Heat of absorption of CO2 in aqueous ammonia and ammonium carbonate/carbamate solutions

A reaction calorimeter was used to determine the enthalpies of absorption of CO₂ in aqueous ammonia and in aqueous solutions of ammonium carbonate at temperatures of 35–80 °C. The heat of absorption of CO₂ with 2.5 wt% aqueous ammonia solution was found to be about 70 kJ/mol CO₂, which is lower than that with MEA (around 85 kJ/mol) at 35 and 40 °C. The value decreases with increased loading, but not to as low a value as expected by the carbonate–bicarbonate reaction (26.88 kJ/mol). The enthalpy of absorption of CO₂ in aqueous ammonia at 60 and 80 °C decreases with loadings at first, then increases between 0.2 mol CO₂/mol NH₃ and 0.6 mol CO₂/mol NH₃, and then decreases again. The behavior of the heat of absorption of CO₂ in 10 wt% ammonium carbonate solution was found to be the same as that of aqueous ammonia at loadings above 0.6 mol CO₂/mol NH₃. The heat of absorption increases with increasing temperature. The heats of absorption are directly related to the extent of the various reactions with CO₂ and can be assessed from the species variation in the liquid phase.     

Kinetics of sulfur dioxide- and oxygen-induced degradation of aqueous monoethanolamine solution during CO2 absorption from power plant flue gas streams

Studies of the kinetics of sulfur dioxide (SO₂)- and oxygen (O₂)-induced degradation of aqueous monoethanolamine (MEA) during the absorption of carbon dioxide (CO₂) from flue gases derived from coal- or natural gas-fired power plants were conducted as a function of temperature and the liquid phase concentrations of MEA, O₂, SO₂ and CO₂. The kinetic data were based on the initial rate which shows the propensity for amine degradation and obtained under a range of conditions typical of the CO₂ absorption process (3–7 kmol/m³ MEA, 6% O₂, 0–196 ppm SO₂, 0–0.55 CO₂ loading, and 328–393 K temperature). The results showed that an increase in temperature and the concentrations of MEA, O₂ and SO₂ resulted in a higher MEA degradation rate. An increase in CO₂ concentration gave the opposite effect. A semi-empirical model based on the initial rate, ?r_MEA = {6.74 × 10⁹ e^?(29,403/RT)[MEA]^0.02([O]^2.91 + [SO₂]^3.52)}/{1 + 1.18[CO₂]^0.18} was developed to fit the experimental data. With the higher order of reaction, SO₂ has a higher propensity to cause MEA to degrade than O₂. Unlike previous models, this model shows an improvement in that any of the parameters (i.e. O₂, SO₂, and CO₂) can be removed without affecting the usability of the model.     

Chilled ammonia process for CO2 capture

The chilled ammonia process absorbs the CO₂ at low temperature (2–10 °C). The heat of absorption of carbon dioxide by ammonia is significantly lower than for amines. In addition, degradation problems can be avoided and a high carbon dioxide capacity is achieved. Hence, this process shows good perspectives for decreasing the heat requirement. However, a scientific understanding of the processes is required. The thermodynamic properties of the NH₃–CO₂–H₂O system were described using the extended UNIQUAC electrolyte model developed by Thomsen and Rasmussen in a temperature range from 0 to 110 °C and pressure up to 100 bars. The results show that solid phases consisting of ammonium carbonate and bicarbonate are formed in the absorber. The heat requirements in the absorber and in the desorber have been studied. The enthalpy calculations show that a heat requirement for the desorber lower than 2 GJ/ton CO₂ can be reached.     

