钴铝类水滑石液相选择性催化甲苯氧化合成苯甲醛

doi:10.3724/SP.J.1095.2014.30364

摘要/Abstract

摘要： 采用共沉淀法制备了不同Co/Al原子比的类水滑石（Cox/Al-LDHs，x=2、3和4）及其焙烧产物（Cox/Al-LDOs），用XRD、FT-IR、BET及ICP等技术手段分别表征了催化剂的结构、组成和比表面积，考察了对甲苯选择性氧化制苯甲醛的催化性能。结果表明，在优化条件甲苯0.6 mL（5.43 mmol），催化剂Co4/Al-LDO 100 mg，过氧化氢叔丁醇21.7 mmol，溶剂乙腈10 mL，反应温度70 ℃，反应时间9 h下，甲苯的转化率为8.2%，苯甲醛的选择性达77.6%。催化剂重复使用7次后其催化活性和选择性未见降低，使用前后催化剂的XRD谱图基本不变，显示较好的结构稳定性。

关键词: 类水滑石, 甲苯, 选择性氧化, 苯甲醛

Abstract: Co/Al layered double hydroxides(LDHs) with different Co/Al ratios（Cox/Al-LDHs， x=2， 3 and 4） and their calcined samples（Cox/Al-LDOs） were prepared and characterized by XRD, FT-IR, BET and ICP techniques. These catalysts were studied for selective oxidation of toluene to benzaldehyde. The results indicate that under the optimized condition(0.6 mL(5.43 mmol) of toluene, 100 mg of Co4/Al-LDO, 21.7 mmol of tert-butyl hydroperoxide（TBHP）, 10 mL of acetonitrile, reaction temperature 70 ℃, and reaction time 9 h), the conversion of toluene is 8.2% and the selectivity of benzaldehyde is 77.6%. Repeated runs indicate that these catalysts are stable up to 7 cycles without obvious change of the catalytic activity and selectivity.

Key words: hydrotalcite-like compounds, toluene, selective oxidation, benzaldehyde

中图分类号:

O625

曹明鸣, 周维友, 仲霞, 孙富安, 何明阳. 钴铝类水滑石液相选择性催化甲苯氧化合成苯甲醛[J]. 应用化学, DOI: 10.3724/SP.J.1095.2014.30364.

CAO Mingming, ZHOU Weiyou, ZHONG Xia, SUN Fu′an, HE Mingyang*. Selective Oxidation of Toluene to Benzaldehyde Catalyzed by Co/Al Hydrotalcite-like Materials in Liquid Phase[J]. Chinese Journal of Applied Chemistry, DOI: 10.3724/SP.J.1095.2014.30364.

参考文献

[1] Meng Y,Liang B,Tang S W. A Study on the Liquid-phase Oxidation of Toluene in Ionic Liquids[J]. Appl Catal A:Gen,2012,439/440:1-7.

[2] Huang G,Xiang F,Li T M,et al. Selective Oxidation of Toluene over the New Catalyst Cobalt Tetra(4-hydroxyl) Phenylporphyrin Supported on Zinc Oxide[J]. Catal Commun,2011,12(10):886-889.

[3] ZHANG Guiquan,ZHANG Xin,QI Min,et al. Superfine Fe-V-O Catalyst for Liquid-Phase Oxidation of Toluene to Benzaldehyde[J]. Chinese J Catal,2012,33(5):870-877(in Chinese).

张贵泉,张昕,祈敏,等. 超细Fe-V-O催化剂上甲苯液相氧化制苯甲醛[J]. 催化学报,2012,33(5):870-877.

[4] LIU Yanxiu,SONG Hua,WANG Baohui. Recent Advances in Synthesis of Benzaldehyde by Oxidizing Toluene Directly[J]. Ind Catal,2005,2(13):25-28(in Chinese).

柳艳修，宋华，王宝辉. 甲苯直接氧化制苯甲醛研究进展[J]. 工业催化,2005,2(13):25-28.

[5] Xue M W,X J N,Chen H,et al. Surface Acidic and Redox Properties of V-Ag-O/TiO2 Catalysts for the Selective Oxidation of Toluene to Benzaldehyde[J]. Catal Lett,2009,128:373-378.

[6] Demel J,Lang K. Layered Hydroxide-Porphyrin Hybrid Materials:Synthesis, Structure, and Properties[J]. Eur J Inorg Chem,2012,2012(23):5154-5164.

[7] Zumreoglu-Karan B,Ay AN. Layered Double Hydroxides-multifunctional Nanomaterials[J]. Chem Pap,2012,66(1):1-10

[8] YU Hongli,HAN Caiyun,LI Hongying,et al. Research Progress of Hydrotalcite-like Compounds:Preparation, Characterization and Application[J]. Mater Rev,2013,27(3):59-66(in Chinese).

禹洪丽,韩彩云,李鸿颍,等. 类水滑石的合成、表征及应用进展[J]. 材料导报,2013,27(3):59-66.

[9] Rives V,Prieto O,Dubey A,et al. Synergistic Effect in the Hydroxylation of Phenol over CoNiAl Ternary Hydrotalcites[J]. J Catal,2003,220(1):161-171.

[10] Chmielarz L,Wegrzyn A,Wojciechowska M,et al. Selective Catalytic Oxidation(SCO) of Ammonia to Nitrogen over Hydrotalcite Originated Mg-Cu-Fe Mixed Metal Oxides[J]. Catal Lett,2011,141(9):1345-1354.

