Absorption of NO and NO2 in Caprolactam Tetrabutyl Ammonium Halide Ionic Liquids

ABSTRACT

To explore environmentally benign solvents for the absorption of NO and NO₂, a series of caprolactam tetrabutyl ammonium halide ionic liquids were synthesized. The solubility of NO and NO₂ was measured at temperatures ranging from 298.2 to 363.2 K and atmospheric pressure, and the following trend in the solubility of NO and NO₂ in ionic liquids with various halide anions was observed, respectively: F > Br > Cl and Br > Cl > F. Moreover, as the temperature increased from 308.15 to 363.15 K and the mole ratio of caprolactam increased from 2:1 to 6:1, the solubility of NO increased. Alternatively, the solubility of NO₂ decreased as the temperature increased from 298.15 to 363.15 K, and the mole ratio of caprolactam increased from 2:1 to 6:1. The absorption and desorption of NO and NO₂ was practically reversible in the ionic liquids, which was characterized by nuclear magnetic resonance. The method, which is at least partially reversible, offers interesting possibilities for the removal of NO and NO₂.

IMPLICATIONS Basic ionic liquids with amino groups were synthesized and used to capture CO₂, SO₂, and H₂S, and to promote hydrogenation of CO₂. In this paper, the authors used caprolactam tetrabutyl ammonium halide ionic liquid (IL) as absorbing medium in which NO_x could be absorbed. NO_x desorbed from the absorbent could be efficiently reduced by right catalysts at high temperature. The absorbed NO and NO₂ gas could be desorbed at higher temperature, allowing the ionic liquids to be reused several times without loss of capability. It was believed that caprolactam tetrabutyl ammonium bromide (CPL-TBAB) ILs may be useful for NO_x removal reagent for pollution control.     

Influence of cosolvents on quinoline sorption by subsurface materials and clays

Quinoline sorption was measured on Na-saturated subsurface materials, a natural clay isolate, and montmorillonite, and was dominated by exchange of the quinolinium ion. In water/methanol and water/acetone mixtures, quinoline sorption on the subsoils and clays was lower than from water. In cosolvent, sorption followed the ionization fraction indicating the continued predominance of ion exchange. The reduction in quinoline sorption by cosolvent was similar for all the subsoils and clays indicating commonality in the surface-solute-solvent interaction. Conditional equilibrium constants (_cK_ex) for quinoline exchange on the subsoils in water/methanol mixtures decreased log-linearly with mole percent cosolvent up to 20% methanol. This decrease closely followed the increase in quinoline solubility in the cosolvent mixtures. Acetone caused greater reduction in sorption than methanol, at comparable mole percent, in accordance with its lower dielectric constant and enhanced solvating power. A generalized thermodynamic approach based on the concept of transfer activity coefficients was developed to account for the cosolvent effect on _cK_ex, and was successfully applied to the quinoline sorption data. The thermodynamic analysis suggested that enhanced solvation of the organic cation in the bulk solvent and desolvation of Na⁺ at the charged surface predominate the cosolvent effect.     

Absorption of NO and NO2 in caprolactam tetrabutyl ammonium halide ionic liquids

To explore environmentally benign solvents for the absorption of NO and NO2, a series of caprolactam tetrabutyl ammonium halide ionic liquids were synthesized. The solubility of NO and NO2 was measured at temperatures ranging from 298.2 to 363.2 K and atmospheric pressure, and the following trend in the solubility of NO and NO2 in ionic liquids with various halide anions was observed, respectively: F > Br > Cl and Br > Cl > F. Moreover, as the temperature increased from 308.15 to 363.15 K and the mole ratio of caprolactam increased from 2:1 to 6:1, the solubility of NO increased. Alternatively, the solubility of NO2 decreased as the temperature increased from 298.15 to 363.15 K, and the mole ratio of caprolactam increased from 2:1 to 6:1. The absorption and desorption of NO and NO2 was practically reversible in the ionic liquids, which was characterized by nuclear magnetic resonance. The method, which is at least partially reversible, offers interesting possibilities for the removal of NO and NO2.     

