Comprehensive analysis of thermodynamic models for CO2 absorption into a blended N,N-diethylethanolamine-1,6-hexamethyl diamine (DEEA-HMDA) amine

In this work, CO₂ equilibrium solubility of 1M N,N-diethylethanolamine (DEEA):2M 1,6-hexamethyl diamine (HMDA), 1.5M DEEA:1.5M HMDA and 2M DEEA:1M HMDA was studied with a temperature range of 298–333 K and CO₂ partial pressure range of 8–100 kPa. Seven thermodynamic models including Empirical model, Kent and Eisenberg (KE) model, Hu–Chakma model, Austgen model, Helei Liu model, Liu et al. model, and Li–Shen model were developed by correlating reaction equilibrium constants with observed equilibrium solubility of CO₂ in mixed amine solvents. The evaluation of those models was conducted in terms of the average absolute relative deviation (AARD). The results indicated that Liu et al. model considering T, [Amine], P_total and [CO₂(aq)] can better represent this complex system with an AARD of 8.06%. Meanwhile, comprehensive comparison and analysis were also performed to identify the contribution of parameters to develop models, which could provide a guideline for the development of accurate thermodynamic models for representation of thermodynamic behaviors.     

Equilibrium solubility of CO<Subscript>2</Subscript> in aqueous binary mixture of 2-(diethylamine)ethanol and 1, 6-hexamethyldiamine

CO₂ solubility data are important for the efficient design and operation of the acid gas CO₂ capture process using aqueous amine mixture. 2-(Diethylamino)ethanol (DEEA) solvent can be manufactured from renewable sources like agricultural products/residue, and 1,6-hexamethyldiamine (HMDA) solvents have higher absorption capacity as well as reaction rate with CO₂ than conventional amine-based solvents. The equilibrium solubility of CO₂ into aqueous binary mixture of DEEA and HMDA was investigated in the temperature range of 303.13-333.13 K and inlet CO₂ partial pressure in the range of 10.133-20.265 kPa. Total concentration of aqueous amine mixtures in the range of 1.0-3.0 kmol/m³ and mole fraction of HMDA in total amine mixture in the range of 0.05-0.20 were taken in this work. CO₂ absorption experiment was performed using semi-batch operated laboratory scale bubble column to measure equilibrium solubility of CO₂ in amine mixture, and CO₂ absorbed amount in saturated carbonated amine mixture was analyzed by precipitation-titration method using BaCl₂. Maximum equilibrium CO₂ solubility in aqueous amine mixture was observed at 0.2 of HMDA mole fraction in total amine mixture with 1.0 kmol/m³ total amine concentration. New solubility data of CO₂ in DEEA+HMDA aqueous mixtures in the current study was compared with solubility data available in previous studies conducted by various researchers. The study shows that the new absorbent as a mixture of DEEA+HMDA is feasible for CO₂ removal from coal-fired power plant stack gas streams.     

Specialty polymeric membranes. V. Selective permeation of carbon dioxide through synthetic polymeric membranes having 2-(N,N-dimethyl)aminoethoxycarbonyl moiety

Permeation of CO₂ was investigated by using synthetic polymeric membranes having a tertiary amine moiety, 2-(N,N-dimethyl)aminoethoxycarbonyl moiety. Permselectivity of the present membranes towards CO₂ was achieved. Through poly{2-(N,N-dimethyl)aminoethyl methacrylate-co-acrylonitrile} (DMAEMA/AN-199) membrane, where DMAEMA mol fraction was 0.199, the separation factor towards CO₂ for CO₂/N₂ separation ranged from 60 to 90, ranging in the CO₂ partial pressure in the feed gas from 61 to 3.6 cmHg. © 1995 John Wiley & Sons, Inc.     

