钾改性氧化铝基羰基硫水解催化剂及其失活机理

天然气、油田伴生气、高炉煤气等化工生产过程中伴生COS气体,不仅会腐蚀管道和毒害催化剂,还会严重污染环境并危害人类健康。COS催化水解反应可在温和条件下高效的将COS脱除,是最具应用前景的COS脱除技术之一。碱金属元素因其具有独特的电子供体性质、表面碱性和静电吸附等特性,常被用作助催化剂以提高Al₂O₃的COS催化水解性能。近年来,以钾为助剂改性的Al₂O₃催化剂(K₂CO₃/Al₂O₃)在COS催化水解反应中得到广泛的应用,但由于负载在Al₂O₃上的K物种的组成复杂,目前研究者对K₂CO₃/Al₂O₃催化剂上COS水解机理的理解仍存在一定的困惑和争议。本论文通过湿法浸渍法合成出一系列钾盐和钠盐改性的Al₂O₃催化剂,并利用各类先进的表征技术对这些催化剂进行分析。活性测试表明,以K₂CO₃、K₂C₂O₄、NaHCO₃、Na₂CO₃和NaC₂O₄改性Al₂O₃催化剂均有助于COS的水解。其中K₂CO₃/Al₂O₃拥有最佳的COS水解性能,连续运行20 h后其COS转化率仍高于~93%,远远优于未改性的Al₂O₃ (~58%)。我们利用原位红外光谱和X射线光电子能谱探明了反应过程中催化剂的化学结构特征,阐明了H₂O分子在K₂CO₃/Al₂O₃上的水解作用机制。原位红外表明COS在K₂CO₃/Al₂O₃上的水解过程中形成了硫代碳酸氢盐中间产物。X射线光电子能谱表征证明催化剂的失活主要是因为催化剂表面积累了硫酸盐和单质硫。此外,我们还研究了水蒸气含量对COS水解性能的影响,研究发现,由于H₂O和COS分子在催化剂表面存在竞争吸附,过量的H₂O会引起催化活性的下降。上述研究表明,K₂CO₃/Al₂O₃催化剂上COS水解性能的提高主要是形成了HO-Al-O-K界面活性位。更为重要的是,所制备的催化剂都是在模拟工业工况条件下进行的,这为后续的工业应用提供了宝贵理论指导。本工作为理解助剂钾在Al₂O₃催化剂上COS水解活性的增强提供了新的见解,这为未来设计稳定高效的COS水解催化剂打开了新的发展方向。     

Multi-guasiparticle excitations of ~(91)Ru

The level structure in neutron-deficient nucleus 91Ru was investigated via the 58Ni(36Ar,2 plnγ)Ru reaction at a beam energy of 111 MeV.Charged particles,neutrons,and y-rays were emitted in this reaction and detected by the DIAMANT CsI ball,Neutron Wall,and the EXOGAM Ge clover array,respectively.In addition to the previously reported levels in 91Ru,new low-to-medium spin states were observed.Angular correlation and linear polarization measurements were performed to unambiguously determine spins and parities of the excited states in 91 Ru.The low-spin states of 91 Ru exhibit a scheme of multi-quasiparticle excitations,which is very similar to that of the neighboring N=47 isotone.These excitations have been interpreted in terms of the shell model.The calculations performed in the configuration space(p3/2,f5/2,p1/2,g9/2)reproduce the experimental excitation energies reasonably well,supporting the interpretation of the newly assigned positive-parity states in terms of the three quasiparticle configurationsπ(g9/2)^-2v(g9/2^-1 and v(g9/2)^-3.     

A≈110质量区奇A核形状演化研究

应用E-GOS（E-Gamma Over Spin）曲线方法研究了A≈110质量区奇A核结构随角动量增加的演化, 发现随着角动量的增加原子核的激发特性从振动逐渐演化为转动。 The E-GOS（E-Gamma Over Spin）curves were used to investigate the structure evolution in the odd A nuclei around A≈110 as a function of spin. The result shows that there is a clear transition from vibration to rotation while increasing spin.     

