Non-isothermal flow of carbon dioxide in injection wells during geological storage

During sequestration, carbon dioxide within injection wells is likely to be in a dense state and therefore its weight within the wellbore will play an important role in determining the bottomhole pressure and thus the injection rate. However, the density could vary significantly along the well in response to the variation in pressure and temperature. A numerical procedure is formulated in this paper to evaluate the flow of carbon dioxide and its mixtures in non-isothermal wells. This procedure solves the coupled heat, mass and momentum equations with the various fluid and thermodynamic properties, including the saturation pressure, of the gas mixture calculated using a real gas equation of state. This treatment is particularly useful when dealing with gas mixtures where experimental data on mixture properties are not available and these must be predicted. To test the developed procedure two wellbore flow problems from the literature, involving geothermal gradients and wellbore phase transitions are considered; production of 97% carbon dioxide and injection of superheated steam. While these are not typical carbon dioxide injection problems they provide field observations of wellbore flow processes which encompass the mechanisms of interest for carbon dioxide injection, such as phase transition, temperature and density variations with depth. These two examples show that the developed procedure can offer accurate predictions. In a third application the role of wellbore hydraulics during a hypothetical carbon dioxide injection application is considered. The results obtained illustrate the potential complexity of carbon dioxide wellbore hydraulics for sequestration applications and the significant role it can play in determining the well bottomhole pressure and thus injection rate.     

Pesticide adsorption on a calcareous soil modified with sewage sludge and quaternary alkyl-ammonium cationic surfactants

BACKGROUND, AIM AND SCOPE: Pesticides are often found in soil as a result of their application to control pests. They can be transported on soil particles to surface waters or they can lixiviate and reach other environmental compartments. Soil modification with amendments, such as sewage sludge, and with surfactants, h been proposed to reduce pesticide environmental fate. METHODS: The sorption of atrazine, methidathion and diazinon using the batch technique has been studied on non-modified soil and soil modified with sewage sludge and cationic surfactants, as well as the effect of their addition on soil properties such as organic carbon (OC) content and exchange cations. RESULTS AND DISCUSSION: The OC content of the surfactant modified soils was the highest with the surfactant with the longest hydrocarbon chain (hexadecyltrimethyl ammonium bromide, HDTMA). The results of the OC content run in parallel with the increase in pesticide retention. When the sorption was n malized to soil OC content, the retention induced by addition of HDTMA was still the highest, which is an indication that the organic matter derived from the organic cations is a more effective medium to retain dissolved contaminants, than organic matter from native soil. The addition of sewage sludge to the soil did only result in a slight increase of the soil CEC and, hence, moderately affected the ability of the cationic surfactant to retain the pesticides. CONCLUSIONS: The addition of cationic surfactants to soil would possibly reduce the movement to groundwater of atrazine, methidathion and diazinon. In the case of HDTMA, the decrease in sorption at high surfactant loadings was very slow, being that the surfactant was able to retain the pesticides at concentration values which clearly exceeded the monolayer coverage. RECOMMENDATIONS AND PERSPECTIVES: Contamination by pesticides, which are present in the soil due to their direct input in this medium or to spills or illegal tipping, may be hindered from migration to groundwater by application of a cationic surfactant.     

Removal of Zn and Ni by adsorption in a fixed bed of wheat straw

Zn⁺² and Ni⁺² in a solution were removed by biosorption in a fixed bed of wheat straw Triticum aestivum. The removal rate and the mass transfer coefficient for Zn⁺² and Ni⁺² were found to be proportional to the liquid superficial velocity to the power of 0.31 for the range of the particle Reynolds number from 18 to 445 (equivalent liquid rates of 0.00070–0.0175 m³ m⁻² s⁻¹). This agrees well with reported literature for mass transfer in a packed bed of solid particles under a laminar flow regime. Effect of the solution pH, temperature and the particle size (0.5, 1.0, 1.5 and 2.0 in.) on biosorption of Zn⁺² and Ni⁺² was also investigated. Biosorption of both Zn⁺² and Ni⁺² increased significantly with the solution pH from 4.0 to 7.0. On the other hand, Zn⁺² and Ni⁺² removal appeared to be insensitive to liquid temperature from 25 to 30 °C. Nevertheless, a 25% increase in the percentage removal of metal ions was observed with further increase of liquid temperature from 30 to 35 °C. However, the biosorbent particle size did not seem to have a systematic effect on the biosorption of Zn⁺² and Ni⁺². In addition, biosorption of Zn⁺² was not affected considerably by co-adsorption of the bimetal solution while biosorption of Ni⁺² decreased about 14%.     