Differences in reactivity of pulverised coal in air (O2/N2) and oxy-fuel (O2/CO2) conditions

The reactivity of four pulverised Australian coals were measured under simulated air (O₂/N₂) and oxy-fuel (O₂/CO₂) environments using a drop tube furnace (DTF) maintained at 1673 K and a thermogravimetric analyser (TGA) run under non-isothermal (heating) conditions at temperatures up to 1473 K. The oxygen concentration, covering a wide and practical range, was varied in mixtures of O₂/N₂ and O₂/CO₂ in the range of 3 to 21 vol.% and 5 to 30 vol.%, respectively. The apparent volatile yield measured in CO₂ in the DTF was greater than in N₂ for all the coals studied. Pyrolysis experiments in the TGA also revealed an additional mass loss in a CO₂ atmosphere, not observed in a N₂ atmosphere, at relatively high temperatures. The coal burnout measured in the DTF at several O₂ concentrations revealed significantly higher burnouts for two coals and similar burnouts for the other two coals in oxy-fuel conditions. TGA experiments with char also revealed higher reactivity at high temperatures and low O₂ concentration. The results are consistent with a char–CO₂ reaction during the volatile yield experiments, but additional experiments are necessary to resolve the mechanisms determining the differences in coal burnout.     

Analysis of equilibrium CO2 solubility and thermodynamic models for aqueous 1-(2-hydoxyethyl)-piperidine solution

1-(2-Hydoxyethyl)-piperidine (1-(2HE)-PP) is a new tertiary amine with desirable properties and can be potentially used to formulate superior absorbents for CO₂ capture. The equilibrium CO₂ solubility of 1-(2HE)-PP solution is measured over temperatures from 298 to 333 K, CO₂ partial pressures from 8.1 to 101.3 kPa and initial amine concentrations from 1 to 5 M. Two thermodynamic models, namely semiempirical model and activity coefficient model are developed for the system. The activity coefficient model shows better estimation solubility with an absolute average relative deviation (AARD) of 7.6%. In the comparison between the two models, a comprehensive analysis is presented. Some suggestions are provided for the similar model development. In addition, the speciation plot of CO₂ loaded 1-(2HE)-PP solution is predicted based on the activity coefficient model. The predictive pH values agree well with experimental data with AARD of 1.0%. Finally, the potential of 1-(2-HE)PP to be an alternative amine in CO₂ capture is evaluated.     

Modeling interfacial tension of (CH4+N2)+H2O and (N2+CO2)+H2O systems using linear gradient theory

The linear gradient theory (LGT) of fluid interfaces in combination with the cubic-plus-association equation of state (CPA EOS) is applied to determine the interfacial tensions of (CH₄+N₂)+H₂O and (N₂+CO₂)+H₂O ternary mixtures from 298–373 K and 10–300 bar. First, the pure component influence parameters of CH₄, N₂, CO₂ and H₂O are obtained. Then, temperature-dependent expressions of binary interaction coefficient for (CH₄+H₂O), (N₂+H₂O) and (CO₂+H₂O) are correlated. These empirical correlations of pure component influence parameters and binary interaction coefficients are applied for ternary mixtures. For (CH₄+N₂)+H₂O and (N₂+CO₂)+H₂O mixtures, the predictions show good agreement with experimental data (overall AAD～1.31%).     

Gas permeation of polymer blends. IV. Poly(vinyl chloride) (PVC)/acrylonitrile–butadiene–styrene (ABS) terpolymer

The transport behavior of He, O₂, N₂, and CO₂ in membranes of poly(vinyl chloride) (PVC)/acrylonitrile–butadiene–styrene (ABS) blends has been studied at 25°C. The blends were further characterized by dynamic mechanical measurements, differential thermal analysis (DTA), density measurements, and x-ray diffraction. The equilibrium sorption of CO₂ and N₂ was measured directly at atmospheric pressure using an electromicrobalance and compared with sorption values obtained as P/D ratios from permeation measurements. The rates of permeation (P) and diffusion (D) increase with increasing ABS content in the blends. The P and D values are not additive, and only slight indications of phase inversion in the blends are observed at 5–10 wt-% ABS in the blends. Experimental densities of the blends are higher than calculated densities assuming volume additivity. The data are interpreted to mean that the PVC/ABS blends form a two-phase system composed of a soft polybutadiene (rubber) phase and a rigid PVC/styrene–acrylonitrile copolymer (SAN) phase of mutually compatible components. DTA and dynamic mechanical measurements also show a two-phase system. Sorption values of CO₂ and N₂ by equilibrium sorption measurements increase with increasing ABS content in the blends without the large fluctuations which have been observed for the sorption values obtained from the time lag method. Comparison of the two types of sorption values (from direct measurements and from P/D ratios) show larger deviations for CO₂ than for N₂. This suggests that the time lag method is not valid for permeants with polar character in heterogeneous two-phase systems where chemical immobilizing effect on the permeant molecules occurs.     