Experimental measurement and modeling of the rate of absorption of carbon dioxide by aqueous ammonia

In this work, the rate of absorption of carbon dioxide by aqueous ammonia solvent has been studied by applying a newly built wetted wall column. The absorption rate in aqueous ammonia was measured at temperatures from 279 to 304 K for 1 to 10 wt% aqueous ammonia with loadings varying from 0 to 0.8 mol CO₂/mol NH₃. The absorption rate in 30 wt% aqueous mono-ethanolamine (MEA) was measured at 294 and 314 K with loadings varying from 0 to 0.4 as comparison.It was found that at 304 K, the rate of absorption of carbon dioxide by 10 wt% NH₃ solvent was comparable to the rates for 30 wt% MEA at 294 and 314 K (a typical absorption temperature for this process). The absorption rate using ammonia was however significantly lower at temperatures of 294 K and lower as applied in the Chilled Ammonia Process. However, at these low temperatures, the rate of absorption in ammonia has only a small temperature dependency.The rate of absorption decreases strongly with decreasing ammonia concentrations and increasing CO₂ loadings.The rate of absorption of carbon dioxide by aqueous ammonia solvent was modeled using the measurements of the unloaded solutions and the zwitter-ion mechanism. The model could successfully predict the experimental measurements of the absorption rate of CO₂ in loaded ammonia solutions.     

Modeling CO2 capture with aqueous monoethanolamine

Hilliard completed several thermodynamic models in Aspen Plus^® for modeling CO₂ removal with amine solvents, including MEA–H₂O–CO₂. This solvent was selected to make a system model for CO₂ removal by absorption/stripping. Both the absorber and the stripper used RateSep? to rigorously calculate mass transfer rates. The accuracy of the new model was assessed using a recent pilot plant run with 35 wt.% (9 m) MEA. Absorber loading and removal were predicted within 6%, and the temperature profile was approached within 5 °C. An average 3.8% difference between measured and calculated values was achieved in the stripper. A three-stage flash configuration which efficiently utilizes solar energy was developed. It reduces energy use by 6% relative to a simple stripper. Intercooling was used to reach 90% removal in the absorber at these optimized conditions.     

Ionic liquids for post-combustion CO2 absorption

The present work is a study to evaluate ionic liquids as a potential solvent for post-combustion CO₂ capture. In order to enhance the absorption performance of a CO₂ capture unit, different ionic liquids have been designed and tested. The main goal was to get a comparison between a reference liquid and selected ionic liquids. As the reference, a solution of 30 w% monoethanolamine (MEA) and water was used. A large range of different pure and diluted ionic liquids was tested with a special screening process to gain general information about the CO₂ absorption performance. Based on these results, a 60 w% ionic liquid solution in water was selected and the vapour–liquid equilibrium was measured experimentally between 40 °C and 110 °C. From these curves the enthalpy of absorption for capturing CO₂ into the ionic liquid was determined. With these important parameters one is able to calculate the total energy demand for stripping of CO₂ from the loaded solvent for comparison of the ionic liquid based solvent with the reference MEA solvent. The energy demand of this 60 w% ionic liquid is slightly lower than that of the reference solution, resulting in possible energy savings between 12 and 16%.     

CO2 removal using membrane gas absorption

The objective of this study is to investigate the potential process for the removal of carbon dioxide (CO₂) from flue gas using fundamental membrane contactor, which is a membrane gas absorption (MGA) system. The experiments consisted of microporous polyvinylidenefluoride (PVDF) flat sheet membrane with 0.1 μm (as module I) and 0.45 μm (as module II) pore size. 2-Amino-2-methyl-1-propanol (AMP) solution was employed as the liquid absorbent. The effect of AMP concentration was studied with variation in the range 1–5 M. In addition, the experiments were carried out with 10%, 20%, 30% and 40% gas ratio of CO₂ to N₂ and pure CO₂ as well. Through contact angle measurement, membranes for module I and module II were obtained with CA values of around 130.25° and 127.77°, respectively. The mass transfer coefficients for module II are lower than those of module I for 1–5 M of AMP. Furthermore, the increase in CO₂ concentration in the feed gas stream enhanced the CO₂ flux as the driving force of the system was increased in sequence from 1 M to 5 M of AMP. However, after the particular percentage (40%) of CO₂ inlet concentration, the CO₂ fluxes seem saturated. The combination of AMP as liquid absorbent and PVDF microporous membrane in MGA system has shown the potential to remove the CO₂ from flue gas. In addition, the higher AMP concentration gave higher mass transfer coefficient at low liquid flow rates.     

