Loss Of CH Research Articles

Systematic Characterisation of the Fragmentation of Flavonoids Using High-Resolution Accurate Mass Electrospray Tandem Mass Spectrometry

Flavonoids are a class of polyphenolic secondary metabolites found in plants. Due to their ubiquity in our daily dietary intake and their major anti-oxidative, anti-inflammatory and anti-mutagenic activities, they have been a major focus of wide-ranging research for the past two decades. Mass spectrometry combined with liquid chromatography is one of the most popular techniques for the analysis of flavonoids. In this study, high-resolution accurate mass electrospray tandem mass spectrometry was used to study 30 flavonoids in both positive and negative ionisation modes. From the data obtained, common losses were summarised and compiled. Dominating neutral losses were tabulated. The radical loss of CH3· was observed in flavonoids containing methoxy groups and three key diagnostic product ions were identified. These were m/z 153 (indicative of two OH groups on ring A) m/z 167 (indicative of one OH and one methoxy group on ring A) and m/z 151 (a flavanol, with no ketone oxygen but two OH groups on ring A). These will be useful in structural elucidation of unknown flavonoids and flavonoid metabolites. Energy breakdown graphs were utilised to distinguish between three pairs of structural isomers, and to help rationalise proposed fragmentation pathways. Lastly, a competition of loss of CH3· and methane was reported for rhamnetin and isorhamnetin in the negative ion mode for the first time. Proposed fragmentation pathways were given to rationalise the differences in peak intensities for this competitive process.

Net primary productivity of paleo-peatlands linked to deep-time glacial periods in the late Carboniferous and early Permian icehouse interval

Peatlands, an important organic carbon reservoir, play a crucial role in the global carbon cycle. The carbon accumulation of peatlands, reflected by net primary productivity (NPP), can have an impact on global carbon cycling and climate change. The late Carboniferous - early Permian is an icehouse period, during which numerous thick coal beds were accumulated in the North China Block (NCB) located within a low-latitude area, providing an opportunity for studying the carbon cycling under the glacial and interglacial climates. In this study, spectral analysis was performed on the natural gamma-ray (GR) logs of the Benxi, Taiyuan and Shanxi formations of the late Carboniferous to early Permian in a borehole section located within the Ordos Basin in western NCB. Cyclic signals related to astronomical orbital parameters were identified, including long eccentricity (~405 kyr), short eccentricity (~125 kyr and ~ 95 kyr), and obliquity (~35.5kyr). A floating astronomical time scale was established by using the long eccentricity signal, and this time scale was further used to constrain the durations of the accumulation of coal-forming paleo-peatlands. The paleo-peatland for the C8 + 9 coal seam (9 m thick) of the Taiyuan Formation lasted approximately 203 kyr, and the paleo-peatland for the C5 coal seam (4 m thick) of the Shanxi Formation lasted approximately 46 kyr. Using this timeframe and an estimation of carbon loss during coalification, the carbon accumulation rates of the late Carboniferous - early Permian low-latitude peatlands are calculated to be 104.7 ± 14.9 g·C·m−2·a−1for the C8+9 coal seam and 192.6 ± 11.6 g·C·m−2·a−1for the C5 coal seam. The NPP of the paleo-peatlands, which deducts a part of carbon loss caused by the loss of CO2 and CH4, can be calculated from the carbon accumulation rates. The calculated average NPP of the paleo-peatlands for the C8+9 seam was 199 ± 28 g·C·m−2·a−1, and that of the C5 seam was 366 ± 22 g·C·m−2·a−1. In combination of the absolute time scale calibrated by high-precision UPb dates from Palougou section in western NCB, the depositional time of the investigated strata was constrained to be from 300.1 ± 0.5 Ma to 294.3 ± 0.5 Ma. The coal seams of the late Carboniferous to early Permian in the NCB corresponds to interglacial interval around ~298 Ma. The peatland with a lower NPP corresponds to the warming stage and the peatland with a higher NPP corresponds to the cooling stage. This implies that a lower NPP of paleo-peatland tend to be less efficient in carbon storage, and could not reduce the atmospheric CO2 substantially. In contrast, a higher NPP of paleo-peatland tend to accelerate carbon fixation, leading to temperature decrease and the termination of interglacial interval in early Permian. The results of this study could provide insights into the relationship between the development of paleo-peatlands and the record of the paleoclimates during the same period, and could be helpful for the prediction of future climate change.

