Phase equilibrium measurements for the I2–H2O and I2–HI–H2O systems of the sulfur–iodine cycle using a continuous-flow apparatus

Liquid–liquid equilibrium (LLE) phase behavior was investigated for the binary iodine–water (I₂–H₂O) and the ternary iodine–hydroiodic acid–water (I₂–HI–H₂O) at the elevated temperatures and pressures of interest for the reactive distillation column of the Sulfur–Iodine Cycle. A continuous-flow apparatus, with wetted parts fabricated from tantalum-tungsten alloys, was designed and constructed for the highly corrosive conditions of this work. A central feature of the apparatus is the equilibrium view cell, which allows for the observation and discernment of vapor-liquid, liquid-liquid, and liquid–liquid–vapor equilibria for HIx systems.     

Ca(OH)2化学解吸固定TEA富液中的CO2

为探究TEA富液在投加Ca(OH)₂的化学解吸方式下的解吸性能,通过单因素法探究不同因素对TEA、TEA+MDEA和MDEA富液的解吸效果,再通过多次吸收-解吸实验对TEA富液的再生性能进行研究。结果表明：n(Ca)/n(C)、pH值等因素对TEA、TEA+MDEA和MDEA富液解吸效果均具有一定的影响,TEA富液的解吸效果最好,TEA+MDEA次之,MDEA最差;在n(Ca)/n(C)=1∶1、pH值为10、温度为20℃、CO₂负荷为0.4 mol/L、搅拌速率为800 r/min以及搅拌时间为10 min的条件下,TEA的解吸率可达82.85%;在5次吸收-解吸实验中TEA的解吸率均保持在80%左右,说明其在投加Ca(OH)₂的化学解吸方式下具有良好的解吸性能。     

The retardation kinetics of magnetite reduction using H2 and H2–H2O mixtures

Cylindrical compacts of magnetite were isothermally reduced at 773–1273 K with pure H₂ or H₂–H₂O mixtures. The initial reduction rates increased with temperature and partial pressures of H₂ in the H₂–H₂O mixtures. However, with progressing reduction, a dense iron layer formed around the wüstite grains and the rate significantly reduced. In this regime, solid state oxygen diffusion through the dense iron layer was rate limiting. This retardation of reduction occurred at degrees of reduction of 51–89%, depending on the temperature and H₂ partial pressure, which has a linear relationship with the dimensionless kinetic parameter, k₁^mixed/k₂^mixed, (k₁^mixed, k₂^mixed: contribution of gaseous mass transport (GMT) and interfacial chemical reaction (ICR) to the reduction rate, respectively) in the reaction-regime controlled by a combination of both mechanisms. However, under certain conditions (H₂, H₂–10%H₂O, 773 K//H₂–10, 20%H₂O, 873 K//H₂–20%H₂O, 973 K) the retardation was absent because of the formation of a microporous iron layer product.     

A novel catalyst–sorbent system for an efficient H2 production with in-situ CO2 capture

This paper presents an experimental investigation for an improved process of sorption-enhanced steam reforming of methane in an admixture fixed bed reactor. A highly active Rh/Ce_αZr_1−αO₂ catalyst and K₂CO₃-promoted hydrotalcite are utilized as novel catalyst/sorbent materials for an efficient H₂ production with in situ CO₂ capture at low temperature (450–500 °C). The process performance is demonstrated in response to temperature (400–500 °C), pressure (1.5–6.0 bar), and steam/carbon ratio (3–6). Thus, direct production of high H₂ purity and fuel conversion >99% is achieved with low level of carbon oxides impurities (<100 ppm). A maximum enhancement of 162% in CH₄ conversion is obtained at a temperature of 450 °C and a pressure of 6 bar using a steam/carbon molar ratio of 4. The high catalyst activity of Rh yields an enhanced CH₄ conversion using much lower catalyst/sorbent bed composition and much smaller reactor size than Ni-based sorption enhanced processes at low temperature. The cyclic stability of the process is demonstrated over a series of 30 sorption/desorption cycles. The sorbent exhibited a stable performance in terms of the CO₂ working sorption capacity and the corresponding CH₄ conversion obtained in the sorption enhanced process. The process showed a good thermal stability in the temperature range of 400–500 °C. The effects of the sorbent regeneration time and the purge stream humidity on the achieved CH₄ conversion are also studied. Using steam purge is beneficial for high degree of CO₂ recovery from the sorbent.     