Kinetics of carbon dioxide absorption into mixed aqueous solutions of MDEA and MEA using a laminar jet apparatus and a numerically solved 2D absorption rate/kinetics model

New comprehensive numerically solved 1D and 2D absorption rate/kinetics models have been developed, for the first time, to interpret the experimental kinetic data obtained with a laminar jet apparatus for the absorption of carbon dioxide (CO₂) in CO₂ loaded mixed solutions of mixed amine system of methyldiethanolamine (MDEA) and monoethanolamine (MEA). Three MDEA/MEA weight ratios ranging from 27/03 to 23/07, over a concentration range of 2.316–1.996 kmol/m³ for MDEA and of 0.490–1.147 kmol/m³ for MEA were studied. The models take into account the coupling between chemical equilibrium, mass transfer, and the chemical kinetics of all possible chemical reactions involved in the CO₂ reaction with MDEA/MEA solvent. The partial differential equations of the 1D model were solved by two numerical techniques; the finite difference method (FDM) based on in-house coded Barakat–Clark scheme and the finite element method (FEM) based on COMSOL software. The FEM comprehensive model was then used to solve the set of partial differential equations in the 2D cylindrical coordinate system setting. Both FDM and FEM produced very accurate results for both the 1D and 2D models, which were much better than our previously published simplified model. The reaction rate constant obtained for MEA blended into MDEA at 298–333 K was k_MEA = 5.127 × 10⁸ exp(−3373.8/T). In addition, the 2D model, for the first time, has provided the concentration profiles of all the species in both the radial and axial directions of the laminar jet, thereby enabling an understanding of the correct sequence in which the reaction steps involved in the reactive absorption of CO₂ in aqueous mixed amines occur.     

Carbonic anhydrase-facilitated CO2 absorption with polyacrylamide buffering bead capture

A novel CO₂ separation concept is described wherein the enzyme carbonic anhydrase (CA) is used to increase the overall rate of CO₂ absorption after which hydrated CO₂ reacts with regenerable amine-bearing polyacrylamide buffering beads (PABB). Following saturation of the material's immobilized tertiary amines, CA-bearing carrier water is separated and recycled to the absorption stage while CO₂-loaded material is thermally regenerated. Process application of this concept would involve operation of two or more columns in parallel with thermal regeneration with low-pressure steam taking place after the capacity of a column of amine-bearing polymeric material was exceeded. PABB CO₂-bearing capacity was evaluated by thermogravimetric analysis (TGA) for beads of three acrylamido buffering monomer ingredient concentrations: 0 mol/kg bead, 0.857 mol/kg bead, and 2 mol/kg bead. TGA results demonstrate that CO₂-bearing capacity increases with increasing PABB buffering concentration and that up to 78% of the theoretical CO₂-bearing capacity was realized in prepared PABB samples (0.857 mol/kg recipe). The highest observed CO₂-bearing capacity of PABB was 1.37 mol of CO₂ per kg dry bead. TGA was also used to assess the regenerability of CO₂-loaded PABB. Preliminary results suggest that CO₂ is partially driven from PABB samples at temperatures as low as 55 °C, with complete regeneration occurring at 100 °C. Other physical characteristics of PABB are discussed. In addition, the effectiveness of bovine carbonic anhydrase for the catalysis of CO₂ dissolution is evaluated. Potential benefits and drawbacks of the proposed process are discussed.     

