Experimental study of pure and mixtures of CO<Subscript>2</Subscript> and CH<Subscript>4</Subscript> adsorption on modified carbon nanotubes

In this work 3-[2-(2-aminoethylamino)ethylamino]propyl trimethoxysilane (TRI) was employed to functionalize MWCNT containing hydroxyl groups (OH-MWCNT), and the XRD, FTIR, TGA and CHNS elemental analysis techniques were used to characterize the resulted adsorbents. The characterization results for amine-MWCNT showed amine groups effectively attached to the surface of the MWCNT. The equilibrium adsorption capacity of pure CO₂ and CH₄ and their binary mixture on the pristine MWCNT, OH-MWCNT and amine-MWCNT was measured through a set of equilibrium adsorption experiments at 303.2 and 318.2 K. Capacities of all three types of adsorbents for CO₂ adsorption were higher than those for methane adsorption. Also, amine-MWCNT demonstrated better performance on CO₂ adsorption than the other two adsorbents, especially at low partial pressures. The capacity of amine-MWCNT for pure CO₂ adsorption was 2.5 and 4 times as much as those for pristine MWCNT and OH-MWCNT, respectively, at the temperature of 303.2 K and the pressure of 0.2 bar. The binary adsorption experiment revealed that CO₂/CH₄ selectivity for pristine MWCNT and amine-MWCNT in all molar fractions of CO₂ is about 1.77 and 7, respectively.     

Adsorption of H<Subscript>2</Subscript>O,NH<Subscript>3</Subscript> and C<Subscript>6</Subscript>H<Subscript>6</Subscript> on alkali metal cations in internal surface of mordenite and in external surface of smectite: a DFT study

Adsorption of H₂O, NH₃ and C₆H₆ on H- and alkali metal-exchanged structures of mordenite and on corresponding cations on the smectite layer is investigated by ab initio density-functional calculations. Proton or an alkali metal cation compensates one Al/Si framework substitution and resides in the extra-framework position of zeolite or above flat smectite layer close to the Al/Si substitution. Pronounced similarities between zeolite and smectite are observed in changes of the adsorption energies and location of the external cation with changing character of the external cation. Calculated adsorption energies exhibit the following trend: E(NH₃) > E(H₂O) > E(C₆H₆). Because of looser contact with the framework, zeolitic cations are stronger adsorption centers and calculated adsorption energies of zeolites are by ~20–30% larger than cations of smectites. The highest adsorption energy is calculated for H-exchanged structures and down the group of alkali metal cations a decrease of the adsorption energy is observed. Deviations from the smooth variation of the adsorption energy are caused by: (1) formation of strong hydrogen bonds in H-exchanged structures, (2) adsorption induced migration of the external Li⁺ cation, and (3) steric hindrances of the flat C₆H₆ molecule adsorbed on the cation in the cage of zeolite.     

Preparation of carbon molecular sieves and its impregnation with Co and Ni for CO<Subscript>2</Subscript>/N<Subscript>2</Subscript> separation

The carbon molecular sieves (CMSs) prepared by carbonaceous materials as precursors are effective in CO₂/N₂ separation. However, selectivity of these materials is too low, since hydrocarbon cracking for developing the desired microporosity in carbonaceous materials has not been done effectively. Hence, in this study, cobalt and nickel impregnation on the precursor was conducted to introduce catalysts for hydrocarbon cracking. Cobalt and nickel impregnation, carbonization under N₂ atmosphere, and chemical vapor deposition (CVD) by benzene were conducted on the extruded mixtures of activated carbon and coal tar pitch under different conditions to prepare CMSs. The best CMS prepared by carbon deposition on the cobalt-impregnated samples exhibited CO₂ adsorption capacity of 54.79 mg/g and uptake ratio of 28.9 at 0 °C and 1 bar. In terms of CO₂ adsorption capacity and uptake ratio, CMSs prepared by carbon deposition on non-impregnated and cobalt-impregnated samples presented the best results, respectively. As benzene concentration and CVD time increased, equilibrium adsorption capacity of CO₂ decreased, and uptake ratio increased. Cobalt was found to be the best catalyst for benzene cracking in the CVD process.     

