RuCl_3一步催化氧化液相乙醇合成1,1-二乙氧基乙烷
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摘要
首先考察了不同金属卤化物对乙醇一步液相氧化合成1,1-二乙氧基乙烷(DEE)的催化性能。结果表明,RuCl_3催化性能最好。然后考察了反应条件的影响,结果表明,以50 mL无水乙醇(0.86 mol)为反应物时,最佳催化反应条件为:反应温度120℃、氧气压力2MPa、反应时间3h、催化剂用量0.004%(以乙醇的物质的量为基准,下同)、搅拌速度600 r/min,此时乙醇转化率达到38.2%,DEE选择性达到78.9%。并且发现,Ru~(3+)不但对乙醇氧化成乙醛具有较高的催化活性,同时RuCl_3是一种温和的路易斯酸,可以较好地催化乙醇与乙醛的缩合反应。最后对RuCl_3催化剂的重复使用性进行了考察,催化剂重复使用20次后,依然有较高的催化活性。
The catalytic performances of various metal halide as catalysts were studied using the synthesis of 1,1-diethoxyethane(DEE) by one-step liquid phase oxidation of ethanol. It was found that RuCl_3 is the best catalyst for this reaction. Subsequently, the effects of synthetic conditions on the catalytic performance were also discussed. When 50 mL ethanol(0.86 mol) were used as reactant, the optimized reaction conditions were obtained as follows: reaction temperature 120 ℃, oxygen pressure 2 MPa, reaction time 3 h, RuCl_3 amount 0.004%(benchmarked against the molar of ethanol, the same below), stirring rate 600 r/min. Under the optimized conditions, the conversion of ethanol reached 38.2% and the selectivity of DEE reached78.9%. Ru~(3+)not only has good catalytic activity for the oxidation of ethanol to aldehyde, but also RuCl_3 is a Lewis acid, which can catalyze the condensation of ethanol and acetaldehyde. At last, the reusability of RuCl_3 was investigated. RuCl_3 catalyst still had high catalytic activity after being reused for 20 times.
The catalytic performances of various metal halide as catalysts were studied using the synthesis of 1,1-diethoxyethane(DEE) by one-step liquid phase oxidation of ethanol. It was found that RuCl_3 is the best catalyst for this reaction. Subsequently, the effects of synthetic conditions on the catalytic performance were also discussed. When 50 mL ethanol(0.86 mol) were used as reactant, the optimized reaction conditions were obtained as follows: reaction temperature 120 ℃, oxygen pressure 2 MPa, reaction time 3 h, RuCl_3 amount 0.004%(benchmarked against the molar of ethanol, the same below), stirring rate 600 r/min. Under the optimized conditions, the conversion of ethanol reached 38.2% and the selectivity of DEE reached78.9%. Ru~(3+)not only has good catalytic activity for the oxidation of ethanol to aldehyde, but also RuCl_3 is a Lewis acid, which can catalyze the condensation of ethanol and acetaldehyde. At last, the reusability of RuCl_3 was investigated. RuCl_3 catalyst still had high catalytic activity after being reused for 20 times.
引文
[1]Rass‐Hansen J,Falsig H,J?rgensen B,et al.Bioethanol:Fuel or feedstock[J].Journal of Chemical Technology&Biotechnology,2007,82(4):329-333.
[2]Bauer J C,Veith G M,Allard L F,et al.Silica-supported Au-CuOx hybrid nanocrystals as active and selective catalysts for the formation of acetaldehyde from the oxidation of ethanol[J].ACS Catalysis,2012,2(12):2537-2546.
[3]Agarwal A K.Biofuels(alcohols and biediesel)applications as fuels for intemal combustion engines[J].Progress in Energy and Combustion Science,2007,33(3):233-271.
[4]Ribeiro N M,Pinto A C,Quintella C M,et al.The role of additives for diesel and diesel blended(ethanol or biodiesel)fuels:?AReview[J].Energy&Fuels,2007,21(4):2433-2445.
[5]Hansen A C,Zhang Q,Lyne P W L.Ethanol-diesel fuel blends-Areview[J].Bioresource Technology,2004,96(3):277-285.
[6]And K E N,Dan H.Reducing the emission of particles from a diesel engine by adding an oxygenate to the fuel[J].Environmental Science&Technology,2005,39(16):6260-6265.
[7]Frusteri F,Spadaro L,Beatrice C,et al.Oxygenated additives production for diesel engine emission improvement[J].Chemical Engineering Journal,2007,134(1):239-245.
[8]Meskens F A J.ChemInform Abstract:Methods for the preparation of acetals from alcohols or oxiranes and carbonyl compounds[J].Cheminform,1981,12(45):501-522.