Potassium-based sorbents from fly ash for high-temperature CO<Subscript>2</Subscript> capture

Potassium-fly ash (K-FA) sorbents were investigated for high-temperature CO₂ sorption. K-FAs were synthesised using coal fly ash as source of silica and aluminium. The synthesised materials were also mixed with Li₂CO₃ and Ca(OH)₂ to evaluate their effect on CO₂ capture. Temperature strongly affected the performance of the K-FA sorbents, resulting in a CO₂ uptake of 1.45 mmol CO₂/g sorbent for K-FA 1:1 at 700 °C. The CO₂ sorption was enhanced by the presence of Li₂CO₃ (10 wt%), with the K-FA 1:1 capturing 2.38 mmol CO₂/g sorbent at 700 °C in 5 min. This sorption was found to be similar to previously developed Li-Na-FA (2.54 mmol/g) and Li-FA (2.4 mmol/g) sorbents. The presence of 10 % Li₂CO₃ also accelerated sorption and desorption. The results suggest that the increased uptake of CO₂ and faster reaction rates in presence of K-FA can be ascribed to the formation of K-Li eutectic phase, which favours the diffusion of potassium and CO₂ in the material matrix. The cyclic experiments showed that the K-FA materials maintained stable CO₂ uptake and reaction rates over 10 cycles.     

混合胺MEA+DETA吸收CO2的影响因素

以MEA为主体,DETA 为添加剂,考察1 h内,在温度298~338 K,压力300~700 kPa,混合胺溶液初始浓度(质量分数)4%~20%范围内,MEA+DETA不同配比的混合吸收剂吸收CO₂的特性。获得MEA+DETA混合胺吸收CO₂的最佳吸收条件为:308 K、500 kPa、总胺质量浓度为20%,MEA与DETA 的配比为8:2。     

Photocatalytic reduction of carbon dioxide over Cu/TiO<Subscript>2</Subscript> photocatalysts

The photocatalytic reduction of CO₂ with H₂O was investigated using Cu/TiO₂ photocatalysts in aqueous solution. For this purpose, Cu/TiO₂ photocatalysts (with 0.2, 0.9, 2, 4, and 6 wt.% of Cu) have been synthesized via sol-gel method. The photocatalysts were extensively characterized by means of inductively coupled plasma optical emission spectrometry (ICP-OES), N₂ physisorption (BET), XRD, UV-vis DRS, FT-IR, Raman spectroscopy, TEM-EDX, and photoelectrochemical measurements. The as-prepared photocatalysts contain anatase as a major crystalline phase with a crystallite size around 13 nm. By increasing the amount of Cu, specific surface area and band gap energy decreased in addition to the formation of large agglomeration of CuO. Results revealed that the photocatalytic reduction of CO₂ decreased in the presence of Cu/TiO₂ in comparison to pure TiO₂, which might be associated to the formation of CuO phase acting as a recombination center of generated electron-hole pair. Decreasing of photoactivity can also be connected with a very low position of conduction band of photocatalysts with high Cu content, which makes H₂ production necessary for CO₂ reduction more difficult.     

The adsorption of benzene and methylethylketone onto activated carbon: thermodynamic aspects.

The adsorption of volatile organic compounds (VOCs), exemplified by benzene and methylethylketone (MEK), onto seven different types of activated carbon was investigated. Results show that for benzene adsorption the adsorption characteristic energy, enthalpy, free energy and entropy are in the range 17.12-36.86, -20.8 to -44.7, -11.89 to -16.22 kJ/mole and -29.4 to -85.3 J/mole/K, respectively. For the adsorption of MEK, the adsorption characteristic energy, enthalpy, free energy and entropy are in the range 14.47-32.34, -18.3 to -40.8, -10.78 to -15.56 kJ/mole and -24.8 to approximately -60.3 J/mole/K, respectively. The adsorption enthalpy can be calculated indirectly from statistical thermodynamic method and directly from the immersion enthalpy method. The adsorption characteristic energy is calculated by the Dubinin-Astokhov equation. The free energy is calculated by the measured equilibrium adsorption constant.     

