Combined Superbase Ionic Liquid Approach to Separate CO2 from Flue Gas

[Image: see text] Superbase ionic liquids (ILs) with a trihexyltetradecylphosphonium cation and a benzimidazolide ([P(66614)][Benzim]) or tetrazolide ([P(66614)][Tetz]) anion were investigated in a dual-IL system allowing the selective capture and separation of CO(2) and SO(2), respectively, under realistic gas concentrations. The results show that [P(66614)][Tetz] is capable of efficiently capturing SO(2) in preference to CO(2) and thus, in a stepwise separation process, protects [P(66614)][Benzim] from the negative effects of the highly acidic contaminant. This results in [P(66614)][Benzim] maintaining >53% of its original CO(2) uptake capacity after 30 absorption/desorption cycles in comparison to the 89% decrease observed after 11 cycles when [P(66614)][Tetz] was not present. Characterization of the ILs post exposure revealed that small amounts of SO(2) were irreversibly absorbed to the [Benzim](−) anion responsible for the decrease in CO(2) capacity. While optimization of this dual-IL system is required, this feasibility study demonstrates that [P(66614)][Tetz] is a suitable sorbent for reversibly capturing SO(2) and significantly extending the lifetime of [P(66614)][Benzim] for CO(2) uptake

Reversible Reaction of CO2 with Superbasic Ionic Liquid [P66614][benzim] Studied with in Situ Photoelectron Spectroscopy

Ionic liquids (ILs) are of significant interest as CO2 capture agents, and one subgroup of ILs that has shown particular promise is that of superbasic ILs. They can absorb large quantities of CO2 in the dry state, but some will have a diminished CO2 capacity when prewetted. In the work presented here, the superbasic IL trihexyl-tetradecylphosphonium benzimidazolide, or [P66614][benzim], was exposed to 3 mbar of CO2, 2 mbar of H2O vapor, and a CO2 + H2O gas mixture and was investigated using near-ambient pressure X-ray photoelectron spectroscopy. The results show that the IL reacts with CO2 to form carbamate and that the reaction is reversible through reduction of the surrounding gas pressure. Regardless of whether the IL was exposed to CO2 or H2O vapor first, the presence of H2O under these experimental conditions does not significantly hinder the IL’s ability to absorb and react with CO2. Furthermore, the IL appears to preferentially react with CO2 over H2O vapor

The addition of CO2 to four superbase ionic liquids: a DFT study

The addition of carbon dioxide to four superbase ionic liquids, [P3333][Benzim], [P3333][124Triz], [P3333][123Triz] and [P3333][Bentriz] was studied using a molecular DFT approach involving anions alone and individual ion pairs. Intermolecular bonding within the individual ion pairs is characterised by a number of weak hydrogen bonds, with the superbase anion geometrically arranged so as to maximize interactions between the heterocyclic N atoms and the cation. The pairing energies show no correlation to the observed CO2 adsorption capacity. Addition of CO2 to the anion alone clearly resulted in the formation of a covalently-bound carbamate function with the strength of binding correlated to experimental capacity. In the ion pair however the cation significantly alters the nature of the bonding such that the overall cohesive energy is reduced. Formation of a strong carbamate function occurs at the expense of weakening the interaction between anion and cation. In the more weakly absorbing ion pairs which contain [123Triz](-) and [Bentriz](-), the carbamate-functionalised systems are very close in energy to adducts in which CO2 is more weakly bound, suggesting an equilibrium between the chemi- and physisorbed CO2

Cryptic species and independent origins of allochronic populations within a seabird species complex (Hydrobates spp.)

Humans are inherently biased towards naming species based on morphological differences, which can lead to reproductively isolated species being mistakenly classified as one if they are morphologically similar. Recognising cryptic diversity is needed to understand drivers of speciation fully, and for accurate estimates of global biodiversity and assessments for conservation. We investigated cryptic species across the range of band-rumped storm-petrels (Hydrobates spp.): highly pelagic, nocturnal seabirds that breed on tropical and sub-tropical islands in the Atlantic and Pacific Oceans. In many breeding colonies, band-rumped storm-petrels have sympatric but temporally isolated (allochronic) populations; we sampled all breeding locations and allochronic populations. Using mitochondrial control region sequences from 754 birds, cytochrome b sequences from 69 birds, and reduced representation sequencing of the nuclear genomes of 133 birds, we uncovered high levels of genetic structuring. Population genomic analyses revealed up to seven unique clusters, and phylogenomic reconstruction showed that these represent seven monophyletic groups. We uncovered up to six independent breeding season switches across the phylogeny, spanning the continuum from genetically undifferentiated temporal populations to full allochronic species. Thus, band-rumped storm-petrels encompass multiple cryptic species, with non-geographic barriers potentially comprising strong barriers to gene flow

Co2 capture and electrochemical conversion using superbasic [p-66614]-[124triz]

The ionic liquid trihexyltetradecylphosphonium 1,2,4- triazolide, [P66614][124Triz], has been shown to chemisorb CO2 through equimolar binding of the carbon dioxide with the 1,2,4-triazolide anion. This leads to a possible new, low energy pathway for the electrochemical reduction of carbon dioxide to formate and syngas at low overpotentials, utilizing this reactive ionic liquid media. Herein, an electrochemical investigation of water and carbon dioxide addition to the [P66614][124Triz] on gold and platinum working electrodes is reported. Electrolysis measurements have been performed using CO2 saturated [P66614][124Triz] based solutions at -0.9 V and -1.9 V on gold and platinum electrodes. The effects of the electrode material on the formation of formate and syngas using these solutions are presented and discussed18338940

Techno-economic feasibility of selective CO2 capture processes from biogas streams using ionic liquids as physical absorbents

