碱液浓度对1,4-丁炔二醇加氢Raney-Ni催化剂结构和性能的影响
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摘要
采用不同质量分数(5%～20%)NaOH溶液浸取商品Ni-Al合金粉(粒径180～250μm)制备Raney-Ni催化剂。通过XRD、TEM、N_2吸附-脱附、EDS等表征手段和1,4-丁炔二醇(BYD)加氢制1,4-丁烯二醇(BED)评价实验,考察不同碱液浓度对Raney-Ni催化剂结构和性能的影响。结果表明:10%质量分数碱液浸取制备的催化剂试样RN10%在2θ为44.3°、51.7°、76.1°处出现了活性组分Ni的特征峰,分别对应于Ni(111)、Ni(200)和Ni(220),即生成了面心立方晶格结构的Ni,且晶粒尺寸较小;比表面积大,为58.07 m~2/g;对Al的浸取量较为适中。评价结果表明,试样RN10%加氢性能最好,BYD转化率为37.46%,BED选择性为91.73%,收率为34.36%。这与该试样活性组分Ni晶粒尺寸小,残余的Ni_2Al_3相充当"结构促进剂",比表面积大,浸取Al含量适中有关。
Raney-Ni catalysts were prepared by leaching commercial Ni-Al alloy(Particle size 180-250 μm) with different mass fractions(5%-20%) of NaOH solution. Effects of different alkali concentrations on the structure and catalytic performance of Raney-Ni catalysts were investigated by XRD, TEM, N_2 adsorption-desorption, EDS and 1,4-butynediol(BYD) hydrogenation to prepare 1,4-butene glycol(BED). Results show that the characteristic peaks of the active component Ni appearing at 2θ is 44.3°, 51.7° and 76.1° for the RN10% catalyst are attributed to Ni(111)(face-centered cubic lattice structure of Ni), Ni(200) and Ni(220). The Ni grain size of RN10% catalyst is smaller than others, with specific surface area of 58.07 m~2/g, with moderate leaching amount of Al. Evaluation results show that the hydrogenation performance of RN10% is the best with the BYD conversion of 37.46%, the BED selectivity and yield of 91.73% and 34.36%, respectively. It is related to the smallest size of Ni grains in the active component of the sample, the residual Ni_2Al_3 phase as the "structural promoter", the largest specific surface area, and the moderate Al leaching content.
Raney-Ni catalysts were prepared by leaching commercial Ni-Al alloy(Particle size 180-250 μm) with different mass fractions(5%-20%) of NaOH solution. Effects of different alkali concentrations on the structure and catalytic performance of Raney-Ni catalysts were investigated by XRD, TEM, N_2 adsorption-desorption, EDS and 1,4-butynediol(BYD) hydrogenation to prepare 1,4-butene glycol(BED). Results show that the characteristic peaks of the active component Ni appearing at 2θ is 44.3°, 51.7° and 76.1° for the RN10% catalyst are attributed to Ni(111)(face-centered cubic lattice structure of Ni), Ni(200) and Ni(220). The Ni grain size of RN10% catalyst is smaller than others, with specific surface area of 58.07 m~2/g, with moderate leaching amount of Al. Evaluation results show that the hydrogenation performance of RN10% is the best with the BYD conversion of 37.46%, the BED selectivity and yield of 91.73% and 34.36%, respectively. It is related to the smallest size of Ni grains in the active component of the sample, the residual Ni_2Al_3 phase as the "structural promoter", the largest specific surface area, and the moderate Al leaching content.
引文
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[16]LEI Hao,SONG Zhen,TAN Dali,et al.Preparation of novel Raney-Ni catalysts and characterization by XRD,SEM and XPS[J].Applied Catalysis A:General,2001,214(1):69-76.
[17]LI H,ZHAO Y,GAO C,et al.Study on deactivation of Ni/Al2O3 catalyst for liquid phase hydrogenation of crude 1,4-butanediol aqueous solution[J].Chemical Engineering Journal,2012,181(1):501-507.
[18]江志东,陈瑞芳,王金渠.雷尼镍催化剂[J].化学工业与工程,1997,14(2):25-34.(JIANG Zhidong,CHEN Ruifang,WANG Jinqu.Raney-Ni catalyst[J].Chemical Industry and Engineering,1997,14(2):25-34.)
[19]寇智宁.多相态条件下雷尼镍在环己烷连续脱氢反应过程中的催化活性和失活现象研究[D].杭州:浙江大学,2013.
[20]LEI Hao,SONGZhen,BAO Xinhe,et al.XRD and XPS studies on the ultra-uniform Raney-Ni catalyst prepared from the melt-quenching alloy[J].Surface and Interface Analysis,2010,32(1):210-213.
