Kinetic study of hydrogen sulfide absorption in aqueous chlorine solution

Hydrogen sulfide (H₂S) is currently removed from gaseous effluents by chemical scrubbing using water. Chlorine is a top-grade oxidant, reacting with H₂S with a fast kinetic rate and enhancing its mass transfer rate. To design, optimize and scale-up scrubbers, knowledge of the reaction kinetics and mechanism is requested. This study investigates the H₂S oxidation rate by reactive absorption in a mechanically agitated gas–liquid reactor. Mass transfer (gas and liquid sides mass transfer coefficients) and hydrodynamic (interfacial area) performances of the gas–liquid reactor were measured using appropriated physical or chemical absorption methods. The accuracy of these parameters was checked by modeling the H₂S absorption in water without oxidant. A sensitivity analysis confirmed the robustness of the model. Finally, reactive absorption of H₂S in chlorine solution for acidic or circumneutral pH allowed to investigate the kinetics of reaction. The overall oxidation mechanism could be described assuming that H₂S is oxidized irreversibly by both hypochlorite anion ClO⁻ (k = 6.75 × 10⁶ L mol⁻¹ s⁻¹) and hypochlorous acid ClOH (k = 1.62 × 10⁵ L mol⁻¹ s⁻¹).     

Prediction of shunt currents in a bipolar electrolyzer stack by difference calculus

A model for predicting shunt/leakage currents in a bipolar electrolyzer stack with dual electrolyte inlets and significant amount of gases in the outlet ports and manifold is presented. Model includes electrolyte, manifold and membrane separator as resistance components in the electric circuit analog of the stack. Activation overvoltage associated with electrodes is taken as Tafel-like. Current balance and potential balance equations are applied to the stack and difference calculus is employed to reduce the problem to a set of linear difference equations with constant coefficients. The model is validated with published results and the effect of each resistance component and number of cells on leakage currents in the stack is presented. The U.S. Goverment’s right to retain a non-exclusive, royalty-free license in and to any copyright is acknowledged.     

Construction,structure and photocatalysis of janus nanofiber modified by g-C3N4 nanosheets heterostructure photocatalysts

The construction of photocatalyst with gradient band structure is guided by the principle of band gap engineering. Rational structural design is advanced and applied to construct a new-typed peculiarly structural and functional carbon-based [TiO₂/C]//[Bi₂WO₆/C] Janus nanofiber modified by g-C₃N₄ nanosheets heterostructure photocatalyst (denoted as TB-JgHP). The flexible carbon-based [TiO₂/C]//[Bi₂WO₆/C] Janus nanofiber with one side responding to ultraviolet light and the other capturing visible light is fabricated by conjugate electrospinning, and then g-C₃N₄ nanosheets are uniformly grown in-situ on the surface of the Janus nanofibers by using gas-solid reaction via gasification of urea. The optimized TB-JgHP possesses remarkable hydrogen evolution efficiency (17.48 mmol h⁻¹ g⁻¹) and methylene blue degradation rate (99.2%) under simulated sunlight illumination for 100 min, demonstrating prominent dual-functional characteristics. The enhanced photocatalytic performance benefits from the unique Janus structure as well as the synergistic effects among the triple heterostructures of TiO₂ and Bi₂WO₆, g-C₃N₄ and TiO₂, g-C₃N₄ and Bi₂WO₆. The formation of gradient band structure among heterostructures is more conducive to the multi-step separation of photo-induced electron-hole pairs and more effective absorption of light. Further, flexible self-standing carbon-based photocatalysts not only have outstanding electron transport performance, but also are easy to separate from solution with preeminent recyclable stability. Based on a series of characterization techniques, it is further proved that TB-JgHP has higher carrier separation efficiency than the counterpart contrast samples. The formation mechanism of TB-JgHP is proposed, and the construction technique is established. The design philosophy and construction technique presented in this work pave a new avenue for research and development of other heterostructure photocatalysts.     

Promoted hydrolysis performances and mechanism of Si-NaBH4-AlCl3 in deionized water

Si-based hydrolysis material system can be used in mobile/portable hydrogen source applications connected to fuel cells but is limited by alkaline solutions. In the present research, we reported an acid/alkaline free hydrolysis system combining silicon with NaBH₄. Samples with different ratios between Si and NaBH₄ are prepared via high energy ball milling and hydrolyzed in deionized water at different temperatures. Synergetic effect between silicon and NaBH₄ was found in the hydrolysis process. 2Si-NaBH₄ sample displays the best hydrolysis performances with the hydrogen yield of 1594 ml⋅g⁻¹ in deionized water at 70 °C. Thereafter, AlCl₃ is added into the 2Si-NaBH₄ sample to further improve its comprehensive properties. The effect of AlCl₃ content and promotion mechanism of the reaction are explored. 2Si-NaBH₄–5 wt% AlCl₃ sample shows a significant improvement with a high hydrogen yield of 1689 ml·g⁻¹ in deionized water at 70 °C and a corresponding conversion rate of 95.8%, indicating that the Si-NaBH₄-AlCl₃ composite is promising to be a hydrogen source in applications of mobile/portable fuel-cell-powered facilities.     

