Tungsten(VI) oxide supported rhodium nanoparticles: Highly active catalysts in hydrogen generation from ammonia borane

Herein, we report the use of tungsten(VI) oxide (WO₃) as support for Rh⁰ nanoparticles. The resulting Rh⁰/WO₃ nanoparticles are highly active and stable catalysts in H₂ generation from the hydrolysis of ammonia borane (AB). We present the results of our investigation on the particle size distribution, catalytic activity and stability of Rh⁰/WO₃ catalysts with 0.5%, 1.0%, 2.0% wt. Rh loadings in the hydrolysis reaction. The results reveal that Rh⁰/WO₃ (0.5% wt. Rh) is very promising catalyst providing a turnover frequency of 749 min^?1 in releasing 3.0 equivalent H₂ per mole of AB from the hydrolysis at 25.0 °C. The high catalytic activity of Rh⁰/WO₃ catalyst is attributed to the reducible nature of support. The report covers the results of kinetics study as well as comparative investigation of activity, recyclability, and reusability of colloidal(0) nanoparticles and Rh⁰/WO₃ (0.5 % wt. Rh) catalyst in the hydrolysis reaction.     

Development of catalysts for hydrogen generation from hydride compounds

Catalytic hydrolysis of NaBH₄ and NH₃BH₃ has been studied. It was shown that the nature of the support and the active component of the catalyst affect the H₂ generation rate. Despite similar sizes of rhodium particles formed on the surface of different supports (γ-Al₂O₃, TiO₂, carbon), their reactivity is different. Rh/TiO₂ with low rhodium concentration (1 wt.%) is the most active catalyst both in the hydrolysis of NaBH₄ and NH₃BH₃. The obtained results show that the rhodium chloride interaction with titania determines the reactivity of rhodium particles formed under action of NaBH₄ medium. TEM, DRS UV–vis and XPS were used to characterize the catalysts.     

硫酸钙氨法制取硫酸钾新工艺的实验研究

利用K2 +2 ,Ca2 +/ /SO2 -4 ,Cl2 -2 ,NH3—H2 O混合体系相图作为工艺指导 ,进行硫酸钙制取硫酸钾工艺的相图研究和分析 ,确定实验优选因素及水平并进行正交实验 ,根据实验结果进行极差分析 ,得出新的结论。合适的工艺条件为 :氨浓度为 40 % ,配料比n( 2KCl) :n(CaSO4 ·2H2 O)为 1:1,反应温度为 5℃ ,反应时间为 1h。     

Inhibiting and deactivating effects of water on the selective catalytic reduction of nitric oxide with ammonia over MnOx/Al2O3

The effect of water on the selective catalytic reduction (SCR) of nitric oxide with ammonia over alumina supported with 2–15 wt.-% manganese oxide was investigated in the temperature range 385–600 K, with the emphasis on the low side of this temperature window. Studies on the effect of 1–5 vol.-% water vapour on the SCR reaction rate and selectivity were combined with TPD experiments to reveal the influence of water on the adsorption of the single SCR reactants. It turned out that the activity decrease due to water addition can be divided into a reversible inhibition and an irreversible deactivation. Inhibition is caused by molecular adsorption of water. TPD studies showed that water can adsorb competitively with both ammonia and nitric oxide. Additional kinetic experiments revealed that adsorbed ammonia is present in excess on the catalyst surface, even in the presence of water. Reduced nitric oxide adsorption is responsible for the observed reversible decrease in the reaction rate; the fractional reaction order changes from 0.79 in the absence of water to 1.07 in its presence. Deactivation is probably due to the dissociative adsorption of water, resulting in the formation of additional surface hydroxyls. As the amount of surface hydroxyls formed is limited to a saturation level, the deactivating effect on the catalyst is limited too. The additional hydroxyls condense and desorb in the temperature range 525–775 K, resulting in a lower degree of deactivation at higher temperature. A high temperature treatment at 775 K results in a complete regeneration. The amount of surface hydroxyls formed per unit surface area decreases at increasing MnO_x-loading. The selectivity to the production of nitrogen is enhanced significantly by the presence of gas phase water.     

Heat transfer enhancement by Marangoni convection in the NH3–H2O absorption process

The objectives of this paper are to quantify the effect of Marangini convection on the absorption performance for the ammonia–water absorption process, and to visualize Marangoni convection that is induced by adding a heat transfer additive, n-octanol. A real-time single-wavelength holographic interferometer is used for the visualization using a He–Ne gas laser. The interface temperature is always the highest due to the absorption heat release near the interface. It was found that the thermal boundary layer (TBL) increased faster than the diffusion boundary layer (DBL), and the DBL thickness increased by adding the heat transfer additive. At 5 s after absorption started, the DBL thickness for 5 mass% NH₃ without and with the heat transfer additive was 3.0 and 4.5 mm, respectively. Marangoni convection was observed near the interface only in the cases with heat transfer additive. The Marangoni convection was very strong just after the absorption started and it weakened as time elapsed. It was concluded that the absorption performance could be improved by increasing the absorption driving potential (x_vb−x_vi) and by increasing the heat transfer additive concentration. The absorption heat transfer was enhanced as high as 3.0–4.6 times by adding the heat transfer additive that generated Marangoni convection.     