Gasification reactivity of char from dried sewage sludge in a fluidized bed

The gasification reactivity of char from dried sewage sludge (DSS) applicable to fluidized bed gasification (FBG) was determined. The char was generated by devolatilizing the DSS with nitrogen at the selected bed temperature and was subsequently gasified by switching the fluidization agent to mixtures of CO₂ and N₂ (CO₂ reactivity tests) and steam and N₂ (H₂O reactivity tests)._. The tests were conducted in the temperature range of 800–900 °C at atmospheric pressure, using partial pressure of the main reactant in the mixture (CO₂ or H₂O) in the range of 0.10–0.30 bar. Expressions for the intrinsic reactivity (free of diffusion effects) as a function of temperature, partial pressure of gas reactant (CO₂ or H₂O) and degree of conversion were obtained for each reaction. For the whole range of conversion it was found that the char reactivity in an H₂O–N₂ mixture was roughly three times higher than that in a mixture with the corresponding partial pressure of CO₂. The reactivity was only influenced by particle size greater than 1.2 mm in the tests with steam at 900 °C. It was demonstrated that the method of char preparation greatly influences the reactivity, highlighting the importance of generating the char in conditions similar to that in FBG.     

Kinetics study of carbon dioxide absorption in aqueous solutions of 1,6-hexamethyldiamine (HMDA) and 1,6-hexamethyldiamine, N,N′ di-methyl (HMDA, N,N′)

A study towards the kinetics of CO₂ in aqueous solutions of 1,6-hexamethyl diamine (HMDA) and 1,6-hexamethyl diamine, N,N′ di-methyl (HMDA, N,N′) was performed at concentrations ranging from 0.5 to 2.5 mol/L and temperatures from 283 up to 303 K. The kinetics data were determined by CO₂ absorption experiments using a stirred cell reactor with a flat interface between gas and liquid. These new CO₂ solvents were identified in earlier work for their high CO₂ capacity and limited corrosiveness. The experimental technique was validated using kinetic experiments for a 2.5 mol/L monoethanolamine solution. In view of double amine functionality and the six carbon chain between the amine groups, attention was paid to whether the amine groups acted independently and whether or not internal cyclisation would affect the carbamate forming mechanism. The reaction order with respect to HMDA was found to vary from 1.4 to 1.8 with increasing temperature. Absorption experiments in an equimolar solution of HMDA with HCl showed that the two amine groups react independently from each other towards CO₂. The reactivity of both diamines was more than five times larger than for monoethanolamine. The secondary diamine HMDA, N,N′ was found to be even more reactive towards CO₂. Additionally, the effect of CO₂ loading on the kinetics was studied for 0.5 mol/L aqueous solutions of HMDA and HMDA, N,N′ at 293 K. Both solvents are from absorption kinetics point of view good candidates for further evaluation as solvent (-component) for CO₂ capture.     