Study of carbon dioxide and methane equilibrium adsorption on silicoaluminophosphate-34 zeotype and T-type zeolite as adsorbent

Carbon dioxide is known as a hazardous material with acidic property that can be found as impurity in natural gas reservoirs with a broad range of 2 up to 40 %. Therefore, many efforts have been directed to remove and separate carbon dioxide from methane to prevent corrosion problems as well as improving the natural gas energy content. In this study, two molecular sieves, silicoaluminophosphate-34 (SAPO-34) zeotype and T-type zeolite, were synthesized by the hydrothermal method for the comparative study of adsorptive separation of carbon dioxide from methane. The synthesized adsorbents were characterized by X-ray diffraction, scanning electron microscopy, energy dispersive X-ray spectroscopy, and Brunner–Emmett–Teller techniques. These characterization tests confirmed formation of both materials with acceptable crystallinity. Both adsorbents were tested in equilibrium adsorption experiments in order to evaluate maximum capacity and adsorption affinity. Adsorption capacity of carbon dioxide and methane on SAPO-34 and zeolite T were measured in a pressure range of 0.1–2.0 MPa and temperature of 288, 298, and 308 K and fitted with the Sips and Langmuir isotherm models. The ideal selectivity of CO₂/CH₄ was determined for SAPO-34 and zeolite T at the studied pressures and temperatures, indicating that the molecular sieves can be properly used for CO₂–CH₄ separation or CO₂ capturing from natural gas.     

Sealing efficiency analysis for shallow-layer caprocks in CO<Subscript>2</Subscript> geological storage

The CO₂ migrated from deeper to shallower layers may change its phase state from supercritical state to gaseous state (called phase transition). This phase transition makes both viscosity and density of CO₂ experience a sharp variation, which may induce the CO₂ further penetration into shallow layers. This is a critical and dangerous situation for the security of CO₂ geological storage. However, the assessment of caprock sealing efficiency with a fully coupled multi-physical model is still missing on this phase transition effect. This study extends our previous fully coupled multi-physical model to include this phase transition effect. The dramatic changes of CO₂ viscosity and density are incorporated into the model. The impacts of temperature and pressure on caprock sealing efficiency (expressed by CO₂ penetration depth) are then numerically investigated for a caprock layer at the depth of 800 m. The changes of CO₂ physical properties with gas partial pressure and formation temperature in the phase transition zone are explored. It is observed that phase transition revises the linear relationship of CO₂ penetration depth and time square root as well as penetration depth. The real physical properties of CO₂ in the phase transition zone are critical to the safety of CO₂ sequestration. Pressure and temperature have different impact mechanisms on the security of CO₂ geological storage.     

Feasibility of CO<Subscript>2</Subscript> adsorption by solid adsorbents: a review on low-temperature systems

In the last few decades of industrialization, the concentration of CO₂ in the atmosphere had increased rapidly. Different organizations have invested considerable funds in research activities worldwide for CO₂ capture and storage. To date, significant work has been done and various technologies have been proposed for CO₂ capture and storage. Both adsorption and absorption are promising techniques for CO₂ capture, but low-temperature adsorption processes using solid adsorbents are the prevailing technique nowadays. In this review paper, a variety of adsorbents such as carbonaceous materials, dry alkali metal-based sorbents, zeolites, metal–organic frameworks (MOFs) and microporous organic polymers (MOPs) have been studied. Various methods of chemical or physical modification and the effects of supporting materials have been discussed to enhance CO₂ capture capacity of these adsorbents. Low-temperature (<100 °C) adsorption processes for CO₂ capture are critically analyzed and concluded on the basis of information available so far in the literature. All the information in CO₂ adsorption using different routes has been discussed, summarized and thoroughly presented in this review article. The most important comparative study of relatively new material MOFs and MOPs is carried out between the groups and with other sorbent as well.     

