Review of proton conductors for hydrogen separation

There is a global push to develop a range of hydrogen technologies for timely adoption of the hydrogen economy. This is critical in view of the depleting oil reserves and looming transport fuel shortage, global warming, and increasing pollution. Molecular hydrogen (H₂) can be generated by a number of renewable and fossil-fuel-based resources. However, given the high cost of H₂ generation by renewable energy at this stage, fossil or carbon fuels are likely to meet the short- to medium-term demand for hydrogen. In view of this, effective technologies are required for the separation of H₂ from a gas feed (by-products of coal or bio-mass gasification plants, or gases from fossil fuel partial oxidation or reforming) consisting mainly of H₂ and CO₂ with small quantities of other gases such as CH₄, CO, H₂O, and traces of sulphur compounds. Several technologies are under development for hydrogen separation. One such technology is based on ion transport membranes, which conduct protons or both protons and electrons. Although these materials have been considered for other applications, such as gas sensors, fuel cells and water electrolysis, the interest in their use as gas separation membranes has developed only recently. In this paper, various classes of proton-conducting materials have been reviewed with specific emphasis on their potential use as H₂ separation membranes in the industrial processes of coal gasification, natural gas reforming, methanol reforming and the water–gas shift (WGS) reaction. Key material requirements for their use in these applications have been discussed.     

On carbon dioxide storage based on biomineralization strategies

This study focuses on the separation and storage of the global warming greenhouse gas CO₂, and the use of natural biocatalysts in the development of technologies to improve CO₂ storage rates and provide new methods for CO₂ capture. Carbonic anhydrase (CA) has recently been used as a biocatalyst to sequester CO₂ through the conversion of CO₂ to HCO^? in the mineralization of CaCO₃. Biomimetic CaCO₃ mineralization for carbon capture and storage offers potential as a stable CO₂ capture technology. In this report, we review recent developments in this field and assess disadvantages and improvements in the use of CA in industrial applications. We discuss the contribution that understanding of mechanisms of CO₂ conversion to CO₃^? in the formation and regeneration of bivalve shells will make to developments in biomimetic CO₂ storage.     

Chemical-looping combustion: Status and research needs

Chemical-Looping Combustion (CLC) has emerged in recent years as a very promising combustion technology for power plants and industrial applications with inherent CO₂ capture, which circumvent the energy penalty imposed on other competing technologies. The process is based on the use of a metal oxide to transport the oxygen needed for combustion in order to prevent direct contact between the fuel and air. CLC is performed in two interconnected reactors, and the CO₂ separation inherent to the process practically eliminates the energy penalty associated with gas separation. The CLC process was initially developed for gaseous fuels, and its application was subsequently extended to solid fuels. The process has been demonstrated in units of different size, from bench scale to MW-scale pilot plants, burning natural gas, syngas, coal and biomass, and using ores and synthetic materials as oxygen-carriers.An overview of the status of the process, starting with the fundamentals and considering the main experimental results and characteristics of process performance, is made both for gaseous and solid fuels. Process modelling of the system for solid and gaseous fuels is also analysed. The main research needs and challenges both for gaseous and solid fuel are highlighted.     

New environmentally attractive separation technology for flue gas mixture

ABSTRACT

Separation of gaseous mixtures produced from any process plant can be a major issue for the industry. In comparison to other separation techniques available, hydrate formation can be an appropriate choice in terms of fuel efficiency and degree of separation. In this work, a three-stage process was designed to capture CO₂ from a hypothetical flue gas mixture (comprising 15?mol% CO_2?+?85?mol% N₂). For the hydrate based CO₂ capture process, a detailed analysis was carried out covering the material and energy balance, energy integration and economic analysis. The results show that, at steady state, 91% of the CO₂ in the flue gas can be recovered, resulting into two streams: Stream-A (94?mol% CO₂?+?6?mol% N₂) and Stream-B (1.5?mol% CO₂?+?98.5?mol% N₂). Per 100?mol of the flue gas feed, 3.9?MW of energy is required to achieve such degree of separation. This amount was reduced to 2.4?MW after energy integration was applied to the process. Overall, the process can help in reducing CO₂ emission via flue gas because of the huge difference in the carbon foot print of its energy requirement (500?g CO₂ per kWh) and the amount of CO₂ captured by the process (2190?g CO₂ per kWh).     