[11] Zhang F Z,Xiang X,Li F,et al. Observation of Electron-Antineutrino Disappearance at Daya Bay[J]. Catal Surv Asia,2012,108(17):253-260.

[12] Velu S,Shah N,Jyothi T M,et al. Effect of Manganse Substitution on the Physicochemical Properties and Catalytic Toluene Oxidation Activities of Mg-Al Layered Double Hydroxide[J]. Micro Meso Mater,1999,33:61-75.

[13] Centi G,Lanzafame P,Perathoner S. Performances of Co-based Catalysts for the Selective Side Chain Oxidation of Toluene in the Gas Phase[J]. Catal Today,2005,99:161-170.

[14] Gabrovska M,Edreva-Kardjieva R,Tenchev K,et al. Effect of Co-content on the Structure and Activity of Co-Al Hydrotalcite-like Materials as Catalyst Precursors for CO Oxidation[J]. Appl Catal A:Gen,2011,399:242-251.

[15] Leroux F,Moujahid E M,Taviot-Gu ho C,et al. Effect of Layer Charge Modification for Co Al Layered Double Hydroxides:Study by X-ray Absorption Spectroscopy[J]. Solid State Sci,2001,3:81-92.

[16] Ionescu R,Pavel O D,B irjega R,et al. Epoxidation of Cyclohexene With H2O2 and Acetonitrile Catalyzed by Mg-Al Hydrotalcite and Cobalt Modified Hydrotalcites[J]. Catal Lett,2010,134:309-317.

[17] Sanchez Valente J,Figueras F,Gravelle M,et al. Basic Properties of the Mixed Oxides Obtained by Thermal Decomposition of Hydrotalcites Containing Different Metallic Compositions[J]. J Catal,2000,189:370-381.

[18] Rives V. Characterisation of Layered Double Hydroxides and Their Decomposition Products[J]. Mater Chem Phys,2002,75:19-25.

[19] XIE Hui,JIAO Qingze,DUAN Xue.Synthesis of Hydrotalcite by Hydrothermal Method[J]. Chinese J Appl Chem,2001,18(1):70-72(in Chinese).

谢晖，矫庆泽，段雪. 镁铝型水滑石水热合成[J]. 应用化学,2001,18(1):70-72.

[20] Dupin J C,Martinez H,Guimon C,et al. Intercalation Compounds of Mg-Al Layered Double Hydroxides with Dichlophenac:Different Methods of Preparation and Physicochemical Characterization[J]. Appl Clay Sci,2004,27:95-106.

[21] Jing F L,Zhang Y Y,Luo S Z,et al. Nano-size MZnAl(M=Cu,Co,Ni) Metal Oxides Obtained by Combining Hydrothermal Synthesis with Urea Homogeneous Precipitation Procedures[J]. Appl Clay Sci,2010,48:203-207.

[22] Velu S,Suzuki K,Hashimoto S,et al. The Effect of Cobalt on the Structural Properties and Reducibility of CuCoZnAl Layered Double Hydroxides and Their Thermally Derived Mixed Oxides[J]. Mater Chem,2001,11:2049-2060.

[23] Pérez-Ramirez J,Mul G,Kapteijn F,et al. On the Stability of the Thermally Decomposed Co-Al Hydrotalcite Against Retrotopotactic Transformation[J]. Mater Res Bull,2001,36(10):1769-1775.

[24] Belló S,Medina F,Tichit D,et al. Study of Alkaline-Doping Agents on the Performance of Reconstructed Mg-Al Hydrotalcites in Aldol Condensations[J]. Appl Catal A Gen,2005,281:191-198.

[25] Greenwell HC,Holliman PJ,Jones W,et al. Studies of the Effects of Synthetic Procedure on Base Catalysis Using Hydroxide-Intercalated Layer Double Double Hydroxides[J]. Catal Today,2006,114:397-402.

[26] IU Qingqing,LANG Chunyan,HUANG Junzuo,et al. Preparation of Hydrotalcite-Like Compound and Its Calcined Product for Catalytic Oxidation of Benzene to Phenol[J]. Ind Catal,2012,4(20):60-63(in Chinese).

刘青青，郎春燕，黄军左，等. 类水滑石的制备及其焙烧产物催化笨制苯酚[J]. 工业催化，2012，4（20）：60-63.

[27] Li F,Zhang L H,Evans DG,et al. Structure and Surface Chemistry of Manganese-doped Copperbased Mixed Metal Oxides Derived from Layered Double Hydroxides[J]. Colloids Surf A:Phys Eng Aspects,2004,244:169-177.

[28] Wang Z P,Shangguan W F,Su J X,et al. Catalytic Oxidation of Diesel Soot on Mixed Oxides Derived from Hydrotalcites[J]. Catal Lett,2006,112:149-154.

[29] HUANG Dengtong,KE Guoliang,SU Shu,et al. Internal Standard Quantitative Characterization of Basic Sites on Mg-Al Hydrotalcites by CO2-TPD-MS Technique[J]. Chinese J Appl Chem,2010,3(27):338-341(in Chinese).

黄登通；柯国梁；苏抒，等. 水滑石型固体碱碱性位的内标CO2-程序升温脱附-MS表征[J]. 应用化学，2010，3（27）：338-341.

[30] Tyagi B,Sharma U,Jasra R V. Epoxidation of Styrene with Molecular Oxygen over Binary Layered Double Hydroxide Catalysts[J]. Appl Catal A:Gen,2011,408:171-177.