Depth of volcanic basalt degassing forecasted from CO2 fluid inclusions

Fluid inclusions have recorded the history of degassing in basalt. Some fluid inclusions in olivine and pyroxene phenocrysts of basalt were analyzed by micro-thermometry and Raman spectroscopy in this paper. The experimental results showed that many inclusions are present almost in a pure CO2 system. The densities of some CO2 inclusions were computed in terms of Raman spectroscopic characteristics of CO2 Fermi resonance at room temperature. Their densities change over a wide range, but mainly between 0.044 g/cm3 and 0.289 g/cm3. Their micro-thermometric measurements showed that the CO2 inclusions examined reached homogenization between 1145.5℃ and 1265℃ . The mean value of homogenization temperatures of CO2 inclusions in basalts is near 1210℃. The trap pressures (depths) of inclusions were computed with the equation of state and computer program. Distribution of the trap depths makes it know that the degassing of magma can happen over a wide pressure (depth) range, but mainly at the depth of 0.48 km to 3.85 km. This implicates that basalt magma experienced intensive degassing and the CO2 gas reservoir from the basalt magma also may be formed in this range of depths. The results of this study showed that the depth of basalt magma degassing can be forecasted from CO2 fluid inclusions, and it is meaningful for understanding the process of magma degassing and constraining the inorganogenic CO2 gas reservoir.     

Ammonia emission from CO<Subscript>2</Subscript> capture pilot plant using aminoethylethanolamine

Amine post-combustion carbon capture technology is based on washing the flue gas with a solvent that captures CO₂. Thus, a small fraction of this solvent can be released together with the cleaned flue gas. This release may cause environmental concerns, both directly and indirectly through subsequent solvent degradation into other substances in the atmosphere. The paper presents the ammonia emission from CO₂ capture pilot plant (1 tonne CO₂ per day) using 40 wt% aminoethylethanolamine solvent, along with the efficiency of the water wash unit. In addition, the temperature effect of lean amine entering the absorber on ammonia emission was studied. Furthermore, the concentrations of other compounds such as SO₂, SO₃, NO₂, CS₂ and formaldehyde were monitored. The literature review on the NH₃ emission from a pilot plant using aminoethylethanolamine solvent has not been published. The results show that the main source of ammonia emission is the absorber and that emission (in the range 27–50 ppm) corresponds to typical NH₃ release from CO₂ capture pilot plant using an amine solvent. The emission of amines and amine degradation products is a complex phenomenon which is difficult to predict in novel solvents, and for this reason the significance of new solvents testing in a pilot scale has been highlighted.     

Using hyperspectral plant signatures for CO<Subscript>2</Subscript> leak detection during the 2008 ZERT CO<Subscript>2</Subscript> sequestration field experiment in Bozeman,Montana

Hyperspectral plant signatures can be used as a short-term, as well as long-term (100-year timescale) monitoring technique to verify that CO₂ sequestration fields have not been compromised. An influx of CO₂ gas into the soil can stress vegetation, which causes changes in the visible to near-infrared reflectance spectral signature of the vegetation. For 29 days, beginning on July 9, 2008, pure carbon dioxide gas was released through a 100-m long horizontal injection well, at a flow rate of 300 kg day⁻¹. Spectral signatures were recorded almost daily from an unmown patch of plants over the injection with a “FieldSpec Pro” spectrometer by Analytical Spectral Devices, Inc. Measurements were taken both inside and outside of the CO₂ leak zone to normalize observations for other environmental factors affecting the plants. Four to five days after the injection began, stress was observed in the spectral signatures of plants within 1 m of the well. After approximately 10 days, moderate to high amounts of stress were measured out to 2.5 m from the well. This spatial distribution corresponded to areas of high CO₂ flux from the injection. Airborne hyperspectral imagery, acquired by Resonon, Inc. of Bozeman, MT using their hyperspectral camera, also showed the same pattern of plant stress. Spectral signatures of the plants were also compared to the CO₂ concentrations in the soil, which indicated that the lower limit of soil CO₂ needed to stress vegetation is between 4 and 8% by volume.     

