Numerical study on laminar burning velocity of ammonia flame with methanol addition

The combustion characteristics of ammonia/methanol mixtures were investigated numerically in this study. Methanol has a dramatic promotive effect on the laminar burning velocity (LBV) of ammonia. Three mechanisms from literature and another four self-developed mechanisms constructed in this study were evaluated using the measured laminar burning velocities of ammonia/methanol mixtures from Wang et al. (Combust.Flame. 2021). Generally, none of the selected mechanisms can precisely predict the measured laminar burning velocities at all conditions. Aiming to develop a simplified and reliable mechanism for ammonia/methanol mixtures, the constructed mechanism utilized NUI Galway mechanism (Combust.Flame. 2016) as methanol sub-mechanism and the Otomo mechanism (Int. J. Hydrogen. Energy. 2018) as ammonia sub-mechanism was optimized and reduced. The reduced mechanism entitled ‘DNO-NH3’, can accurately reproduce the measured laminar burning velocities of ammonia/methanol mixtures under all conditions. A reaction path analysis of the ammonia/methanol mixtures based on the DNO-NH3 mechanism shows that methanol is not directly involved in ammonia oxidation, instead, the produced methyl radicals from methanol oxidization contribute to the dehydrogenation of ammonia. Besides, NO_x emission analysis demonstrates that 60% methanol addition results in the highest NO_x emissions. The most important reactions dominating the NO_x consumption and production are identified in this study.     

Mechanistic implications of the solvent kinetic isotope effect in the hydrolysis of NaBH4

The sodium borohydride, NaBH₄, hydrolysis mechanism is studied via the H₂O/D₂O kinetic isotope effect (KIE). This reaction is of importance as NaBH₄ is considered as a hydrogen storage material. Nowadays, hydrogen is thought to be one of the most promising and efficient clean energy carriers. In order to control the rate of the hydrogen evolution reaction (HER), one has to understand the mechanism of its production. The H₂O/D₂O KIE of the reactions of NaBH₄ and NaBD₄ with water was studied in solutions containing a ratio of H₂O/D₂O = 1.00. The separation factor, α, of both reactions is α = 5.0 ± 1.0. The rate of the hydrolysis of BD₄^? in H₂O is faster than that of BH₄^?. The results point out that the rate-determining step in all hydrolysis stages is the H–OH bond scission.     

Chitosan-catalyzed n-butyraldehyde self-condensation reaction mechanism and kinetics

The chitosan was found to possess an excellent catalytic performance in n-butyraldehyde selfcondensation to 2E2H. Under suitable conditions, the conversion of n-butyraldehyde, the yield and selectivity of 2E2H separately attained 96.0%, 86.0% and 89.6%. The chitosan catalyst could be recovered and used for 5 times without a significant deactivation after being treated with ammonium hydroxide. In order to elucidate the reaction mechanism, the adsorption and desorption of n-butyraldehyde on the surface of chitosan were studied using in situ FT-IR spectroscopy analysis. The result showed that n-butyraldehyde interacts with-NH₂ group of chitosan to form an intermediate species with an enamine structure. Then the reaction process of n-butyraldehyde self-condensation was monitored by React-IR technique and it was found that n-butyraldehyde self-condensation to 2-ethyl-3-hydroxyhexanal followed by a dehydration reaction to 2-ethyl-2-hexenal. On this basis, chitosan-catalyzed n-butyraldehyde self-condensation reaction mechanism was speculated and its reaction kinetics was investigated. The self-condensation reaction follows auto-catalytic reaction characteristics and then the corresponding kinetic model was established.     

Investigation on elemental mercury removal by cerium modified semi-coke

Coal-fired power plant is the largest anthropogenic mercury source. Active carbon injection technique has been widely used to control the mercury emissions. However, high operation cost limits its development and it is necessary to find other potential mercury sorbents. In this study, raw semi-coke and a series of novel cerium (Ce) modified semi-cokes were synthesized and utilized for removing elemental mercury (Hg⁰) from simulated flue gas. It is noteworthy that the efficiencies were tested without hydrogen chloride (HCl) in order to evaluate the sorbents efficacy for low-chlorine (Cl) coal. The results show that the modified sorbents exhibited the best performance at 150 °C. The performance of sorbent could be reinforced due to the existence of oxygen (O₂), nitric oxide (NO) and HCl. The adverse effect caused by sulfur dioxide (SO₂) reduced dramatically after Ce modification. The negative impact of ammonia (NH₃) on Hg⁰ removal in this study could be neglected owing to the tiny concentration of NH₃. Raw semi-coke provided sufficient carbon content, which is favorable to mercury adsorption. As Ce loading increased, the carbon structure changed and the crystal of cerium oxide was formed in the modified semi-coke. The mass fraction of cerium oxide on the sorbent was over 4.4% when the concentration of Ce modification solution was higher than 0.2 mol L⁻¹. The redox reaction activity and the oxygen storage ability of Ce³⁺/Ce⁴⁺ gave a huge boost to the performance of modified semi-coke. The addition of Ce also had an impact on the proportion of oxygen species.     