Techno-economic assessment of fossil fuel power plants with CO2 capture – Results of EU H2-IGCC project

In order to address the ever-increasing demand for electricity, need for security of energy supply, and to stabilize global warming, the European Union co-funded the H₂-IGCC project, which aimed to develop and demonstrate technological solutions for future generation integrated gasification combined cycle (IGCC¹) plants with carbon capture. As a part of the main goal, this study evaluates the performance of the selected IGCC plant with CO₂ capture from a techno-economic perspective. In addition, a comparison of techno-economic performance between the IGCC plant and other dominant fossil-based power generation technologies, i.e. an advanced supercritical pulverized coal (SCPC²) and a natural gas combined cycle (NGCC³), have been performed and the results are presented and discussed here. Different plants are economically compared with each other using the cost of electricity and the cost of CO₂ avoided. Moreover, an economic sensitivity analysis of every plant considering the realistic variation of the most uncertain parameters is given.     

Effect of N2/CO2 dilution on laminar burning velocity of H2–air mixtures at high temperatures

The laminar burning velocities of H₂–air mixtures diluted with N₂ or CO₂ gas at high temperatures were obtained from planar flames observed in externally heated diverging channels. Experiments were conducted for an equivalence ratio range of 0.8–1.3 and temperature range of 350–600 K with various dilution rates. In addition, computational predictions for burning velocities and their comparison with experimental results and detailed flame structures have been presented. Sensitivity analysis was carried out to identify important reactions and their contribution to the laminar burning velocity. The computational predictions are in reasonably good agreement with the present experimental data (especially for N₂ dilution case). The burning velocity maxima was observed for slightly rich mixtures and this maxima was found to shift to higher equivalence ratios (Ф) with a decrease in the dilution. The effect of CO₂ dilution was more profound than N₂ dilution in reducing the burning velocity of mixtures at higher temperatures.     

Energy requirement of HI separation from HI–I2–H2O mixture using electro-electrodialysis and distillation

The separation of HI from HI–I₂–H₂O mixture is an essential subsection of the Iodine–Sulfur (IS) process for thermochemical hydrogen production. The energy requirement of the separation determines, to a large extent, the hydrogen production efficiency of the IS process. In order to examine duty of the separation using electro-electrodialysis (EED) and distillation, a process simulation study was carried out using an analytical model of EED based on ideal membrane properties and properties of the reported EED experiments using a Nafion^® membrane and graphite electrodes. For both of the ideal-membrane case and Nafion-membrane case, effects of the operating parameters on heat duty were estimated, which comprised column pressure, HI molality in the column feed, and the flow rate ratio of the input from Bunsen section to distillate rate. Low column pressure, and high HI molality in the column feed were preferable for the ideal-membrane case; column pressure of 1.0 MPa and optimized HI molality in the column feed were desired for the Nafion-membrane case. The flow rate ratio had little effect on the minimum heat duty in the ideal-membrane case; a value in the vicinity of the lower limit of the flow rate ratio was optimal for the Nafion-membrane case. The difference of the inclination of parameters resulted from the fractional vaporization of the column feed in the ideal-membrane case and weight of the EED cell duty on the total duty due to the membrane voltage drop. The optimization of these parameters was also carried out. The minimum total heat duty of the Nafion-membrane case was 3.07 × 10⁵ J/mol-HI, and that of the ideal-membrane case was 12.5% of this value.     

Evaluating cubic equations of state for calculation of vapor–liquid equilibrium of CO2 and CO2-mixtures for CO2 capture and storage processes

Proper solution of vapor liquid equilibrium (VLE) is essential to the design and operation of CO₂ capture and storage system (CCS). According to the requirements of engineering applications, cubic equations of state (EOS) are preferable to predict VLE properties. This paper evaluates the reliabilities of five cubic EOSs, including PR, PT, RK, SRK and 3P1T for predicting VLE of CO₂ and binary CO₂-mixtures containing CH₄, H₂S, SO₂, Ar, N₂ or O₂, based on the comparisons with the collected experimental data. Results show that SRK is superior in the calculations about the saturated pressure of pure CO₂; while for the VLE properties of binary CO₂-mixtures, PR, PT and SRK are generally superior to RK and 3P1T. The impacts of binary interaction parameter k_ij were also analyzed. k_ij has very clear effects on the calculating accuracy of an EOS in the property calculations of CO₂-mixtures. In order to improve the calculation accuracy, the binary interaction parameter was calibrated for all of the studied EOSs regarding every binary CO₂-mixture.     

