焙烧温度对固体超强酸SO_4~(2-)/ZrO_2-Al_2O_3催化合成丙烯酸酯的影响
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摘要
采用共沉淀和浸渍法制备SO_4~(2-)/ZrO_2-Al_2O_3酯化催化剂。借助XRD、FT-IR、TG-DSC等手段,对500、600和700℃不同焙烧温度下制备的催化剂进行表征。发现随着焙烧温度的升高,催化剂中ZrO2的四方晶型增多;600℃焙烧时,催化剂形成的S-O键的红外吸收峰最强;TG-DSC分析显示,高于700℃后催化剂质量损失较严重,酸中心被破坏。以丙烯酸和十八醇的酯化反应为探针反应,对不同焙烧温度下制备的催化剂进行活性评价。结果表明,催化剂的活性随焙烧温度的升高先增大后减小,其中焙烧温度为600℃时催化剂活性最好;且当反应温度为120℃、酸/醇摩尔比为1.25、催化剂添加量为0.8g、反应8h时,酯化收率达到97%以上。
SO_4~(2-)/ZrO_2-Al_2O_3 catalysts were prepared by the co-precipitation and impregnation method for esterification.The catalysts calcined at 500,600 and 700℃ were analyzed and characterized by XRD,FT-IR and TG-DSC.The increase of tetragonal phase of ZrO_2 in the catalysts were found with the increase of calcination temperature.The catalyst calcined at 600℃formed the strongestSObond IRabsorptionpeak.TG-DSC showed that the losingmass of the catalysts was serious and the acid center was damaged when the temperature approximately was above700℃.The activity was evaluated in the esterificationreaction by using octadecanol and acrylicacidasraw materials.The results showed that the catalyticactivity first increased and then decreased with increasing calcination temperature.Catalyst calcined at 600℃ has the highest esterification rate,which is above 97%.
SO_4~(2-)/ZrO_2-Al_2O_3 catalysts were prepared by the co-precipitation and impregnation method for esterification.The catalysts calcined at 500,600 and 700℃ were analyzed and characterized by XRD,FT-IR and TG-DSC.The increase of tetragonal phase of ZrO_2 in the catalysts were found with the increase of calcination temperature.The catalyst calcined at 600℃formed the strongestSObond IRabsorptionpeak.TG-DSC showed that the losingmass of the catalysts was serious and the acid center was damaged when the temperature approximately was above700℃.The activity was evaluated in the esterificationreaction by using octadecanol and acrylicacidasraw materials.The results showed that the catalyticactivity first increased and then decreased with increasing calcination temperature.Catalyst calcined at 600℃ has the highest esterification rate,which is above 97%.
引文
[1]张拂晓,方龙,聂兆广,等.高凝原油降凝剂的制备及其降凝机理[J].石油学报(石油加工),2009,25(6):801-806.(ZHANG Fuxiao,FANG Long,NIE Zhaoguang,et al.Preparation and mechanism of a pour point depressant for high pour point crude oil[J].Acta Petrolei Sinica(Petroleum Processing Section),2009,25(6):801-806.)
[2]YANG F,LI Y,ZHANG Q,et al.Selective conversion of cotton cellulose to glucose and 5-hydroxymethyl furfural with SO42-/MxOy solid superacid catalyst[J].Carbohydrate Polymers,2015,131:9-14.
[3]KULKARNI M G,GOPINATH R,MEHER L C,et al.Solid acid catalyzed biodiesel production by simultaneous esterification and transesterification[J].Green Chemistry,2006,8(8):1056-1062.
[4]牟一蒙,梁红,李树华.焙烧温度对Mn/Al2O3-TiO2催化剂结构及氧化NO性能的影响[J].无机化学学报,2016,32(4):602-608.(MOU Yimeng,LIANG Hong,LI Shuhua.Effect of calcination temperature on the structure and performance of Mn/Al2O3-TiO2catalyst in the catalytic oxidation of NO[J].Chinese Journal of Inorganic Chemistry,2016,32(4):602-608.)
[5]GB/T 1668-2008,增塑剂酸值及酸度的测定[S].
[6]宋华,董鹏飞,张旭.制备条件对Pt-S2O82-/ZrO2-Al2O3异构化催化性能的影响[J].石油学报(石油加工),2010,26(6):877-882.(SONG Hua,DONG Pengfei,ZHANG Xu.Effect of preparation conditions on the catalytic isomerization performance of Pt-S2O82-/ZrO2-Al2O3[J].Acta Petrolei Sinica(Petroleum Processing Section),2010,26(6):877-882.)