Clathrate hydrates: recent advances on CH4 and CO2 hydrates,and possible new frontiers

Gas hydrates continue to attract enormous attention throughout the energy industry, as both a hindrance in conventional production and a substantial unconventional resource. Scientists continue to be fascinated by the hydrates’ ability of sequestering large amounts of hydrophobic gases, unusual thermal transport properties and unique molecular structures. Technologically, clathrate hydrates promise advantages in applications as diverse as carbon sequestration and water desalination. The communities interested in hydrates span traditional academic disciplines, including earth science, physical chemistry and petroleum engineering. The studies on this field are equally diverse, including field expeditions to attempt the production of natural gas from hydrate deposits accumulated naturally on the seafloor, to lab-scale studies to exchange CO₂ for CH₄ in hydrates; from theoretical studies to understand the stability of hydrates depending on the guest molecules, to molecular simulations probing nucleation mechanisms. This review highlights a few fundamental questions, with focus on knowledge gaps representing some of the barriers that must be addressed to enable growth in the practical applications of hydrate technology, including natural gas storage, water desalination, CO₂ – CH₄ exchange in hydrate deposits and prevention of hydrate plugs in conventional energy transportation.     

Combustion processes for carbon capture

A review of the technologies for coal-based power generation closest to commercial application involving carbon capture is presented. Carbon capture and storage (CCS) developments are primarily adaptations of conventional combustion systems, with additional unit operations such as bulk oxygen supply, CO₂ capture by sorbents, CO₂ compression, and storage. They use pulverized coal combustion in entrained flow—the dominant current technology for coal-based power, or gasification in entrained flow, although similar concepts apply to other solid-gas contacting systems such as fluidized beds. Currently, the technologies have similar generation efficiencies and are associated with efficiency penalties and electricity cost increases due to operations required for carbon capture. The R&D challenges identified for the combustion scientist and engineer, with current understanding being detailed, are those of design, optimisation and operational aspects of new combustion and gasification plant, controlling the gas quality required by CCS related units and associated emission compliance, and gas separations. Fundamental research needs include fuel reactions at pressure, and in O₂/CO₂ atmospheres, as few studies have been made in this area. Laboratory results interpreted and then included in CFD models of combustion operations are necessary. Also identified, but not detailed, are combustion issues in gas turbines for IGCC and IGCC-CCS. Fundamental studies should be a component of pilot-plant and demonstrations at practical scale being planned. Concepts for new designs of combustion equipment are also necessary for the next generation of technologies. The challenges involved with the design and operation of these integrated systems, while supplying electricity on demand, are considerable.     

Holey Graphitic Carbon Derived from Covalent Organic Polymers Impregnated with Nonprecious Metals for CO2 Capture from Natural Gas

Natural gas (NG), as a renewable and clean energy gas, is considered to be one of the most attractive energy carriers owing to its high calorific value, low price, and less pollution. Efficiently capturing CO₂ from NG is a very important issue since CO₂ reduces energy density of natural gas and corrodes equipment in the presence of water. In this study, the authors use holey graphene‐like carbon derived from covalent organic polymers (COP) impregnated with nonprecious metals, i.e., COP graphene, as highly efficient separation materials. The dual‐site Langmuir–Freundlich adsorption model based ideal absorbed solution theory is applied to explore the adsorption selectivity. The experimental results along with first principles calculations show Mn‐impregnated COP graphene exhibits greater CO₂/CH₄ selectivity than Fe and Co impregnated materials. Particularly, the selectivity of C–COP–P–Mn reaches 11.4 at 298 K and 12 bars, which are much higher than those in many reported conventional porous materials and can be compared to the highest separation performance under similar condition. Importantly, all the three COP graphene show remarkably high regenerability (R > 77%), which are much better than many reported promising zeolites, active carbon, and metal organic frameworks. Accordingly, COP graphene are promising cyclic adsorbents with high selectivity for separation and purification of CO₂ from natural gas.     