Laminar burning velocities and flame characteristics of CO–H2–CO2–O2 mixtures

Laminar burning velocities of CO–H₂–CO₂–O₂ flames were measured by using the outwardly spherical propagating flame method. The effect of large fraction of hydrogen and CO₂ on flame radiation, chemical reaction, and intrinsic flame instability were investigated. Results show that the laminar burning velocities of CO–H₂–CO₂–O₂ mixtures increase with the increase of hydrogen fraction and decrease with the increase of CO₂ fraction. The effect of hydrogen fraction on laminar burning velocity is weakened with the increase of CO₂ fraction. The Davis et al. syngas mechanism can be used to calculate the syngas oxyfuel combustion at low hydrogen and CO₂ fraction but needs to be revised and validated by additional experimental data for the high hydrogen and CO₂ fraction. The radiation of syngas oxyfuel flame is much stronger than that of syngas–air and hydrocarbons–air flame due to the existence of large amount of CO₂ in the flame. The CO₂ acts as an inhibitor in the reaction process of syngas oxyfuel combustion due to the competition of the reactions of H + O₂ = O + OH, CO + OH = CO₂ + H and H + O₂(+M) = HO₂(+M) on H radical. Flame cellular structure is promoted with the increase of hydrogen fraction and is suppressed with the increase of CO₂ fraction due to the combination effect of hydrodynamic and thermal-diffusive instability.     

H2 and CO production over a stable Ni–MgO–Ce0.8Zr0.2O2 catalyst from CO2 reforming of CH4

Ni–Ce_0.8Zr_0.2O₂ and Ni–MgO–Ce_0.8Zr_0.2O₂ catalysts were investigated for H₂ production from CO₂ reforming of CH₄ reaction at a very high gas hourly space velocity of 480,000 h⁻¹. Ni–MgO–Ce_0.8Zr_0.2O₂ exhibited higher catalytic activity and stability (CH₄ conversion >95% at 800 °C for 200 h). The outstanding catalytic performance is mainly due to the basic nature of MgO and an intimate interaction between Ni and MgO.     

Start-up behaviors of a H2SO4–H2O distillation column for the 50 NL H2/H sulfur–iodine cycle

The sulfur–iodine (SI) cycle to produce hydrogen from water requires a multistage distillation column to concentrate a sulfuric acid solution. To design a concentration process of a sulfuric acid solution that can be applied to the cycle, its static and dynamic simulation is essentially demanded. A 50 NL H₂/h scale SI test facility to be operated under a pressurized environment has been constructed in Korea. This study focuses on the sulfuric acid multi-stage distillation column (SAMDC-50L) for the 50 NL H₂/h SI test facility. The SAMDC-50L was designed and installed in 2012. Based on the design specifications and operation method, a start-up behavior of the SAMDC-50L has been analyzed using the simulation code “KAERI-DySCo”. As a result of the start-up dynamic simulation, it is confirmed that the SAMDC-50L will approach to the steady state value within 30,000 s to fulfill the hydrogen production rate of 50 NL H₂/h. On the other hand, it is expected that the operation time approaching a steady state decreases with an increase in the set point of the condenser temperature until a dew point of the top vapor product and the time required for the transition to the complete steady state is increased with an increasing reflux ratio and reboiler hold-up.     

Pd–Ag thin film membrane for H2 separation. Part 2. Carbon and oxygen diffusion in the presence of CO/CO2 in the feed and effect on the H2 permeability

The effect of CO and CO₂ on the performance and stability of Pd–Ag thin film membranes prepared by electroless plating deposition (EPD) was investigated, observing the presence of dissociation to carbon and oxygen which slowly diffuse in the membrane influencing also H₂ permeability. The effect of the two carbon oxides was investigated both separately and combined in the 400–450 °C temperature range over long-term cumulative experiments (up to over 350 h) on a membrane that already worked for over 350 h in H₂ or H₂–N₂ mixtures. An increase of the H₂ permeation flux was observed feeding only CO₂ in the range 10–20%. This effect was interpreted as deriving from the facilitated H₂ flux caused from oxygen diffusion (deriving from CO₂ dissociation) in the membrane. CO induces instead a partial inhibition on the H₂ flux deriving from the negative effect of CO competitive chemisorption as well as C diffusion in the membrane, which overcome the positive effect associated to oxygen diffusion in the membrane. Carbon and oxygen diffuse through the membrane with a rate two order of magnitude lower than hydrogen, and recombinate at the permeate side forming CO, CO₂ and CH₄ which amount increases with time-on-stream. The effect is reversible and not associated with the creation of cracks or defects in the membrane, as supported by leak tests.     