Catalytic gasification of biomass (<Emphasis Type="Italic">Miscanthus</Emphasis>) enhanced by CO<Subscript>2</Subscript> sorption

The main objective of this work concerns the coupling of biomass gasification reaction and CO₂ sorption. The study shows the feasibility to promote biomass steam gasification in a dense fluidized bed reactor with CO₂ sorption to enhance tar removal and hydrogen production. It also proves the efficiency of CaO-Ca₁₂Al₁₄O₃₃/olivine bi-functional materials to reduce heavy tar production. Experiments have been carried out in a fluidized bed gasifier using steam as the fluidizing medium to improve hydrogen production. Bed materials consisting of CaO-based oxide for CO₂ sorption (CaO-Ca₁₂Al₁₄O₃₃) deposited on olivine for tar reduction were synthesized, their structural and textural properties were characterized by Brunauer–Emmett–Teller (BET), X-ray diffraction (XRD), and temperature-programmed reduction (TPR) methods, and the determination of their sorption capacity and stability analyzed by thermogravimetric analysis (TGA). It appears that this CaO-Ca₁₂Al₁₄O₃₃/olivine sorbent/catalyst presents a good CO₂ sorption stability (for seven cycles of carbonation/decarbonation). Compared to olivine and Fe/olivine in a fixed bed reactor for steam reforming of toluene chosen as tar model compound, it shows a better hydrogen production rate and a lower CO₂ selectivity due to its sorption on the CaO phase. In the biomass steam gasification, the use of CaO-Ca₁₂Al₁₄O₃₃/olivine as bed material at 700 °C leads to a higher H₂ production than olivine at 800 °C thanks to CO₂ sorption. Similar tar concentration and lighter tar production (analyzed by HPLC/UV) are observed. At 700 °C, sorbent addition allows to halve tar content and to eliminate the heaviest tars.     

Accelerated carbonation of wood combustion ash for CO<Subscript>2</Subscript> removal from gaseous streams and storage in solid form

In this work, ash generated by the combustion of wood in a central heating plant was used to remove and permanently store by accelerated carbonation CO₂ contained in a gas mixture simulating biogas. The process was studied as an alternative treatment to the ones currently available on the market for biogas upgrading. The process was investigated at laboratory scale by setting up a facility for directly contacting the wood ash and the synthetic biogas in a fixed bed reactor. The process was able to completely remove CO₂ during its initial phase. After about 30 h, CO₂ started to appear again in the outlet stream and its concentration rapidly increased. The specific CO₂ uptake achieved in solid carbonate form was of about 200 g/kg of dry wood ash. This value is an order of magnitude higher than the ones found for waste incineration bottom ash carrying out similar experiments. The difference was ascribed to the physicochemical properties of the ash, characterized by a fine particle size (d₅₀ <?0.2 mm) and high content of reactive phases with CO₂ (e.g., Ca hydroxides). The leaching behavior of the wood ash was examined before and after the accelerated carbonation process showing that the release of several elements was lower after the treatment; Ba leaching in particular decreased by over two orders of magnitude. However, the release of the critical elements for the management of this type of residues (especially Cr and sulfates) appeared not to be significantly affected, while V leaching increased.     