An experimental/computational study of steric hindrance effects on CO2 absorption in (non)aqueous amine solutions

The reaction kinetics and molecular mechanisms of CO₂ absorption using nonaqueous and aqueous monoethanolamine (MEA)/methyldiethanolamine (MDEA)/2-amino-2-methy-1-propanol (AMP) solutions were analyzed by the stopped-flow technique and ab initio molecular dynamics (AIMD) simulations. Pseudo first-order rate constants (k₀) of reactions between CO₂ and amines were measured. A kinetic model was proposed to correlate the k₀ to the amine concentration, and was proved to perform well for predicting the relationship between k₀ and the amine concentration. The experimental results showed that AMP/MDEA only took part in the deprotonation of MEA-zwitterion in nonaqueous MEA + AMP/MEA + MDEA solutions. In aqueous solutions, AMP can also react with CO₂ through base-catalyzed hydration mechanism beside the zwitterion mechanism. Molecular mechanisms of CO₂ absorption were also explored by AIMD simulations coupled with metadynamics sampling. The predicted free-energy barriers of key elementary reactions verified the kinetic model and demonstrated the different molecular mechanisms for the reaction between CO₂ and AMP.     

Pseudopeptide bioconjugate additives for CO2 separation membranes

1:1[α/α‐N^α‐Bn‐hydrazino] pseudopeptide?polymer bioconjugates were synthesized and investigated as additives in a reference gas separation membrane (Pebax®) for CO₂ capture. Pebax® is a polyether block amide thermoplastic elastomer provided by Arkema and is already well known for its good performance for CO₂ separations. First, dimer and tetramer pseudopeptides were synthesized and their terminal amine was modified into a ‘clickable’ alkyne group in view of coupling. Second, an α‐azido acrylic poly(ethylene glycol)‐based oligomer was obtained by single‐electron transfer living radical polymerization and the two partners were coupled using copper(I) catalyzed alkyne‐azide cycloaddition (CuAAC) ‘click’ chemistry. The pseudopeptides and their bioconjugates were then assessed as original additives in Pebax® membranes for CO₂/CH₄ and CO₂/N₂ separations. The permeation data were analyzed according to the solution‐diffusion model. Compared to pseudopeptides, the pseudopeptide?polymer bioconjugates enabled the membrane properties to be greatly improved with better permeability (×1.5) and a good constant selectivity for CO₂ capture. The best membrane properties were obtained with 3 eq. wt% of the tetramer‐based bioconjugate with a CO₂ permeability of 194 Barrer (+46% compared to that of Pebax®) and constant selectivity (αCO₂/N₂ = 44 and αCO₂/CH₄ = 13). © 2016 Society of Chemical Industry     

Rolltruded Poly(Aryl Ether Ether Ketone) (PEEK) for Membrane Applications

Abstract

An investigation of the transport and separation of several permanent gases (CO₂, N₂, CH₄, and H₂) and vapors (H₂O and ethanol) in unprocessed and rolltruded poly(aryl ether ether ketone) (PEEK) thin films has been conducted to evaluate PEEK for membrane applications requiring thermally and chemically stable materials. Transport coefficients and separation factors have been determined at permeation temperatures ranging from 40 to ca. 180°C. The gas transport coefficients were found to increase by up to 30% depending on the processing conditions. Actual separation factors, determined for a CO₂/N₂ gas mixture (24.6 vol% CO₂), were depressed slightly in comparison to the ideal values obtained from pure component data. In contrast, water and ethanol vapor permeabilities declined between 10 and 15% as a result of processing. For a 39.1 wt% vapor mixture of H₂O in EtOH, ideal and actual separation factors, determined at 130°C, were in good agreement. In contrast, order of magnitude improvements in the actual versus ideal separation factors were found for 11.7 and 7.6 wt% mixtures of H₂O in EtOH in both unprocessed and rolltruded PEEK. A comparison with other membranes considered for high temperature vapor dehydrations suggests that PEEK may be an excellent polymer for these applications.     

