微乳法制备纳米Ru/NaY催化剂及其催化对苯二酚加氢
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摘要
采用曲拉通X-100(Triton X-100)/正己醇/正庚烷/RuCl_3·3H_2O水溶液构成微乳液,以水合肼为还原剂,制备了纳米Ru颗粒,再破乳将其负载于NaY分子筛得到M-Ru/NaY催化剂.通过XRD、BET、XPS、SEM、TEM及DSC分析方法对催化剂进行了表征.表征结果表明,M-Ru/NaY催化剂具有金属钌平均粒径小,分布均匀,高度分散等优点.以对苯二酚加氢制1,4-环己二醇为探针反应,对微乳法和传统浸渍法制备的催化剂活性和选择性进行了比较,深入研究了催化剂用量,反应温度,氢气压力对对苯二酚加氢活性的影响及最佳反应时间的确定.实验结果表明,M-Ru/NaY催化剂在反应温度150℃,氢气压力4.0 MPa,m(M-Ru/NaY)∶m(对苯二酚)=0.2∶1,溶剂为异丙醇,此条件下反应30 min,对苯二酚转化率为100%,1,4-环己二醇的选择性高达92.6%.还考察了M-Ru/NaY催化剂的稳定性.最后,探讨了对苯二酚加氢反应路径.
Using Triton X-100,n-hexanol,n-heptane and RuCl_3·3H_2O aqueous solution to form microemulsion.The ruthenium nanoparticles were prepared by the hydrate hydrazine reducing. The demulsifier was added to the ruthenium microemulsion system,the Ru nanoparticles were loaded on the NaY to get the M-Ru/NaY catalysts. The catalysts were characterized by XRD,BET,XPS,SEM,TEM,and DSC. The results of characterization show that the M-Ru/NaY catalysts have the advantages when the average size of Ru particles is small( 1 ~ 2 nm),uniformly and highly dispersed,comparing with the Ru/NaY catalysts prepared by microemulsion and impregnation for application in the hydrogenation of hydroquinone to 1,4-cyclohexanediol.The influence of reaction conditions on hydrogenation activity was investigated in detail. The results show that the optimized reaction temperature is 1 50 ℃,hydrogen pressure is 4.0 MPa,m( M-Ru/NaY) ∶ m( hydroquinone) = 0.2 ∶ 1 and the solvent is isopropyl alcohpl. Under the optimal conditions,the reaction was carried out 30 min,the M-Ru/NaY catalysts exhibited high activity.The conversion of hydroquinone was 100% and the selectivity of 1,4-cyclohexanediol was up to 92.6%. In addition,the M-Ru/NaY catalyst has good stability. Finally,the reaction pathways were also analyzed preliminarily.
Using Triton X-100,n-hexanol,n-heptane and RuCl_3·3H_2O aqueous solution to form microemulsion.The ruthenium nanoparticles were prepared by the hydrate hydrazine reducing. The demulsifier was added to the ruthenium microemulsion system,the Ru nanoparticles were loaded on the NaY to get the M-Ru/NaY catalysts. The catalysts were characterized by XRD,BET,XPS,SEM,TEM,and DSC. The results of characterization show that the M-Ru/NaY catalysts have the advantages when the average size of Ru particles is small( 1 ~ 2 nm),uniformly and highly dispersed,comparing with the Ru/NaY catalysts prepared by microemulsion and impregnation for application in the hydrogenation of hydroquinone to 1,4-cyclohexanediol.The influence of reaction conditions on hydrogenation activity was investigated in detail. The results show that the optimized reaction temperature is 1 50 ℃,hydrogen pressure is 4.0 MPa,m( M-Ru/NaY) ∶ m( hydroquinone) = 0.2 ∶ 1 and the solvent is isopropyl alcohpl. Under the optimal conditions,the reaction was carried out 30 min,the M-Ru/NaY catalysts exhibited high activity.The conversion of hydroquinone was 100% and the selectivity of 1,4-cyclohexanediol was up to 92.6%. In addition,the M-Ru/NaY catalyst has good stability. Finally,the reaction pathways were also analyzed preliminarily.
引文
[1]GALAL A M,GUL W,SLADE D,et al.Synthesis and evaluation of dihydroartemisinin and dihydroartemisitene acetal dimers showing anticancer and antiprotozoal activity[J].Bioor&Med Chem,2009,17(2):741-751.