Reactively sputtered MoO3 films for ammonia sensing

We report the gas-sensing properties of ion-beam sputter deposited MoO₃ thin-films. The change in the DC conductivity was measured in dry N₂ with 10% O₂ in the presence of up to 490 ppm of NH₃, NO, NO₂, C₃H₆, CO and H₂. At ∼440 °C the film was found to be very sensitive to NH₃, with 490 ppm increasing the conductivity by approximately a factor of 70. This was approximately 17 times greater than the response to the other gases. The NH₃ response was strongly affected by the accompanying levels of O₂, NO₂ and H₂O. For example, changing the accompanying O₂ levels from 1% to 20% decreased the NH₃ response by approximately a factor of 20. Similarly, the presence of 100 ppm NO₂ (in 10% O₂) decreased the NH₃ response by approximately a factor of three, and 1% water vapor decreased it by more than a factor of two. The NH₃ response, however, was relatively unaffected by 100 ppm of accompanying NO, C₃H₆, CO or H₂. XPS measurements show that the increased conductivity in the presence of NH₃ was also accompanied by a partial reduction of the surface MoO₃. We observed an increase in the resistance of the films after extended time at elevated temperatures.     

Energy and economic analysis of a hydrogen and ammonia co-generation system based on double chemical looping

In this work, a model of hydrogen production by double chemical looping is introduced. The efficiency benefit obtained was investigated. The chemical looping hydrogen generation unit is connected in series to the downstream of a chemical looping gasification unit as an additional system for 100 MW·h coal gasification, with the function of supplementary combustion to produce hydrogen. Using Aspen Plus software for process simulation, the production of H_2 and N_2 in the series system is higher than that in the independent Chemical looping gasification and Chemical looping hydrogen generation systems, and the production of hydrogen is approximately 25.63% and 12.90% higher, respectively; The study found that when the gasification temperature is 900 °C, steam-carbon ratio is 0.84 and oxygen-carbon ratio is 1.5,the hydrogen production rate of the system was the maximum. At the same time, through heat exchange between logistics, high-pressure steam at 8.010×10~4 kg·h~(-1) and medium-pressure steam at 1.101×10~4 kg·h~(-1) are generated, and utility consumption is reduced by 61.58%, with utility costs decreasing by 48.69%. An economic estimation study found that the production cost of ammonia is 108.66 USD·(t NH_3)~(-1). Finally, cost of equipment is the main factors influencing ammonia production cost were proposed by sensitivity analysis.     

液氨铁路罐车装卸设计中的安全防护

通过对液氨性质的分析，讨论了罐车设计和工作参数的确定过程，提出了液氨罐车装卸设计中的安全问题。     

Study of the NOχ reaction with reducing gases on Fe/ZrO2 catalyst

The Fe/ZrO₂ catalyst (1% Fe by weight) shows a strong adsorption capacity toward the nitric oxide (at room temperature the ratio NOFe is ca. 0.5) as a consequence of the formation of a highly dispersed iron phase after reduction at 500–773 K. Nitric oxide is adsorbed mainly as nitrosyl species on the reduced surface where the Fe²⁺ sites are prevailing, but it is easily oxidised by oxygen forming nitrito and nitrato species adsorbed on the support. However, in the presence of a reducing gas such as hydrogen, carbon monoxide, propane and ammonia at 473–573 K the Fe-nitrosyl species react producing nitrogen, nitrous oxide, carbon dioxide and water, as detected by FTIR and mass spectrometers. The results show that nitric oxide reduction is more facile with hydrogen containing molecules than with CO, probably due the co-operation of spillover effects. Experiments carried out with the same gases in the presence of oxygen show, however, a reduced dissociative activity of the surface iron sites toward the species NO_χ formed by NO oxidation and therefore the reactivity is shifted to higher temperatures.     

A model of ammonia volatilisation from a dairy farm: an examination of abatement strategies

A model (MAST) to calculate the mass flow of NH₃ through amodel dairy farm has been developed. Updated emission factors for UKagriculturewere used to examine different abatement strategies available for a typicaldairy farm. A range of annual NH₃ emissions was calculated for bothslurry and FYM based dairy systems. Emission for the slurry based system ranged between 27 kg NH₃-N ha^–1 yr^–1, achieved using a combination of abatementstrategies, and 107 kg NH₃-N ha^–1 yr^–1, calculated for a worst casescenario. For FYM, this range was between 33 and 86 kg NH₃-Nha^–1 yr^–1. The greatest reductionswereachieved by manipulating options linked to fertiliser usage and manureapplication.