A numerical study on the effects of H2 addition in non-premixed turbulent combustion of C3H8–H2–N2 mixture using a steady flamelet approach

This study has been implemented in two sections. At first, the turbulent jet flame of DLR-B is simulated by combining the k–ε turbulence model and a steady flamelet approach. The DLR-B flame under consideration has been experimentally investigated by Meier et al. who obtained velocity and scalar statistics. The fuel jet composition is 33.2% H₂, 22.1% CH₄ and 44.7% N₂ by volume. The jet exit velocity is 63.2 m/s resulting in a Reynolds number of 22,800. Our focus in the first part is to validate the developed numerical code. Comparison with experiments showed good agreement for temperature and species distribution. At the second part, we exchanged methane with propane in the fuel composition whilst maintaining all other operating conditions unchanged. We investigated the effect of hydrogen concentration on C₃H₈–H₂–N₂ mixtures so that propane mole fraction extent is fixed. The hydrogen volume concentration rose from 33.2% up to 73.2%. The achieved consequences revealed that hydrogen addition produces elongated flame with increased levels of radiative heat flux and CO pollutant emission. The latter behavior might be due to quenching of CO oxidation process in the light of excessive cold air downstream of reaction zone.     

HI extraction by H3PO4 in the Sulfur–Iodine thermochemical water splitting cycle: Composition optimization of the HI/H2O/H3PO4/I2 biphasic quaternary system

Iodine excess separation from hydriodic acid (HI) is one of the most challenging steps of the Sulfur–Iodine thermochemical water splitting cycle. One promising method is the extraction of HI by using phosphoric acid (H₃PO₄), with the subsequent separation of gaseous hydriodic acid from water and H₃PO₄ by a distillation step.     

O2/CO2气氛添加CaCO3对徐州烟煤PM2.5排放的影响

采用管式炉研究了在O2/CO2气氛下添加CaCO3对PM2.5(空气动力学直径小于2.5,μm的颗粒物)排放特性的影响.试验采用荷电低压撞击器(ELPI)采集和分析燃烧后的PM2.5.结果表明,添加CaCO3是燃烧过程中影响PM2.5生成的重要因素.添加CaCO3后,生成PM1的数密度和质量浓度均降低,而PM1-2.5的数密度和质量浓度均略有增加,PM2.5粒径分布均呈双峰分布,峰值点分别出现在0.2,μm和2.0,μm左右.随着CaCO3添加质量分数的增加,PM2.5中的S、Pb、Cu、Na和K几种元素的浓度呈下降趋势.     

Adiabatic burning velocity of H2–O2 mixtures diluted with CO2/N2/Ar

Global warming due to CO₂ emissions has led to the projection of hydrogen as an important fuel for future. A lot of research has been going on to design combustion appliances for hydrogen as fuel. This has necessitated fundamental research on combustion characteristics of hydrogen fuel. In this work, a combination of experiments and computational simulations was employed to study the effects of diluents (CO₂, N₂, and Ar) on the laminar burning velocity of premixed hydrogen/oxygen flames using the heat flux method. The experiments were conducted to measure laminar burning velocity for a range of equivalence ratios at atmospheric pressure and temperature (300 K) with reactant mixtures containing varying concentrations of CO₂, N₂, and Ar as diluents. Measured burning velocities were compared with computed results obtained from one-dimensional laminar premixed flame code PREMIX with detailed chemical kinetics and good agreement was obtained. The effectiveness of diluents in reduction of laminar burning velocity for a given diluent concentration is in the increasing order of argon, nitrogen, carbon dioxide. This may be due to increased capabilities either to quench the reaction zone by increased specific heat or due to reduced transport rates. The lean and stoichiometric H₂/O₂/CO₂ flames with 65% CO₂ dilution exhibited cellular flame structures. Detailed three-dimensional simulation was performed to understand lean H₂/O₂/CO₂ cellular flame structure and cell count from computed flame matched well with the experimental cellular flame.     