A study of nano-micro-bubble process for CO2 absorption in water for biogas upgrading application

The work proposed a novel micro-bubble system using swirling jet flow method for improving the physical absorption of CO2 in water. The effects of operating conditions; e.g. gas flow rate (from 500 to 2000 mL/min), inlet pressure (2 and 3.5 bar) and inlet CO2 concentration (from 5 to 60% v/v in CO2/N2 gas mixture) on the physical absorption of CO2 were studied. It was found that the CO2 absorption system reached to steady state after 30 minutes with the outlet CO2 concentrations of 2.9% and 8.8% at 40% and 60% of inlet CO2 concentrations, respectively. These outlet CO2 concentrations demonstrated the standard of bio-methane for replacing natural gas in vehicle use, from which less than 10% CO2 is required. Moreover, the increase of gas flow rate resulted in increase of outlet CO2 concentration. The rising of inlet pressure from 2 to 3.5 bars let to reduction of the outlet CO2 concentration together with enhancing the dissolved CO2 concentration in water from 49.1 to 51.7 mg/L at gas flow rate of 2000 mL/min and 60% of inlet CO2 concentration. The highest efficiency of CO2 removal was 98.41% under gas flow rate at 500 mL/min with 60% of inlet CO2 concentration. Under the optimized conditions, this system was tested with real biogas as raw material containing mainly 57.7% of CH4 and 40.3% of CO2 which achieved to remove the 95.1% of CO2 removal and no significant loss of CH4. This highlight demonstrated the potential application of this technology for biogas upgrading or purification further.

Theoretical and experimental study on the pyrolysis of N-methylpyrrolidone

As a widely used organic solvent, N-methylpyrrolidone (NMP) may suffer thermal decomposition during large-scale industrial usage. The complex potential energy surface and corresponding pressure-dependent rate coefficients of NMP and NMP radicals were obtained at a high level of theory. The intermediates and products of NMP pyrolysis within 900–1200 K were identified and measured by synchrotron vacuum ultraviolet photoionization mass spectrometry. Theoretical calculations show that the Keto-enol tautomerization and direct ring-opening channel yielding C2H4, CO, and CH3NCH2 exhibit the highest rate coefficient among NMP unimolecular reactions at low and high temperatures, respectively. However, the fuel decomposition process cannot be exclusively dominated by single low-barrier channel. The ring-opening reaction forming imino aldehyde radical and following decarbonylation reactions are favored channels during the NMP radical decomposition, while the formation of the dihydropyrrolidone via H or CH3 loss competes with them at higher temperatures. Various smaller heterocycle radicals can be produced and act as intermediates for the multi-step isomerization of the ring-opening products with a relatively low energy barrier, changing the position of the functional group and radical site. A variety of nitrogenous and oxygenated species were observed in the experiment, such as ketene, methyl isocyanate, pyrrole, benzene, and different kinds of imines. Among them, C2H4, HCN, and CO are the major products for NMP decomposition. Potential reaction pathways from NMP to the major experimentally observed products were inferred based on the calculated results and existing knowledge on the pyrolysis of nitrogenous and oxygenated compounds. These results shed light on the complex C/H/O/N reaction system. The calculated rate coefficients and extensive mole fractions data could provide good support for the modeling of a detailed reaction mechanism in the future.