Dipole bands in nucleus ~(139)Pm

High-spin states in nucleus 139Pm have been studied using the reaction 116Cd(27Al,4n)139Pm.Two dipole cascades have been found.Spin and parity assignments were based on the Directional Correlation of Oriented Nuclei(DCO) ratios and systematic behavior in neighboring odd-proton nuclei.The level structures of 139Pm are compared with those of the N =78 isotone 141Eu in which two dipole bands have been confirmed as magnetic rotational bands.The close similarity between them suggests that the dipole bands in 139...     

^209Fr的能级结构研究

利用能量为 90— 1 0 5MeV的16 O束流 ,通过197Au( 16 O ,4n)反应研究了2 0 9　Fr的高自旋态能级结构 .进行了γ射线的激发函数、γ γ延迟符合及γ射线的角分布测量 .首次建立了由 2 1条γ射线构成的2 0 9Fr的能级纲图 ,其中包括一个半寿命为 ( 52± 2 0 )ns的同质异能态 .基于2 0 9Fr与2 0 8Rn低位能级结构的相似性 ,用一个h9/ 2 价质子与2 0 8Rn激发态的弱耦合解释了2 0 9Fr的低位能级结构 .     

Particle-core coupling in 141Nd

High-spin states in 141Nd have been studied using in-beam γ-ray spectroscopic techniques via the 130Te(16O, 5nγ)141Nd reaction. The level scheme of 141Nd has been extended up to an excitation energy of 7614.5 kev including 12 new γ rays deexciting 15 new levels. According to particle-vibrator coupling and semi-empirical shell model calculations, the level structure of 141Nd can be well interpreted by coupling an h11/2 neutron-hole to the respective excited states in 142Nd core.     

169Re的转动带结构研究

利用在束γ谱学方法,通过反应¹⁴⁴Sm(²⁸Si,1p3n)¹⁶⁹Re研究了¹⁶⁹Re的激发态能级结构.实验进行了X-γ符合、γ-γ符合、DCO系数和带内B(M1)/B(E2)比率测量.基于这些测量,建立了组态为π9/2^－[514]的强耦合带和组态为π1/2^－[541]的退耦合带.通过比较¹⁶⁹Re的转动带与邻近奇质子核已知转动带的结构和B(M1)/B(E2)比率,指定了¹⁶⁹Re转动带的组态.实验观测到π9/2^－[514]和π1/2^－[541]转动带的中子AB带交叉的转动频率分别为0.23和0.27MeV.着重讨论了¹⁶⁹Re转动带的中子AB带交叉频率、转动角动量顺排和旋称劈列等,并讨论了奇ARe核转动带结构的系统性     

双奇核142Pm高自旋态能级纲图

利用能量为75—95MeV19F束流,通过反应¹²⁸Te(¹⁹F,5nγ)¹⁴²Pm研究了双奇核¹⁴²Pm的高自旋态能级结构.实验中进行了γ射线的激发函数、γ射线单谱和γγ符合测量.建立了激发能达7030.0keV的¹⁴²Pm的能级纲图,其中包括新发现的25条γ射线和13个新能级.基于实验测量的γ跃迁各向异性度,建议了¹⁴²Pm能级的自旋值.     

Lifetimes of Excited Levels in ^131Ce

The fusion-evaporation reaction ^116Sn (^19F, p3n)^131 Ce at projectile energy of 95 MeV is used to populate high spin states in ^131Ce. The de-exciting γ-rays are detected in γ-γ coincidence measurement with Compton-suppressed BGO-HPGe detectors. Level lifetimes of ^131 Ce were determined by using the Doppler shift attenuation method.The experimental results indicate that collectivity of ^131 Ce is reduced relative to that of ^130Ce and it follows that deformation decreases with increase of the neutron number on the basis of systematic comparison of transition quadrupole moments for the light cerium isotopes.     

利用气体分子相对速度的各向同性导出平均相对速率

首先通过类比发现理想气体分子相对速度分布与速度分布具有相同的函数形式,但是困难在于确定前者的常数因子.我们发现一个常用的公式恰好可以帮助确定这个常数.最终通过类比平均速率的推导直接得到了平均相对速率公式.