B40 fullerene: An efficient material for CO2 capture,storage and separation

Novel nanomaterials are promising for capture, storage and separation of CO₂. By density functional calculations, we find that the newly discovered B₄₀ fullerene is a suitable candidate. CO₂ forms stable chemisorptions with B₄₀ on specific sites, which is validated by the high adsorption energy, large charge transfer, and kinetic feasibility for B₄₀(CO₂) complexes. Due to the strong chemisorption, B₄₀ shows high adsorption capacity for CO₂ (up to 13.87 mmol/g). In addition, B₄₀ shows good selectivity for CO₂ and is efficient in separating it from gas mixtures like CO₂/N₂, CO₂/H₂, and CO₂/CH₄.     

The Ca-looping process for CO<Subscript>2</Subscript> capture and energy storage: role of nanoparticle technology

The calcium looping (CaL) process, based on the cyclic carbonation/calcination of CaO, has come into scene in the last years with a high potential to be used in large-scale technologies aimed at mitigating global warming. In the CaL process for CO₂ capture, the CO₂-loaded flue gas is used to fluidize a bed of CaO particles at temperatures around ~?650 °C. The carbonated particles are then circulated into a calciner reactor wherein the CaO solids are regenerated at temperatures near ~?950 °C under high CO₂ concentration. Calcination at such harsh conditions causes a marked sintering and loss of reactivity of the regenerated CaO. This main drawback could be however compensated from the very low cost of natural CaO precursors such as limestone or dolomite. Another emerging application of the CaL process is thermochemical energy storage (TCES) in concentrated solar power (CSP) plants. Importantly, carbonation/calcination conditions to maximize the global CaL-CSP plant efficiency could differ radically from those used for CO₂ capture. Thus, carbonation could be carried out at high temperatures under high CO₂ partial pressure for maximum efficiency, whereas the solids could be calcined at relatively low temperatures in the absence of CO₂ to promote calcination. Our work highlights the critical role of carbonation/calcination conditions on the performance of CaO derived from natural precursors. While conditions in the CaL process for CO₂ capture lead to a severe CaO deactivation with the number of cycles, the same material may exhibit a high and stable conversion at optimum CaL-CSP conditions. Moreover, the type of CaL conditions influences critically the reaction kinetics, which plays a main role on the optimization of relevant operation parameters such as the residence time in the reactors. This paper is devoted to a brief review on the latest research activity in our group concerning these issues as well as the possible role of nanoparticle technology to enhance the activity of Ca-based materials at CaL conditions for CO₂ capture and energy storage.     

Applications of “Dry” Processing in the Microelectronics Industry Using Carbon Dioxide

Condensed carbon dioxide (CO₂) has emerged as a leading enabler of advanced semiconductor manufacturing processes. By exploiting the physical properties of CO₂, some of the current challenges encountered in microelectronics processing related to shrinking feature sizes and materials compatibility have been addressed. Furthermore, the potential for reduction of chemicals used in processing is realized. Applications of CO₂ in microelectronics operations such as wafer cleaning, spin-coating, development, and stripping of photoresists, drying, low-k film preparation and repair, etching, and metal deposition are discussed.     

Prediction of transport properties of CO2-N2 binary mixtures via the inversion of reduced-viscosity collision integrals

In the present study, the main purpose is to extract information about the effective intermolecular potential energy function for binary mixture of nitrogen and carbon dioxide by the usage of a direct inversion of the experimentally reduced viscosity and second virial coefficient data and then to reproduce the dilute gas transport properties from the inverted potential energy. The Lennard-Jones (12, 6) potential energy function has been employed as the initial potential model required by the inversion method. The MSV potential obtained in this way is in reasonable agreement with the independently known Co₂-N₂ potential energy function. Using the inverted pair potential energies, the Chapman-Enskog scheme is employed to calculate transport properties of CO₂-N₂ in a wide composition and temperature range. The close agreement between the predicted values and the literature results of transport properties demonstrate the predictive power of the inversion scheme.     

