负载碱催化剂在Prins反应中的应用
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摘要
分别采用浸渍法和共沉淀法制备了负载金属氧化物的固体碱催化剂MnO/Al2O3(M=Na,K,Cs,Mg,Ca,Sr;n=1,2)和C-Cs2O/Al2O3,测定了催化剂的碱量和pKa值,分别采用CO2-TPD、X射线衍射、N2物理吸附表征了催化剂的物理化学性质。以异丁烯与多聚甲醛经Prins反应制备3-甲基-3-丁烯-1-醇(MBO)为体系考察催化剂活性。结果表明,催化剂的碱性和结构直接影响其催化活性,采用共沉淀法制备的Cs2O/Al2O3催化剂具有更强的碱性,表现出了优越的反应活性,甲醛的转化率和产物MBO的选择性分别为100.0%和86.0%。探讨了固体碱催化反应的机理,发现碱性位可以活化异丁烯的α-H,促进Prins反应。
Solid base catalysts MnO/Al2O3(M=Na, K, Cs, Mg, Ca, Sr, n=1 or 2) prepared by impregnation method and C-Cs2O/Al2O3 by co-precipitation method were applied in Prins reaction. Their base amount and p Ka in water were determined. The structure and physico-chemical properties of the carrier and prepared catalysts were characterized by CO2-TPD, X-ray diffraction, and nitrogen adsorption. The performance of catalysts was evaluated by condensation reaction of isobutene with paraformaldehyde to produce 3-methyl-3-buten-1-ol. The results showed that the performance of catalysts related directly with their basic property and structure. The C-Cs2O/Al2O3 catalyst had stronger basicity and showed superior catalytic performance, and the conversion of formaldehyde and selectivity to MBO reached up to 100.0% and 86.0% respectively. The mechanism of Prins reaction over solid base catalyst was also discussed. The base sites could active the α-H of isobutene, and so could promote the Prins reaction.
Solid base catalysts MnO/Al2O3(M=Na, K, Cs, Mg, Ca, Sr, n=1 or 2) prepared by impregnation method and C-Cs2O/Al2O3 by co-precipitation method were applied in Prins reaction. Their base amount and p Ka in water were determined. The structure and physico-chemical properties of the carrier and prepared catalysts were characterized by CO2-TPD, X-ray diffraction, and nitrogen adsorption. The performance of catalysts was evaluated by condensation reaction of isobutene with paraformaldehyde to produce 3-methyl-3-buten-1-ol. The results showed that the performance of catalysts related directly with their basic property and structure. The C-Cs2O/Al2O3 catalyst had stronger basicity and showed superior catalytic performance, and the conversion of formaldehyde and selectivity to MBO reached up to 100.0% and 86.0% respectively. The mechanism of Prins reaction over solid base catalyst was also discussed. The base sites could active the α-H of isobutene, and so could promote the Prins reaction.
引文
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[23]Zhou Jinghong(周静红),Wang Xuefeng(王雪峰),Liu Guocai(刘国才),Sui Zhijun(隋志军),Zhou Xinggui(周兴贵),Yuan Weikang(袁渭康).Solid base supported Ru catalysts for sorbitol hydrogenolysis[J].CIESC Journal(化工学报),2014,65:2761-2769.
[24]Li Weimin(李伟民),Zheng Xiaolin(郑晓林),Xu Chunming(徐春明),Xu Ge(徐鸽),Wu Guoying(邬国英).Preparation and its properties of biodiesel by using solid base catalyst[J].Journal of Chemical Industry and Engineering(China)(化工学报),2004,56:711-716.
[25]Nesterenko N S,Ponomoreva O A,Yuschenko V V,Ivanova I I,Testa F,Di Renzo F,Fajula F.Dehydrogenation of ethylbenzene and isobutane over Ga-and Fe-containing mesoporous silicas[J].Appl.Catal.A-Gen.,2003,254(2):261-272.
[26]Kantam M L,Yadav J,Laha S,Sreedhar B,Bhargava S.Nanocrystalline magnesium oxide-stabilized molybdenum:an efficient heterogeneous catalyst for the aerobic oxidation of alcohols to carbonyl compounds[J].Adv.Synth.Catal.,2008,350(16):2575-2582.
[27]Boumaza A,Favaro L,Lédion J,Sattonnay G,Brubach J B,Berthet P,Huntz A M,Roy P,Tetot R.Transition alumina phases induced by heat treatment of boehmite:an X-ray diffraction and infrared spectroscopy study[J].J.Solid State Chem.,2009,182:1171-1176.
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[29]Yuan Q,Yin A X,Luo C,Sun L D,Zhang Y W,Duan W T,Liu H C,Yan C H.Facile synthesis for ordered mesoporousγ-aluminas with high thermal stability[J].J.Am.Chem.Soc.,2008,130:3465-3472.