Ligand and Metal Effects in the Gas‐Phase Fragmentation of Thiomethoxymethyl Complexes

While the collision‐induced dissociation (CID) of the mass‐selected cation [(Ph3P)2Pt(CH2SCH3)]+ selectively liberates PPh3, the diphosphine complex [(dppe)Pt(CH2SCH3)]+ (dppe = 1,2‐bis(diphenylphosphino)ethane) ejects C2H4, CH2S, and (CH3)2S instead. The analogous palladium complexes [(Ph3P)2Pd(CH2SCH3)]+ and [(dppe)Pd(CH2SCH3)]+ show similar reactivity, except that C–H‐bond activation is completely lacking. For other bidentate diphosphine ligands such as dppm, dppv, dppp, dppb, dppbz, dppf, and xantphos, a correlation of the dominant reaction channels with the bite angle is observed. For bite angles > 90°, hydrogen‐atom transfer is favored, as evidenced by an increase in dimethyl‐sulfide loss. For smaller bite angles (< 90°), intramolecular activation of the thiomethoxymethyl ligand predominates, thus resulting in increased losses of thioformaldehyde and ethene. The results of the CID experiments are compared with those for [(bipy)Pt(CH2SCH3)]+, for which the loss of C2H4 is observed as the main process. DFT calculations for the complexes [(dppe)Pt(CH2SCH3)]+ and [(bipy)Pt(CH2SCH3)]+ together with the experimental findings uncover subtle differences in the underlying reaction mechanisms.

Oxygenation of Earth's atmosphere induced metabolic and ecologic transformations recorded in the Lomagundi-Jatuli carbon isotopic excursion.

The oxygenation of Earth's atmosphere represents the quintessential transformation of a planetary surface by microbial processes. In turn, atmospheric oxygenation transformed metabolic evolution; molecular clock models indicate the diversification and ecological expansion of respiratory metabolisms in the several hundred million years following atmospheric oxygenation. Across this same interval, the geological record preserves 13C enrichment in some carbonate rocks, called the Lomagundi-Jatuli excursion (LJE). By combining data from geologic and genomic records, a self-consistent metabolic evolution model emerges for the LJE. First, fermentation and methanogenesis were major processes remineralizing organic carbon before atmospheric oxygenation. Once an ozone layer formed, shallow water and exposed environments were shielded from UVB/C radiation, allowing the expansion of cyanobacterial primary productivity. High primary productivity and methanogenesis led to preferential removal of 12C into organic carbon and CH4. Extreme and variable 13C enrichments in carbonates were caused by 13C-depleted CH4 loss to the atmosphere. Through time, aerobic respiration diversified and became ecologically widespread, as did other new metabolisms. Respiration displaced fermentation and methanogenesis as the dominant organic matter remineralization processes. As CH4 loss slowed, dissolved inorganic carbon in shallow environments was no longer highly 13C enriched. Thus, the loss of extreme 13C enrichments in carbonates marks the establishment of a new microbial mat ecosystem structure, one dominated by respiratory processes distributed along steep redox gradients. These gradients allowed the exchange of metabolic by-products among metabolically diverse organisms, providing novel metabolic opportunities. Thus, the microbially induced oxygenation of Earth's atmosphere led to the transformation of microbial ecosystems, an archetypal example of planetary microbiology.IMPORTANCEThe oxygenation of Earth's atmosphere represents the most extensive known chemical transformation of a planetary surface by microbial processes. In turn, atmospheric oxygenation transformed metabolic evolution by providing oxidants independent of the sites of photosynthesis. Thus, the evolutionary changes during this interval and their effects on planetary-scale biogeochemical cycles are fundamental to our understanding of the interdependencies among genomes, organisms, ecosystems, elemental cycles, and Earth's surface chemistry through time.

Effect of different microalgae-bacterium-fungus symbiont technologies on nutrient removal from aquaculture wastewater and biogas upgrading under a variety of mixed light wavelengths