High pressure measurements and molecular modeling of the water content of acid gas containing mixtures

Water content of three carbon dioxide containing natural gas mixtures in equilibrium with an aqueous phase was measured using a dynamic saturation method. Measurements were performed up to high temperatures (477.6 K = 400°F) and pressures (103.4 MPa = 15,000 psia). The perturbed chain form of the statistical associating fluid theory was applied to predict water content of pure carbon dioxide (CO₂), hydrogen sulfide (H₂S), nitrous oxide (N₂O), nitrogen (N₂), and argon (Ar) systems. The theory application was also extended to model water content of acid gas mixtures containing methane (CH₄). To model accurately the liquid‐liquid equilibrium at subcritical conditions, cross association between CO₂, H₂S, and water was included. The agreement between the model predictions and experimental data measured in this work was found to be good up to high temperatures and pressures. © 2015 American Institute of Chemical Engineers AIChE J, 61: 3038–3052, 2015     

CO2 Absorption into Aqueous Solutions of a Polyamine (PZEA), a Sterically Hindered Amine (AMP), and their Blends

Among numerous techniques existing for reducing CO₂ emissions, CO₂ capture by absorption in aqueous alkanolamine solutions was specifically studied in this work. For the choice of the adequate amine solution, two major criteria must be taken into account: absorption performances (higher with primary and secondary amines) and energy costs for solvent regeneration (more interesting with tertiary and sterically hindered amines). The different types of amines can also be mixed in order to combine the specific advantages of each type of amines, an activation phenomenon being observed. Aqueous solutions of (piperazinyl‐1)‐2‐ethylamine (PZEA, a polyamine known as absorption activator) and 1‐amino‐2‐propanol (AMP, a sterically hindered amine), pure or mixed with other amines, are experimentally compared with respect to CO₂ removal performances by means of absorption test runs achieved in a special gas‐liquid contactor at 25 °C. The positive impact of addition of PZEA to monoethanolamine (MEA), N‐methyldiethanolamine (MDEA), and AMP solutions was clearly highlighted. The absorption performances have also been satisfactorily simulated with coherent physicochemical data.     

Separation of N2O and CO2 using Room-Temperature Ionic Liquid [bmim][Ac]

We have developed a ternary equation of state (EOS) model for the N₂O/CO₂/1-butyl-3-methylimidazolium acetate ([bmim][Ac]) system in order to understand the separation of N₂O and CO₂ using room-temperature ionic liquids (RTILs). The present model is based on a generic RK (Redlich-Kwong) EOS, with empirical interaction parameters for each binary system. The interaction parameters have been determined using our measured VLE (vapor-liquid-equilibrium) data for N₂O/[bmim][Ac] and literature data for CO₂/[bmim][Ac] and N₂O/CO₂. The binary EOS model for the N₂O/[bmim][Ac] system correctly predicted the liquid-liquid phase separation found in VLLE experiments. The validity of the ternary EOS model has been checked by conducting VLE experiments for the N₂O/CO₂/[bmim][Ac] system over a temperature range from 296 to 313 K. With this EOS model, solubility (VLE) behavior has been calculated for various (T, P, and feed compositions) conditions. Over a range of N₂O/CO₂ feed ratios, the N₂O/CO₂ gas selectivity [α _{N 2 O/CO 2}  = (y _{N 2 O} /x _{N 2 O} )/(y _{CO 2} /x _{CO 2} )] increases by at least 5 orders of magnitude when adding [bmim][Ac] (α = 1 × 10² to 1 × 10⁷), compared with the absence of the ionic liquid (α = 0.96 to 0.98). The addition of [bmim][Ac] may provide a practical means of separating CO₂ and N₂O.

Supplemental materials are available for this article. Go to the publisher's online edition of Separation Science and Technology to view the free supplemental file.     

A study of gas transport through interfacially formed poly(N,N-dimethylaminoethyl methacrylate) membranes

Gas transport through interfacially formed poly(N,N-dimethylaminoethyl methacrylate) membranes was investigated. The membrane performance for the separation of binary CO₂/N₂, CO₂/CH₄ and CO₂/H₂ mixtures was studied, and the coupling effects between the permeating species were evaluated by comparing the permeance of individual components in the mixture with their pure gas permeance. For the permeation of these binary gas mixtures, the presence of CO₂ was shown to influence the permeation of the other components (i.e., N₂, H₂ and CH₄), whereas the permeation of CO₂ was not affected by these components. In consideration that water vapor is often encountered in applications involving CO₂ separation, the presence of water vapor on the membrane permselectivity was also studied. When hydrated, the membrane was shown to be more permeable to CO₂, while the membrane selectivity did not change significantly. Unlike membranes based on size-sieving of penetrant molecules, the present membranes exploit the favorable interactions between the hydrophilic quaternary amines in the membrane and CO₂, especially in the presence of water vapor in the feed.     

