Novel polyimide ionomers: CO2 plasticization, morphology, and ion distribution

Aluminum crosslinked 6FDA-6FpDA:DABA 2:1 and 1:2 copolyimide membranes were synthesized and their CO₂-induced plasticization was investigated. The membranes are unstable against CO₂ plasticization in long-term permeation tests at 40 atm CO₂ feed pressure at 35 °C. To correlate the plasticization with the polymer morphology, scanning transmission electron microscopy (STEM) was used to image the ionomers. STEM shows Al-rich aggregates in both ionomers, but the aggregate size and shape distribution in the 1:2 film is much more heterogeneous than in the 2:1. The 1:2 ionomer contains spherical aggregates with diameters from ∼5 to 25 nm, chainlike assemblies of small spherical aggregates, vesicular aggregates, large distorted vesicular aggregates, and long band-like structures that extend up to 1000 nm in one dimension. The 2:1 ionomer only contains a few approximately spherical aggregates. Large fractions of both ionomers do not exhibit visible aggregates on the STEM length scale. IR spectroscopy reveals a neutralization level of the acid groups above 60% and transmission electron microscopy detects unreacted neutralizing agent in the polymer. Small angle and wide angle X-ray scattering patterns show scattering patterns that can be linked to the solid-state structure of the polymer backbone rather than the ionic aggregates.     

CO2 sorption and transport behavior of ODPA-based polyetherimide polymer films

Plasticization phenomena can significantly reduce the performance of polymeric membranes in high-pressure applications. Polyetherimides (PEIs) are a promising group of membrane materials that combine relatively high CO₂/CH₄ selectivities with high chemical and thermal stability. In this work sorption, swelling, and mixed gas separation performance of 3,3′,4,4′-oxydiphthalic dianhydride (ODPA)-based PEI polymers, with 1, 2 or 3 para-aryloxy substitutions in the diamine moeiety, is investigated under conditions where commercial membranes suffer from plasticization. Particular focus is on the influence of the amount of para-aryloxy substitutions and the film thickness. Results are compared with those of commercially available polymeric membrane materials (sulphonated PEEK, a segmented block-co-polymer PEBAX and the polyimide Matrimid).The glassy polymers display increasing CO₂ sorption with increasing T_g. The larger extent of sorption results from a larger non-equilibrium excess free volume. Swelling of the polymers is induced by sorption of CO₂ molecules in the non-equilibrium free volume as well as from molecules dissolved in the matrix. Dilation of the polymer is similar for each molecule sorbed. Correspondingly, the partial molar volume of CO₂ is similar for molecules present in both regions.Mixed gas separation experiments with a 50/50% CO₂/CH₄ feed gas mixture showed high CO₂/CH₄ selectivities for the ODPA PEI films at elevated pressure. This shows that these materials could potentially be interesting for high-pressure gas separation applications, although additional gas permeation experiments using different feed gas compositions and thin films are required.     

CO2-induced polymorphous phase transition of isotactic poly-1-butene with form III upon annealing

In-situ high-pressure FTIR was used to investigate the polymorphous phase transition of isotactic poly-1-butene (iPB-1) with form III upon annealing at temperatures ranging from 75 to 100 °C and CO₂ pressures ranging from 2 to 12 MPa. It was shown that the phase transition of form III changed from form III to II not through form III to I′ with increasing temperature and application of CO₂ increased the content of generated form I′. Wide-angle X-ray diffraction (WAXD) measurement on the annealed iPB-1 with form III verified the phase transition of form III. The crystalline morphology of the annealed iPB-1 films was investigated using polarized optical microscopy (POM). The results implied that the phase transition of form III to I′ might process via a solid-solid transition, which did not affect the orientation of the lamellar stacks. The orientation of form II lamellar stacks depended strongly on the formation process. To obtain strong orientation, the formation process displayed the following order: melt crystallization at ambient condition > melt recrystallization under CO₂ > phase transition upon annealing at ambient condition. Avrami equation could be well established to describe the phase transition of form III to I′ through a solid-solid phase transition.     