To develop and characterize novel microalgae-based technology under different mixed light-emitting diode (LED) light wavelengths for simultaneous treatment of actual aquaculture tailwater and biogas upgrading, the performance of four microalgal cultivations in bamboo shrimp aquaculture tailwater treatment and biogas upgrading were systematically examined and analyzed. The results demonstrated that Chlorella vulgaris (C. vulgaris)-endophytic bacterium (S395-2)-Clonostachys rosea (C. rosea) symbiont had the highest growth rate, daily production rate and carbonic anhydrase activity at the 7th d treatment time-point under Red(5): Blue(5) LED mixed light source. After 10d treatment, the nutrient removal efficiency of C. vulgaris-S395-2-C. rosea symbiont under Red(5): Blue(5) LED mixed wavelengths reached up to 93.7% for total inorganic nitrogen, 97.4% for ammonium nitrogen, 96.9% for nitrate nitrogen and 98.8% for phosphate; carbon dioxide (CO2) removal rate maintained at 53.1% without significantly affecting methane (CH4) level. In summary, the present study demonstrates that Red (5): Blue(5) LED mixed wavelengths optimally increase the performance of C. vulgaris-S395-2-C. rosea symbiont in nutrient and CO2 removal without loss of CH4, providing a framework for future simultaneous performing actual aquaculture tailwater treatment and biogas upgrading using microalgae-endophytic bacteria-fungus symbiont.

Net Methane Production Predicted by Patch Characteristics in a Freshwater Wetland

AbstractMethane (CH4) dynamics in wetlands are spatially variable and difficult to estimate at ecosystem scales. Patches with different plant functional types (PFT) represent discrete units within wetlands that may help characterize patterns in CH4 variability. We investigate dissolved porewater CH4 concentrations, a representation of net CH4 production and potential source of atmospheric flux, in five wetland patches characterized by a dominant PFT or lack of plants. Using soil, porewater, and plant variables we hypothesized to influence CH4, we used three modeling approaches—Classification and regression tree, AIC model selection, and Structural Equation Modeling—to identify direct and indirect influences on porewater CH4 dynamics. Across all three models, dissolved porewater CO2 concentration was the dominant driver of CH4 concentrations, partly through the influence of PFT patches. Plants in each patch type likely had variable influence on CH4 via root exudates (a substrate for methanogens), capacity to transport gas (both O2 from and CH4 to the atmosphere), and plant litter quality which impacted soil respiration and production of CO2 in the porewater. We attribute the importance of CO2 to the dominant methanogenic pathway we identified, which uses CO2 as a terminal electron acceptor. We propose a mechanistic relationship between PFT patches and porewater CH4 dynamics which, when combined with sources of CH4 loss including methanotrophy, oxidation, or plant‐mediated transport, can provide patch‐scale estimates of CH4 flux. Combining these estimates with the distribution of PFTs can improve ecosystem CH4 flux estimates in heterogenous wetlands and improve global CH4 budgets.

Surface Volatile Composition as Evidence for Hydrothermal Processes Lasting Longer in Triton’s Interior than Pluto’s

Ocean worlds, or icy bodies in the outer solar system that have or once had subsurface liquid water oceans, are among the most compelling topics of astrobiology. Typically, confirming the existence of a subsurface ocean requires close spacecraft observations. However, combining our understanding of the chemistry that takes place in a subsurface ocean with our knowledge of the building blocks that formed potential ocean worlds provides an opportunity to identify tracers of endogenic activity in the surface volatiles of Pluto and Triton. We show here that the current composition of the volatiles on the surfaces and in the atmospheres of Pluto and Triton are deficient in carbon, which can only be explained by the loss of CH4 through a combination of aqueous chemistry and atmospheric processes. Furthermore, we find that the relative nitrogen and water abundances are within the range observed in building block analogs, comets, and chondrites. A lower limit for N/Ar in Pluto’s atmosphere also suggests source building blocks that have a cometary or chondritic composition, all pointing to an origin for their nitrogen as NH3 or organics. Triton’s lower abundance of CH4 compared to Pluto, and the detection of CO2 at Triton but not at Pluto points to aqueous chemistry in a subsurface ocean that was more efficient at Triton than Pluto. These results have applications to other large Kuiper Belt objects as well as the assessment of formation locations and times for the four giant planets given future probe measurements of noble gas abundances and isotope ratios.