Highly Efficient Extraction of Rhodium(III) from Hydrochloric Acid Solution with Amide-Containing Tertiary Amine Compounds

Extraction of Rh(III) from a HCl solution with N,N-disubstituted amide–containing tertiary amine (ACTA) compounds (N,N-di-n-hexyl(N-methyl-N-n-octyl-ethylamide)amine (MonoAA), N-n-hexyl-bis(N-methyl-N-n-octyl-ethylamide)amine (BisAA), and tris(N-methyl-N-n-octyl-ethylamide)amine (TrisAA)) was investigated. The ACTAs extract Rh(III) more efficiently than tri-n-octylamine (TOA), and the extraction efficiency increases with increasing number of amide groups: TrisAA > BisAA > MonoAA ? TOA. For all ACTAs, the predominant Rh(III) complex extracted from 2 M HCl is probably {[RhCl₅(H₂O)]·(ACTA·H)₂}. The apparent basicity of the ACTAs and TOA varies in the opposite order from that observed for the Rh(III) extraction efficiency. Rh(III) can be readily back-extracted using 10 M HCl solution possessing a high selectivity over similarly loaded Pd(II) and Pt(IV).     

Phase equilibrium (solid-liquid-gas) in polyethyleneglycol-carbon dioxide systems

Phase equilibria (solid-liquid-gas) for polyethyleneglycol (with molar masses 1500, 4000, 8000 and 35 000 g mol⁻¹) and carbon dioxide mixtures were determined. It was found that the S-L-V lines in P-T projection for all polyethyleneglycols studied show a temperature minimum and a temperature maximum. These phenomena have not been reported previously in the literature. If a reduced temperature (obtained by dividing the temperature of the solid-liquid transition under pressure by the melting point of PEG at 1 bar) is introduced, the S-L transition of all binary systems are represented by one line. The solubility of CO₂ in liquid polyethyleneglycols is influenced by pressure and temperature, and is almost independent of the molecular mass of polyethyleneglycol. In a P-T projection, the vapour-liquid equilibrium is represented by a straight line if isopleths are plotted as a function of the reduced temperature. By combining the P-T_red projections of the S-L and L-V transitions, one master diagram can obtained which is valid for all binary mixtures of polyethyleneglycol and CO₂ in the pressure and temperature range investigated.     

A water‐soluble CO2‐triggered viscosity‐responsive copolymer of N,N‐dimethylaminoethyl methacrylate and acrylamide

A series of copolymers PDAMs were synthesized with varying monomer ratio of acrylamide (AM) and N,N‐dimethylaminoethyl methacrylate (DMAEMA). The resulting copolymer solution shows an interesting property of viscosity‐response which is CO₂‐triggered and N₂‐enabled. Tertiary amine groups of PDAMs experience a reversible transition between hydrophobic and hydrophilic state upon CO₂ addition and its removal, which induced different rheological behavior. A combination of zeta‐potential, laser particle‐size analysis, and electrical conductivity analysis indicated that, when the monomer mole ratio of DMAEMA and AM is less than or equal to 3 : 7, the hydrophobic association structure between the copolymer molecules was destroyed by the leading of CO₂ and caused a viscosity decrease in its solution. On the contrary, when the monomer mole ratio of DMAEMA and AM is more than 3 : 7, a more extended conformation due to the protonated tertiary amine groups is formed and the enhanced repulsive interactions among the copolymer molecule results in a rise of its solution viscosity. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40872.