Behavior and mechanism of in-situ synthesis of auxiliary electrode for electrochemical sulfur sensor by calcium aluminate system

The behavior and mechanism of in-situ synthesis of the auxiliary electrode for sulfur sensor were investigated in this work, aiming for better application of calcium aluminate system in synthesizing the auxiliary electrode used for sulfur sensor. The in-situ reaction experiment was developed. In addition, the thermodynamic and kinetic calculations were adopted to further study the in-situ reaction possibility and the reaction rate. The results indicated that the value of lg(a_[S]/a_[O]) should be greater than a particular value to ensure the occurrence of the in-situ reaction. After immersion into the molten iron, the CaS phase was synthesized in the calcium aluminate system. The relationship between the reaction rate and reaction time was exponential, and the initial reaction rate was affected by the CaO content incorporated in the calcium aluminate system and the sulfur content in the molten iron. The initial in-situ reaction rate greatly increased with the increase of the CaO content and sulfur content. For example, the initial reaction rate was as high as 14.87 s^-1 when the calcium aluminate system containing 60 wt% of CaO and for a sulfur content of 0.077 wt% in the molten iron. Moreover, the reason that the sulfur sensor fabricated by the ZrO₂(MgO) tube with the calcium aluminate coating with different components had the same response time when measuring the different sulfur contents in the molten iron was further explained.     

Kinetics and mechanistic studies of methane dry reforming over Ca promoted 1Co–1Ce/AC-N catalyst

The mechanism and kinetic features of dry reforming with methane (DRM) over Ca promoted 1Co–1Ce/AC-N catalyst was investigated. The mechanistic pathway studies have conducted by FTIR and XPS analysis, structure-activity correlations demonstrated the CH₄ and CO₂ could adsorb on catalyst active sites and generate intermediate CH_x, OH and CH_xO, continue to generate CO and H₂ and then desorbed from active sites. Moreover, CH₄ could also oxidized by Ce⁴⁺ and CO₂ reduced by Ce³⁺, the same content of Ce⁴⁺ and Ce³⁺ on promoted catalyst greatly improved the reaction rate. The kinetic of dry reforming with methane was examined for temperature between 650 and 850 at 800 °C. The research was carried out by changing the CH₄/CO₂ ratios between 0.3 and 3.0. The obtained experiment data were fitted by three typical kinetic models (Power Law, Eley-Rideal and Langmuir-Hinshelwood), the fitting results demonstrated that the best prediction of reforming rates can provided by Langmuir-Hinshelwood model for the reaction temperatures between 650 and 800 °C. Moreover, activation energies of methane and carbon dioxide consumption were ?117 and ?47 kJ/mol, indicating that much higher energy barrier is needed for methane activation compared to carbon dioxide.     

Comparative study on pyrolysis characteristics and kinetics of oleaginous yeast and algae

The pyrolysis processes of oleaginous yeast and algae were studied and compared using a non-isothermal thermogravimetric analyzer at heating rates of 10–50 °C/min, and the most probable mechanism function and kinetic analyses of the main stage of pyrolysis were carried out by the Popuse method, Starink method, and Fridemen method. The main pyrolysis stage of the samples could be described by the Jander equation and Z–L–T equation and the activation energy of the three biomass was 108–117, 107–121 and 93–108 kJ/mol, respectively. For the three kinds of biomass, the DTG curves were divided based on the four pseudo-components by performing Gaussian fitting which are carbohydrates, proteins, lipids, others, and the weight coefficients of them could be identified. The activation energy of each pseudo-component was obtained in the range of 58.36–140.44 kJ/mol by the Kissinger method. The four-pseudo-component model based on Gaussian fitting provides effective data for the design of oleaginous yeast and algae thermal decomposition systems and the kinetic analysis of the pyrolysis process.     

Multistage homogenization process of aluminum alloy 2618

Single-, two-, and three-stage homogenization treatments of heat-resistant alloy 2618 were conducted in this study. Results reveal a low melting point Al₂CuMg phase and high melting point Al₂Cu phase in the as-cast aluminum alloy 2618. After single-stage homogenization at 495 °C for 10 h, the Al₂CuMg phase dissolves completely, but the Al₂Cu phase cannot be completely dissolved even once the homogenization time is prolonged to 18 h. After the alloy 2618 are homogenized using two stages: 495 °C for 10 h and 520 °C for 8 h, a portion of the Al₂Cu phase remains in the alloy. The Al₂Cu phase remains undissolved even after prolonged time. After the two-stage homogenization treatment at 495 °C for 10 h and 540 °C for 5 h, the high melting point Al₂Cu phase completely dissolves but overburn occurs. After the alloy 2618 are homogenized using three stages at 495 °C for 10 h, 520 °C for 5 h, and 540 °C for 3 h, the Al₂Cu phase completely dissolves and no overburn is detected. The three-stage homogenization treatment is an effective method for dissolving the high melting point Al₂Cu phase in the alloy 2618 and increasing their overburn temperature and solid solution temperature.     

Experimental evaluation of Pt/TiO2/rGO as an efficient HER catalyst via artificial photosynthesis under UVB & visible irradiation

The study investigated the synergistic effects of rGO and Pt over TiO₂ for the HER via artificial photosynthesis under UVB and visible light irradiation. The introduction of glycerol and industrial wastewater to the system as sacrificial reductants signifies that the major reaction pathway is photocatalytic partial water splitting. The material characterizations revealed successful heterojunction formation and provided insight into chemistry behind the activity of the photocatalysts. Amongst various combinations of rGO on TiO₂, 1GNT exhibited an HER yield five times that of bare TiO₂ under UVB light. Addition of Pt led to the formation of a strong Schottky barrier at the heterojunction and consequently boosted HER performance. 1P0.5 GT presented the highest of 28.5 mmol g⁻¹ h⁻¹ with glycerol and 9.6 mmol g⁻¹ h⁻¹ with wastewater under UVB light respectively. For both binary and ternary photocatalysts, the HER performances dwindled under visible light irradiation, accentuating the insufficient activation of the TiO₂. In addition, 1PT outperformed all the other photocatalysts thereby elucidating the impression that rGO and Pt does not work well together in enhancing HER despite quenching the exciton recombination rate of TiO₂ significantly. The role of pH in the synthesis and the experiments has been discussed. Finally, the underlying mechanisms in the photodeposition and photoreformation have been proposed.