Enhancement of phenanthrene adsorption on a clayey soil and clay minerals by coexisting lead or cadmium

Phenanthrene is commonly present together with heavy metals at many contaminated sites. This study investigated the influence of coexisting lead (Pb²⁺) or cadmium (Cd²⁺) on phenanthrene adsorption on soils. Batch experiments were conducted under different geochemical conditions including pH, mineral structure, organic matter content, and varying amounts of heavy metals. The results showed that the presence of heavy metals in solution at a fixed pH of 5.8 ± 0.1 enhanced phenanthrene adsorption, the extent of which was closely related to the concentrations and the electro-negativity of the metals. The enhancement on phenanthrene adsorption was positively correlated to the amount of adsorbed metals. Although Cd²⁺ is a softer Lewis acid, Pb²⁺ displayed a more significant effect as it was adsorbed to a greater extent on the soil surfaces. Thus, density of cation accumulation appears to be more influential than metal softness in enhancing phenanthrene adsorption. Moreover, with a portion of organic matter removed by heating at 550 °C, there was a stronger enhancement of phenanthrene adsorption by coexisting Pb²⁺, indicating an increasingly dominant mechanisms associated with Pb²⁺ at a lower organic matter content. Similar enhancement phenomenon was observed on bentonite and kaolinite, probably resulting from the cation-π bonding between the adsorbed soft metal cations and the aromatic ring of phenanthrene in solution. The desorption experiments further suggested that the bonding of phenanthrene adsorption was strengthened in the presence of Pb²⁺ and that a larger proportion of adsorbed phenanthrene remained on the soils (residual fraction) even after sequential methanol extractions. Further spectroscopic analyses and surface characterization are required to provide direct evidence of the formation and relative significance of cation-π bond for phenanthrene adsorption.     

Sorptive domains of pine chars as probed by benzene and nitrobenzene

Chars were generated by pyrolyzing pine wood at temperatures between 300 °C and 700 °C for 6 h and at 500 °C for 10-300 min. Their organic content and surface acidity decreased, and BET surface area increased, with increasing pyrolytic temperature and time. The uptake of benzene and nitrobenzene increased with increasing pyrolytic temperature and time with isotherms characterized by a transition from less to more concave-downward. The isotherms with low-temperature and short-time chars were fitted to the dual Langmuir-partition model, whereas those with high-temperature chars to the dual-Langmuir model. Calculations suggest that the organic phases of chars functioned as partition media and the uptake of benzene and nitrobenzene on carbonized chars occurred first in micropores via pore-filling and later in larger pores through capillary condensation and adsorption. It is concluded that chars may be considered to consist of the partition domain, the high-energy micropores domain and the low-energy large pores domain.     

Reduction of dioxin emission by a multi-layer reactor with bead-shaped activated carbon in simulated gas stream and real flue gas of a sinter plant

A laboratory-scale multi-layer system was developed for the adsorption of PCDD/Fs from gas streams at various operating conditions, including gas flow rate, operating temperature and water vapor content. Excellent PCDD/F removal efficiency (>99.99%) was achieved with the multi-layer design with bead-shaped activated carbons (BACs). The PCDD/F removal efficiency achieved with the first layer adsorption bed decreased as the gas flow rate was increased due to the decrease of the gas retention time. The PCDD/F concentrations measured at the outlet of the third layer adsorption bed were all lower than 0.1 ng I-TEQ Nm⁻³. The PCDD/Fs desorbed from BAC were mainly lowly chlorinated congeners and the PCDD/F outlet concentrations increased as the operating temperature was increased. In addition, the results of pilot-scale experiment (real flue gases of an iron ore sintering plant) indicated that as the gas flow rate was controlled at 15 slpm, the removal efficiencies of PCDD/F congeners achieved with the multi-layer reactor with BAC were better than that in higher gas flow rate condition (20 slpm). Overall, the lab-scale and pilot-scale experiments indicated that PCDD/F removal achieved by multi-layer reactor with BAC strongly depended on the flow rate of the gas stream to be treated.     

Sorption of apolar and polar organic contaminants by waste tire rubber and its chars in single- and bi-solute systems

Single- and bi-solute sorption of organic compounds [1,3-dichlorbenzene (DCB), 1,3-dinitrobenzene (DNB) and 2,4-dichlorophenol (DCP)] on ground tire rubber and its chars was studied. The chars were prepared by pyrolyzing tire rubber at different temperatures (200-800 °C). Their surface area, aromaticity and hydrophobicity increase greatly with pyrolytic temperature, and the polymeric phase is partly converted into a condensed phase. The sorption of DNB and DCP increases with pyrolytic temperature and is characterized by a transition from a partition dominant to an adsorption dominant process. However, the sorption of DCB linearly decreases with the pyrolytic temperature. The enhanced adsorption of DNB and DCP on carbonized phase is primarily attributed to nonhydrophobic interactions such as π-π electron-donor-acceptor interactions and/or H bonding. The higher partition of DCB to polymeric phase is attributed to its high hydrophobicity. Competitive sorption between DCB and DCP on the tire chars is highly dependent on dissociation of the latter.     