Impacts of mineralogical compositions on different trapping mechanisms during long-term CO<Subscript>2</Subscript> storage in deep saline aquifers

Deep saline aquifers in sedimentary basins are considered to have the greatest potential for CO₂ geological storage in order to reduce carbon emissions. CO₂ injected into a saline sandstone aquifer tends to migrate upwards toward the caprock because the density of the supercritical CO₂ phase is lower than that of formation water. The accumulated CO₂ in the upper portions of the reservoir gradually dissolves into brine, lowers pH and changes the aqueous complexation, whereby induces mineral alteration. In turn, the mineralogical composition could impose significant effects on the evolution of solution, further on the mineralized CO₂. The high density of aqueous phase will then move downward due to gravity, give rise to “convective mixing,” which facilitate the transformation of CO₂ from the supercritical phase to the aqueous phase and then to the solid phase. In order to determine the impacts of mineralogical compositions on trapping amounts in different mechanisms for CO₂ geological storage, a 2D radial model was developed. The mineralogical composition for the base case was taken from a deep saline formation of the Ordos Basin, China. Three additional models with varying mineralogical compositions were carried out. Results indicate that the mineralogical composition had very obvious effects on different CO₂ trapping mechanisms. Specific to our cases, the dissolution of chlorite provided Mg²⁺ and Fe²⁺ for the formation of secondary carbonate minerals (ankerite, siderite and magnesite). When chlorite was absent in the saline aquifer, the dominant secondary carbon sequestration mineral was dawsonite, and the amount of CO₂ mineral trapping increased with an increase in the concentration of chlorite. After 3000 years, 69.08, 76.93, 83.52 and 87.24 % of the injected CO₂ can be trapped in the solid (mineral) phase, 16.05, 11.86, 8.82 and 6.99 % in the aqueous phase, and 14.87, 11.21, 7.66 and 5.77 % in the gas phase for Case 1 through 4, respectively.     

Selection of coals of different maturities for CO2 Storage by modelling of CH4 and CO2 adsorption isotherms

CO₂ injection in unmineable coal seams could be one interesting option for both storage and methane recovery processes. The objective of this study is to compare and model pure gas sorption isotherms (CO₂ and CH₄) for well-characterised coals of different maturities to determine the most suitable coal for CO₂ storage. Carbon dioxide and methane adsorption on several coals have been investigated using a gravimetric adsorption method. The experiments were carried out using both CO₂ and CH₄ pure gases at 25 °C from 0.1 to 5 MPa (1 to 50 bar). The experimental results were fitted using Temkin's approach but also with the corrected Langmuir's and the corrected Tóth's equations. The two last approaches are more accurate from a thermodynamical point of view, and have the advantage of taking into account the fact that experimental data (isotherms) correspond to excess adsorption capacities. These approaches allow better quantification of the adsorbed gas. Determined CO₂ adsorption capacities are from 0.5 to 2 mmol/g of dry coal. Modelling provides also the affinity parameters of the two gases for the different coals. We have shown these parameters determined with adsorption models could be used for classification and first selection of coals for CO₂ storage. The affinity ratio ranges from a value close to 1 for immature coals to 41 for high rank coals like anthracites. This ratio allows selecting coals having high CO₂ adsorption capacities. In our case, the modelling study of a significant number of coals from various ranks shows that anthracites seem to have the highest CO₂ storage capacities. Our study provides high quality affinity parameters and values of CO₂ and CH₄ adsorption capacities on various coals for the future modelling of CO₂ injection in coal seams.     

Variability of the gas transfer velocity of CO<Subscript>2</Subscript> in a macrotidal estuary (the Scheldt)

We report a large set of 295 interfacial carbon dioxide (CO₂) flux measurements obtained in the Scheldt estuary in November 2002 and April 2003, using the floating chamber method. From concomitant measurements of the air-water CO₂ gradient, we computed the gas transfer velocity of CO₂. The gas transfer velocity is well correlated to wind speed and a simple linear regression function gives the most consistent fit to the data. Based on water current measurements, we estimated the contribution of water current induced turbulence to the gas transfer velocity, using the conceptual relationship of O'Connor and Dobbins (1958). This allowed us to construct an empirical relationship to compute the gas transfer velocity of CO₂ that accounts for the contribution of wind and water current. Based on this relationship, the spatial and temporal variability of the gas transfer velocity in the Scheldt estuary was investigated. Water currents contribute significantly to the gas transfer velocity, but the spatial and temporal variability (from daily to seasonal scales) is mainly related to wind speed variability.     