[9]Kaufhold M,Elchahawi M.Process for preparing acetaldehyde diethyl acetal:US5527969A[P].1996-06-18.
[10]Mookherjee B D,Trenkle R W,Zampino M J,et al.Flavor and fragrance compositions produced using process for quantitatively and qualitatively substantially continuously analyzing the aroma emitted from a living fruit:US5321005[P].1994-06-14.
[11]Capeletti M R,Balzano L,Puente G D L,et al.Synthesis of acetal(1,1-diethoxyethane)from ethanol and acetaldehyde over acidic catalysts[J].Applied Catalysis A General,2000,198(1/2):L1-L4.
[12]Silva V M T M,Rodrigues A E.Synthesis of diethylacetal:Thermodynamic and kinetic studies[J].Chemical Engineering Science,2001,56(4):1255-1263.
[13]Silva V M T M,Rodrigues A E.Novel process for diethylacetal synthesis[J].AIChE Journal,2005,51(10):2752-2768.
[14]Gomez M F,Arrúa L A,Ma C A.Synthesis of 1,1‐diethoxyethane using a continuous flow reactor:catalyst deactivation and effect of feed purity and of solvent addition[J].Journal of Chemical Technology&Biotechnology Biotechnology,2004,79(4):391-396.
[15]Moiseev N N.Thefirst all-union congress on theoretical and applied mechanics[J].Uspekhi Matematicheskikh Nauk,1960,4(94):227-238.
[16]Ketley A D,Fisher L P.The reactions of alkene palladium chloride complexes with alcohols[J].Journal of Organometallic Chemistry,1968,13(1):243-248.
[17]Lloyd W G,Luberoff B J.Oxidations of olefins with alcoholic palladium(Ⅱ)salts[J].Journal of Organic Chemistry,1969,34(12):3949-3952.
[18]Tanaka T,Takenaka S,Funabiki T,et al.Photocatalytic oxidation of ethanol over tantalum oxide supported on silica[J].Studies in Surface Science&Catalysis,1994,90:485-490.
[19]Liu H,Iglesia E.Selective oxidation of methanol and ethanol on supported ruthenium oxide clusters at low temperatures[J].Journal of Physical Chemistry B,2005,109(6):2155-2163.
[20]Bueno A C,Gon?alves J A,Gusevskaya E V.Palladium-catalyzed oxidation of primary alcohols:Highly selective direct synthesis of acetals[J].Applied Catalysis A General,2007,329(10):1-6.
[21]Thavornprasert K,Ménorval B D L G D,Capron M,et al.Selective oxidation of ethanol towards a highly valuable product over industrial and model catalysts.[J].Biofuels,2012,3(1):25-34.
[22]Liu H,Iglesia E.Process and catalysts for the oxidation of methanol and/or ethanol:US20050059839[P].2005-03-17.
[23]Gomez M F,Arrúa L A,Abello M C.Synthesis of 1,1-Diethoxyethane from bioethanol.Influence of catalyst acidity[J].Reaction Kinetics&Catalysis Letters,2001,73(1):143-149.
[24]Silva V M T M,Rodrigues A E.Dynamics of a fixed‐bed adsorptive reactor for synthesis of diethylacetal[J].AIChE Journal,2002,48(3):625-634.
[25]Gaspar A B,Esteves A M L,Mendes F M T,et al.Chemicals from ethanol-The ethyl acetate one-pot synthesis[J].Applied Catalysis AGeneral,2009,363(1):109-114.
[26]Li M,Long Y,Deng Z,et al.Ruthenium trichloride as a new catalyst for selective production of dimethoxymethane from liquid methanol with molecular oxygen as sole oxidant[J].Catalysis Communications,2015,68:46-48.
[27]Liu Peng(刘鹏),Deng Zhiyong(邓志勇),Yang Xiangui(杨先贵),et al.One-step oxidation of liquid methanol to dimethoxymethane with CuCl/oxime complex as catalyst[J].Natural Gas Chemical Industry(天然气化工),2013(6):16-19.
[28]Long Yan(龙焱),Li Meilan(李美兰),Deng Zhiyong(邓志勇),et al.One-step oxidation of liquid methanol to dimethoxymethane with CuBr2 as catalyst[J].Natural Gas Chemical Industry(天然气化工),2016,41(6):7-9.
[29]Zhao Lingfeng(赵凌峰),Zhai Gang(翟刚),Deng Zhiyong(邓志勇),et al.One-step oxidation of liquid methanol to dimethoxymethane with CuBr2-pyridine ionic liquids as catalyst[J].Fine Chemicals(精细化工),2018,35(9):1542-1547.
[30]Bilgrien C,Davis S,Drago R S.The selective oxidation of primary alcohols to aldehydes by oxygen employing a trinuclear ruthenium carboxylate catalyst[J].Journal of the American Chemical Society,1987,109:3786-3787.