Influence of Vertical Hydrologic Exchange Flow, Channel Flow, and Biogeochemical Kinetics on CH4 Emissions From Rivers

AbstractCH4 emissions from inland water are highly uncertain in the current global CH4 budget, especially for rivers and streams due to sparse measurements and the uncertainty of measurements caused by turbulent water flow. A previous study has revealed that vertical hydrologic exchange flow (VHEF) is the main regulator of CH4 emissions from riverbed sediments. However, to what extent the understanding obtained from the plot‐scale can be extended to the reach scale and basin scale remains unknown. To address this challenge, we developed a process‐based model to estimate CH4 flux at the air‐water interface using the attributes available in the national hydrography data set. It calculates the annual mean flux of VHEF, CH4 production in sediments, and CH4 transport in the river channel in a sequential manner. Model performance is evaluated by CH4 efflux observed at the Hanford reach of the Columbia River. We show that reach‐wise sediment hydrologic and biogeochemical conditions estimated from the national hydrography data set could serve as a good indicator of CH4 emissions from rivers. Aerobic methane oxidation and export to the downstream are the dominant ways of total CH4 loss for the large lowland river. The hotspots of CH4 emissions are likely to be at the reaches with fine sediments and slow channel velocity. This study demonstrates the possibility of quantifying CH4 emissions at the reach scale and the modeling framework has the potential to be extended to the basin scale to improve estimates of CH4 emissions from lotic inland water.

Unraveling the Unimolecular Ion Chemistry of Protonated Isoprene and Prenol.

The atmospheric chemistries of isoprene and prenol have been studied extensively; however, much of that research has focused on neutral or radical chemistry. Recent studies have demonstrated that under acidic conditions, isoprene and prenol can become protonated in the atmosphere, and we have explored the unimolecular chemistry of protonated isoprene and prenol with tandem mass spectrometry (using a triple-quadrupole mass spectrometer) and density functional theory. The collision-induced dissociation of protonated isoprene revealed two product ion channels: the neutral losses of C2H4 and H2, the former dominating over the latter. Protonated prenol dissociates by four product ion channels: the neutral losses of water, formaldehyde, methanol, and propene, with the former two being minor channels and the latter two being major channels. Density functional theory supplemented with CBS-QB3 single-point calculations revealed the underlying mechanisms to explain the breakdown behavior. The two competing channels from protonated isoprene could easily be rationalized due to the relative energy difference between key transition states along the reaction coordinates. However, in the case of protonated prenol, it was revealed that the minor products observed in the breakdown of protonated prenol had significantly lower reaction barriers when compared to the major products, an apparent contradiction. This could be rationalized if the initial ion population entering the collision cell is comproed of several isomeric species on the minimum energy reaction pathway, species populated by collisional excitation in the ion source region.

Probing adsorption of methane onto vanadium cluster cations via vibrational spectroscopy.

Photofragment spectroscopy is used to measure the vibrational spectra of V2+(CH4)n (n = 1-4), V3+(CH4)n (n = 1-3), and Vx+(CH4) (x = 4-8) in the C-H stretching region (2550-3100 cm-1). Spectra are measured by monitoring loss of CH4. The experimental spectra are compared to simulations at the B3LYP+D3/6-311++G(3df,3pd) level of theory to identify the geometry of the ions. Multi-reference configuration interaction with Davidson correction (MRCI+Q) calculations are also carried out on V2+ and V3+. The methane binding orientation in V2+(CH4)n (n = 1-4) evolves from η3 to η2 as more methane molecules are added. The IR spectra of metal-methane clusters can give information on the structure of metal clusters that may otherwise be hard to obtain from isolated clusters. For example, the V3+(CH4)n (n = 1-3) experimental spectra show an additional peak as the second and third methane molecules are added to V3+, which indicates that the metal atoms are not equivalent. The Vx+(CH4) show a larger red shift in the symmetric C-H stretch for larger clusters with x = 5-8 than for the small clusters with x = 2, 3, indicating increased covalency in the interaction of larger vanadium clusters with methane.