Assessment of surface area normalisation for interpreting distribution coefficients (Kd) for uranium sorption

Adsorption of radionuclides on soils and sediments is commonly quantified by distribution coefficients (K_d values). This paper examines the relationship between K_d values for uranium(VI) adsorption and the specific surface area (SSA) of geologic materials. We then investigate the potential applicability of normalising uranium (U) K_d measurements using the SSA, to produce ‘K_a values’ as a generic expression of the affinity of U for the surface. The data for U provide a reasonably coherent set of K_a values on various solid phases, both with and without ligands. The K_a representation provides a way of harmonising datasets obtained for materials having different specific surface areas, and accounting for the effects of ligands in different systems. In addition, this representation may assist in developing U sorption models for complex materials. However, a significant limitation of the K_a concept is that sorption of radionuclides at trace levels can be dominated by interactions with specific surface sites, whose abundances are not reflected by the SSA. Therefore, calculated K_a values should be interpreted cautiously.     

Adsorption behavior of RH‐5992 insecticide onto sandy and clay loam forest soils

Abstract

Adsorption‐desorption behavior of RH‐5992 [Mimic®, N'‐t‐butyl‐N'‐(3,5‐dimethylbenzoyl)‐N‐(4‐ethylbenzoyl) hydrazine] in sandy and clay loam forest soils was studied using the batch equilibrium method. Adsorption was higher in the clay loam soil than in the sandy loam, and increased linearly with RH‐5992 concentration, but decreased with increasing pH and temperature. The adsorption data fit better to the Freundlich, than to the Langmuir equation. The K_D (linear adsorption constant) and K_F (Freundlich constant) were similar for each soil at 5, 15 and 25°C and decreased with increase of temperature, indicating that the enthalpy of adsorption was negative. The exponent of the Freundlich equation was close to unity for both soils at all three temperatures. The low E_a (energy of activation) indicated a diffusion‐controlled process during the initial stages of adsorption. The desorption isotherm differed from that of adsorption, and the linear desorption constant, K_D(d), was ca 25 times higher than the K_D, indicating that adsorption of RH‐5992 was not readily reversible. Evaluation of thermo‐dynamic parameters confirmed the presence of strong bonds between the solute and soil. These findings suggest that RH‐5992 has a limited potential for downward mobility leading to groundwater contamination.     

Neptunium(V) adsorption to calcite

The migration behavior of the actinyl ions U(VI)O₂²⁺, Np(V)O₂⁺ and Pu(V,VI)O₂^(+,2+) in the geosphere is to a large extend controlled by sorption reactions (inner- or outer-sphere adsorption, ion-exchange, coprecipitation/structural incorporation) with minerals. Here NpO₂⁺ adsorption onto calcite is studied in batch type experiments over a wide range of pH (6.0–9.4) and concentration (0.4 μM–40 μM) conditions. pH is adjusted by variation of CO₂ partial pressure. Adsorption is found to be pH dependent with maximal adsorption at pH 8.3 decreasing with increasing and decreasing pH. pH dependence of adsorption decreases with increasing Np(V) concentration. EXAFS data of neptunyl adsorbed to calcite and neptunyl in the supernatant shows differences in the Np(V)-O-yl distance, 1.85 ± 0.01 Å for the adsorbed and 1.82 ± 0.01 Å for the solution species. The equatorial environment of the neptunyl in solution shows about 5 oxygen neighbours at 2.45 ± 0.02 Å. For adsorbed neptunyl there are also about 5 oxygen neighbours at 2.46 ± 0.01 Å. An additional feature in the adsorbed species' R-space spectrum can be related to carbonate neighbours, 3 to 6 carbon backscatterers (C-eq) at 3.05 ± 0.03 Å and 3 to 6 oxygen backscatterers (O-eq2) at 3.31 ± 0.02 Å. The differences in the Np(V)-O-yl distance and the C-eq and O-eq2 backscatterers which are only present for the adsorbed species indicate inner-sphere bonding of the adsorbed neptunyl species to the calcite surface. Experiments on adsorption kinetics indicate that after a fast surface adsorption process a continuous slow uptake occurs which may be explained by incorporation via surface dissolution and reprecipitation processes. This is also indicated by the part irreversibility of the adsorption as shown by increased K_D values after desorption compared to adsorption.