CF自由基5pπE2Пr(ν’=1)←X2П(ν’’=0)带的转动分析

The two-photon resonance-enhanced multiphoton ionization spectrum between 285 and 288.5 nm of the 5pπE2Πr(v’=1)←X2Πr(v’’=0) band of CF radical is reported. The band is rotationally analyzed, and the spectroscopic constants of the state are first derived: σ0 = 69566.38±0.52 cm-1, A'v= 46.4±0.3 cm-1, B'v= 2.565±0.017 cm-1, D' v = (8.6±1.2)×10-6cm-1.     

利用生物质气化合成气在FeCuZnAlK催化剂上高效制备清洁生物燃料

研究了生物质气化合成气在Fe_1.5Cu₁Zn₁Al₁K_0.117催化剂上高效转化为清洁生物燃料的合成过程. 利用生物质气化合成气合成的生物燃料最大产率为1.59 kg/(kgcatal·h), 其中醇占0.57 kg/(kgcatal·h), 液体烃占1.02 kg/(kgcatal·h). 在生物燃料中, 醇类产物主要为C2⁺醇(主要为C2-C6高碳醇), 其含量占总醇的7     

利用双段床反应器从生物油重整合成气合成甲醇

一种组合了合成气在线调整和甲醇合成的双段床反应器,成功应用于由生物油重整得到的富CO₂合成气的高效合成甲醇．在前段催化床反应器内,富含CO2的原始生物质合成气在CuZnAlZr催化剂的催化作用下可以有效地转化为含CO的合成气．经过450 oC的合成气在线调整之后,CO₂/CO的比率由6.3大幅降至1.2．经过调整后的生物质基合成气在后段催化床反应器内由工业CuZnAl催化剂催化合成甲醇,当反应条件为260 oC 和5.5 MPa时得到每小时每kg催化剂的最大甲醇     

C12A7-Mg催化剂水蒸汽重整生物油、石脑油和CH4制氢

Hydrogen production by catalytic steam reforming of the bio-oil, naphtha, and CH4 was investigated over anovel metal-doped catalyst of (Ca24Al28O64)4+￠4O-/Mg (C12A7-Mg). The catalytic steam reforming wasinvestigated from 250 to 850 ±C in the ˉxed-bed continuous °ow reactor. For the reforming of bio-oil, theyield of hydrogen of 80% was obtained at 750 ±C, and the maximum carbon conversion is nearly close to95% under the optimum steam reforming condition. For the reforming of naphtha and CH4, the hydrogenyield and carbon conversion are lower than that of bio-oil at the same temperature. The characteristics ofcatalyst were also investigated by XPS. The catalyst deactivation was mainly caused by the deposition ofcarbon in the catalytic steam reforming process.     

Effects of Current upon Electrochemical Catalytic Reforming of Anisole

The reforming of anisole (as model compound of bio-oil) was performed over the NiCuZn-Al₂O₃ catalyst, using a recently-developed electrochemical catalytic reforming (ECR). The influence of the current on the anisole reforming in the ECR process has been investigated. It was observed that anisole reforming was significantly enhanced by the current approached over the catalyst in the electrochemical catalytic process, which was due to the non-uniform temperature distribution in the catalytic bed and the role of the thermal electrons orig-inating from the electrified wire. The maximum hydrogen yield of 88.7% with a carbon conversion of 98.3% was obtained through the ECR reforming of anisole at 700 oC and 4 A. X-ray diffraction was employed to characterize catalyst features and their alterations in the anisole reforming. The apparent activation energy for the anisole reforming is calculated as 99.54 kJ/mol, which is higher than ethanol, acetic acid, and light fraction of bio-oil. It should owe to different physical and chemical properties and reforming mechanism for different hydrocarbons.     