Fragmentation of Multiply Charged C10H8 Isomers Produced in keV Range Proton Collision

The dissociation of multiply charged C10H8 isomers produced in fast proton collisions (velocities between 1.41 and 2.4 a.u.) is discussed in terms of their fundamental molecular dynamics, in particular the processes that produce different carbon clusters in such a collision. This aspect is assessed with the help of a multi-hit analysis of daughter ions detected in coincidence with the elimination of H+ and CHn+ (n = 0 to 3). The elimination of H+/C+ is found to be significantly different from CH3+ loss. The loss of CH3+ proceeds through a cascade of momentum-correlated dissociations with the formation of heavy ions such as C9H5+, C9H52+ and C7H3+. The structure of such large fragment ions is predicted with the help of their calculated ground state electronic energies and the multi-hit time-of-flight (ToF) correlation between the second and third hit fragments if detected. Furthermore, we report experimentally the super-dehydrogenation of naphthalene and azulene targets, with evidence of complete dehydrogenation in a single collision.

Comparative Evaluation of PSA, PVSA, and Twin PSA Processes for Biogas Upgrading: The Purity, Recovery, and Energy Consumption Dilemma

The current challenges of commercial cyclic adsorption processes for biogas upgrading are associated with either high energy consumption or low recovery. To address these challenges, this work evaluates the performance of a range of configurations for biogas separations, including pressure swing adsorption (PSA), pressure vacuum swing adsorption (PVSA), and twin double-bed PSA, by dynamic modelling. Moreover, a sensitivity analysis was performed to explore the effect of various operating conditions, including adsorption time, purge-to-feed ratio, biogas feed temperature, and vacuum level, on recovery and energy consumption. It was found that the required energy for a twin double-bed PSA to produce biomethane with 87% purity is 903 kJ/kg CH4 with 90% recovery, compared to 961 kJ/kg CH4 and 76% recovery for a PVSA process. With respect to minimum purity requirements, increasing product purity from 95.35 to 99.96% resulted in a 32% increase in energy demand and a 23% drop in recovery, illustrating the degree of loss in process efficiency and the costly trade-off to produce ultra-high-purity biomethane. It was concluded that in processes with moderate vacuum requirements (>0.5 bar), a PVSA should be utilised when a high purity biomethane product is desirable. On the other hand, to minimise CH4 loss and enhance recovery, a twin double-bed PSA should be employed.

Beyond vanilla: The dissociation mechanism of vanillin in four charge states

We compare the unimolecular decay mechanism of vanillin in four charge states. The unimolecular thermal decomposition of the neutral and dissociative ionization reactions in the cation have already been addressed in synchrotron-based photoionization studies. The picture is completed here by studying the collision-induced dissociation mechanism of protonated vanillin cations and deprotonated vanillin anions in the 5–30 eV collision energy range. The mass spectrometric observations are rationalized by ab initio calculations, which reveal the mechanism and the energetics of dissociation pathways. In the positive ion mode, the aldehyde oxygen is protonated, after which CO is lost. In contrast to previous results, CO loss is found to be the sole primary fragmentation pathway of protonated vanillin. Two hydrogen migration steps to the benzene ring open sequential CH3OH and CH3 loss channels to yield C6H5O+ and C6H6O2+, respectively. The former fragment ion can continue to lose CO, associated with ring contraction and producing the cyclopentadiene cation, C5H5+. In the negative ion mode, the proton is removed from the hydroxyl group. The primary dissociation channel of deprotonated vanillin corresponds to (C)OCH3 bond breaking in the methoxy group to form C7H4O3− at m/z 136. This species goes on to produce C6H4O2− and C6H4O− anions via CO and CO2 loss, respectively, in sequential dissociation processes at higher collision energies. We compare the protonated and deprotonated vanillin fragmentation pathways with those observed in the decomposition of neutral vanillin and with the dissociation pathways of the vanillin cation. The initial decomposition step for neutral, cationic, and deprotonated vanillin is methyl loss by direct CO bond breaking, often followed by loss of CO. In contrast, protonated vanillin first loses CO after isomerization.