[2]陈海红.1,4-丁二醇生产工艺及其技术进展[J].精细石油化工进展,2014,15(1):46-49.(CHEN Haihong.Production process and its technical progress of1,4-butanediol[J].Advances in Fine Petrochemicals,2014,15(1):46-49.)
[3]周树理.1,4-丁二醇生产技术及市场前景分析[J].当代石油化工,2014,22(6):35-40.(ZHOU Shuli.Technology and market prospects of 1,4-butanediol[J].Petroleum Petrochemical Today,2014,22(6):35-40.)
[4]刘响,廖启江,张敏卿.1,4-丁炔二醇加氢过程研究进展[J].化工进展,2017,36(8):2787-2797.(LIUXiang,LIAO Qijiang,ZHANG Minqing.Research progress of 1,4-butynediol hydrogenation process[J].Chemical Industry and Engineering Progress,2017,36(8):2787-2797.)
[5]LOW F G.Hydrogenation debutynediol aqueux sur catalyze nickel-aluminum:BE,745225[P].1969.
[6]BECKER R,BROCKER F J,KAIBEL G,et al.Process for preparing 1,4-butanediol by catalytic hydrogenation of1,4-butinediol:US,6262317[P].2001.
[7]EUGENE V H,WALDO R D.Raney nickel catalysts:BE,745225[P].1983.
[8]孟琦,吴跃东,万颖,等.用超声波技术制备的Raney Ni催化剂及其催化加氢活性[J].催化学报,2004,25(7):529-532.(MENG Qi,WU Yuedong,WAN Ying,et al.Preparation of Raney-Ni by ultrasonic wave and its catalytic activity in benzene hydrogenation[J].Chinese Journal of Catalysis,2004,25(7):529-532.)
[9]LEI He,HUANG Yanqiang,WANG Aiqin et al.H2Production by selective decomposition of hydrous hydrazine over Raney-Ni catalyst under ambient conditions[J].American Institute of Chemical Engineers,2013,59(11):4297-4302.
[10]雷浩.快凝Ni-Al合金结构及衍生骨架Ni催化剂加氢特性的研究[D].北京:中国科学院研究生院,2003.
[11]尾崎萃.催化剂手册[M].北京:化学工业出版社,1982:210-223.
[12]莫文龙,马凤云,刘月娥,等.焙烧温度对CO2-CH4重整制合成气NiO/γ-Al2O3催化剂性能的影响[J].无机材料学报,2016,31(3):234-240.(MO Wenlong,MAFengyun,LIU Yue′e,et al.Influence of calcination temperature on performance of NiO/γ-Al2O3catalyst for CO2-CH4reforming to produce syngas[J].Journal of Inorganic Materials,2016,31(3):234-240.)
[13]莫文龙,肖艳,马凤云,等.焙烧条件对浆态床CO甲烷化Ni-Al2O3催化剂性能的影响[J].燃料化学学报,2018,46(1):84-91.(MO Wenlong,XIAO Yan,MAFengyun,et al.Influence of calcination conditions on the performance of Ni-Al2O3catalyst for CO methanation in slurry-bed reactor[J].Journal of Fuel Chemistry and Technology,2018,46(1):84-91.)
[14]XU Junke,ZHOU Wei,WANG Jihui,et al.Characterization and analysis of carbon deposited during the dry reforming of methane over Ni/La2O3/Al2O3catalysts[J].Chinese Journal of Catalysis,2009,30(11):1076-1084.
[15]谢琅.3,5-二羟基苯甲酸催化加氢制备3,5-二氧代环己烷羧酸的研究[D].天津:天津大学,2004.
[16]LEI Hao,SONG Zhen,TAN Dali,et al.Preparation of novel Raney-Ni catalysts and characterization by XRD,SEM and XPS[J].Applied Catalysis A:General,2001,214(1):69-76.
[17]LI H,ZHAO Y,GAO C,et al.Study on deactivation of Ni/Al2O3 catalyst for liquid phase hydrogenation of crude 1,4-butanediol aqueous solution[J].Chemical Engineering Journal,2012,181(1):501-507.
[18]江志东,陈瑞芳,王金渠.雷尼镍催化剂[J].化学工业与工程,1997,14(2):25-34.(JIANG Zhidong,CHEN Ruifang,WANG Jinqu.Raney-Ni catalyst[J].Chemical Industry and Engineering,1997,14(2):25-34.)
[19]寇智宁.多相态条件下雷尼镍在环己烷连续脱氢反应过程中的催化活性和失活现象研究[D].杭州:浙江大学,2013.
[20]LEI Hao,SONGZhen,BAO Xinhe,et al.XRD and XPS studies on the ultra-uniform Raney-Ni catalyst prepared from the melt-quenching alloy[J].Surface and Interface Analysis,2010,32(1):210-213.