Cu/Zn/Al催化甲醇乙醇一步合成异丁醛
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摘要
采用水热合成-并流共沉淀法制备了CuO-ZnO-Al_2O_3三元催化剂用于甲醇乙醇一步合成异丁醛反应。通过H_2-TPR、XRD、BET对CuO-ZnO-Al_2O_3进行了详细的表征,并考察了CuO-ZnO-Al_2O_3催化剂催化合成异丁醛时的n(甲醇)∶n(乙醇)、反应温度及反应压力等条件对催化活性的影响。结果表明,反应温度为250℃、反应压力为2.3 MPa、n(甲醇)∶n(乙醇)=2.7∶1,乙醇转化率最高可达95.1%,异丁醛收率为69.8%。与共沉淀CuO/ZnO/Al_2O_3催化剂进行对比,结果表明,反应时间360 h,以CuO-ZnO-Al_2O_3为催化剂时,乙醇转化率最高为78.1%,异丁醛收率为45.9%;以CuO/ZnO/Al_2O_3为催化剂时,乙醇转化率最高为70.5%,异丁醛收率为39.9%。水热合成-并流共沉淀法制备的CuO-ZnO-Al_2O_3催化剂具有更优异的催化活性。
CuO-ZnO-Al_2O_3 ternary catalyst was prepared by hydrothermal synthesis-coprecipitation for the one-step synthesis of isobutyraldehyde from methanol and ethanol.The structure of CuO-ZnO-Al_2O_3 was characterized by H_2-TPR,XRD and BET.The molar ratio of raw materials,reaction temperature,and reaction pressure during the catalytic process over CuO-ZnO-Al_2O_3 catalyst were investigated.The results showed that when reaction temperature was 250 ℃,reaction pressure was 2.3 MPa,and the molar ratio of methanol to ethanol was 2.7∶1,ethanol conversion was up to 95.1%,and the yield of isobutyraldehyde was 69.8%.Compared with coprecipitated CuO/ZnO/Al_2O_3 catalyst,the results showed that when reaction time was 360 h,the ethanol conversion was 78.1% and the yield of isobutyraldehyde was 45.9% when CuO-ZnO-Al_2O_3 was used as catalyst,and the ethanol conversion was 70.5% and the yield of isobutyraldehyde was 39.9% when CuO/ZnO/Al_2O_3 was used as catalyst.It was proved that CuO-ZnO-Al_2O_3 catalyst prepared by hydrothermal synthesis-coprecipitation method had better catalytic activity.
CuO-ZnO-Al_2O_3 ternary catalyst was prepared by hydrothermal synthesis-coprecipitation for the one-step synthesis of isobutyraldehyde from methanol and ethanol.The structure of CuO-ZnO-Al_2O_3 was characterized by H_2-TPR,XRD and BET.The molar ratio of raw materials,reaction temperature,and reaction pressure during the catalytic process over CuO-ZnO-Al_2O_3 catalyst were investigated.The results showed that when reaction temperature was 250 ℃,reaction pressure was 2.3 MPa,and the molar ratio of methanol to ethanol was 2.7∶1,ethanol conversion was up to 95.1%,and the yield of isobutyraldehyde was 69.8%.Compared with coprecipitated CuO/ZnO/Al_2O_3 catalyst,the results showed that when reaction time was 360 h,the ethanol conversion was 78.1% and the yield of isobutyraldehyde was 45.9% when CuO-ZnO-Al_2O_3 was used as catalyst,and the ethanol conversion was 70.5% and the yield of isobutyraldehyde was 39.9% when CuO/ZnO/Al_2O_3 was used as catalyst.It was proved that CuO-ZnO-Al_2O_3 catalyst prepared by hydrothermal synthesis-coprecipitation method had better catalytic activity.
引文
[1] 邱显清,刘金尧,梁瑜.甲醇与乙醇一步合成异丁醛用CuO-ZnO-Al2O3催化剂[J].催化学报,1998,19(6):546-549.
[2] DOW W P.Yttria-stabilized zirconia supported copper oxide catalyst:I.Effect of oxygen vacancy of support on copper oxide reduction[J].J Catal,1996,160(2):155-170.
[3] WANG F L,LEE W S.Catalyic synthesis of isobutyraldehyde from methanol and ethanol over titanium oxide supported vanadium oxide catalysts[J].J Chem Soc Chem Commun,1991(24):1760-1761.
[4] REDDY B M,MANOHAR B.Synthesis of isobutyraldehyde from methanol and ethanol over mixed oxide supported vanadium oxide catalysts[J].Appl Catal A,1993,96(2):1-5.
[5] FORZATTI P,TRONCONI E,ELMI A S.Methanol oxidation over vanadia-based catalysts[J].Applied Catalysis A:General,1997,157(1):387-408.