Enhanced UV-B and Elevated CO<Subscript>2</Subscript> Impacts Sub-Arctic Shrub Berry Abundance,Quality and Seed Germination

This study investigated the effects of long-term-enhanced UV-B, and combined UV-B with elevated CO₂ on dwarf shrub berry characteristics in a sub-arctic heath community. Germination of Vaccinium myrtillus was enhanced in seeds produced at elevated UV-B, but seed numbers and berry size were unaffected. Elevated UV-B and CO₂ stimulated the abundance of V. myrtillus berries, whilst UV-B alone stimulated the berry abundance of V. vitis-idaea and Empetrum hermaphroditum. Enhanced UV-B reduced concentrations of several polyphenolics in V. myrtillus berries, whilst elevated CO₂ increased quercetin glycosides in V. myrtillus, and syringetin glycosides and anthocyanins in E. hermaphroditum berries. UV-B × CO₂ interactions were found for total anthocyanins, delphinidin-3-hexoside and peonidin-3-pentosidein in V. myrtillus berries but not E. hermaphroditum. Results suggest positive impacts of UV-B on the germination of V. myrtillus and species-specific impacts of UV-B × elevated CO₂ on berry abundance and quality. The findings have relevance and implications for human and animal consumers plus seed dispersal and seedling establishment.     

Effect of nuclear power on CO<Subscript>2</Subscript> emission from power plant sector in Iran

Introduction  

It is predicted that demand for electricity in Islamic Republic of Iran will continue to increase dramatically in the future due to the rapid pace of economic development leading to construction of new power plants. At the present time, most of electricity is generated by burning fossil fuels which result in emission of great deal of pollutants and greenhouse gases (GHG) such as SO₂, NO_x, and CO₂. The power industry is the largest contributor to these emissions. Due to minimal emission of GHG by renewable and nuclear power plants, they are most suitable replacements for the fossil-fueled power plants. However, the nuclear power plants are more suitable than renewable power plants in providing baseload electricity. The Bushehr Nuclear Power Plant, the only nuclear power plant of Iran, is expected to start operation in 2010. This paper attempts to interpret the role of Bushehr nuclear power plant (BNPP) in CO₂ emission trend of power plant sector in Iran.     

Study of fuel oxygenates solubility in aqueous media as a function of temperature and tert-butyl alcohol concentration

Methyl tert-butyl ether (MTBE) is the most widely used oxygenate in gasoline blending and has become one of the world’s most widespread groundwater and surface water pollutants. Alternative oxygenates to MTBE, namely ethyl tert-butyl ether (ETBE), tert-amyl ether (TAME) and diisopropyl ether (DIPE) have been hardly studied yet. The solubility of these chemicals is a key thermodynamic information for the assessment of the fate and transport of these pollutants. This work reports experimental data of water solubility at the range from 278.15 to 313.15 K and atmospheric pressure of ethers used in fuels (MTBE, ETBE, TAME and DIPE) due to the strong influence of temperature on its trend. From the experimental data, temperature dependent polynomials were fitted, thermodynamic parameters were calculated and theoretical models were used for prediction. Finally, the tert-butyl alcohol (TBA) influence in the solubility of MTBE and ETBE in aqueous media was studied.     

Absorption and Reaction Kinetics of Amines and Ammonia Solutions with Carbon Dioxide in Flue Gas

Abstract

The removal system for the absorption of CO₂ with amines and NH₃ is an advanced air pollution control device to reduce greenhouse gas emissions. Absorption of CO₂ by amines and NH₃ solutions was performed in this study to derive the reaction kinetics. The absorption of CO₂ as encountered in flue gases into aqueous solutions of monoethanolamine (MEA), diethanolamine (DEA), and NH₃ was carried out using a stirred vessel with a plane gas-liquid interface at 50 °C. Various operating parameters were tested to determine the effect of these variables on the absorption kinetics of the reactants in both gas and liquid phases and the effect of competitions between various reactants on the mass-transfer rate.

The observed absorption rate increases with increasing gas-liquid concentration, solvent concentration, temperature, and gas flow rate, but changes with the O₂ concentration and pH value. The absorption efficiency of MEA is better than that of NH₃ and DEA, but the absorption capacity of NH₃ is the best. The active energies of the MEA and NH₃ with CO₂ are 33.19 and 40.09 kJ/mol, respectively.     

