为创建洁净高效的酚类化合物硝化工艺,以杂多酸H6 PMo9 V3 O40(PMAV3)为活性组分,硅胶为载体,浸渍法制备了负载型催化剂PMAV3/SiO2,采用红外光谱、X射线衍射谱、N2吸附-脱附法及TG-DSC分析等测试技术对该催化剂的结构及热稳定性进行了表征;考察了该催化剂对多种酚类化合物硝化反应的催化性能.结果显示,该催化剂对多种酚类化合物的硝化反应具有很强的催化活性和区域选择性,产率为83.7% ~ 94.5%,其中苯酚、邻甲酚、邻氯苯酚和邻氟苯酚以邻位硝化产物居多,水杨酸的对位硝化产物占绝对优势;负载催化剂的织构性质与载体相近,但随负载量增加,比表面积逐渐降低;PMAV3/SiO2的热稳定性好于本体PMAV3.催化剂回收容易,重复使用5次,活性基本不变.
参考文献
[1] | Olah G A,Malhotra R,Narang S C.Nitration Methods and Mechanism[M].New York:VCH Press,1989:5-15. |
[2] | Zaldivar J M,Molgab E,Alos M A,et al.Aromatic Nitrations by Mixed Acid.Fast Liquid-Liquid Reaction Regime[J].Chem Eng Process,1996,35(2):91-105. |
[3] | Mellor J M,Mittoo S,Parkes R,et al.Improved Nitrations Using Metal Nitrate-Sulfuric Acid Systems[J].Tetrahedron,2000,56(40):8019-8024. |
[4] | Selvam J J P,Suresh V,Rajesh K,et al.Highly Efficient Nitration of Phenolic Compounds by Zirconyl Nitrate[J].Tetrahedron Lett,2006,47 (15):2507-2509. |
[5] | Anuradha V,Srinivas P V,Aparna P,et al.p-Toluenesulfonic Acid Catalyzed Regiospecific Nitration of Phenols with Metal Nitrates[J].Tetrahedron Lett,2006,47 (28):4933-4935. |
[6] | Pourali A R,Fatemi F.Selective Nitration of Phenols Using Bismuth Subnitrate/Charcoal in the Presence of Trichloroisocyanuric Acid under Aprotic Conditions[J].Chinese Chem Lett,2010,21 (11):1283-1286. |
[7] | Nowrouzi N,Jonaghani M Z.Nitration of Aromatic Compounds under Neutral Conditions Using the Ph2PCl/I2/AgNO3 Reagent System[J].Tetrahedron Lett,2011,52 (39):5081-5082. |
[8] | Wang P C,Lu M.Regioselectivity Nitration of Aromatics with N2 O5 in PEG-based Dicationic Ionic Liquid[J].Tetrahedron Lett,2011,52 (13):1452-1455. |
[9] | Ma X M,Li B D,Chen L,et al.Selective Nitration of Aromatic Compounds Catalyzed by H beta Zeolite Using N2 O5[J].Chinese Chem Lett,2012,23(7):809-812. |
[10] | Parida K M,Rath D.Studies on MCM-41:Effect of Sulfate on Nitration of Phenol[J].J Mol Catal A:Chem,2006,258(1/2):381-387. |
[11] | Khder A S,Ahmed A I.Nitration of Phenol over Nanosized Tungsten Oxide Supported on Sulfated SnO2 as a Solid Acid Catalyst[J].Appl Catal A,2009,354(1/2):153-160. |
[12] | Kemdeo S M,Sapkal V S,Chaudhari G N.TiO2-SiO2 Mixed Oxide Supported MoO3 Catalyst:Physicochemical Characterization and Activities in Nitration of Phenol[J].J Mol Catal A:Chem,2010,323(1/2):70-77. |
[13] | Timofeeva M N.Acid Catalysis by Heteropoly Acids[J].Appl Catal A,2003,256(1/2):19-35. |
[14] | Shaabani A,Behnam M,Rezayan A H.Tungstophosphoric Acid (H3PW12O40) Catalyzed Oxidation of Organic Compounds with NaBrO3[J].Catal Commun,2009,10(7):1074-1078. |
[15] | Rafiee E,Joshaghani M,Tork F,et al.Esterification of Mandelic Acid Catalyzed by Heteropoly Acid[J].J Mol Catal A:Chem,2008,283(1/2):1-4. |
[16] | Feng S J,Zhang L,Ren Y H,et al.Catalytic Hydroxylation of Benzene to Phenol with Hydrogen Peroxide over Cesium Salts of Keggin-type Heteropoly Acids[J].Acta Chim Sin,2012,70(22):2316-2322. |
[17] | Mallick S,Parida K M.Selective Nitration of Phenol over Silicotungstic Acid Supported Zirconia[J].Catal Commun,2007,8(10):1487-1492. |
[18] | Kumar A S H,Rao K T V,Upendar K,et al.Nitration of Methyl 5-Nitrosalicylate Catalyzed by H6PMoV3O40 Supported on Silica Gel[J].Catal Commun,2012,18:37-40 |
[19] | WU Jinming,SHEN Aibao.Synthesis of Methyl 5-Nitrosalicylate Catalyzed by H6 PMoV3 O40 Supported on Silica Gel[J].Fine Chem,2011,28(6):603-605(in Chinese).吴锦明,沈爱宝.硅胶负载H6 PMo9 V3 O40催化制备5-硝基水杨酸甲酯[J].精细化工,2011,28(6):603-605. |
[20] | WU Jinming,TANG Yanfeng,SHEN Aibao.Synthesis of 5-Nitrosalicylaldehyde Catalyzed by H6 PMo9 V3 O40 Supported on Silica Gel[J].ChineseJAppl Chem,2012,29(5):545-550(in Chinese).吴锦明,汤艳峰,沈爱宝.硅胶负载H6PMo9 V3 O40催化合成5-硝基水杨醛[J].应用化学,2012,29(5):545-550. |
[21] | PEI Supeng,YUE Bin,CHENG Jifang,et al.Selective Oxidation of Methane on SBA-15 Supported P-Mo-V Oxide Catalysts[J].Acta Chim Sin,2008,66(8):902-908(in Chinese).裴素朋,岳斌,程记芳,等.负载型P-Mo-V/SBA-15催化剂上的甲烷选择氧化反应[J].化学学报,2008,66(8):902-908. |
[22] | RodriguesJ A R,Filho A P O,MoranP J S,et al.Regioselectivity of the Nitration of Phenol by Acetyl Nitrate Adsorbed on Silica Gel[J].Tetrahedron,1999,22(55):6733-6738. |
[23] | HE Yigong,LI Fen,WANG Peng,et al.Adsorption,Acidity and Physico-chemical Properties of Heteropolyacid Catalysts[J].Pet Process Petrochem,1996,27(8):12-16(in Chinese).何奕工,李奋,王蓬,等.杂多酸催化剂的吸附、酸性和物化性质[J].石油炼制与化工,1996,27(8):12-16. |
[24] | QIAN Hua,LIU Dabin,YE Zhiwen.Selective Nitration of Chlorobenzene with N2 O5 Assisted by Heteropolyacids[J].Chiense J Appl Chem,2009,26(6):676-680(in Chinese).钱华,刘大斌,叶志文.负载杂多酸催化下N2 O5对氯苯的选择性硝化[J].应用化学,2009,26(6):676-680. |
上一张
下一张
上一张
下一张
计量
- 下载量()
- 访问量()
文章评分
- 您的评分:
-
10%
-
20%
-
30%
-
40%
-
50%