[2]Fan Zhao-xin(范兆馨),Gu Chao-ran(顾超然),Yang Zhong-bao(杨忠保).Production process and catalyst of1,4-cyclohexanedimethanol(1,4-环己二甲醇生产工艺及催化剂)[J].Petrkchem Technol(石油化工),2004,33(z1):1029-1031.
[3]Anon.Pharmaceutical and liquid crystal materials monomer-1,4-cyclohexanediol(医药和液晶材料单体-1,4-环己二醇)[J].Rea Fine Chem(试剂与精细化学品),2006,(2):13-13.
[4]a.Gao Hong-bin(高鸿宾).Orginic Chemistry(有机化学(第4版))[M].Beijing:Higher Education Press(北京:高等教育出版社),2009,155-349.b.Sun Hai-jie(孙海杰),Zhu Bing(朱冰),Huang Zhen-xu(黄振旭),et al.Effect of the concentration of the promoter precursor Zn SO4on the performance of the Ru-Zn catalyst for selective hydrogenation of benzene to cyclohexene(助剂前体Zn SO4浓度对苯选择加氢制环己烯Ru-Zn催化剂性能的影响)[J].J Mol Catal(China)(分子催化),2016,30(2):105-114.
[5]MoRan(莫然).Market prospects for hydroquinone(苯二酚市场前景十分乐观)[J].Zhejiang Chem Ind(浙江化工),2006,37(3):38-39.
[6]LI G X,DONG P,WANG X R,et al.Study of catalytic hydrogenation of 1,4-benzenediol over Ru/HY catalyst[J].J Mol Catal,2012,26(01):26-31.
[7]Li H,Ji D,Li Y,et al.Effect of alkaline earth metals on the liquid-phase hydrogenation of hydroquinone over Rubased catalysts[J].Sol Sta Sci,2015,50:85-90.
[8]Wang Hong-jun(王洪军),Wang Xing-quan(汪星全),Zhang Li(张丽),et al.Study on the synthesis of 1,4-cyclohexanediol through catalytic hydrogenation of hydroquinone(对苯二酚催化加氢制备1,4-环己二醇的研究)[J].J Mol Catal(China)(分子催化),2010,24(4):315-321.
[9]Sun Liang(孙亮),Rong Ze-ming(荣泽明),Zhang Wen-jun(张文君),et al.Selective hydrogenation of hydroquinone to 1,4-cyclohexanediol over Ru-Rh/AC catalyst(Ru-Rh/AC催化对苯二酚选择性加氢制备1,4-环己二醇)[J].Petrkchem Technol(石油化工),2013,42(2):146-151.
[10]Li Gui-xian(李贵贤),Gao Yuan(高远),Sun Lie-dong(孙烈东),et al.Preparation of Ru-B/γ-Al2O3amorphous alloy catalyst and study on its catalytic performance in the hydrogenation of hydroquinone(Ru-B/γ-Al2O3非晶态催化剂的制备及其对苯二酚加氢催化性能的研究)[J].Mod Chem Ind(现代化工),2017,37(5):115-119.
[11]Boutonnet M,Kizling J,Stenius P,et al.The preparation of monodisperse colloidal metal particles from microemulsions[J].Coll Surf,1982,5(3):209-225.
[12]Li Zhao-hui(李朝晖),Dai Wei(戴伟),Fu Ji-quan(傅吉全).Advances in preparation of nano-catalyst by micro-emulsification(微乳液法制备纳米催化剂的应用研究进展)[J].Chem Ind Eng Prog(化工进展),2008,27(4):499-502.
[13]Chen Wei(陈葳),Xiao Yi-hong(肖益鸿),Zhang Ying-ying(詹瑛瑛),et al.Au/Fe2O3Water-gas shift catalyst prepared by microemulsion methodⅠ.effect of synthesis parameters on catalyst activity(微乳法制备Au/Fe2O3水煤气变换反应催化剂Ⅰ.制备参数对催化剂活性的影响)[J].Chin J Catal(催化学报),2003,24(11):867-871.
[14]Jin Xiao-ping(金小平),Cong Yu(丛昱),Zhou Zhijiang(周志江),et al.A novel deposition method for preparation of Ag/Si O2catalyst in microemulsions(以新的沉积方法在微乳液中制备Ag/Si O2催化剂(英文))[J].Chin J Catal(催化学报),2005,26(7):536-538.