The synthesis and morphology characteristic study of BAO-ODPA polyimide/TiO2 nano hybrid films

Hybrid nanocomposite films of titanium dioxide (TiO₂) in polyimide (PI) from 2,5-bis(4-aminophenyl)-1,3,4-oxadiazole (BAO) and 4,4′-oxydiphthalic anhydride (ODPA) have been successfully fabricated by an in situ sol-gel process. These nanocomposite films exhibit fair good optical transparency up to 40 wt% of TiO₂ content. X-ray diffraction spectroscopy shows three sharp peaks in pure BAO-ODPA PI. It results from the intermolecular regularity. However, the intermolecular regularity in the hybrid film is disrupted by the introduction of TiO₂ nanoparticles with no sharp peak in XRD spectra. Fourier transform infrared (FTIR) and X-ray photoelectron spectroscopy (XPS) results confirm the formation of TiO₂ particles in PI matrix. The surface Ti content is much lower than the theoretical bulk content in all hybrid films. The ratio of the former to the latter increases with the TiO₂ content and levels off at TiO₂ wt%≥20. Transmission electron microscope (TEM) images show that the TiO₂ phase is well dispersed in the polymer matrix. The size of the TiO₂ phase increases from 10 to 40 nm when the TiO₂ content is 5-30 wt%, respectively.     

Theoretical study on interaction between CO2 and carbonyl compounds: Influence of CO2 on infrared spectroscopy and activity of CO

The interactions between CO₂ and carbonyl compounds at different CO₂ pressures have been studied both experimentally and theoretically. In situ high-pressure FTIR on carbonyl compounds, i.e., acetaldehyde, acetone, and crotonaldehyde, in supercritical CO₂ have been measured at various CO₂ pressures varying from 6 to 22 MPa. In order to get insights into the mechanism, theoretical study has been conducted concerning the effect of CO₂ on frequency shift of CO in acetaldehyde, acetone, benzaldehyde, crotonaldehyde and cinnamaldehyde at different CO₂ pressures. It has been shown that the experimental frequency shifts can be well simulated by the theoretical model calculations using particular structures, in which a carbonyl compound interacts with a few CO₂ molecules, depending on the carbonyl compounds examined, except for acetaldehyde.The interaction energies between CO₂ and those carbonyl compounds are also given. In addition, the effect of CO₂ on hydrogenation of crotonaldehyde and benzaldehyde has been discussed by means of the local softness (s⁺) calculated at CO₂ pressures of 0-22 MPa, which can explain the reactivity difference in the crotonaldehyde and benzaldehyde hydrogenations in supercritical CO₂.     

Techno-economic evaluation of a PVAm CO2-selective membrane in an IGCC power plant with CO2 capture

Published data for an operating power plant, the ELCOGAS 315 MWe Puertollano plant, has been used as a basis for the simulation of an integrated gasification combined cycle process with CO₂ capture. This incorporated a fixed site carrier polyvinylamine membrane to separate the CO₂ from a CO-shifted syngas stream. It appears that the modified process, using a sour shift catalyst prior to sulphur removal, could achieve greater than 85% CO₂ recovery at 95 vol% purity. The efficiency penalty for such a process would be approximately 10% points, including CO₂ compression. A modified plant with CO₂ capture and compression was calculated to cost €2320/kW, producing electricity at a cost of 7.6 € cents/kWh and a CO₂ avoidance cost of about €40/tonne CO₂.     

Synthesis of vicinal diamines via Zn–H2O–CO2-induced reduction of aromatic imines in supercritical carbon dioxide

Zn–H₂O–CO₂ is a good reducing reagent for the reduction of imines in supercritical carbon dioxide (scCO₂). They provide the corresponding vicinal diamines in moderate to good yields. The results showed that carbon dioxide plays an important role as both solvent and reagent.     