[6] 李九龙.甲醇乙醇催化合成异丁醛的工艺研究[D].郑州:郑州大学,2014.
[7] 李慧兰.成膜助剂醇酯十二的合成与表征[D].长春:吉林大学,2015.
[8] 郑茂芬.负载型Cu-Co尖晶石复合氧化物催化剂的制备及其性能研究[D].扬州:扬州大学,2016.
[9] 陈文凯,许娇,徐瑾,等.负载Cu-Mn催化剂催化甲醇与乙醇一步合成异丁醛[J].科技通报,2002,18(6):490-494.
[10] 刘翠改,吴静,王康军,等.双助剂对CuO/SiO2催化甲醇乙醇合成异丁醛的影响[J].石油化工,2011,40(5):550-553.
[11] 胡虹,姚剑峰,施力.低碳醇一步合成异丁醛的研究[J].石油与天然气化工,2006,35(2):96-97.
[12] 赵锡武,张新立.异丁醛衍生物系列产品的综合利用[J].黑龙江石油化工,1997,8(2):8-13.
[13] HU X,LEI L,CHU H P.Copper/activated carbon as catalyst for organic wastewater treatment[J].Carbon,1999,37(4):631-637.
[14] BAO J,LIU Z L,ZHANG Y.Preparation of Cu/ZnO catalyst and its applicationin low-temperature methanol synthesis[J].Catalysis Communications,2008,9(5):913-918.
[15] SU H Y-W,MOON S-H.Active sites in Cu/ZnO/ZrO2 catalysts for methanol synthesis from CO/H2[J].Catal Today,2000,63(2):447-452.
[16] CAO Y,CHEN L F,DAI W L.Preparation of high performance Cu/ZnO/Al2O3 catalyst for ethanol synthesis from CO2 hydrogenation by coprecipitation-reduction[J].Chemical Journal of Chinese Universities,2003,24(7):1296-1298.
[2] DOW W P.Yttria-stabilized zirconia supported copper oxide catalyst:I.Effect of oxygen vacancy of support on copper oxide reduction[J].J Catal,1996,160(2):155-170.
[3] WANG F L,LEE W S.Catalyic synthesis of isobutyraldehyde from methanol and ethanol over titanium oxide supported vanadium oxide catalysts[J].J Chem Soc Chem Commun,1991(24):1760-1761.
[4] REDDY B M,MANOHAR B.Synthesis of isobutyraldehyde from methanol and ethanol over mixed oxide supported vanadium oxide catalysts[J].Appl Catal A,1993,96(2):1-5.
[5] FORZATTI P,TRONCONI E,ELMI A S.Methanol oxidation over vanadia-based catalysts[J].Applied Catalysis A:General,1997,157(1):387-408.
[6] 李九龙.甲醇乙醇催化合成异丁醛的工艺研究[D].郑州:郑州大学,2014.
[7] 李慧兰.成膜助剂醇酯十二的合成与表征[D].长春:吉林大学,2015.
[8] 郑茂芬.负载型Cu-Co尖晶石复合氧化物催化剂的制备及其性能研究[D].扬州:扬州大学,2016.
[9] 陈文凯,许娇,徐瑾,等.负载Cu-Mn催化剂催化甲醇与乙醇一步合成异丁醛[J].科技通报,2002,18(6):490-494.
[10] 刘翠改,吴静,王康军,等.双助剂对CuO/SiO2催化甲醇乙醇合成异丁醛的影响[J].石油化工,2011,40(5):550-553.
[11] 胡虹,姚剑峰,施力.低碳醇一步合成异丁醛的研究[J].石油与天然气化工,2006,35(2):96-97.
[12] 赵锡武,张新立.异丁醛衍生物系列产品的综合利用[J].黑龙江石油化工,1997,8(2):8-13.
[13] HU X,LEI L,CHU H P.Copper/activated carbon as catalyst for organic wastewater treatment[J].Carbon,1999,37(4):631-637.
[14] BAO J,LIU Z L,ZHANG Y.Preparation of Cu/ZnO catalyst and its applicationin low-temperature methanol synthesis[J].Catalysis Communications,2008,9(5):913-918.
[15] SU H Y-W,MOON S-H.Active sites in Cu/ZnO/ZrO2 catalysts for methanol synthesis from CO/H2[J].Catal Today,2000,63(2):447-452.
[16] CAO Y,CHEN L F,DAI W L.Preparation of high performance Cu/ZnO/Al2O3 catalyst for ethanol synthesis from CO2 hydrogenation by coprecipitation-reduction[J].Chemical Journal of Chinese Universities,2003,24(7):1296-1298.