[15]Eriksson S,Nylén U,Rojas S,et al.Preparation of catalysts from microemulsions and their applications in h eterogeneous catalysis[J].Appl Catal A Gener,2004,265(2):207-219.
[16]Gao Shuang(高爽),Yan Jian-biao(颜见标),Cong De-quan(丛德全),et al.Preparation of Sn-modified Ru/H-CMK-3 catalysts and their application in the hydrogenation of cinnamaldehyde(Sn改性的Ru/H-CMK-3催化剂的制备及其肉桂醛选择性加氢性能的研究)[J].Acta Phys-Chim Sin(物理化学学报),2015,37(7):1391-1398.
[17]Yang Xiao-long(杨晓龙),Xia Chun-gu(夏春谷),Tang Li-ping(唐立平),et al.Effect of alumina support and barium oxide on the structure and catalytic activity of ruthenium catalysts for ammonia synthesis(氧化铝载体和氧化钡助剂对钌基氨合成催化剂结构和性能的影响)[J].Acta Phys-Chim Sin(物理化学学报),2010,26(12):3263-3272.
[18]Larichev Y V,Moroz B L,Bukhtiyarov V I.Electronic state of ruthenium deposited onto oxide supports:An XPS study taking into account the final state effects[J].Appl Surf Sci,2011,258(4):1541-1550.
[19]Wang Zi-qing(王自庆),Chen Geng(陈赓),Lin Jianxin(林建新),et al.Preparation of Ru/Ba-Zr O2catalyst and its performance for ammonia synthesis(Ru/Ba-Zr O2催化剂的制备及其氨合成性能研究)[J].Acta Chim Sin(化学学报),2013,71(2):205-212.
[20]Shen J Y,Adnot A,Kaliaguine S.An ESCA study of the interaction of oxygen with the surface of ruthenium[J].Appl Surf Sci,1991,51(1/2):47-60.
[21]Wang Rong(王榕),Wei Ke-mei(魏可镁),Lin Jianxin(林建新),et al.Preparation of Ru/AC ammonia synthesis catalyst reduced with hydrazine hydrate(用水合肼还原的Ru/AC氨合成催化剂的制备)[J].Chin J Catal(催化学报),2003,24(12):929-932.
[22]Xu San-kui(徐三魁),Wang Xiao-dong(王晓栋),Li Li-min(李利民),et al.Effect of supercritical methanol treatment on the properties and structures of Ru/AC catalysts(超临界甲醇处理对Ru/C催化剂结构及性能的影响)[J].J Mol Catal(China)(分子催化),2010,24(6):516-522.
[23]Wei Guo-bin(卫国宾),Yang Si-yuan(杨思源),Zhang Jing-chang(张敬畅),et al.Supported Pd nanoparticle catalyst prepared by microemulsion method for selective hydrogenation of acetylene(微乳液法制备Pd负载型催化剂及其催化性能)[J].Petrkchem Technol(石油化工),2012,41(11):1239-1244.
[24]Zhang Su-juan(张素娟).Preparation of solid base catalyst for synthesis of DMC by transesterification(酯交换法合成碳酸二甲酯固体碱催化剂的制备)[D].Master dissertion of China University of Petroleum(中国石油大学硕士论文).2009.
[25]Wang Zhen-xin(王振新),Zeng Chong-yu(曾崇余).Effect of hydrogen partial pressure on terephthalic acid hydrogenation(氢气分压对对苯二甲酸加氢反应的影响)[J].Chin Synth Fib Ind(合成纤维工业),2004,27(5):21-23.
[26]Wang An-jie(王安杰),Zhou Yu-zhi(周裕之),Zhao Bei(赵蓓).Chemical reaction engineering(化学反应工程学)[M].Beijing:Chemical Industry Press(北京:化学工业出版社),2005,29.
[27]Li Cheng-lie(李承烈).Catalyst Deactivation(催化剂失活)[M].Beijing:Chemical Industry Press(北京:化学工业出版社),1989,1-3.
[28]Guczi L,Kónya Z,Koppány Z,et al.Influence of pretreatment conditions on acidity of cobalt-based bimetallic systems in Na Y zeolite[J].Catal Lett,1997,44(1):7-10.