In situ study of ionic conductivity for polyether-LiCF3SO3 electrolytes with subcritical and supercritical CO2

In situ measurements of the ionic conductivity were performed on polyethers, poly(ethylene oxide) (PEO) and poly(oligo oxyethylene methacrylate) (PMEO), with lithium triflate (LiCF₃SO₃) as crystalline and amorphous electrolytes, and at CO₂ pressures up to 20 MPa. Both PEO and PMEO systems in subcritical and supercritical CO₂ increased more than five fold in ionic conductivity at 40 °C composed to atmospheric pressure. The pressure dependence of the ionic conductivity for PEO electrolytes was positive under CO₂, and increased by two orders of magnitude under pressurization from 0 to 20 MPa, whereas it decreases with increasing pressure of N₂. The enhancement is caused by the plasticizing effect of CO₂ molecules that penetrate into the electrolytes.     

Thermodynamic performance of O2/CO2 gas turbine cycle with chemical recuperation by CO2-reforming of methane

This paper proposes a novel power cycle system composed of chemical recuperative cycle with CO₂–NG (natural gas) reforming and an ammonia absorption refrigeration cycle. In which, the heat is recovered from the turbine exhaust to drive CO₂–NG reformer firstly, and then lower temperature heat from the turbine exhaust is provided with the ammonia absorption refrigeration system to generate chilled media, which is used to cool the turbine inlet gas except export. In this paper, a detailed thermodynamic analysis is carried out to reveal the performance of the proposed cycle and the influence of key parameters on performance is discussed. Based on 1 kg s⁻¹ of methane feedstock and the turbine inlet temperature of 1573 K, the simulation results shown that the optimized net power generation efficiency of the cycle rises up to 49.6% on the low-heating value and the exergy efficiency 47.9%, the new cycle system reached the net electric-power production 24.799 MW, the export chilled load 0.609 MW and 2.743 kg s⁻¹ liquid CO₂ was captured, achieved the goal of CO₂ and NO_x zero-emission.     

Impact of SO2 concentration on the corrosion rate of X70 steel and iron in water-saturated supercritical CO2 mixed with SO2

The corrosion behavior of X70 steel and iron in water-saturated supercritical CO₂ mixed with SO₂ was investigated using weight-loss measurements. As a comparison, the instantaneous corrosion rate in the early stages for iron in the same corrosion environment was measured by resistance relaxation method. Surface analyzes using SEM/EDS, XRD and XPS were applied to study the morphology and chemical composition of the corroded sample surface. Weight-loss method results showed that the corrosion rate of X70 steel samples increased with SO₂ concentration, while the corrosion rate increased before decreasing with SO₂ concentration for iron sample. Comparing resistance relaxation method results with weight-loss method results, it is found that the instantaneous corrosion rate of iron is much higher than the uniform corrosion rate of the iron tablet specimens which are covered with thick corrosion product films after a long period of corrosion. The corrosion product films were mainly composed of FeSO₄ and FeSO₃ hydrates. The possible reaction mechanism under such environment was also analyzed, and the electrochemical reaction between the dissolved SO₂ in the condensed water film with iron is the critical reaction step.     

A rate equation for Ca(OH)2 and CO2 reaction in a spouted bed reactor at low gas concentrations

In the present study, the carbonation reaction of hydrated lime in semi-dry condition is investigated experimentally in a laboratory-scale spouted bed reactor. Results show that for operating conditions where the concentration of CO₂ is low, the capture efficiency is raised by increasing the inlet CO₂ concentration. Additionally, because of the inconsistency between the experimental reaction rate and the calculated values based on the previous proposed equations, a new rate equation is introduced that considers the dependency of CO₂ concentration too. To validate the proposed equation, its predictions were compared with another set of experimental data.     