[7]陈颖,孙雪,李慧,等.稀土改性对SO42-/ZrO2固体酸催化剂结构与催化性能的影响[J].燃料化学学报,2012,40(4):412-417.(CHEN Ying,SUN Xue,LI Hui,et al.Effect of rare earth modification on structure and catalytic properties of SO42-/ZrO2solid acid catalyst[J].Journal of Fuel Chemistry and Technology,2012,40(4):412-417.)
[8]马惠琴,王卫,马媛媛.La改性固体超强酸S2O82-/ZrO2-Al2O3的制备及催化性能研究[J].材料导报B:研究篇,2014,28(3):48-52.(MA Huiqin,WANG Wei,MA Yuanyuan.Preparation and catalytic properties study of solid superacid catalyst S2O82-/ZrO2-Al2O3 modified by lanthanum[J].Materials Review B:Research Article,2014,28(3):48-52.)
[9]王宇红,王越慜,李俊.钒改性对SO42-/ZrO2-Al2O3固体酸催化剂结构与催化性能的影响[J].催化学报,2008,29(8):758-764.(WANG Yuhong,WANG Yuemin,LI Jun.Effect of vanadium modification on structure and catalytic properties of SO42-/ZrO2-Al2O3solid acid catalyst[J].Chinese Journal of Catalysis,2008,29(8):758-764.)
[10]石文平.硫酸根促进的金属氧化物塑固体超强酸在酯化反应中的稳定性与失活[D].北京:北京化工大学,2014.
[11]REDDY B M,SREEKANTH P M,LAKSHMANAN P,et al.Synthesis,characterization and activity study of SO42-/CexZr1-xO2solid superacid catalyst[J].Journal of Molecular Catalysis A:Chemical,2006,244:1-7.
[2]YANG F,LI Y,ZHANG Q,et al.Selective conversion of cotton cellulose to glucose and 5-hydroxymethyl furfural with SO42-/MxOy solid superacid catalyst[J].Carbohydrate Polymers,2015,131:9-14.
[3]KULKARNI M G,GOPINATH R,MEHER L C,et al.Solid acid catalyzed biodiesel production by simultaneous esterification and transesterification[J].Green Chemistry,2006,8(8):1056-1062.
[4]牟一蒙,梁红,李树华.焙烧温度对Mn/Al2O3-TiO2催化剂结构及氧化NO性能的影响[J].无机化学学报,2016,32(4):602-608.(MOU Yimeng,LIANG Hong,LI Shuhua.Effect of calcination temperature on the structure and performance of Mn/Al2O3-TiO2catalyst in the catalytic oxidation of NO[J].Chinese Journal of Inorganic Chemistry,2016,32(4):602-608.)
[5]GB/T 1668-2008,增塑剂酸值及酸度的测定[S].
[6]宋华,董鹏飞,张旭.制备条件对Pt-S2O82-/ZrO2-Al2O3异构化催化性能的影响[J].石油学报(石油加工),2010,26(6):877-882.(SONG Hua,DONG Pengfei,ZHANG Xu.Effect of preparation conditions on the catalytic isomerization performance of Pt-S2O82-/ZrO2-Al2O3[J].Acta Petrolei Sinica(Petroleum Processing Section),2010,26(6):877-882.)
[7]陈颖,孙雪,李慧,等.稀土改性对SO42-/ZrO2固体酸催化剂结构与催化性能的影响[J].燃料化学学报,2012,40(4):412-417.(CHEN Ying,SUN Xue,LI Hui,et al.Effect of rare earth modification on structure and catalytic properties of SO42-/ZrO2solid acid catalyst[J].Journal of Fuel Chemistry and Technology,2012,40(4):412-417.)
[8]马惠琴,王卫,马媛媛.La改性固体超强酸S2O82-/ZrO2-Al2O3的制备及催化性能研究[J].材料导报B:研究篇,2014,28(3):48-52.(MA Huiqin,WANG Wei,MA Yuanyuan.Preparation and catalytic properties study of solid superacid catalyst S2O82-/ZrO2-Al2O3 modified by lanthanum[J].Materials Review B:Research Article,2014,28(3):48-52.)
[9]王宇红,王越慜,李俊.钒改性对SO42-/ZrO2-Al2O3固体酸催化剂结构与催化性能的影响[J].催化学报,2008,29(8):758-764.(WANG Yuhong,WANG Yuemin,LI Jun.Effect of vanadium modification on structure and catalytic properties of SO42-/ZrO2-Al2O3solid acid catalyst[J].Chinese Journal of Catalysis,2008,29(8):758-764.)
[10]石文平.硫酸根促进的金属氧化物塑固体超强酸在酯化反应中的稳定性与失活[D].北京:北京化工大学,2014.
[11]REDDY B M,SREEKANTH P M,LAKSHMANAN P,et al.Synthesis,characterization and activity study of SO42-/CexZr1-xO2solid superacid catalyst[J].Journal of Molecular Catalysis A:Chemical,2006,244:1-7.