Removal of H2S from Biogas Using Thiobacillus sp.: Batch and Continuous Studies

Anaerobic digestion produces biogas which usually contains 60-70% of methane (CH4), 30-40% of carbon-di-oxide (CO2), and 10-2,000 ppm hydrogen sulfide (H2S). The concentration of H2S depends upon the type of substrate. H2S tends to corrode pipes and machines carrying them. The high concentrations of H2S present in biogas may adversely affect electricity generation. Hence, the removal of H2S and enrichment of biogas with CH4 is an essential step towards higher energy production. In the present study, the biological method of removing H2S using Thiobacillus sp. was demonstrated for a one cu.m anaerobic co-digestion (ACD) unit running on an organic fraction of municipal solid waste (OFMSW) and septage sludge. Initial lab scale studies were conducted by collecting the biogas generated from 1 cu.m digesters, and continuous experiments were optimized for the process parameters such as flow rate, the volume of medium with culture, time, the height of the column, column composition, etc. The raw biogas was purged in a liquid medium (LM) with a culture containing Thiobacillus sp. The studies with the LM containing Thiobacillus sp. culture showed a 68% removal of H2S in the first 8 min, and the saturation occurred at 75 min when the time-dependent experiment was studied. The smaller flow rate (0.48 L.min-1) and highest volume of culture (500 mL) showed better results than other parameters. The highest and average oxidation rates of sulfate were recorded as 39 and 40.3 ppm.sec-1, respectively, for 0.48 L.min-1 flow rate and 500 mL of the culture volume. In the column studies, a column containing cocopeat (CP) was studied for its efficiency in removing H2S. At a flow rate of 0.9 L.min-1, 25% adsorption was encountered and reached saturation at 90 min. The bed height of 9 inches with CP and plastic support (PS) showed a 20% H2S removal. The filling ratio of CP and PS (1:1) was the best ratio for proper gas passage with optimal time for adsorption/absorption. The kinetic, isotherm, and continuous models helped to understand the capacity of the adsorbent. Freundlich, Yoon-Nelson, and BDST model were best fit for the present study. A pilot scale setup for one cu.m biogas reactor showed an average of 50% removal of H2S for LM with culture, and an additional 20% removal was possible by the introduction of a column along with the liquid bed in series. An overall efficiency of 70-75% of H2S removal was achieved. No significant CH4 loss was encountered during the study.

Probing Intermediates of Ion/Molecule Reactions by their Independent Gas‐Phase Synthesis and Fragmentation – The Thiomethoxymethyl Complexes [(bipy)M(CH2SCH3)]+ (M=Pt, Pd, Ni)

AbstractIn the ion/molecule reaction (IMR) of “rollover”‐cyclometalated [(bipy−H)Pt]+ with (CH3)2S, the loss of C2H4 from the encounter complex was observed as the main process some years ago. The cationic complex [(bipy)Pt(CH2SCH3)]+ was identified as a crucial intermediate by DFT calculations. In order to prove its key role experimentally, the cation has now been generated independently and studied by collision‐induced dissociation (CID). The main process is C2H4 loss, which proves [(bipy)Pt(CH2SCH3)]+ to be an intermediate also in the IMR of [(bipy−H)Pt]+ with (CH3)2S. Based on DFT calculations, the thiomethoxymethyl complexes [(bipy)M(CH2SCH3)]+ (M=Pd and Ni) would also serve as intermediates in the IMRs of [(bipy−H)M]+. While these IMRs cannot be studied explicitly, because the parent ions cannot be generated, the potential intermediate [(bipy)M(CH2SCH3)]+ has been subjected to CID. The main fragmentation channels for both metals corresponds to C2H4 loss. The CID experiments thus provide insights into the hypothetical IMRs of [(bipy−H)M]+ with (CH3)2S. The comparison of the DFT calculations for all three metals Ni, Pd, and Pt with the experimental findings uncovers subtle aspects of the underlying reaction mechanisms. This work highlights the suitability of CID experiments of potential reaction intermediates for the elucidation of reaction mechanisms of IMRs as well as the limitations of this approach.