Comparative study of the heats of absorption of post-combustion CO2 absorbents

Heats of absorption of CO₂ with different solvents were measured in this work in a commercially available reaction calorimeter CPA-122 (Chemisens AS, Sweden) as function of temperature, loading and solvent composition over the temperature range from 40 to 120 °C. Studied amines include primary amines (monoethanolamine and 2-amino-2-methyl-1-propanol), tertiary amines (N-methyldiethanolamine and N,N-diethylethanolamine), diamines (1-(2-aminoethyl)-aminoethanol and N-methyl-1,3-propanediamine), triamine (diethylenetriamine), and cyclic amine (piperazine). Combinations of these amines and also mixtures of potassium carbonate and piperazine were tested. Experimental heats of absorption of CO₂ with these systems are compared.     

Analytical solution for estimating storage efficiency of geologic sequestration of CO2

During injection of carbon dioxide (CO₂) into deep saline aquifers, the available pore volume of the aquifer may be used inefficiently, thereby decreasing the effective capacity of the repository for CO₂ storage. Storage efficiency is the fraction of the available pore space that is utilized for CO₂ storage, or, in other words, it is the ratio between the volume of stored CO₂ and the maximum available pore volume. In this note, we derive and present simple analytical expressions for estimating CO₂ storage efficiency under the scenario of a constant-rate injection of CO₂ into a confined, homogeneous, isotropic, saline aquifer. The expressions for storage efficiency are derived from models developed previously by other researchers describing the shape of the CO₂-brine interface. The storage efficiency of CO₂ is found to depend on three dimensionless groups, namely: (1) the residual saturation of brine after displacement by CO₂; (2) the ratio of CO₂ mobility to brine mobility; (3) a dimensionless group (which we call a “gravity factor”) that quantifies the importance of CO₂ buoyancy relative to CO₂ injection rate. In the particular case of negligible residual brine saturation and negligible buoyancy effects, the storage efficiency is approximately equal to the ratio of the CO₂ viscosity to the brine viscosity. Storage efficiency decreases as the gravity factor increases, because the buoyancy of the CO₂ causes it to occupy a thin layer at the top of the confined formation, while leaving the lower part of the aquifer under-utilized. Estimates of storage efficiency from our simple analytical expressions are in reasonable agreement with values calculated from simulations performed with more complicated multi-phase-flow simulation software. Therefore, we suggest that the analytical expressions presented herein could be used as a simple and rapid tool to screen the technical or economic feasibility of a proposed CO₂ injection scenario.     

Computational chemistry study of reactions,equilibrium and kinetics of chemical CO2 absorption

The chemical reactions involved in CO₂ absorption in amine systems are studied. For each mechanism, available experimental data are considered and quantum mechanical calculations carried out. Base-catalyzed bicarbonate formation is found to be a likely mechanism for all amine bases, not only tertiary amines. Direct formation of bicarbonate species from carbamate species is found to be unlikely. The carbamate formation has been proposed to take place through a single-step termolecular reaction, or through a two step mechanism with a zwitterionic intermediate. Quantum mechanical calculations suggest that if there is such a zwitterionic intermediate, it is likely to be short-lived.Quantum mechanical calculations together with solvation models are shown to predict the base strength and carbamate stability of different amine solvents with a useful degree of accuracy. Solvent effects and electron donation and withdrawal through bonds are identified as important factors in determining the overall reactivity of different amine solvents. Results suggest a strong correlation between the carbamate stability and base strength of amine solvents and their reaction kinetics.     

Toxicity measurements in aqueous solution during ozonation of mono-chlorophenols

The Microtox toxicity and Oxygen Uptake Rate (OUR) inhibition tests were conducted to monitor the variation of toxicity during ozonation of 2-chlorophenol (2-CP), 3-chlorophenol (3-CP) and 4-chlorophenol (4-CP) under neutral conditions. The results revealed that the oxidized 2-CP solution exhibited new toxicity to pure bacteria and mixed microorganisms in the early stage of ozonation. The largest inhibition of OUR appeared at one mol of applied ozone dosage per mol of initial 2-CP, and the percentage of inhibition was 63.8%. In addition, ozonated 3-CP and 4-CP also significantly induced new aqueous toxicity, if these toxic intermediates were not further ozonated. Comparing the variation of toxicity and the hydroxylated/chlorinated intermediates formed, 3-chloro-catechol, 2-chloro-2, 4-hexadienedioic acid and the dimmer compounds may be related to the sources of toxicity during the ozonation of 2-CP.     

