Dipole moment derivatives of H2O and H2S

The dipole and quadrupole derivatives of H₂O and H₂S are calculated analytically, using the coupled Hartree—Fock method first proposed by Gerratt and Mills. The greater efficiency, of this method allows SCF wave functions very, close to the Hartree—Fock limit to be used. Agreement, with experimental data is good.     

A quantum-mechanical study of the lone-pairs in H2O and H2S

It is shown from SCF-MO studies using localised orbitals that the angles between the lone-pairs in H₂O and H₂S are 115° and 127°, in agreement with the qualitative predictions of the Sidgwick-Powell theory.     

Collisional ionization of fast K atoms by H2S and D2S

The process K + H₂S/D₂S → HS^?/DS^? + K⁺+ H/D has been investigated for K impact energies from near threshold to ≈100 eV. Positive and negative ion energy spectra have been obtained in the forward direction. The threshold for HS^? or DS^?production corresponds to the HS^?/DS^?+ H/D limit of the ²A₁ H₂S^?/D₂S^? state at 1.55 eV.     

不同P负载量对Co-Mo/γ-Al_2O_3煤焦油加氢脱硫性能影响的研究

以分步浸渍法在固定MoO_3、CoO含量(质量分数)为13.50%、2.11%的条件下,通过改变磷酸浓度,制备了不同P负载量的Co-Mo/γ-Al_2O_3催化剂。考察了不同的P负载量催化剂对内蒙古赤峰中温煤焦油加氢脱硫性能的影响。并以NH3程序升温脱附(NH_3-TPD)、X射线衍射(XRD)、X射线光电子能谱(XPS)等手段对催化剂的结构性质进行了表征。结果表明,适宜的P负载量可减弱活性组分与载体间的相互作用,利于活性组分均匀分散在载体表面,改善了催化剂的还原、硫化性能和酸性分布,从而提高了催化剂的加氢脱硫活性。当磷酸质量分数为4%时,催化剂表现出最佳的加氢脱硫性能,硫脱除率达到96.98%。不同P负载量Co-Mo/γ-Al_2O_3催化剂加氢脱硫活性对应的磷酸浓度顺序为:4%2%6%1%08%。     

金前驱液pH值对Au-Pd/SiO2催化剂上噻吩加氢脱硫活性的影响

考察了金前驱液的pH值对Au-Pd/SiO2双金属催化剂用于噻吩加氢脱硫反应活性的影响,应用N2吸附,X-光粉末衍射(XRD)、程序升温还原(TPR)等技术对该催化剂的物性与结构进行了表征.发现当金前驱液的pH值为7时制得的双金属催化剂具有较好的加氢脱硫活性,并具有最小的孔径,该催化剂以PdO相与Au0相共存.与Pd/SiO2催化剂相比,Au-Pd/SiO2催化剂的稳定性明显提高.虽然AuxPdy合金相的生成对提高双金属催化剂的脱硫活性不利,但能明显改善催化剂的抗硫中毒能力.     

H2S/H2硫化温度对MoP/SiO2催化剂硫醚化性能的影响

以负载磷酸钼为前驱体,采用程序升温还原法制备了MoP/SiO₂催化剂,以体积分数3%H₂S/H₂对其进行了硫化处理,利用XRD、CO化学吸附、NH₃-TPD、HRTEM-EDX、ICP-AES以及XPS等手段对催化剂进行了表征,研究了硫化温度对MoP/SiO₂催化剂结构和异戊二烯与正丁硫醇硫醚化性能的影响。结果表明,即使在400℃硫化处理也未改变MoP/SiO₂催化剂中MoP体相结构;随着硫化温度提高,催化剂表面酸量增加、金属位数量减少,降低了催化剂C-S键氢解及异戊二烯深度加氢活性,但同时也提高了催化剂烯烃聚合活性。经120℃硫化处理的MoP/SiO₂兼具较佳硫醚化及异戊二烯选择加氢性能。     

The solubility of H2S in liquid sulfur

The need for fundamental data describing the dissolution of hydrogen sulfide, H₂S, in Claus recovered liquid sulfur prompted an examination of equilibrium H₂S solubility at typical industrial condensation temperatures and partial pressures. An FT/IR absorption technique has been described and new H₂S solubility measurements have been reported for partial H₂S pressures from 0.4 to 56 kPa and temperatures from 120 to 155 °C. The measurements were combined with previously reported values for atmospheric pressures of H₂S and used to calibrate a semi-empirical equation for the Henry's law solubility in liquid sulfur as a function of temperature. Estimations were compared to Claus plant field data and appear to underestimate the H₂S solubility for the first and second catalyst condenser stages. This underestimation was attributed to rapid condensation resulting in super-saturation of the recovered sulfur liquid, or an inaccurate measurement of the condensation temperatures.     