Fabrication of high-selective hollow fiber DD3R zeolite membrane modules for high-pressure CO2/CH4 separation

All-silica Decadodecasil 3 R (DD3R) zeolite membranes, possessing small pore size of 0.36 nm × 0.44 nm, have been attractive in CO2 removal from natural gas. In this work, hollow fiber DD3R zeolite membrane modules with membrane length of 40 cm and effective membrane area of 811 cm2 for each were successfully fabricated by ensemble synthesis strategy. Different membrane segments including that was grown on sealing glaze have similar thickness in the range of 4–6 μm. The ozone detemplation time of membrane unit was reduced by a half with the assistance of Teflon spiral column. The resulting membrane module exhibited a good CO2/CH4 separation selectivity (105) as well as a stage-cut of 25.7% at high feed pressure of 3.1 MPa. Effects of feed pressure, feed gas flow rate and permeate pressure on separation performance of the membrane module and concentration polarization were investigated extensively. When the feed gas flow rate was 2 L min−1, the retentate CO2 concentration was lowered to 9.45% and the CH4 loss was limited to 4.87% at the feed and permeate pressures of 3.1 MPa and 2 kPa. The concentration polarization effect became more serious at higher feed pressure or lower feed gas flow rate.

Overcoming the Trade-Off between C2 H2 Sorption and Separation Performance by Regulating Metal-Alkyne Chemical Interaction in Metal-Organic Frameworks.

Designing porous materials for C2 H2 purification and safe storage is essential research for industrial utilization. We emphatically regulate the metal-alkyne interaction of PdII and PtII on C2 H2 sorption and C2 H2 /CO2 separation in two isostructural NbO metal-organic frameworks (MOFs), Pd/Cu-PDA and Pt/Cu-PDA. The experimental investigations and systematic theoretical calculations reveal that PdII in Pd/Cu-PDA undergoes spontaneous chemical reaction with C2 H2 , leading to irreversible structural collapse and loss of C2 H2 /CO2 sorption and separation. Contrarily, PtII in Pt/Cu-PDA shows strong di-σ bond interaction with C2 H2 to form specific π-complexation, contributing to high C2 H2 capture (28.7 cm3 g-1 at 0.01 bar and 153 cm3 g-1 at 1 bar). The reusable Pt/Cu-PDA efficiently separates C2 H2 from C2 H2 /CO2 mixtures with satisfying selectivity and C2 H2 capacity (37 min g-1 ). This research provides valuable insight into designing high-performance MOFs for gas sorption and separation.

Copolyimide asymmetric hollow fiber membranes for high‐pressure natural gas purification

AbstractThe current process to purify contaminated natural gas reserves employs a highly energy‐intensive amine scrubbing technology. To satisfy the growing demand for natural gas coupled with the tight regulations on CO2 emissions, researchers worldwide are investigating the use of polymeric membranes for acid gas removal from natural gas streams, to reduce the energy consumption and carbon emission of the nowadays used technology. Placing a polymeric membrane unit at the upstream of the amine scrubbing column reduces the energy consumption during the regeneration process of saturated amines. Hence, the preparation of polymeric membranes in form of hollow fibers is a key step towards their industrial implementation for natural gas processing. The following study demonstrates the potential separation performance of 6FDA‐Durene/6FDA‐CARDO (5000:5000) in an integrally skinned defect‐free asymmetric hollow fiber geometry. The initial screening studies of the membrane shows good pure‐gas performance as it exhibits CO2/CH4 selectivity coefficients around 28 and CO2 permeance between 310 and 350 GPU. Feed pressures of up to 900 psig and stage cuts ranging from 5% to 20% were tested for a quaternary sweet mixed‐gas feed to assess the membrane performance under operating conditions that mimic those in industrial settings. Mixed‐gas permeance of all gases, and CO2/CH4 selectivity remain somewhat constant as the feed pressure increases up to 900 psig. Both mixed‐gas CO2 permeance and CO2/CH4 selectivity decline as the stage cut increases. As expected, as CO2 recovery is maximized, CO2 purity is minimized and CH4 loss increases with increasing stage cut. As a result of the trade‐off between recovery and purity, the data and analyses reported herein can provide insights into the limitations that certain operating parameters can pose on CO2 separation performance with similar polymeric hollow fiber membranes.