[2]Fan Zhao-xin(范兆馨),Gu Chao-ran(顾超然),Yang Zhong-bao(杨忠保).Production process and catalyst of1,4-cyclohexanedimethanol(1,4-环己二甲醇生产工艺及催化剂)[J].Petrkchem Technol(石油化工),2004,33(z1):1029-1031.
[3]Anon.Pharmaceutical and liquid crystal materials monomer-1,4-cyclohexanediol(医药和液晶材料单体-1,4-环己二醇)[J].Rea Fine Chem(试剂与精细化学品),2006,(2):13-13.
[4]a.Gao Hong-bin(高鸿宾).Orginic Chemistry(有机化学(第4版))[M].Beijing:Higher Education Press(北京:高等教育出版社),2009,155-349.b.Sun Hai-jie(孙海杰),Zhu Bing(朱冰),Huang Zhen-xu(黄振旭),et al.Effect of the concentration of the promoter precursor Zn SO4on the performance of the Ru-Zn catalyst for selective hydrogenation of benzene to cyclohexene(助剂前体Zn SO4浓度对苯选择加氢制环己烯Ru-Zn催化剂性能的影响)[J].J Mol Catal(China)(分子催化),2016,30(2):105-114.
[5]MoRan(莫然).Market prospects for hydroquinone(苯二酚市场前景十分乐观)[J].Zhejiang Chem Ind(浙江化工),2006,37(3):38-39.
[6]LI G X,DONG P,WANG X R,et al.Study of catalytic hydrogenation of 1,4-benzenediol over Ru/HY catalyst[J].J Mol Catal,2012,26(01):26-31.
[7]Li H,Ji D,Li Y,et al.Effect of alkaline earth metals on the liquid-phase hydrogenation of hydroquinone over Rubased catalysts[J].Sol Sta Sci,2015,50:85-90.
[8]Wang Hong-jun(王洪军),Wang Xing-quan(汪星全),Zhang Li(张丽),et al.Study on the synthesis of 1,4-cyclohexanediol through catalytic hydrogenation of hydroquinone(对苯二酚催化加氢制备1,4-环己二醇的研究)[J].J Mol Catal(China)(分子催化),2010,24(4):315-321.
[9]Sun Liang(孙亮),Rong Ze-ming(荣泽明),Zhang Wen-jun(张文君),et al.Selective hydrogenation of hydroquinone to 1,4-cyclohexanediol over Ru-Rh/AC catalyst(Ru-Rh/AC催化对苯二酚选择性加氢制备1,4-环己二醇)[J].Petrkchem Technol(石油化工),2013,42(2):146-151.
[10]Li Gui-xian(李贵贤),Gao Yuan(高远),Sun Lie-dong(孙烈东),et al.Preparation of Ru-B/γ-Al2O3amorphous alloy catalyst and study on its catalytic performance in the hydrogenation of hydroquinone(Ru-B/γ-Al2O3非晶态催化剂的制备及其对苯二酚加氢催化性能的研究)[J].Mod Chem Ind(现代化工),2017,37(5):115-119.
[11]Boutonnet M,Kizling J,Stenius P,et al.The preparation of monodisperse colloidal metal particles from microemulsions[J].Coll Surf,1982,5(3):209-225.
[12]Li Zhao-hui(李朝晖),Dai Wei(戴伟),Fu Ji-quan(傅吉全).Advances in preparation of nano-catalyst by micro-emulsification(微乳液法制备纳米催化剂的应用研究进展)[J].Chem Ind Eng Prog(化工进展),2008,27(4):499-502.
[13]Chen Wei(陈葳),Xiao Yi-hong(肖益鸿),Zhang Ying-ying(詹瑛瑛),et al.Au/Fe2O3Water-gas shift catalyst prepared by microemulsion methodⅠ.effect of synthesis parameters on catalyst activity(微乳法制备Au/Fe2O3水煤气变换反应催化剂Ⅰ.制备参数对催化剂活性的影响)[J].Chin J Catal(催化学报),2003,24(11):867-871.
[14]Jin Xiao-ping(金小平),Cong Yu(丛昱),Zhou Zhijiang(周志江),et al.A novel deposition method for preparation of Ag/Si O2catalyst in microemulsions(以新的沉积方法在微乳液中制备Ag/Si O2催化剂(英文))[J].Chin J Catal(催化学报),2005,26(7):536-538.