Interactions between basalts and oil source rocks in rift basins： CO2 generation

Basalts interbedded with oil source rocks are discovered frequently in rift basins of eastern China, where CO2 is found in reservoirs around or within basalts, for example in the Binnan reservoir of the Dongying Depression. In the reservoirs, CO2 with heavy carbon isotopic composition (δ13C>-10‰ PDB) is in most cases accounts for 40% of the total gas reserve, and is believed to have resulted from degassing of basaltic magma from the mantle. In their investigations of the Binnan reservoir, the authors suggested that the CO2 would result from interactions between the source rocks and basalts. As the source rocks around basalts are rich in carbonate minerals, volcanic minerals, transition metals and organic matter, during their burial history some of the transition metals were catalyzed on the thermal degradation of organic matter into hydrocarbons and on the decomposition of carbonate minerals into CO2, which was reproduced in thermal simulations of the source rocks with the transition metals (Ni and Co). This kind of CO2 accounts for 55%-85% of the total gas reserve generated in the process of thermal simulation, and its δ13C values range from -11‰- -7.2‰ PDB, which are very similar to those of CO2 found in the Binnan reservoir. The co-generation of CO2 and hydrocarbon gases makes it possible their accumulation together in one trap. In other words, if the CO2 resulted directly from degassing of basaltic magma or was derived from the mantle, it could not be accumulated with hydrocarbon gases because it came into the basin much earlier than hydrocarbon generation and much earlier than trap formation. Therefore, the source rocks around basalts generated hydrocarbons and CO2 simultaneously through catalysis of Co and Ni transition metals, which is useful for the explanation of co-accumulation of hydrocarbon gases and CO2 in rift basins in eastern China.     

CO<Subscript>2</Subscript> leakage through an abandoned well: problem-oriented benchmarks

The efficiency and sustainability of carbon dioxide (CO₂) storage in deep geological formations crucially depends on the integrity of the overlying cap-rocks. Existing oil and gas wells, which penetrate the formations, are potential leakage pathways. This problem has been discussed in the literature, and a number of investigations using semi-analytical mathematical approaches have been carried out by other authors to quantify leakage rates. The semi-analytical results are based on a number of simplifying assumptions. Thus, it is of great interest to assess the influence of these assumptions. We use a numerical model to compare the results with those of the semi-analytical model. Then we ease the simplifying restrictions and include more complex thermodynamic processes including sub- and supercritical fluid properties of CO₂ and non-isothermal as well as compositional effects. The aim is to set up problem-oriented benchmark examples that allow a comparison of different modeling approaches to the problem of CO₂ leakage.     

CO<Subscript>2</Subscript> mineralization of natural wollastonite into porous silica and CaCO<Subscript>3</Subscript> powders promoted via membrane electrolysis

CO₂ is a greenhouse gas, whose emissions threaten the existence of human beings. Its inherently safe sequestration can be performed via CO₂ mineralization, which is relatively slow under natural conditions. In this work, an energy-saving membrane electrolysis technique was proposed for accelerating the CO₂ mineralization of wollastonite into SiO₂ and CaCO₃ products. The electrolysis process involved splitting NH₄Cl into HCl and NH₃·H₂O via hydrogen oxidation and water reduction at the anode and cathode of the electrolytic system, respectively. In contrast to the chlor-alkali electrolysis, this method did not involve Cl^? oxidation and the standard potential of the anode was reduced. Additionally, NH₄Cl was used as the electrolyte instead of NaCl; as a result, the generation of NH₃·H₂O instead of NaOH occurred in the catholyte and the cathodic pH dramatically decreased, thus reducing the cathodic potential for hydrogen evolution. The observed changes led to a 73.5% decrease in the energy consumption. Moreover, after the process of CO₂ mineralization was optimized, SiO₂ with a specific surface area of 221.8 m² g^?1 and CaCO₃ with a purity of 99.9% were obtained.     