Promoter effect of nickel in thiophene hydrodesulfurization as monitored by sulfur uptake and cyclohexane conversion

Hydrodesulfurization (HDS) activity and activation energy (ε′_TH) values were determined and compared with irreversible sulfur uptake (S_irr) by 5 Al₂O₃-supported (MoO_x, Ni and three NiMoO_x) catalysts and, in unsulfided form with the cyclohexane conversion activity. Synergy between Ni and Mo in catalytic activity and a correlation between HDS activity and the amounts of S_irr was found. Some explanations for the differences in catalytic behavior of the different samples are presented.     

丙炴醇聚合膜对铁在酸性溶液中的缓蚀作用

The formation of polymer film of propargyl alcohol(PA) and its protective ability against corrosion in Fe/H_2SO_4 and Fe/H_2SO_4+H_2S systems have been investigated using impedance measurement. The composition and morphology of the corrosion surface of iron, on which PA polymerized at different bines, were obtained with the aid of SEM and AFM as well as EDX. The results showed that PA polymerized into compact polymer film in Fe/H_2SO_4 and Fe/ H_2SO_4 + H_2S systems, which made iron surface smooth and have a morphologies of regular square structure in microscopic level. In Fe/H_2SO_4 system, macroscopic continuous polymer film of PA was not formed leading to local corrosion on electrode surface. In Fe/H_2SO_4 +H_2S system, the adsorption of H_2S and HS - on electrode surface slowed down the formation of polymer film of PA. However, the iron sulfide, produced after a longer time, increased the continuity of the polymer film of PA and therefore, the polymer film could perform its long-te...更多rm inhibition action.     

The diffusion coefficient of H2S in liquid sulfur

The diffusion coefficient of H₂S in liquid sulfur is a key kinetic parameter that has been missing in literature. In this paper, a pressure decay method was applied to measure the diffusion coefficients of H₂S in liquid sulfur at 403 and 423 K. This pressure decay process was then modeled by taking the simultaneous diffusion and reversible chemical reactions between H₂S and liquid sulfur into consideration. The diffusion coefficients and reaction rate constants were numerically determined by fitting theoretical curves to experimental data using Finite Element Method and Genetic Algorithm. The solubility of H₂S in liquid sulfur at 403 and 423 K was also calculated and the results agreed with the semi-empirical correlation lately reported in literature. This study further extended the validity of the correlation to higher partial H₂S pressure conditions.     

Molecular simulation on hydrodesulfurization of thiophenic compounds over MoS2 using ZINDO

In order to develop a fundamental understanding of the HDS mechanism of thiophenic compounds over molybdenum disulfide (MoS₂), a molecular simulation of the hydrodesulfurization (HDS) of thiophenic compounds over MoS₂ has been performed using Zerner's Intermediate Neglect of Differential Overlap (ZINDO) program. On the basis of the calculated edge structure, stoichiometry of MoS₂, shape of the crystal, and the size corresponding to real MoS₂ particles, a single-slab cluster, Mo₂₇S₅₄, has been proposed for modeling the highly dispersed MoS₂. The proposed cluster is a regular hexagon with ( 010) and (30 0) edge planes only. According to the calculated electronic properties of the surface, the coordinately unsaturated Mo_IV in the (30 0) plane is expected to be the active site for hydrogenation of thiophenic and aromatic compounds. The most stable adsorption configuration of thiophene on the Mo_IV is a flat adsorption configuration via the η⁵-bound coordination, whereas the most stable adsorption configuration of tetrahydrothiophene (THT) on the Mo_IV is a tilted adsorption configuration via the S-bound coordination. HDS mechanism of thiophene through the hydrogenation pathway over the (30 0) plane of MoS₂ is discussed according to quantum chemical insights in combination with experimental results from the literature.     

An unusual oxidation-dealkylation of 3,4-dihydropyrimidin-2(1H)-ones mediated by Co(NO3)2·6H2O/K2S2O8 in aqueous acetonitrile

4-Aryl-6-methyl-3,4-dihydropyrimidin-2(1H)-one (DHPM) scaffolds of Biginelli type were oxidized using Co(II)/S₂O₈²⁻ and the reaction afforded 6-unsubstituted pyrimidin-2(1H)-ones through an unprecedented dealkylation process. 4-Alkyl DHPMs under similar conditions afforded yet another unusual product, ethyl tetrahydropyrimidin-2,4(1H,3H)-dione-5-carboxylate.     

Mono- and heterometallic carbonyl precursor based RuMo/Al2O3 catalysts: hydrodesulfurization activity and temperature programmed studies

The effects of preparation process and starting material on hydrodesulfurization (HDS) activity of alumina supported ruthenium, molybdenum and ruthenium–molybdenum hydrotreating catalysts were investigated. Conventional impregnation method and gradual gas phase adsorption were compared as a preparation route. The HDS tests showed that controlled gas phase deposition is advantageous in the preparation of the monometallic catalyst systems. The most promising HDS activity was achieved with the RuMo/Al₂O₃ catalyst prepared from binuclear organometallic complex. This suggests that the direct ruthenium–molybdenum bond in the structure of the catalyst precursor favors the formation of highly active surface phase. The oxidation and reduction behavior of the catalysts was studied by oxygen pulse chemisorption (PCO) and temperature programmed reduction (TPR). A clear relationship was observed between the method of preparation and the reactivity of the surface species.     