Open-path Fourier transform spectroscopy of gas emissions from Oldoinyo Lengai volcano, Tanzania

We report here novel field spectroscopic measurements of the proportions of H₂O, CO₂, CO and SO₂ in gas emissions from Oldoinyo Lengai, the world's unique, active carbonatite volcano. We found that CO₂ constitutes <40 mol% of emissions from a lava lake, and 25 mol% from a cooler fumarole vent. These results suggest that H₂O is the predominant gas phase rather than CO₂, as reported in previous studies based on conventional sampling (Trans. Am. Geophys. Union 69 (1998) 1466; J. Geophys. Res. 101 (1996) 13819), though it is possible that water is introduced by remelting of older hydrated lava flows. We also observed rapid variations in CO₂/CO molar ratios (between 450 and 750 in 1 h) in the lava lake emissions, which could reflect mixing of gases exsolved from deep and shallow magma. Lengai's measured CO₂ flux (J. Geophys. Res. 101 (1996) 13819; Geology 23 (1995) 933) exceeds the time-averaged magma discharge rate, suggesting efficient separation of carbon and water-rich fluids from unerupted silicate magma. This may play an important role in parental magma differentiation.     

Effect of high CO2 concentration on char formation through mineral reaction during biomass pyrolysis

O₂/CO₂ combustion has attracted considerable attention as a promising technology for CO₂ capture. Using biomass for fuel is considered carbon neutral, and O₂/CO₂ biomass combustion can mitigate the deleterious environmental effect of greenhouse. In this study, the effect of CO₂, the main component gas in O₂/CO₂ combustion, on the pyrolysis characteristics of biomass is investigated. Cellulose, lignin, and metal-depleted lignin pyrolysis experiments were performed using a thermobalance. Information on the surface chemistry of the chars was obtained by Fourier transform infrared (FTIR) spectroscopy to investigate changes in the surface chemistry during pyrolysis under different surrounding gasses. When the temperature increased to 1073 K at heating rate of 1 K s^?1, the char yield of lignin in the presence of CO₂ increased by about 10% compared with that under Ar. However, for cellulose and metal-depleted lignin, no significant difference appeared between pyrolysis under CO₂ and that under Ar. FT-IR showed that a strong peak corresponding to carbonate ions appeared in the char derived from lignin under CO₂. Therefore, salts such as Na₂CO₃ or K₂CO₃ formed during the lignin pyrolysis under CO₂. At around 1650–1770 cm^?1, a significant difference appeared in the FTIR spectra of chars formed under CO₂ and those formed under Ar. C=O groups not associated with an aromatic ring were found only in chars formed under CO₂. It was suggested that these salts affected the char formation reaction, in that the char formed during lignin pyrolysis under CO₂ had unique chemical bands that did not appear in the lignin-derived char prepared under Ar.     

Leed and thermal desorption studies of small molecules (H2, O2, CO,CO2, NO,C2H4, C2H2 AND C) chemisorbed on the rhodium (111) and (100) surfaces

The chemisorption of H₂, O₂, CO, CO₂, NO, C₂H₄, C₂H₂ and C has been studied on the clean Rh(111) and (100) surfaces. LEED, AES and thermal desorption were used to determine the surface structures, disordering and desorption temperatures, displacement and decomposition characteristics for each species. All of the molecules studied readily chemisorbed on both surfaces. A large variety of ordered structures was observed, especially on the (111) surface. The disordering temperatures of most ordered surface structures on the (111) surface were below 100°C. It was necessary to adsorb the gases at 25° C or below in order to obtain well-ordered surface structures. Chemisorbed oxygen was readily removed from the surface by H₂ or CO gas at crystal temperatures above 50°C. CO₂ appears to dissociate to CO upon adsorption on both rhodium surfaces as indicated by the identical ordering and desorption characteristics of these two molecules. C₂H₄ and C₂H₂ also had very similar ordering and desorption characteristics and it is likely that the adsorbed species formed by both molecules is the same. Decomposition of ethylene produced a sequence of ordered carbon surface structures on the (111) face as a result of a bulk-surface carbon equilibrium. The chemisorption properties of rhodium appear to be generally similar to those of iridium, nickel and palladium.     