A solution against well cement degradation under CO2 geological storage environment

Capturing and storing carbon dioxide (CO₂) underground for thousands of years is one way to reduce atmospheric greenhouse gases, often associated with global warming. Leakage through wells is one of the major issues when storing CO₂ in depleted oil or gas reservoirs. CO₂-injection candidates may be new wells, or old wells that are active, closed or abandoned. In all cases, it is critical to ensure that the long-term integrity of the storage wells is not compromised. The loss of well integrity may often be explained by the geochemical alteration of hydrated cement that is used to isolate the annulus across the producing/injection intervals in CO₂-related wells. However, even before any chemical degradation, changes in downhole conditions due to supercritical CO₂ injections can also be responsible for cement debonding from the casing and/or from the formation, leading to rapid CO₂ leakage. A new cement with better CO₂ resistance is compared with conventional cement using experimental procedure and methodology simulating the interaction of set cement with injected, supercritical CO₂ under downhole conditions. Geochemical experimental data and a mechanical modeling approach are presented. The use of adding expanding property to this new cement to avoid microannulus development during the CO₂ injection is discussed.     

Pre-treating biosorbents for purification of bioethanol from aqueous solution

Cost-effective biosorbents made from the byproducts of agriculture, forest, and related industries, such as barley straw, canola meal, and wood sawdust, have significant water adsorption capacity, showing a great potential for selective water removal from bioalcohols to produce fuel grade products. However, there is a challenge that the biosorbents are not stable when they come in contact with aqueous solution. There are organic carbons released from biosorbents to liquid phase, which needs to be addressed before this technology is applied in the industrial purification of bioalcohols. In this work, raw barley straw representing an abundant group of cellulosic materials in the above-mentioned industries was used as a model material. A methodology of chemical and physical treatment was developed to treat barley straw which successfully enhanced the stability and reduced the total organic carbon release from the material into the aqueous solution. In addition, the pre-treated barley straw biosorbent had significantly increased micropores, and the Brunauer--Emmett--Teller surface area favored by water adsorption compared with raw barley straw. It also had higher water uptake and dynamic water adsorption selectivity. The pre-treated barley straw was able to selectively remove water and generate concentrated ethanol.     

Minimising the regeneration heat duty of post-combustion CO2 capture by wet chemical absorption: The misguided focus on low heat of absorption solvents

An ideal solvent for CO₂ capture by chemical absorption has to meet a number of requirements, such as high CO₂ capacity, high rate of reaction, low costs, low corrosive behaviour, low degradation and low vapour pressure; above all, it has to show a low regeneration heat duty. This heat can be approximated as the sum of three terms: the sensible heat to raise the solvent from absorber to desorber temperature, the heat of evaporation required to produce the stripping steam in the reboiler, and the heat necessary to desorb the CO₂ from the solution (heat of absorption).Many solvent screening studies focus almost exclusively on solvents that show a low heat of absorption. In these studies, the strong dependence of the three contributors to the overall regeneration heat duty on the chosen process parameters and on one another are often neglected.This work explains why the focus on solvents with a low heat of absorption, without considering the overall process, is not sufficient in quantifying the energy performance of alternative solvents. By using thermodynamic interrelations and underpinned by process simulations it is shown that operating parameters of the process, in particular the desorber pressure, must be taken into consideration in the evaluation of new solvents.     

Adsorption of basic dye from aqueous solution onto fly ash

The fly ash treated by H₂SO₄ was used as a low-cost adsorbent for the removal of a typical dye, methylene blue, from aqueous solution. An increase in the specific surface area and dye-adsorption capacity was observed after the acid treatment. The adsorption isotherm and kinetics of the treated fly ash were studied. The experimental results were fitted using Langmuir and Freundlich isotherms. It shows that the Freundlich isotherm is better in describing the adsorption process. Two kinetic models, pseudo-first order and pseudo-second order, were employed to analyze the kinetic data. It was found that the pseudo-second-order model is the better choice to describe the adsorption behavior. The thermodynamic study reveals that the enthalpy (ΔH⁰) value is positive (5.63 kJ/mol), suggesting an endothermic nature of the adsorption.     