Activity of MoSe2/Al2O3 catalysts in decomposition of thiophene and selenophene

The rate of thiophene decomposition was shown to be independent of the type of chalcogens used in catalysts MoX₂/Al₂O₃, where X = S, Se. On the contrary, the rate of selenophene decomposition was shown to be higher on catalysts MoSe₂ than that on MoS₂. This observation suggests that the decomposition proceeds on anion vacancies. The decomposition of either thiophene over MoSe₂ or selenophene over MoS₂ results in the formation of partially substituted chalcogenides. At that, the molar ratios of the substituted chalcogen to Mo were shown to coincide in both cases. The fact that the rate of the thiophene decomposition does not depend on the degree of anion exchange indicates that the decomposition is not associated with hydrogenolysis.     

清代北京私家名园万柳堂考述(上)*

核电站发生严重事故时,会产生大量氢气,需要进行处理,而氢气催化氧化技术是一种较好的处理方式可用于核电站的氢气处理,其关键是依靠氢氧化合催化剂得以实现.我们综述了催化剂的活性成分、载体和制备方法,以及催化剂的改性方法对催化性能的影响.目前催化剂的改性研究主要集中于对金属粒子的尺寸和分散性的改善,尽可能利用载体表面的金属粒子以获得高的催化剂活性.同时,催化反应容易受到"有毒"物质干扰,可以通过活性成分合金化、改变负载在载体表面的金属粒子形貌(如核壳结构)等方式改善,从而达到提升催化活性的目的.     

Kinetic studies of thiolane synthesis from tetrahydrofurane and H2S

Kinetic studies of tetrahydrofuran reaction with H₂S were carried out in a flow-circulation reactor. Presumably, the reaction takes place through dissociative chemisorption of reactants and the interaction of surface structures formed to produce thiolane and water. A kinetic equation that agrees with the suggested mechanism has been derived.

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- H₂S. , . , .

     

Activity of catalysts in 1-butanol reaction with H2S

Reaction of 1-butanol with H₂S has been studied at 300 °C and 0.1 MPa on catalysts of various composition. The catalysts that contain mainly strong proton sites on their surface accelerate dehydration of alcohol alone. In the presence of catalysts possessing acidic and basic Lewis sites 1-butanethiol is formed. Reaction rate increases as the concentration and strength of Lewis acid sites increase.     

Electrochemical behaviour of iron in H2SO4 containing thiophene

The effect of thiophene on the corrosion of iron in H₂SO₄ has been studied by double-layer capacity and polarisation measurements. No change in mechanism was observed by the addition of thiophene, but a significant decrease in the rate of hydrogen evolution was observed. The inhibitor concentration was found to have a significant influence on the behaviour of the open-circuit capacitance, while the change in potential was small. The results show that thiophene is adsorbed on the iron surface according to the Temkin isotherm. The inhibitor efficiencies, as determined from current-voltage curves and the weight loss method, were consistent.     

Co-aggregation of fullerene C60 and thiophene in the non-aromatic solvent cyclohexene

Co-aggregation of fullerene C₆₀ and thiophene has been studied calorimetrically in cyclohexene at 25 °C. The total aggregation heat is found to depend on initial concentration of thiophene and fall between −1.9 and −5.8 kJ mol⁻¹. The corresponding thiophene/fullerene molar ratio (“co-aggregation number”) ranges from 7 to 12. The data are rationalized by formation of heteromolecular nanoaggregates with intermolecular contacts of both fullerene–thiophene and fullerene–fullerene types. A physical model describing interaction between fullerenes and π-donors in solution is substantiated and used to explain heterogeneity of composites containing fullerenes.     

H2O, H2S与双卤分子间相互作用的电子密度拓扑研究

运用量子化学微扰理论MP2和密度泛函B3LYP方法, 采用6-311＋＋G(d,p)基组, 对H₂O, H₂S与双卤分子XY (XY＝F₂, Cl₂, Br₂, ClF, BrF, BrCl)形成的卤键复合物进行构型全优化, 并计算得到了这些体系的分子间相互作用能. 利用电子密度拓扑分析方法对卤键复合物的拓扑性质进行了分析研究, 探讨了该类分子间卤键的作用本质. 结果表明, 形成卤键后, 作为电子受体的双卤分子X—Y键长增长, 振动频率减小. 复合物体系中的卤键介于共价键与离子键之间, 偏于静电作用成分为主.