Liquid–liquid equilibrium tie-line compositions at elevated temperatures and pressures for the I2–H2O and HI–I2–H2O systems of the Sulfur–Iodine Cycle

Liquid–liquid equilibrium (LLE) tie-line compositions were measured for the binary system iodine–water and the ternary system hydrogen iodide–iodine–water (HI–I₂–H₂O) at 199.1 and 252.2 °C, at pressures of 60 bar, conditions of interest for the reactive distillation column of the Sulfur–Iodine Cycle. To keep the HI decomposition reaction negligible, a continuous-flow apparatus was used to minimize residence times at the elevated temperatures. Sixteen equilibrium tie lines were measured, using overall feed compositions ranging from 0.0 to 3.3 mol % HI, and the plait-point composition for 199.1 °C was estimated. Sample compositions for the lighter, water-rich phase and the heavier, I₂-rich phase were both determined via titration of HI and I₂, with water being obtained by difference. The phase behavior indicates that the selectivity of HI for the aqueous phase can be large, ranging from 10 to 100+ for tie lines removed from the critical region.     

Techno-economic analysis (TEA) for CO2 reforming of methane in a membrane reactor for simultaneous CO2 utilization and ultra-pure H2 production

Techno-economic analysis (TEA) for CO₂ reforming of methane in a membrane reactor (MR) was conducted by using process simulation and economic analysis. Parametric studies for key operating conditions like a H₂ permeance, a H₂O sweep gas flow rate, operating temperature, and a CO₂/CH₄ ratio were carried out for a conventional packed-bed reactor (PBR) and a MR using Aspen HYSYS^®, a commercial process simulator program and some critical design guidelines for a MR in terms of a H₂O sweep gas flow rate and a CO₂/CH₄ ratio were obtained. Further economic analysis based on process simulation results showed about 42% reduction in a unit H₂ production cost in a MR (6.48 $ kgH₂^?1) than a PBR (11.18 $ kgH₂^?1) mostly due to the elimination of a pressure swing adsorption (PSA) system in a MR. In addition, sensitivity analysis (SA) revealed that reactant price and labor were the most influential economic factors to determine a unit H₂ production cost for both a PBR and a MR. Lastly, profitability analysis (PA) from cumulative cash flow diagram (CCFD) in Korea provided positive net present value (NPV) of $443,760～$240,980, discounted payback period (DPBP) of 3.03–3.18 y, and present value ratio (PVR) of 7.51–4.97 for discount rates from 2 to 10% showing economic feasibility of the use of a MR as simultaneous CO₂ utilization and ultra-pure H₂ production.     

Benchmarking of the pre/post-combustion chemical absorption for the CO2 capture

The aim of the article was to compare the pre- and post-combustion CO₂ capture process employing the chemical absorption technology. The integration of the chemical absorption process before or after the coal combustion has an impact on the power plant efficiency because, in both cases, the thermal energy consumption for solvent regeneration is provided by the steam extracted from the low pressure steam turbine. The solvent used in this study for the CO₂ capture was monoethanolamine (MEA) with a weight concentration of 30%. In the case of the pre-combustion integration, the coal gasification was analysed for different ratios air/fuel (A/F) in order to determine its influences on the syngas composition and consequently on the low heating value (LHV). The LHV maximum value (28 MJ/kg) was obtained for an A/F ratio of 0.5 kg_air/kg_fuel, for which the carbon dioxide concentration in the syngas was the highest (17.26%). But, considering the carbon dioxide capture, the useful energy (the difference between the thermal energy available with the syngas fuel and the thermal energy required for solvent regeneration) was minimal. The maximum value (61.59 MJ) for the useful energy was obtained for an A/F ratio of 4 kg_air/kg_fuel. Also, in both cases, the chemical absorption pre- and post-combustion process, the power plant efficiency decreases with the growth of the L/G ratio. In the case of the pre-combustion process, considering the CO₂ capture efficiency of 90%, the L/G ratio obtained was of 2.55 mol_solvent/mol_syngas and the heat required for the solvent regeneration was of 2.18 GJ/tCO₂. In the case of the post-combustion CO₂ capture, for the same value of the CO₂ capture efficiency, the L/G ratio obtained was of 1.13 mol_solvent/mol_{flue gas} and the heat required was of 2.80 GJ/tCO₂. However, the integration of the CO₂ capture process in the power plant leads to reducing the global efficiency to 30% in the pre-combustion case and to 38% to the post-combustion case.