Dispersion by wind of CO2 leaking from underground storage: Comparison of analytical solution with simulation

The concentration of CO₂ in air near the ground needs to be predicted to assess environmental and health risks from leaking underground storage. There is an exact solution to the advection–diffusion equation describing trace gases carried by wind when the wind profile is modeled with a power-law dependence on height. The analytical solution is compared with a numerical simulation of the coupled air–ground system with a source of CO₂ underground at the water table. The two methods produce similar results far from the boundaries, but the boundary conditions have a strong effect; the simulation imposes boundary conditions at the edge of a finite domain while the analytic solution imposes them at infinity. The reverse seepage from air to ground is shown in the simulation to be very small, and the large difference between time scales suggests that air and ground can be modeled separately, with gas emissions from the ground model used as inputs to the air model.     

Development and Experimental Study of CO2 Expander in CO2 Supercritical Refrigeration Cycles

Abstract

As one of the natural working fluids for the refrigeration system, CO₂ has been attracting increasing attention over the last ten years. But CO₂ has to work at the supercritical region for the so-called “condensation” process regarding the conventional refrigerants and evaporate at the two-phase region, and therefore results in larger throttling loss for the practical refrigeration application. Consequently, new technologies must be developed to improve the performance efficiency of the CO₂ transcritical cycle, and make it to be equal or closer to that of the refrigeration system with the conventional refrigerants. In this study, an expander is employed in the CO₂ transcritical cycle to replace the throttling valve, and as a result the throttling loss can be decreased significantly. The paper presents the development of a rolling piston expander and the activity items in the expander design, including the seal technology, the contact friction control, the suction design, etc. The performance experiments for the expander are conducted in the present testing system for the CO₂ transcritical cycle. The results show that the recovery power of the expander is related to the revolution speed of the expander. The efficiency of the expander prototype is observed to be about 32%.     

Characterization of cation-pi interactions in aqueous solution using deuterium nuclear magnetic resonance spectroscopy

Chemical interactions of aromatic organic contaminants control their fate, transport, and toxicity in the environment. Recent molecular modeling studies have suggested that strong interactions can occur between the pi electrons of aromatic molecules and metal cations in aqueous solutions and/or on mineral surfaces, and that such interactions may be important in some environmental systems. However, spectroscopic evidence for these so-called cation-pi interactions has been extremely limited to date. In this paper, cation-pi interactions in aqueous salt solutions were characterized via 2H nuclear magnetic resonance (NMR) spin-lattice relaxation times (T1) and calculations of molecular correlation times (tau(c)) for a series of perdeuterated (d6-benzene) benzene-cation complexes. The T1 values for d6-benzene decreased with increasing concentrations of LiCl, NaCl, KCl, RbCl, CsCl, and AgNO3, with the largest effects observed in the AgNO3 and CsCl solutions. Upon normalizing tau(c) values by solution viscosity effects, an overall affinity trend of Ag+ > Cs+ > K+ > Rb+ > Na+ > Li+ was derived for the d6-benzene-cation complexes. The ability of Ag+ to complex d6-benzene was significantly reduced upon addition of NH3, which strongly coordinates Ag+ at high pH. Results with d6-benzene, d8-naphthalene, d2-dichloromethane, and d12-cyclohexane in 0.1 M methanolic salt solutions confirmed that spin-lattice relaxation rates are characterizing cation-pi interactions. The relatively strong cation-pi bonding observed between Ag+ and aromatic hydrocarbons probably results from covalent interactions between the aromatic pi electrons and the d orbitals of Ag+, in addition to the normal electrostatic interaction.