[31]Ji Hongbing(纪红兵),Wang Lefu(王乐夫).Oxidative properties and mechanisms of Ru with different valences[J].Chemistry(化学通报),2003,66(2):35-39.
[32]Sasaki Y,Endo T,Tanaka N,et al.Pretreatment of lignocellulosic biomass associated with the autoxidation of ethanol to acetal[J].Green Chemistry,2009,11,27-30.
[33]Haryanto A,Fernando S,Murali N,et al.Current status of hydrogen production techniques by steam reforming of ethanol:?A review[J].Energy&Fuels,2005,19(5):2098-2106.
[34]Jalama K.Carbon dioxide hydrogenation over nickel-,ruthenium-,and copper-based catalysts:Review of kinetics and mechanism[J].Catalysis Reviews,2017,59(34):1-70.
[35]Filonenko G A,Conley M P,Copéret C,et al.The impact of metal-ligand cooperation in hydrogenation of carbon dioxide catalyzed by ruthenium PNP pincer[J].ACS Catalysis,2013,3(11):2522-2526.
[36]Sgro M J,Stephan D W.Frustrated Lewis pair inspired carbon dioxide reduction by a ruthenium tris(aminophosphine)complex[J].Angewandte Chemie International Edition 2012.51(45):11505-11507.
[37]Suo Quanling(索全伶),Yin Yuanqi(殷元骐),Jin Daosen(金道森).Homogeneous catalysis of CO hydrogenation by Ru polyhydride[J].Journal of Inner Mongolia Polytecheic University(内蒙古工业大学学报),1994,13(2):9-14.
[2]Bauer J C,Veith G M,Allard L F,et al.Silica-supported Au-CuOx hybrid nanocrystals as active and selective catalysts for the formation of acetaldehyde from the oxidation of ethanol[J].ACS Catalysis,2012,2(12):2537-2546.
[3]Agarwal A K.Biofuels(alcohols and biediesel)applications as fuels for intemal combustion engines[J].Progress in Energy and Combustion Science,2007,33(3):233-271.
[4]Ribeiro N M,Pinto A C,Quintella C M,et al.The role of additives for diesel and diesel blended(ethanol or biodiesel)fuels:?AReview[J].Energy&Fuels,2007,21(4):2433-2445.
[5]Hansen A C,Zhang Q,Lyne P W L.Ethanol-diesel fuel blends-Areview[J].Bioresource Technology,2004,96(3):277-285.
[6]And K E N,Dan H.Reducing the emission of particles from a diesel engine by adding an oxygenate to the fuel[J].Environmental Science&Technology,2005,39(16):6260-6265.
[7]Frusteri F,Spadaro L,Beatrice C,et al.Oxygenated additives production for diesel engine emission improvement[J].Chemical Engineering Journal,2007,134(1):239-245.
[8]Meskens F A J.ChemInform Abstract:Methods for the preparation of acetals from alcohols or oxiranes and carbonyl compounds[J].Cheminform,1981,12(45):501-522.
[9]Kaufhold M,Elchahawi M.Process for preparing acetaldehyde diethyl acetal:US5527969A[P].1996-06-18.
[10]Mookherjee B D,Trenkle R W,Zampino M J,et al.Flavor and fragrance compositions produced using process for quantitatively and qualitatively substantially continuously analyzing the aroma emitted from a living fruit:US5321005[P].1994-06-14.
[11]Capeletti M R,Balzano L,Puente G D L,et al.Synthesis of acetal(1,1-diethoxyethane)from ethanol and acetaldehyde over acidic catalysts[J].Applied Catalysis A General,2000,198(1/2):L1-L4.
[12]Silva V M T M,Rodrigues A E.Synthesis of diethylacetal:Thermodynamic and kinetic studies[J].Chemical Engineering Science,2001,56(4):1255-1263.
[13]Silva V M T M,Rodrigues A E.Novel process for diethylacetal synthesis[J].AIChE Journal,2005,51(10):2752-2768.
[14]Gomez M F,Arrúa L A,Ma C A.Synthesis of 1,1‐diethoxyethane using a continuous flow reactor:catalyst deactivation and effect of feed purity and of solvent addition[J].Journal of Chemical Technology&Biotechnology Biotechnology,2004,79(4):391-396.
[15]Moiseev N N.Thefirst all-union congress on theoretical and applied mechanics[J].Uspekhi Matematicheskikh Nauk,1960,4(94):227-238.
[16]Ketley A D,Fisher L P.The reactions of alkene palladium chloride complexes with alcohols[J].Journal of Organometallic Chemistry,1968,13(1):243-248.