在Ni/HZSM-5催化剂上低温水蒸汽重整生物油制氢

We investigated high catalytic activity of Ni/HZSM-5 catalysts synthesized by the impregna-tion method, which was successfully applied for low-temperature steam reforming of bio-oil. The influences of the catalyst composition, reforming temperature and the molar ratio of steam to carbon fed on the stream reforming process of bio-oil over the Ni/HZSM-5 catalysts were investigated in the reforming reactor. The promoting effects of current passing through the catalyst on the bio-oil reforming were also studied using the electrochemical catalytic re-forming approach. By comparing Ni/HZSM-5 with commonly used Ni/Al₂O₃ catalysts, the Ni₂₀/ZSM catalyst with Ni-loading content of about 20% on the HZSM-5 support showed the highest catalytic activity. Even at 450 oC, the hydrogen yield of about 90% with a near complete conversion of bio-oil was obtained using the Ni₂₀/ZSM catalyst. It was found that the performance of the bio-oil reforming was remarkably enhanced by the HZSM-5 supporter and the current through the catalyst. The features of the Ni/HZSM-5 catalysts were also investigated via X-ray diffraction, inductively coupled plasma and atomic emission spectroscopy, hydrogen temperature-programmed reduction, and Brunauer-Emmett-Teller methods.     

多种金属掺杂的镍基催化剂用于中温重整生物油制氢的设计

一种新的由共沉淀法合成的多种金属(铜、镁、铈)掺杂的镍基混合氧化物催化剂,在250～500 oC用于生物油高效重整制氢. 摩尔比为Ni:Cu:Mg:Ce:Al=5.6:1.1:1.9:1.0:9.9的催化剂表现出较高的催化重整活性,在传统的水蒸气重整模式和500 oC条件下,氢产率达82.8%;电催化重整模式中,在400 oC 和3.1 A,氢产率达91.1%.ECR模式中重整温度和通过催化剂电流促进生物油的重整和热裂解.另外催化剂在300～600 oC显示出较高的水煤气变化反应活性,生物油重整过程中催化剂性质的变化利用ICP、XRD、XPS和BET进行了表征. 生物油重整机理基于基元反应、催化剂表征进行了讨论.     

溶胶-凝胶法制备多孔晶体材料C12A7-C1~-

利用溶胶-凝胶法制备了多孔晶体材料C12A7-Cl~-(Ca_(12)Al_(14)O_(32)Cl_2),制备凝胶的原料是四水合硝酸钙、九水合硝酸铝、氯化钙、尿素和乙二醇.混合溶液经过搅拌2-3 h形成溶胶,再经350℃热处理后形成凝胶体,最终在流动氩气气氛中1000℃烧结后得到材料.用X射线衍射,场发射扫描电子显微镜,热重分析,电子顺磁共振和离子色谱等方法表征合成的C12A7-Cl~-多孔晶体材料.结果表明,利用溶胶.凝胶法成功地生成了C12A7结构,氯负离子是材料中存储的主要负离子.此外,从C12A7-Cl~-晶体材料表面发射的氯负离子也被飞行时间质谱观测到.上述结果说明溶胶-凝胶法可被用于制备C12A7-Cl~-晶体材料.     

Ab initio Study of the Potential Energy Surface and Product Branching Ratios for Reaction of O(1D) with C2H5Cl

用QCISD(T)/6-311++G(d,p)//MP2/6-31G(d,p)方法研究了O(1D)与CH3CH2Cl的反应．计算表明此反应存在一个插入-消去机理．此反应先形成IM1和IM2两个中间体,两个中间体再分解成各种产物．用RRKM理论计算了碰撞能分别为0、20.9、41.8、62.7、83.6、104.5和125.4 kJ/mol时通过IM1、IM2分解的各个通道的分支比率．IM1的主要分解产物是HCl,IM2的主要分解产物是CH2OH．因为IM1比IM2稳定,HCl很可能是反应的主要产物．计算结果能够提供反应机理而且可以对以后的实验提供可能的解释．     

用NiCuZnAl催化剂最大化生物油自热水蒸汽重整制氢

在较低的温度下,通过将放热的部分氧化反应和吸热的水蒸汽重整反应耦合起来的自热方式实现了高效的制氢过程. 在氧碳比(O/C)为0.34,水碳比(S/C)为3,温度为600 oC时生物油接近完全转化,得到最高氢产率为64.3%. 自热水蒸汽重整反应条件温度、O/C、S/C、质量空速等可以用来控制反应氢产率和气体产物分布. 对自热过程和普通水蒸汽重整过程做了比较,并对反应机理进行了探讨.