Effect of carriers on deposition morphologies and catalytic performances of NiCo2O4

In this study, NiCo₂O₄ with different morphologies were fabricated using carriers by homogeneous coprecipitation combined with a sintering method. The phase and microstructure were characterized by XRD, SEM, EDS, TEM and BET, and the catalytic performances were investigated by NaBH₄ hydrolysis experiments. These studies revealed that the deposition morphology of NiCo₂O₄ can be adjusted by using different kinds of carrier templates, and the supported NiCo₂O₄ samples presented the pine-needle-like, network-like, ball-cactus-like and dandelion-like morphologies respectively. The optimal catalytic activity, durability and stability make the network-like NiCo₂O₄ an appropriate catalyst for hydrogen generation of NaBH₄ hydrolysis. It was found that the network-like NiCo₂O₄ is the most reusable and durable catalyst for ten consecutive cycles and 100% hydrogen generation conversion rate without obvious decrease among these morphologies.     

The use of channel flow cells for electrochemical kinetic studies in high temperature aqueous solutions

It has been shown that, for the case of one-step reactions of arbitrary order, the relationship between the average current density and the limiting current density on a working electrode mounted on the inner radius of an annular flow channel of arbitrary length obeys, with great accuracy, the same relations as does a reaction on a uniformly accessible surface. This allows us to combine the advantages of non-uniformly accessible surfaces (high sensitivity, and no need to use rotating contacts) with the advantages of uniformly accessible surface systems (simple treatment of experimental data). This feature can be very important when investigating systems at high temperatures and pressures, where RDEs are difficult to employ. Using this approach, and by employing previously measured polarization data, the kinetic parameters (exchange current density and anodic transfer coefficient) for the oxidation of hydrogen on platinized nickel in 0.1 M NaOH + 0.7 × 10⁻³ m H₂ at temperatures between 25 °C and 300 °C have been derived. The anodic transfer coefficient is found to be almost temperature independent with a value of 0.43. The exchange current density displays Arrhenius behavior with temperature, increasing from 1.9 × 10⁻⁴ A cm⁻² at 25 °C to 3.9 × 10⁻³ A cm⁻² at 300 °C.     

气相法聚乙烯熔融指数的影响因素及控制

文章针对目前全密度聚乙烯装置运行操作中的中控产品质量指标——熔融指数,做了较全面的分析。阐述了聚乙烯分子量及支链数与熔融指数的关系。结合装置生产实际,讨论了各种反应条件的变化对熔融指数的影响,其中,重点分析了氢气对熔融指数的调节作用,并对熔融指数的控制做了实例分析。     

In‐situ Remediation of Hydrogen Fluoride During a Detonation Event

Hydrogen fluoride (HF) is a known product from the combustion or detonation of explosives formulated with fluoropolymer binder systems. This presents the user with elevated risk levels during unintended combustion events or detonations in confined situations. In an effort to remediate the production of HF, calcium disilicide (CaSi₂) was added to explosive formulations and the amount of HF formed was monitored. Viton A/calcium disilicide mixtures were made and the thermal decomposition characteristics studied using thermal gravimetric/differential thermal analysis (TG/DTA). The activation energy ranged from 145–190 kJ mol⁻¹, indicative of C F scission in the Viton A binder prior to calcium fluoride formation. An energetic formulation was prepared which consisted of approximately a 5/3 mass ratio of Viton A/CaSi₂. Combustion calorimetry in oxygen and air, and subsequent analysis of the residues using X‐ray diffraction (XRD) showed evidence of calcium fluoride (CaF₂) formation. The decrease in HF formation was determined by trapping off gases and subsequent analysis in anion exchange chromatography of combustion and detonation products. Upon introduction of calcium disilicide into the formulation, a small decrease in HF formation was observed along with appearance of calcium fluoride and free Si in the residue. Such products are consistent with the mechanism following a general decomposition path of 2F⁻+CaSi₂→CaF₂+2Si. Under detonation conditions, the decomposition path followed nearly the same route with a net ca. 30 % decrease in HF formation, but with a portion of the silicon oxidizing slightly further to SiO₂.     

Yield of hydrogen during cathodic polarisation of Al–Sn alloys

The results presented in this paper were obtained with three Al–Sn binary alloys (0.09, 0.2 and 0.4 wt.% Sn, respectively) that had been prepared on super pure (99.999%) Al base. The yield of hydrogen evolved during cathodic polarisation of Al–Sn alloys in a 2 M NaCl solution was measured volumetrically as a function of current density, temperature and tin content in the alloy. The yield was established to be somewhat below 2 at all current densities and at low temperatures, while with increasing temperature it approached the value of 4. With the increase of tin content in the alloy, the yield of hydrogen decreases, which depends on the degree of hyperactivity that occurs in Al–Sn alloys in the region of high cathodic potentials.     

Compromise Between Bromate Ion Formation and Pesticides Degradation and/or Manganese Removal

Ozonation is a widely used technology within the water industry. Bromate ion formed by oxidation of water containing bromide ion was studied with the Gas Ozone Test and Pilot Scale Ozonation. Bromate ion formation was investigated along with the removal of triazines and/or manganese. Under identical conditions of ozonation, BrO₃ ^? formation is specific for each water and depends on parameters such as Total Organic Carbon, UV absorbance at 254 nm, applied ozone and ozone residual. Pesticides degradation by ozonation alone cannot be achieved without the formation of BrO₃ ^? at a high concentration. Hydrogen peroxide, at a constant ozone dose, reduces the BrO₃ ^? formation. However, even with the use of hydrogen peroxide, the concentration of BrO₃ ^? can remain in excess of the provisional Maximum Contaminant Level (10 μg/L). For certain types of water, pesticide degradation is difficult to achieve if the MCL for BrO₃ ^? has to be met. Manganese oxidation by ozone appears to be achieved without high bromate formation; indeed the presence of manganese hinders BrO₃ ^? formation.