A new method for measurement of air change rate based on indoor PM<Subscript>2.5</Subscript> removal

Outdoor PM_2.5 easily flows into indoor and seriously influences indoor air quality due to its characteristics of flow, diffusion and penetration. It is a proper ‘gas’ tracer similar to CO₂ to study building ventilation. Therefore, in this paper, a model for calculating air change rates by removing indoor PM_2.5 was deduced. Also, some factors influencing the air change rate were qualitatively analyzed and the expression of possible air change rate error was given. The comparison between the results from PM_2.5 removal method and the data from CO₂ decay method validated the model. The relative error between the results of the two methods is less than 10%. On the basis of validating the model, this paper presented the research of air change rates in ten naturally ventilated house rooms in three Chinese cities. It is found that the rooms with the ventilation rates of 1.15–6.75 m³/h/person have inadequate ventilation.     

Uncertainties of geochemical modeling during CO<Subscript>2</Subscript> sequestration applying batch equilibrium calculations

One of the uncertainties in the field of carbon dioxide capture and storage (CCS) is caused by the parameterization of geochemical models. The application of geochemical models contributes significantly to calculate the fate of the CO₂ after its injection. The choice of the thermodynamic database used, the selection of the secondary mineral assemblage as well as the option to calculate pressure dependent equilibrium constants influence the CO₂ trapping potential and trapping mechanism. Scenario analyses were conducted applying a geochemical batch equilibrium model for a virtual CO₂ injection into a saline Keuper aquifer. The amount of CO₂ which could be trapped in the formation water and in the form of carbonates was calculated using the model code PHREEQC. Thereby, four thermodynamic datasets were used to calculate the thermodynamic equilibria. Furthermore, the equilibrium constants were re-calculated with the code SUPCRT92, which also applied a pressure correction to the equilibrium constants. Varying the thermodynamic database caused a range of 61% in the amount of trapped CO₂ calculated. Simultaneously, the assemblage of secondary minerals was varied, and the potential secondary minerals dawsonite and K-mica were included in several scenarios. The selection of the secondary mineral assemblage caused a range of 74% in the calculated amount of trapped CO₂. Correcting the equilibrium constants with respect to a pressure of 125 bars had an influence of 11% on the amount of trapped CO₂. This illustrates the need for incorporating sensitivity analyses into reaction pathway modeling.     

Photocatalytic degradation of imidacloprid in aqueous suspension of TiO<Subscript>2</Subscript> supported on H-ZSM-5

The composite of TiO₂ and zeolite H-ZSM-5 has great photocatalytic ability for organic contaminants over a very large specific surface area and highlighted adsorption capacity. To describe abiotic degradation of imidacloprid, the photoinduced degradation of the pesticide imidacloprid in aqueous solutions, in the presence of TiO₂ supported on H-ZSM-5 as photocatalyst, was performed. The study focused on the comparison of the imidacloprid degradation between photolysis and photocatalysis. The experimental results showed that the degradation of imidacloprid was more rapid in the condition of photocatalytic than that of photolysis or TiO₂-only. The identification of possible intermediate products during the degradation was investigated by the high-performance liquid chromatography coupled with electrospray time-of-flight mass spectrometry (HPLC/TOF-MS). The main photocatalytic products were identified as chloronictinic acid, 1-[(6-chloro-3-pyridinyl) methyl]-2-imidazolidinone and 1-[(6-chloro-3-pyridinyl) methyl]-N-nitroso-2-imidazolidimine.     

The Starzach site in Southern Germany: a site with naturally occurring CO<Subscript>2</Subscript> emissions recovering from century-long gas mining as a natural analog for a leaking CCS reservoir

In this paper, we present the Starzach site, a region featuring numerous natural CO₂ emission spots, such as mofettes, that reappeared after a longer period of extensive industrial CO₂ mining. We discuss the results of a detailed literature study on the geological setting and the activities related to the gas mining in combination with own measurements to introduce the site as an example on how gas leakage from an insecure CCS reservoir could manifest at the surface. The site is in particular interesting for such investigations as the CO₂ emissions started to replenish after the end of the CO₂ mining and offers the unique possibility to investigate an increase in degassing activity as it might be expected for an active CCS site where leakage is suspected. Based on the geological setting and soil, gas emission, and isotope investigations, we further discuss the source of the CO₂ emission and the gas ascent to the ground surface via deep-reaching faults, latter being so far excluded by previous work. The combination of our extensive literature review and recent field investigations allowed us to draw new geological conclusions for the site that were under discussion for a long time and to give insight into the site’s potential for CCS-related analog studies in the future.