[30]Sun L B,Yang J,Kou J H,Gu F N,Chun Y,Wang Y,Zhu J H,Zou Z G.One-pot synthesis of potassium-functionalized mesoporous gamma-alumina:a solid superbase[J].Angew.Chem.Int.Ed.,2008,47(18):3418-3421.
[31]Spivey J J.Catalysis[M].Cambridge:The Royal Society of Chemistry,2000:221.
[32]Liu Jiquan(刘季铨),Li Liandi(李连地),Wen Xia(闻霞),Peng Weicai(彭伟才),Xiao Fukui(肖福魁),Wei Wei(魏伟),Sun Yuhan(孙予罕).Synthesis of 3-methyl-3-buten-1-ol via thermal formaldehydeisobutene condensation[J].Fine Chemicals(精细化工),2011,28(3):293-296.
[33]Geng Zhang,Hideshi Hattoriand Kozo Tanabe.Aldol addition of acetone,catalyzed by solid base catalysts:magnesium oxide,calcium oxide,strontium oxide,barium oxide,lanthanum(Ⅲ)oxide and zirconium oxide[J].Appl.Catal.,1988,36:189-197.
[34]Guisnet M.Heterogeneous Catalysis and Fine ChemicalsⅡ[M].New York:Elsevier,1993:35.
[2]Pandolfi L,Cafarelli P,Kaciulis S,Tomlinson A A.XPS analysis of several zeolitic and clay-based nanoporous materials for C4hydrocarbon conversions[J].Microporous.Mesoporous.Mater.,2008,110(1):64-71.
[3]Wang W J,Shao L L,Cheng W P,Yang J G,He M Y.Br?nsted acidic ionic liquids as novel catalysts for Prins reaction[J].Catal.Commun.,2008,9:337-341.
[4]Ji M,Li X F,Wang J,Zhu J,Zhou L.Grafting Sn Cl4 catalyst as a novel solid acid for the synthesis of 3-methylbut-3-en-1-ol[J].Catal.Today,2011,173(1):28-31.
[5]Arundale E,Mikeska L.The olefin-aldehyde condensation.The Prins reaction[J].Chem.Rev.,1952,51(3):505-555.
[6]Jyothi T M,Kaliya M L,Landau M V.A Lewis acid catalyst anchored on silica grafted with quaternary alkylammonium chloride moieties[J].Chem.Commun.,2001,40:2881-2884.
[7]Ghosh A K,Keyes C,Veitschegger A M.Fe Cl3-catalyzed tandem Prins and Friedel-Crafts cyclization:a highly diastereoselective route to polycyclic ring structures[J].Tetrahedron.Lett.,2014,55(30):4251-4254.
[8]Dumitriu E,Trong On D,Kaliaguine S.Isoprene by Prins condensation over acidic molecular sieves[J].J.Catal.,1997,170(1):150-160.
[9]Dumitriu E,Hulea V,Fechete I,Catrinescu C,Auroux A,Lacaze J F,Guimon C.Prins condensation of isobutylene and formaldehyde over Fe-silicates of MFI structure[J].Appl.Catal.A-Gel.,1999,181(1):15-28.
[10]Yashima T,Katoh Y,Komatsu T.Synthesis of 3-methyl-3-butene-1-ol from isobutene and formaldehyde on Fe MCM-22 zeolites[J].Stud.Surf.Sci.Catal.,1999,125:507-514.
[11]Pillai U R,Sahle-Demessie E.Mesoporous iron phosphate as an active,selective and recyclable catalyst for the synthesis of nopol by Prins condensation[J].Chem.Commun.,2004,(7):826-827.
[12]Villa A L,Correa L F,Alarcón E A.Kinetics of the nopol synthesis by the Prins reaction over tin impregnated MCM-41 catalyst[J].Chem.Eng.J.,2013,215/216:500-507.
[13]Costa V V,Bayahia H,Kozhevnikova E F,Gusevskaya E V,Kozhevnikov I V.Highly active and recyclable metal oxide catalysts for the Prins condensation of biorenewable feedstocks[J].Chemcatchem.,2014,6(7):2134-2139.
[14]Walter M,Schinzer D.Prins cyclization using magnesium halides:mild access to 4-halogenated polysubstituted tetrahydropyrans with a special feature[J].Syn.lett.,2014,25(6):817-820.
[15]Wang X Y,Wang T,Hua W M,Yue Y H,Gao Z.Synthesis of zirconia porous phosphate heterostructures(Zr-PPH)for Prins condensation[J].Catal.Commun.,2014,43:97-101.
