石油化工,2010,27(3):15-18.
[9]韩蔚,刘靖,潭涓.TS-1分子筛催化H2O2环氧化苯乙烯制环氧苯乙烷[J].石油化工,2008,37(10):1003-1008.
[10]刘媛,祖苏苏,宋睿智.Zn Mg Al三元类水滑石催化合成ε-己内酯[J].硅酸盐通报,2014,33(5):1119-1122.
[11]杨杰,谢光银.Zn Al Ce三元类水滑石的制备及对亚甲基蓝的催化降解性能[J].硅酸盐通报,2014,33(4):974-979.
[12]叶达洲,卓广澜.氟插层水滑石催化烯烃环氧化反应[J].催化学报,2008,29(12):1259-1265.
[13]荣媛,李海明,邰燕芳.环氧苯乙烷的合成[J].合肥师范学院学报,2013,31(6):55-57.
[14]孙琪,詹明坤.H2O2为氧源Li/Mg O催化苯乙烯环氧化[J].辽宁师范大学学报(自然科学版),2013,36(3):365-368.
[15]Ol Snye U,Akporiaye D,Rytter E,et al.On the stability of mixed M2+/M3+oxides[J].Appl.Catal.A,2002,224(1-2):39-49.
[16]Yamaguchi K,Mori K,Mizugaki T,et al.Epoxidation ofα,β-unsaturated ketones using hydrogen peroxide in the presence of basic hydrotalcite catalysts[J].J.Org.Chem.,2000,65(21):6897-6903.
[17]杨永杰,曾虹燕,王亚举,等.镁铝物质的量之比对水滑石纳米材料及其催化性能的影响[J].化学反应工程与工艺,2011,27(4):358-362.
[18]王永在,王丽娜.Mg-Al水滑石纳米晶热分解行为的TG-MS研究[J].矿物岩石,2008,28(3):19-23.
[19]Ueno S,Yamaguchi K,Yoshida K,et al.Hydrotalcite catalysis:heterogeneous epoxidation of olefins using hydrogen peroxide in the presence of nitriles[J].Chem.Commun.,1998,3:295-296.
[20]卢新宁,林海强.镁基复合氧化物催化烯烃环氧化反应[J].催化学报,2010,31(12):1457-1464.