Biogas from anaerobic digestion of sewage sludge is a renewable resource with high energy content, which is composed mainly of CH4 (40-75 vol %) and CO2 (15-60 vol %). Other components, such as water (H2O, 5-10 vol %) and trace amounts of hydrogen sulfide and siloxanes, can also be present. A CH4-rich stream can be produced by removing the CO2 and other impurities so that the upgraded biomethane can be injected into the natural gas grid or used as a vehicle fuel. The main objective of this paper is to assess the technical and economic performance of biogas upgrading processes using ionic liquids that physically absorb CO2. The simulation methodology is based on the COSMO-SAC model as implemented in Aspen Plus. Three different ionic liquids, namely, 1-ethyl-3-methylimidazolium bis(trifluoromethyl)sulfonylimide, 1-hexyl-3-methylimidazoliumbis(trifluoromethyl)sulfonylimide, and trihexyl(tetradecyl)phosphonium bis(trifluoromethyl)sulfonylimide, are considered for CO2 capture in a pressure-swing regenerative absorption process. The simulation software Aspen Plus and Aspen Process Economic Analyzer is used to account for mass and energy balances as well as equipment cost. In all cases, the biogas upgrading plant consists of a multistage compressor for biogas compression, a packed absorption column for CO2 absorption, a flash evaporator for solvent regeneration, a centrifugal pump for solvent recirculation, a preabsorber solvent cooler, and a gas turbine for electricity recovery. The evaluated processes are compared in terms of energy efficiency, capital investment, and biomethane production costs. The overall plant efficiency ranges from 71 to 86%, and the biomethane production cost ranges from 9.18-11.32 per GJ (LHV). A sensitivity analysis is also performed to determine how several technical and economic parameters affect the biomethane production costs. The results of this study show that the simulation methodology developed can predict plant efficiencies and production costs of large scale CO2 capture processes using ionic liquids without having to rely on gas solubility experimental data

Improving chronological control for environmental sequences from the last glacial period

Recognition of palaeoclimatic instability in the Greenland ice cores has spurred researchers to identify corresponding evidence in other terrestrial records from the last glacial stage. Such evidence is critical for establishing how much environmental stress precipitated Neanderthal and Late Pleistocene megafaunal extinctions, although a need for improved chronology has been consistently highlighted. In formerly glaciated and periglaciated areas of northern Europe, palaeoenvironmental sequences are frequently discontinuous. These often yield high-resolution proxy-based quantitative palaeotemperature estimates but can be hard to date, due to difficulties in removing contamination from biological samples at the limits of the radiocarbon technique (c.30-50kya). Here we demonstrate, for the first time using samples with independent age control, that different radiocarbon pretreatments can generate different age data and that gentler, less effective treatments applied to avoid sample loss may not yield reliable age-estimates. We advocate alternative harsher pretreatment using a strong acid-base-acid protocol. This provides an acceptable balance between contamination removal and excessive sample loss and generates more accurate ages, significantly enhancing our ability to detect and understand the impacts of palaeoclimatic instability in the terrestrial record of the last glacial

Second trimester inflammatory and metabolic markers in women delivering preterm with and without preeclampsia.

ObjectiveInflammatory and metabolic pathways are implicated in preterm birth and preeclampsia. However, studies rarely compare second trimester inflammatory and metabolic markers between women who deliver preterm with and without preeclampsia.Study designA sample of 129 women (43 with preeclampsia) with preterm delivery was obtained from an existing population-based birth cohort. Banked second trimester serum samples were assayed for 267 inflammatory and metabolic markers. Backwards-stepwise logistic regression models were used to calculate odds ratios.ResultsHigher 5-α-pregnan-3β,20α-diol disulfate, and lower 1-linoleoylglycerophosphoethanolamine and octadecanedioate, predicted increased odds of preeclampsia.ConclusionsAmong women with preterm births, those who developed preeclampsia differed with respect metabolic markers. These findings point to potential etiologic underpinnings for preeclampsia as a precursor to preterm birth

The impact of multiple single day blood pressure readings on cardiovascular risk estimation: The Atherosclerosis Risk in Communities study

To determine the magnitude of change in estimated cardiovascular disease risk when multiple same day blood pressure measurements are used in estimating coronary heart disease (CHD), heart failure (HF) and stroke risks

Game fence presence and permeability influences the local movement and distribution of South African mammals

Fences are utilized throughout the world to restrict the movements of wildlife, protecting them from threats and reducing human-wildlife conflict. In South Africa the number of privately-owned fenced game reserves has greatly increased in recent years, but little is known about how fencing affects the distribution and movements of target and non-target mammals. We surveyed 2m either side of the complete fence line of a recently established commercial game reserve in South Africa, identifying signs of animal presence (spoor, scat, foraging or other field signs) while also recording damage (holes) to the fence. Every 250m we carried out 100m perpendicular transects either side of the fence, recording vegetation cover and height at 10m intervals along the transect. We found that livestock (largely cattle) were excluded from the reserve. However, 12% of records of large animal species were recorded outside of the fence line. These species had been introduced to the reserve, strongly suggesting that they had crossed the boundary into the surrounding farmland. Sixteen naturally present wild species were found on both sides of the fence, but we found more evidence of their presence inside the reserve. Observational evidence suggests that they were regularly crossing the boundary, particularly where the fence was damaged, with hole size affecting species recorded. We also found evidence that the construction of the fence had led to a difference in vegetation structure with plant diversity and percentage of non-woody plant cover significantly higher inside the fence. While fencing was highly effective at preventing movement of livestock, introduced and wild animals were able to cross the boundary, via holes in the fence. This work shows that the efficacy of the most common approach to preventing animal movement around protected areas depends on the species being considered and fence condition