[16]Sushkevich V L,Ordomsky V V,Ivanova I I.Synthesis of isoprene from formaldehyde and isobutene over phosphate catalysts[J].Appl.Catal.A-Gen.,2012,441:21-29.
[17]Hattori H.Heterogeneous basic catalysis[J].Chem.Rev.,1995,95(3):537-558.
[18]Yan S,Di Maggio C,Mohan S,Kim M,Salley S O.Advancements in heterogeneous catalysis for biodiesel synthesis[J].Top.Catal.,2010,53(11/12):721-736.
[19]Busca G.Bases and basic materials in industrial and environmental chemistry:a review of commercial processes[J].Ind.Eng.Chem.Res.,2009,48:6486-6511.
[20]Kouzu M,Hidaka J.Transesterification of vegetable oil into biodiesel catalyzed by Ca O:a review[J].Fuel,2012,93:1-12.
[21]Xie W,Peng H,Chen L.Transesterification of soybean oil catalyzed by potassium loaded on alumina as a solid-base catalyst[J].Appl.Catal.A-Gen.,2006,300(1):67-74.
[22]Kim M,Di Maggio C,Yan S,Salley S O,Ng K Y S.The effect of support material on the transesterification activity of Ca O-La2O3 and Ca O-Ce O2 supported catalysts[J].Green Chem.,2011,13(2):334-339.
[23]Zhou Jinghong(周静红),Wang Xuefeng(王雪峰),Liu Guocai(刘国才),Sui Zhijun(隋志军),Zhou Xinggui(周兴贵),Yuan Weikang(袁渭康).Solid base supported Ru catalysts for sorbitol hydrogenolysis[J].CIESC Journal(化工学报),2014,65:2761-2769.
[24]Li Weimin(李伟民),Zheng Xiaolin(郑晓林),Xu Chunming(徐春明),Xu Ge(徐鸽),Wu Guoying(邬国英).Preparation and its properties of biodiesel by using solid base catalyst[J].Journal of Chemical Industry and Engineering(China)(化工学报),2004,56:711-716.
[25]Nesterenko N S,Ponomoreva O A,Yuschenko V V,Ivanova I I,Testa F,Di Renzo F,Fajula F.Dehydrogenation of ethylbenzene and isobutane over Ga-and Fe-containing mesoporous silicas[J].Appl.Catal.A-Gen.,2003,254(2):261-272.
[26]Kantam M L,Yadav J,Laha S,Sreedhar B,Bhargava S.Nanocrystalline magnesium oxide-stabilized molybdenum:an efficient heterogeneous catalyst for the aerobic oxidation of alcohols to carbonyl compounds[J].Adv.Synth.Catal.,2008,350(16):2575-2582.
[27]Boumaza A,Favaro L,Lédion J,Sattonnay G,Brubach J B,Berthet P,Huntz A M,Roy P,Tetot R.Transition alumina phases induced by heat treatment of boehmite:an X-ray diffraction and infrared spectroscopy study[J].J.Solid State Chem.,2009,182:1171-1176.
[28]Hattori H.Solid base catalysts:generation of basic sites and application to organic synthesis[J].Appl.Catal.A-Gen.,2001,222(1/2):247-259.
[29]Yuan Q,Yin A X,Luo C,Sun L D,Zhang Y W,Duan W T,Liu H C,Yan C H.Facile synthesis for ordered mesoporousγ-aluminas with high thermal stability[J].J.Am.Chem.Soc.,2008,130:3465-3472.
[30]Sun L B,Yang J,Kou J H,Gu F N,Chun Y,Wang Y,Zhu J H,Zou Z G.One-pot synthesis of potassium-functionalized mesoporous gamma-alumina:a solid superbase[J].Angew.Chem.Int.Ed.,2008,47(18):3418-3421.
[31]Spivey J J.Catalysis[M].Cambridge:The Royal Society of Chemistry,2000:221.
[32]Liu Jiquan(刘季铨),Li Liandi(李连地),Wen Xia(闻霞),Peng Weicai(彭伟才),Xiao Fukui(肖福魁),Wei Wei(魏伟),Sun Yuhan(孙予罕).Synthesis of 3-methyl-3-buten-1-ol via thermal formaldehydeisobutene condensation[J].Fine Chemicals(精细化工),2011,28(3):293-296.
[33]Geng Zhang,Hideshi Hattoriand Kozo Tanabe.Aldol addition of acetone,catalyzed by solid base catalysts:magnesium oxide,calcium oxide,strontium oxide,barium oxide,lanthanum(Ⅲ)oxide and zirconium oxide[J].Appl.Catal.,1988,36:189-197.
[34]Guisnet M.Heterogeneous Catalysis and Fine ChemicalsⅡ[M].New York:Elsevier,1993:35.