Numerical solution of Boltzmann tranport equation for TEA CO2 laser having nitrogen-lean gas mixtures to predict laser characteristics and gas lifetime

Selective laser isotope separation by TEA CO₂ laser often needs short tail-free pulses. Using laser mixtures having very little nitrogen almost tail free laser pulses can be generated. The laser pulse characteristics and its gas lifetime is an important issue for long-term laser operation. Boltzmann transport equation is therefore solved numerically for TEA CO₂ laser gas mixtures having very little nitrogen to predict electron energy distribution function (EEDF). The distribution function is used to calculate various excitation and dissociation rate of CO₂ to predict laser pulse characteristics and laser gas lifetime, respectively.Laser rate equations have been solved with the calculated excitation rates for numerically evaluated discharge current and voltage profiles to calculate laser pulse shape. The calculated laser pulse shape and duration are in good agreement with the measured laser characteristics. The gas lifetime is estimated by integrating the equation governing the dissociation of CO₂. An experimental study of gas lifetime was carried out using quadrapole mass analyzer for such mixtures to estimate the O₂ being produced due to dissociation of CO₂ in the pulse discharge. The theoretically calculated O₂ concentration in the laser gas mixture matches with experimentally observed value. In the present TEA CO₂ laser system, for stable discharge the O₂ concentration should be below 0.2%.     

The combined effect of H2O and SO2 on CO2 uptake and sorbent attrition during fluidised bed calcium looping

The effect of steam and sulphur dioxide on CO₂ capture by limestone during calcium looping was studied in a novel lab-scale twin fluidised bed device (Twin Beds – TB). The apparatus consists of two interconnected batch fluidised bed reactors which are connected to each other by a duct permitting a rapid and complete pneumatic transport of the sorbent (limestone) between the reactors. Tests were carried out under typical calcium looping operating conditions with or without the presence of H₂O and/or SO₂ during the carbonation stage. Carbonation was carried out at 650°C in presence of 15% CO₂, 10% steam (when present) and by investigating two SO₂ levels, representative of either raw (1500?ppm) or pre-desulphurised (75?ppm) typical flue gas derived from coal combustion. The sorbent used was a reactive German limestone. Its performance was evaluated in terms of CO₂ capture capacity, sulphur uptake, attrition and fragmentation. Results demonstrated the beneficial effect of H₂O and the detrimental effect of SO₂ on the CO₂ capture capacity. When both species were simultaneously present in the gas, steam was still able to enhance the CO₂ capture capacity even outweighing the negative effect of SO₂ at low SO₂ concentrations. A clear relationship between degrees of Ca carbonation and sulphation was observed. As regards the mechanical properties of the sorbent, both H₂O and SO₂ hardened the particle surface inducing a decrease of the measured attrition rate, that was indeed always very low. Conversely, the fragmentation tendency increased in presence of H₂O and SO₂ most likely due to the augmented internal stresses within the particles. Clear bimodal particle size distributions for in-bed sorbent fragments were observed. Microstructural scanning electron microscope and porosimetric characterisations aided in explaining the observed trends.     

Distinct transport properties of O2 and CH4 across a carbon nanotube

It is of fundamental importance to investigate either O₂ or CH₄ molecules across nanochannels in many areas such as breathing or separation. Thus, many researches have focused on such a single type of molecules across nanochannels. However, O₂ and CH₄ can often appear together and crucially affect human life, say, in a mine. On the basis of molecular dynamics simulations, here we attempt to investigate the mixture of O₂ and CH₄, in order to identify their different transport properties in a nanochannel. We take a single-walled carbon nanotube (SWCNT) as a model nanochannel, and find that their transport properties are distinctly different. As the concentration of O₂ increases up to a high value of 0.8, it is always faster for CH₄ molecules to transport across the SWCNT, and the total number of gas molecules transporting across the SWCNT is decreased. Meanwhile, CH₄ molecules are always dominant in the SWCNT, and the total number of O₂ or CH₄ inside the SWCNT is a constant. By calculating the van der Waals interaction between the SWCNT and O₂ or CH₄, we find that the net interaction between CH₄ and the SWCNT is much stronger. Our findings may offer some hints on how to separate CH₄ from O₂, and/or store CH₄ efficiently.     