Effect of TiO2 particle size on the photocatalytic reduction of CO2

Pure TiO₂ anatase particles with a crystallite diameters ranging from 4.5 to 29 nm were prepared by precipitation and sol–gel method, characterized by X-ray diffraction (XRD), BET surface area measurement, UV–vis and scanning electron microscopy (SEM) and tested in CO₂ photocatalytic reduction. Methane and methanol were the main reduction products. The optimum particle size corresponding to the highest yields of both products was 14 nm. The observed optimum particle size is a result of competing effects of specific surface area, charge–carrier dynamics and light absorption efficiency.     

Partial O2-fired coal power plant with post-combustion CO2 capture: A retrofitting option for CO2 capture ready plants

In the work presented in this paper, an alternative process concept that can be applied as retrofitting option in coal-fired power plants for CO₂ capture is examined. The proposed concept is based on the combination of two fundamental CO₂ capture technologies, the partial oxyfuel mode in the furnace and the post-combustion solvent scrubbing. A 330 MW_el Greek lignite-fired power plant and a typical 600 MW_el hard coal plant have been examined for the process simulations. In a retrofit application of the ECO-Scrub technology, the existing power plant modifications are dominated by techno-economic restrictions regarding the boiler and the steam turbine islands. Heat integration from processes (air separation, CO₂ compression and purification and the flue gas treatment) can result in reduced energy and efficiency penalties. In the context of this work, heat integration options are illustrated and main results from thermodynamic simulations dealing with the most important features of the power plant with CO₂ capture are presented for both reference and retrofit case, providing a comparative view on the power plant net efficiency and energy consumptions for CO₂ capture. The operational characteristics as well as the main figures and diagrams of the plant’s heat balances are included.     

Cetirizine solubility in supercritical CO2 at different pressures and temperatures

A simple static technique was used to obtain the solubility of cetirizine in supercritical carbon dioxide. The solubility measurements were performed at temperatures and pressures ranging from 308.15 to 338.15 K and 160 to 400 bar, respectively; resulting in mole fractions in the 1.05 × 10⁻⁵ to 4.92 × 10⁻³ range. The Chrastil, Bartle, Kumar & Johnston and the Mendez-Santiago and Teja (MST) models were used to correlate the experimental data. The calculated solubilities showed good agreement with the experimental data in the temperature and pressure ranges studied.     

Grafting of polypropylene with N-cyclohexylmaleimide and styrene simultaneously using supercritical CO2

Monomer mixture of styrene (St) and N-cyclohexylmaleimide (ChMI) and initiator benzoyl peroxide (BPO) were first impregnated into isotactic polypropylene (iPP) films simultaneously using supercritical carbon dioxide (SC CO₂) as a solvent and swelling agent at 35.0 °C. The composites were obtained after the monomers were grafted onto the iPP matrix at 70 °C. The effects of various conditions, such as pressure, monomer concentration, and the molar ratio of the two monomers in the soaking process, on the composition of the composites were determined. The molar ratios of St to ChMI in the composites were estimated by Fourier transform infrared spectroscopy. The thermal properties, the morphology, and the mechanical properties of the composites were characterized by different techniques. The results demonstrated that the phase size of the grafted St-ChMI was very small and the phase boundary was very ambiguous. The composites had better thermal stability than the original iPP film. The Young's modulus and tensile strength of the film increased continuously with increasing grafting percentage. The two grafted monomers in the composites had good synergetic effect.     

