Thermal oxidation of degradation products from thermoplastic polyvinyl alcohol: Determination on oxidation temperature and residence time.

The degradable protective articles made of thermoplastic polyvinyl alcohol (TPVA) are widely used in nuclear power plants, and they are thermally decomposed after use to reduce solid waste. However, in the real decomposition of TPVA, the temperature in the oxidation reactor is not self-sustaining; as a result, the degradation products contain a lot of CO, resulting in more pollution and energy waste. In this paper, jet stirred reactor (JSR) and Chemkin software were used to study the reaction kinetics characteristics of the oxidation process of degradation products from TPVA in the range of 550 °C-700 °C. Both experiments and kinetic simulation show that a higher average temperature of the oxidation reactor is needed to achieve lower CO emissions. When using 5% or 10% TPVA degradation solution, the average temperature should not befall below 625 °C or 675 °C. The corresponding residence time should be greater than 6 s and 5 s respectively. The combination of research findings and engineering practice provides great help to the optimization of the actual work process.

A kinetic evaluation and optimization study on NOx reduction by reburning under pressurized oxy-combustion.

Pressurized oxy-combustion is an emerging and more efficient technology for carbon capture, utilization, and storage than the first generation (atmospheric) oxy-combustion. NOx is a major conventional pollutant produced in pressurized oxy-combustion. In pressurized oxy-combustion, the utilization of latent heat from moisture and removal of acid gases (NOx and SOx) are mainly conducted in an integrated direct-contact wash column. Recent studies have shown that NOx particular inlet concentration should be maintained before direct contact wash column to remove NOx and SOx efficiently. As a result, minimizing NOx for environmental reasons, avoiding corrosion in carbon capture, utilization, and storage, and achieving effective NOx and SOx removal in direct contact wash columns are crucial. Reburning is a capable and affordable technology for NOx reduction; however, this process is still less studied at elevated pressure, particularly in pressurized oxy-combustion. In this paper, the kinetic evaluation and optimization study on NOx reduction by reburning under pressurized oxy-combustion was conducted. First, the most suitable mechanism was selected by comparing the results of different kinetic models with the experimental data in literature at atmospheric and elevated pressures. Based on the validated mechanism, a variety of parameters were studied at high pressure, i.e., comparing the effects of oxy and the air environment, different reburning fuels, residence time, H2O concentration, CH4/NO ratio, and equivalence ratio on the NO reduction. The results show that de-NOx efficiency in an oxy environment is significantly enhanced compared to the air environment. Improvement in the de-NOx efficiency is considerably higher with a pressure increase of up to 10 atm, but the effect is less prominent above 10 atm. The formation of HCN is significantly reduced while the N2 formation is enhanced as the pressure increases from 1 to 10 atm. The residence time required for the maximum NO reduction decreases as the pressure increases from 1 atm to 15 atm. At the higher pressure, the NO reduction rises prominently when the ratio of CH4/NO increases from 1 to 2; however, the effect fades after that. At higher pressure, the NO reduction by CH4 reburning decreases as the H2O concentration increases from 0 to 35%. The optimum equivalence ratio and high pressure for maximum NO reduction are 1.5 and 10 atm, respectively. This study could provide guidance for designing and optimizing a pressurized reburning process for NOx reduction in POC systems.

Model Development and Exergy Analysis of a Microreactor for the Steam Methane Reforming Process in a CFD Environment.

Steam methane reforming (SMR) is a dominant technology for hydrogen production. For the highly energy-efficient operation, robust energy analysis is crucial. In particular, exergy analysis has received the attention of researchers due to its advantage over the conventional energy analysis. In this work, an exergy analysis based on the computational fluid dynamics (CFD)-based method was applied to a monolith microreactor of SMR. Initially, a CFD model of SMR was developed using literature data. Then, the design and operating conditions of the microreactor were optimized based on the developed CFD model to achieve higher conversion efficiency and shorter length. Exergy analysis of the optimized microreactor was performed using the custom field function (CFF) integrated with the CFD environment. The optimized catalytic monolith microreactor of SMR achieved higher conversion efficiency at a smaller consumption of energy, catalyst, and material of construction than the reactor reported in the literature. The exergy analysis algorithm helped in evaluating length-wise profiles of all three types of exergy, namely, physical exergy, chemical exergy, and mixing exergy, in the microreactor.

Combustion and kinetic parameters estimation of torrefied pine, acacia and Miscanthus giganteus using experimental and modelling techniques.

A novel approach, linking both experiments and modelling, was applied to obtain a better understanding of combustion characteristics of torrefied biomass. Therefore, Pine, Acacia and Miscanthus giganteus have been investigated under 260°C, 1h residence time and argon atmosphere. A higher heating value and carbon content corresponding to a higher fixed carbon, lower volatile matter, moisture content, and ratio O/C were obtained for all torrefied biomass. TGA analysis was used in order to proceed with the kinetics study and Chemkin calculations. The kinetics analysis demonstrated that the torrefaction process led to a decrease in Ea compared to raw biomass. The average Ea of pine using the KAS method changed from 169.42 to 122.88kJ/mol. The changes in gaseous products of combustion were calculated by Chemkin, which corresponded with the TGA results. The general conclusion based on these investigations is that torrefaction improves the physical and chemical properties of biomass.

A Signature of Roaming Dynamics in the Thermal Decomposition of Ethyl Nitrite: Chirped-Pulse Rotational Spectroscopy and Kinetic Modeling.

Chirped-pulse (CP) Fourier transform rotational spectroscopy is uniquely suited for near-universal quantitative detection and structural characterization of mixtures that contain multiple molecular and radical species. In this work, we employ CP spectroscopy to measure product branching and extract information about the reaction mechanism, guided by kinetic modeling. Pyrolysis of ethyl nitrite, CH3CH2ONO, is studied in a Chen type flash pyrolysis reactor at temperatures of 1000-1800 K. The branching between HNO, CH2O, and CH3CHO products is measured and compared to the kinetic models generated by the Reaction Mechanism Generator software. We find that roaming CH3CH2ONO → CH3CHO + HNO plays an important role in the thermal decomposition of ethyl nitrite, with its rate, at 1000 K, comparable to that of the radical elimination channel CH3CH2ONO → CH3CH2O + NO. HNO is a signature of roaming in this system.