Particle imaging of ignition and devolatilization of pulverized coal during oxy-fuel combustion

Oxy-fuel combustion of coal is a promising technology for cost-effective power production with carbon capture and sequestration that has ancillary benefits of emission reductions and lower flue gas cleanup costs. To fully understand the results of pilot-scale tests of oxy-fuel combustion and to accurately predict scale-up performance through CFD modeling, fundamental data are needed concerning coal and coal char combustion properties under these unconventional conditions. In the work reported here, the ignition and devolatilization characteristics of both a high-volatile bituminous coal and a Powder River Basin subbituminous coal were analyzed in detail through single-particle imaging at a gas temperature of 1700 K over a range of 12–36 vol % O₂ in both N₂ and CO₂ diluent gases. The bituminous coal images show large, hot soot cloud radiation whose size and shape vary with oxygen concentration and, to a lesser extent, with the use of N₂ versus CO₂ diluent gas. Subbituminous coal images show cooler, smaller emission signals during devolatilization that have the same characteristic size as the coal particles introduced into the flow (nominally 100 μm). The measurements also demonstrate that the use of CO₂ diluent retards the onset of ignition and increases the duration of devolatilization, once initiated. For a given diluent gas, a higher oxygen concentration yields shorter ignition delay and devolatilization times. The effect of CO₂ on coal particle ignition is explained by its higher molar specific heat and its tendency to reduce the local radical pool. The effect of O₂ on coal particle ignition results from its effect on the local mixture reactivity. CO₂ decreases the rate of devolatilization because of the lower mass diffusivity of volatiles in CO₂ mixtures, whereas higher O₂ concentrations increase the mass flux of oxygen to the volatiles flame and thereby increase the rate of devolatilization.     

Atmospheric modelling using FASCOD to identify CO2 absorption bands and their suitability analysis in variable concentrations for remote sensing applications

Recent climate studies have proven that both temperature and CO₂ content of the earth's atmosphere followed a regular 100,000-year cycle of change and that they are closely correlated. Moreover, the observed increase of CO₂ in the atmosphere exceeds the predicted values extrapolated from historical data. Other than industrialization and rapid urbanization, geo-natural hazards such as leakage from hydrocarbon reservoirs and spontaneous combustion of coal contribute a considerable amount of CO₂ to the atmosphere. Several researchers have studied the possibilities and reliabilities of atmospheric CO₂ retrieval by the point-based method (nearly accurate but much localized) and globally (wider observation but many uncertainties). Radiative transfer codes, such as FASCOD (Fast Atmospheric Signature Code) with the HITRAN (High-Resolution Transmission) spectral database can simulate atmospheric transmission and path radiance with customized gas composition (CO₂, water vapour, CO, etc.) and concentration in order to understand the phenomena in a specific wavelength region. In the present study, a number of atmospheric models were constructed with different CO₂ concentrations (ppmv) with a combination of water vapour and other atmospheric gases such as CO, CH₄, N₂O, SO₂, etc., to find out the interference patterns of these gases over CO₂ absorption bands. The transmission features of these gas combinations were analysed by partial least-squares regression models. These models show that the most suitable CO₂ absorption bands are located around 2 μm, such as 1.998 and 2.001 μm. The spectral information derived from different concentrations of CO₂ can be fitted in multivariate models to predict the CO₂ concentration from spectral information in a controlled environment. Furthermore, the present study explores the sensitivity of some available remote sensing sensors in variable CO₂ concentrations for use in real world.     

理论研究二氧化碳在有机吸收剂1，3-二苯胍中的氢键相互作用

如今碳捕获和储存技术已得到了迅速发展以减少对环境的二氧化碳排放. 研究发现胺基有机分子溶剂能有效地吸收二氧化碳,并通过氢键和二氧化碳形成的碳酸氢盐相互作用. 最近,实验报道了一种1,3-二苯基胍溶液,在室温条件下能捕获环境中的二氧化碳并将其转化为有价值的化学品. 然而,1,3-二苯基胍分子在溶液状态下如何与二氧化碳相互作用的机理仍不清楚. 在这项工作中,利用分子动力学方法模拟研究了溶液相中1,3-二苯基胍分子与二氧化碳的复杂作用细节. 模拟结果表明,质子化的1,3-二苯基胍分子和碳酸氢根离子倾向通过不同的双氢键模式作用形成稳定的复合物. 精确的密度泛函方法计算表明,这些双氢键复合物在热力学上相当稳定. 本研究有助于理解溶液相中1,3-二苯基胍分子中催化转化二氧化碳的机理.