[17]Lloyd W G,Luberoff B J.Oxidations of olefins with alcoholic palladium(Ⅱ)salts[J].Journal of Organic Chemistry,1969,34(12):3949-3952.
[18]Tanaka T,Takenaka S,Funabiki T,et al.Photocatalytic oxidation of ethanol over tantalum oxide supported on silica[J].Studies in Surface Science&Catalysis,1994,90:485-490.
[19]Liu H,Iglesia E.Selective oxidation of methanol and ethanol on supported ruthenium oxide clusters at low temperatures[J].Journal of Physical Chemistry B,2005,109(6):2155-2163.
[20]Bueno A C,Gon?alves J A,Gusevskaya E V.Palladium-catalyzed oxidation of primary alcohols:Highly selective direct synthesis of acetals[J].Applied Catalysis A General,2007,329(10):1-6.
[21]Thavornprasert K,Ménorval B D L G D,Capron M,et al.Selective oxidation of ethanol towards a highly valuable product over industrial and model catalysts.[J].Biofuels,2012,3(1):25-34.
[22]Liu H,Iglesia E.Process and catalysts for the oxidation of methanol and/or ethanol:US20050059839[P].2005-03-17.
[23]Gomez M F,Arrúa L A,Abello M C.Synthesis of 1,1-Diethoxyethane from bioethanol.Influence of catalyst acidity[J].Reaction Kinetics&Catalysis Letters,2001,73(1):143-149.
[24]Silva V M T M,Rodrigues A E.Dynamics of a fixed‐bed adsorptive reactor for synthesis of diethylacetal[J].AIChE Journal,2002,48(3):625-634.
[25]Gaspar A B,Esteves A M L,Mendes F M T,et al.Chemicals from ethanol-The ethyl acetate one-pot synthesis[J].Applied Catalysis AGeneral,2009,363(1):109-114.
[26]Li M,Long Y,Deng Z,et al.Ruthenium trichloride as a new catalyst for selective production of dimethoxymethane from liquid methanol with molecular oxygen as sole oxidant[J].Catalysis Communications,2015,68:46-48.
[27]Liu Peng(刘鹏),Deng Zhiyong(邓志勇),Yang Xiangui(杨先贵),et al.One-step oxidation of liquid methanol to dimethoxymethane with CuCl/oxime complex as catalyst[J].Natural Gas Chemical Industry(天然气化工),2013(6):16-19.
[28]Long Yan(龙焱),Li Meilan(李美兰),Deng Zhiyong(邓志勇),et al.One-step oxidation of liquid methanol to dimethoxymethane with CuBr2 as catalyst[J].Natural Gas Chemical Industry(天然气化工),2016,41(6):7-9.
[29]Zhao Lingfeng(赵凌峰),Zhai Gang(翟刚),Deng Zhiyong(邓志勇),et al.One-step oxidation of liquid methanol to dimethoxymethane with CuBr2-pyridine ionic liquids as catalyst[J].Fine Chemicals(精细化工),2018,35(9):1542-1547.
[30]Bilgrien C,Davis S,Drago R S.The selective oxidation of primary alcohols to aldehydes by oxygen employing a trinuclear ruthenium carboxylate catalyst[J].Journal of the American Chemical Society,1987,109:3786-3787.
[31]Ji Hongbing(纪红兵),Wang Lefu(王乐夫).Oxidative properties and mechanisms of Ru with different valences[J].Chemistry(化学通报),2003,66(2):35-39.
[32]Sasaki Y,Endo T,Tanaka N,et al.Pretreatment of lignocellulosic biomass associated with the autoxidation of ethanol to acetal[J].Green Chemistry,2009,11,27-30.
[33]Haryanto A,Fernando S,Murali N,et al.Current status of hydrogen production techniques by steam reforming of ethanol:?A review[J].Energy&Fuels,2005,19(5):2098-2106.
[34]Jalama K.Carbon dioxide hydrogenation over nickel-,ruthenium-,and copper-based catalysts:Review of kinetics and mechanism[J].Catalysis Reviews,2017,59(34):1-70.
[35]Filonenko G A,Conley M P,Copéret C,et al.The impact of metal-ligand cooperation in hydrogenation of carbon dioxide catalyzed by ruthenium PNP pincer[J].ACS Catalysis,2013,3(11):2522-2526.
[36]Sgro M J,Stephan D W.Frustrated Lewis pair inspired carbon dioxide reduction by a ruthenium tris(aminophosphine)complex[J].Angewandte Chemie International Edition 2012.51(45):11505-11507.
[37]Suo Quanling(索全伶),Yin Yuanqi(殷元骐),Jin Daosen(金道森).Homogeneous catalysis of CO hydrogenation by Ru polyhydride[J].Journal of Inner Mongolia Polytecheic University(内蒙古工业大学学报),1994,13(2):9-14.