Polymer melt rheology with high-pressure CO2 using a novel magnetically levitated sphere rheometer

A magnetically levitated sphere rheometer (MLSR) designed to measure viscosity of fluids exposed to high-pressure carbon dioxide has been developed. This device consists of a magnetic sphere submerged inside a test fluid within a high-pressure housing and levitated at a fixed point. The housing is constructed from an optically transparent sapphire tube. The cylindrical tube can be moved vertically to generate a shear flow around the levitated sphere. The difference in magnetic force required to levitate the sphere at rest and under fluid motion can be directly related to fluid viscosity. Rheological properties, specifically zero shear viscosities, of transparent high-pressure materials can be measured to a precision of about 5% and over a wide range of viscosities. In addition, operation at constant pressure, in concentration regimes from a pure polymer to an equilibrated polymer/supercritical fluid solution, and at shear rates over several orders of magnitude is possible, eliminating many of the disadvantages associated with other high-pressure rheometers. Experiments performed at different temperatures with a poly(dimethylsiloxane) melt at atmospheric pressure are compared with data from a commercial Couette rheometer to demonstrate device sensitivity and viability. Measurements of a PDMS melt plasticized by high-pressure CO₂ are performed to illustrate the utility of the new rheometer under high-pressure conditions. Experimental data are obtained at 30 °C, for pressures up to 20.7 MPa and CO₂ concentrations reaching 30 wt%. Viscosity reductions of nearly two orders of magnitude compared with the pure polymer viscosity at atmospheric pressure are observed. Additionally, the effects of pressure on a polymer/CO₂ system are directly investigated taking advantage of the constant pressure operation mode of the MLSR. This allows us, for the first time in experiments of polymers with supercritical fluids, to decouple the effects of CO₂ concentration and pressure in a single device.     

Simultaneous easy CO2 recovery and drastic reduction of SOx and NOx in O2/CO2 coal combustion with heat recirculation

Coal combustion with O₂/CO₂ is promising because of its easy CO₂ recovery, extremely low NO_x emission and high desulfurization efficiency. Based on our own fundamental experimental data combined with a sophisticated data analysis, its characteristics were investigated. It was revealed that the conversion ratio from fuel-N to exhausted NO in O₂/CO₂ pulverized coal combustion was only about one fourth of conventional pulverized coal combustion. To decrease exhausted NO further and realize simultaneous easy CO₂ recovery and drastic reduction of SO_x and NO_x, a new scheme, i.e. O₂/CO₂ coal combustion with heat recirculation, was proposed. It was clarified that in O₂/CO₂ coal combustion, with about 40% of heat recirculation, the same coal combustion intensity as that of coal combustion in air could be realized even at an O₂ concentration of as low as 15%. Thus exhausted NO could be decreased further into only one seventh of conventional coal combustion. Simultaneous easy CO₂ recovery and drastic reduction of SO_x and NO_x could be realized with this new scheme.     

Alicyclic photoresists for CO2-based next-generation microlithography: A tribute to James E. McGrath

Addition polymerization of norbornene-based monomers has been pursued toward the fabrication of photoresists for next-generation microlithography, using condensed carbon dioxide as the developing solvent. Addition polymers containing a norbornyl backbone, for dry plasma etch resistance and high thermal stability, were synthesized to include fluorinated moieties and chemical amplification switching groups. These materials have been characterized and their lithographic properties evaluated. Solubility differences between exposed and non-exposed resist have been observed in these novel systems, which should provide the necessary contrast for high-resolution imaging. Lithographic imaging produced dense lines as small as 3 μm.     

Foaming of polymers with supercritical CO2: An experimental and theoretical study

Microcellular polystyrene (PS) foams and porous structures of the biodegradable poly(d,l-lactic acid) (P_d,lLA) were prepared with the batch foaming technique (pressure quench) using supercritical CO₂ as blowing agent. The effect of pressure, temperature and depressurization rate on the final porous structure was investigated. The results revealed that the size of the pores decreases and their population density increases with pressure increase, or decrease of temperature, and/or increase of the depressurization rate. The results were correlated by combining nucleation theory with NRHB model in order to account for and emphasize the physical mechanism related to nucleation of bubbles inside the supersaturated polymer matrix. A satisfactory agreement between correlations and experimental data was obtained indicating that the nucleation theory yields quantitative correlations when variables such as sorption, degree of plasticization, and surface tension of the system polymer-supercritical fluid are accurately described.