Thermodynamic analysis of in situ gasification-chemical looping combustion (<Emphasis Type="Italic">i</Emphasis>G-CLC) of Indian coal

Chemical looping combustion (CLC) is an inherent CO₂ capture technology. It is gaining much interest in recent years mainly because of its potential in addressing climate change problems associated with CO₂ emissions from power plants. A typical chemical looping combustion unit consists of two reactors—fuel reactor, where oxidation of fuel occurs with the help of oxygen available in the form of metal oxides and, air reactor, where the reduced metal oxides are regenerated by the inflow of air. These oxides are then sent back to the fuel reactor and the cycle continues. The product gas from the fuel reactor contains a concentrated stream of CO₂ which can be readily stored in various forms or used for any other applications. This unique feature of inherent CO₂ capture makes the technology more promising to combat the global climate changes. Various types of CLC units have been discussed in literature depending on the type of fuel burnt. For solid fuel combustion three main varieties of CLC units exist namely: syngas CLC, in situ gasification-CLC (iG-CLC) and chemical looping with oxygen uncoupling (CLOU). In this paper, theoretical studies on the iG-CLC unit burning Indian coal are presented. Gibbs free energy minimization technique is employed to determine the composition of flue gas and oxygen carrier of an iG-CLC unit using Fe₂O₃, CuO, and mixed carrier—Fe₂O₃ and CuO as oxygen carriers. The effect of temperature, suitability of oxygen carriers, and oxygen carrier circulation rate on the performance of a CLC unit for Indian coal are studied and presented. These results are analyzed in order to foresee the operating conditions at which economic and smooth operation of the unit is expected.     

Study on the removal of elemental mercury from simulated flue gas by Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>-CeO<Subscript>2</Subscript>/AC at low temperature

Fe₂O₃ and CeO₂ modified activated coke (AC) synthesized by the equivalent-volume impregnation were employed to remove elemental mercury (Hg⁰) from simulated flue gas at a low temperature. Effects of the mass ratio of Fe₂O₃ and CeO₂, reaction temperature, and individual flue gas components including O₂, NO, SO₂, and H₂O (g) on Hg⁰ removal efficiency of impregnated AC were investigated. The samples were characterized by Brunauer–Emmett–Teller (BET), X-ray diffraction (XRD), scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS). Results showed that with optimal mass percentage of 3 % Fe₂O₃ and 3 % CeO₂ on Fe3Ce3/AC, the Hg⁰ removal efficiency could reach an average of 88.29 % at 110 °C. Besides, it was observed that O₂ and NO exhibited a promotional effect on Hg⁰ removal, H₂O (g) exerted a suppressive effect, and SO₂ showed an insignificant inhibition without O₂ to some extent. The analysis of XPS indicated that the main species of mercury on used Fe3Ce3/AC was HgO, which implied that adsorption and catalytic oxidation were both included in Hg⁰ removal. Furthermore, the lattice oxygen, chemisorbed oxygen, and/or weakly bonded oxygen species made a contribution to Hg⁰ oxidation.     

Reducing Interference Effects in the Chemiluminescent Measurement of Nitric Oxides from Combustion Systems

Experiments were carried out to determine the relative chemiluminescence quenching efficiencies as a function of third body concentration for each of the common combustion products, H₂O, CO₂, CO, H₂, O₂ and Ar. These results are compared with those of other investigators. The effect of reaction chamber pressure on analyzer response and the development of an analyzer design which incorporates an adjustable sample capillary inlet capable of maintaining a constant molar flow rate of sample gas to the reaction chamber are discussed. The effect of carbon monoxide interference on chemiluminescent NO_x measurement has been isolated and found to be significant. A means of correcting NO, measurements for these CO interference effects is described. Quantification of NO and NO₂ absorption in liquid water in NO_x sampling systems has been made. Recommendations for sample system designs to handle the presence of water in the sample gas are made.     