[15]Eriksson S,Nylén U,Rojas S,et al.Preparation of catalysts from microemulsions and their applications in h eterogeneous catalysis[J].Appl Catal A Gener,2004,265(2):207-219.
[16]Gao Shuang(高爽),Yan Jian-biao(颜见标),Cong De-quan(丛德全),et al.Preparation of Sn-modified Ru/H-CMK-3 catalysts and their application in the hydrogenation of cinnamaldehyde(Sn改性的Ru/H-CMK-3催化剂的制备及其肉桂醛选择性加氢性能的研究)[J].Acta Phys-Chim Sin(物理化学学报),2015,37(7):1391-1398.
[17]Yang Xiao-long(杨晓龙),Xia Chun-gu(夏春谷),Tang Li-ping(唐立平),et al.Effect of alumina support and barium oxide on the structure and catalytic activity of ruthenium catalysts for ammonia synthesis(氧化铝载体和氧化钡助剂对钌基氨合成催化剂结构和性能的影响)[J].Acta Phys-Chim Sin(物理化学学报),2010,26(12):3263-3272.
[18]Larichev Y V,Moroz B L,Bukhtiyarov V I.Electronic state of ruthenium deposited onto oxide supports:An XPS study taking into account the final state effects[J].Appl Surf Sci,2011,258(4):1541-1550.
[19]Wang Zi-qing(王自庆),Chen Geng(陈赓),Lin Jianxin(林建新),et al.Preparation of Ru/Ba-Zr O2catalyst and its performance for ammonia synthesis(Ru/Ba-Zr O2催化剂的制备及其氨合成性能研究)[J].Acta Chim Sin(化学学报),2013,71(2):205-212.
[20]Shen J Y,Adnot A,Kaliaguine S.An ESCA study of the interaction of oxygen with the surface of ruthenium[J].Appl Surf Sci,1991,51(1/2):47-60.
[21]Wang Rong(王榕),Wei Ke-mei(魏可镁),Lin Jianxin(林建新),et al.Preparation of Ru/AC ammonia synthesis catalyst reduced with hydrazine hydrate(用水合肼还原的Ru/AC氨合成催化剂的制备)[J].Chin J Catal(催化学报),2003,24(12):929-932.
[22]Xu San-kui(徐三魁),Wang Xiao-dong(王晓栋),Li Li-min(李利民),et al.Effect of supercritical methanol treatment on the properties and structures of Ru/AC catalysts(超临界甲醇处理对Ru/C催化剂结构及性能的影响)[J].J Mol Catal(China)(分子催化),2010,24(6):516-522.
[23]Wei Guo-bin(卫国宾),Yang Si-yuan(杨思源),Zhang Jing-chang(张敬畅),et al.Supported Pd nanoparticle catalyst prepared by microemulsion method for selective hydrogenation of acetylene(微乳液法制备Pd负载型催化剂及其催化性能)[J].Petrkchem Technol(石油化工),2012,41(11):1239-1244.
[24]Zhang Su-juan(张素娟).Preparation of solid base catalyst for synthesis of DMC by transesterification(酯交换法合成碳酸二甲酯固体碱催化剂的制备)[D].Master dissertion of China University of Petroleum(中国石油大学硕士论文).2009.
[25]Wang Zhen-xin(王振新),Zeng Chong-yu(曾崇余).Effect of hydrogen partial pressure on terephthalic acid hydrogenation(氢气分压对对苯二甲酸加氢反应的影响)[J].Chin Synth Fib Ind(合成纤维工业),2004,27(5):21-23.
[26]Wang An-jie(王安杰),Zhou Yu-zhi(周裕之),Zhao Bei(赵蓓).Chemical reaction engineering(化学反应工程学)[M].Beijing:Chemical Industry Press(北京:化学工业出版社),2005,29.
[27]Li Cheng-lie(李承烈).Catalyst Deactivation(催化剂失活)[M].Beijing:Chemical Industry Press(北京:化学工业出版社),1989,1-3.
[28]Guczi L,Kónya Z,Koppány Z,et al.Influence of pretreatment conditions on acidity of cobalt-based bimetallic systems in Na Y zeolite[J].Catal Lett,1997,44(1):7-10.