Aqueous solubility, Henry's law constants and air/water partition coefficients of n-octane and two halogenated octanes

New data on the aqueous solubility of n-octane, 1-chlorooctane and 1-bromooctane are reported between 1 degree C and 45 degrees C. Henry's law constants, K(H), and air/water partition coefficients, K(AW), were calculated by associating the measured solubility values to vapor pressures taken from literature. The mole fraction aqueous solubility varies between (1.13-1.60)x10(-7) for n-octane with a minimum at approximately 23 degrees C, (3.99-5.07)x10(-7) for 1-chlorooctane increasing monotonically with temperature and (1.60-3.44)x10(-7) for 1-bromooctane with a minimum near 18 degrees C. The calculated air-water partition coefficients increase with temperature and are two orders of magnitude lower for the halogenated derivatives compared to octane. The precision of the results, taken as the average absolute deviations of the aqueous solubility, the Henry's law constants, or the air/water partition coefficients, from appropriate smoothing equations as a function of temperature is of 3% for n-octane and of 2% and 4% for 1-chlorooctane and 1-bromooctane, respectively. A new apparatus based on the dynamic saturation column method was used for the solubility measurements. Test measurements with n-octane indicated the capability of measuring solubilities between 10(-6) and 10(-10) in mole fraction, with an estimated accuracy better than +/-10%. A thorough thermodynamic analysis of converting measured data to air/water partition coefficients is presented.     

Hydrogen production using thermocatalytic decomposition of methane on Ni<Subscript>30</Subscript>/activated carbon and Ni<Subscript>30</Subscript>/carbon black

Hydrogen is an energy carrier of the future need. It could be produced from different sources and used for power generation or as a transport fuel which mainly in association with fuel cells. The primary challenge for hydrogen production is reducing the cost of production technologies to make the resulting hydrogen cost competitive with conventional fuels. Thermocatalytic decomposition (TCD) of methane is one of the most advantageous processes, which will meet the future demand, hence an attractive route for CO_x free environment. The present study deals with the production of hydrogen with 30 wt% of Ni impregnated in commercially available activated carbon and carbon black catalysts (samples coded as Ni₃₀/AC and Ni₃₀/CB, respectively). These combined catalysts were not attempted by previous studies. Pure form of hydrogen is produced at 850 °C and volume hourly space velocity (VHSV) of 1.62 L/h g on the activity of both the catalysts. The analysis (X-ray diffraction (XRD)) of the catalysts reveals moderately crystalline peaks of Ni, which might be responsible for the increase in catalytic life along with formation of carbon fibers. The activity of carbon black is sustainable for a longer time compared to that of activated carbon which has been confirmed by life time studies (850 °C and 54 sccm of methane).     

Temperature dependence of PCBs in the UK atmosphere

A thermodynamic approach was taken to assess the state of equilibrium between air and the Earth’s surface for PCBs at a variety of sites located in urban and rural areas. The Clausius–Clapeyron equation was applied to atmospheric PCB data, relating PCB partial vapour pressure (ln P) to inverse temperature (1/K); essentially representing the temperature controlled transition between condensed phases and the atmospheric gas phase. The slopes of the resulting plots ranged from −3100 to −8272 for a range of congeners at two city sites, significantly steeper than those generated at two rural locations, where there was little or no correlation between ln P and temperature. It was inferred that advection and variable meteorological conditions mask any localised, temperature dependent, air–surface exchange at these rural locations when weekly or two weekly integrated samples were taken. At a third rural site, close to Lancaster University, an intensive highly time-resolved sampling regime, carried out during very stable meteorological conditions resulted in highly correlated plots (r²>0.6), with slopes ranging from −7151 to −14 148 for different congeners. By reducing meteorological variables in this manner localised temperature controlled air–surface exchange became evident. Enthalpies of phase change generated from the temperature coefficients were similar to literature values for the enthalpy of vapourisation and the enthalpy of phase change from octanol to air. This suggests that, under these stable conditions, equilibrium was achieved as a function of either vapour pressure (P^°_L) or the octanol–air partition coefficient (K_OA).