Development of CO2 Selective Poly(Ethylene Oxide)-Based Membranes: From Laboratory to Pilot Plant Scale

Membrane gas separation is one of the most promising technologies for the separation of carbon dioxide (CO₂) from various gas streams. One application of this technology is the treatment of flue gases from combustion processes for the purpose of carbon capture and storage. For this application, poly(ethylene oxide)-containing block copolymers such as Pebax^® or PolyActive™ polymer are well suited. The thin-film composite membrane that is considered in this overview employs PolyActive™ polymer as a selective layer material. The membrane shows excellent CO₂ permeances of up to 4 m³(STP)·(m²·h·bar)⁻¹ (1 bar = 10⁵ Pa) at a carbon dioxide/nitrogen (CO₂/N₂) selectivity exceeding 55 at ambient temperature. The membrane can be manufactured reproducibly on a pilot scale and mounted into flat-sheet membrane modules of different designs. The operating performance of these modules can be accurately predicted by specifically developed simulation tools, which employ single-gas permeation data as the only experimental input. The performance of membranes and modules was investigated in different pilot plant studies, in which flue gas and biogas were used as the feed gas streams. The investigated processes showed a stable separation performance, indicating the applicability of PolyActive™ polymer as a membrane material for industrial-scale gas processing.     

Multifunctional CuO nanowire embodied structural supercapacitor based on woven carbon fiber/ionic liquid–polyester resin

Novel structural supercapacitors based on CuO nanowires and woven carbon fiber (WCF) has been developed for the first time employing vacuum assisted resin transfer molding (VARTM) process. The growth of CuO nanowires on WCF is an efficient process and can be used in structural capacitors which can trigger the electric vehicle industries toward a new direction. The specific surface area of the carbon fiber was enhanced by NaOH etching (41.36 m² g⁻¹) and by growing CuO nanowires (132.85 m² g⁻¹) on the surface of the WCF. The specific capacitance of the CuO–WCF based supercapacitor was 2.48 F g⁻¹, compared with 0.16 F g⁻¹ for the bare WCF-based supercapacitor. The usage of ionic liquid and lithium salt improved the capacitance to 5.40 and 6.75 F g⁻¹ with lowest ESR and R_p values of 133 and 1240 Ω along with improving mechanical properties within an acceptable range. The energy and power densities were also increased up to 106.04 mW h kg⁻¹ and 12.57 W kg⁻¹. Thus, this study demonstrated that growing CuO nanowires on the surface of WCF is a novel approach to improve multifunctionality that could be exploited in diverse applications such as electric cars, unmanned aerial vehicles (UAVs), and portable electronic devices.     

Zr doped anatase supported reticulated ceramic foams for photocatalytic water purification

Titanium dioxide films were deposited on macroporous reticulated Al₂O₃ and alumina–mullite foams with pore sizes of 15 ppi (pores per inch). Coatings were prepared from suspensions of precursor powders of Aeroxide^® P25 nanopowder and precipitated TiO₂ by using a dip coating process. The TiO₂ forms films with a thickness of ～2–20 μm. The photocatalytic activity was characterized as the mineralization rate of an aqueous phenol solution under UVA irradiation by the TOC technique. Precipitated TiO₂ films have nearly the same photocatalytic activity as a titania suspension, in which powder aggregates have a size comparable with the thickness of the films. Samples made of Aeroxide^® P25 nanopowder, in which the size of aggregates is ～0.1 μm show higher efficiency of photodecomposition in suspensions with films. The doping of precipitated anatase with Zr(IV) in the atomic ratio Zr/Ti = 0.008 significantly improves the photocatalytic activity of the foam supported titania. Zr doped anatase films show better performance as the films prepared only from Aeroxide^® P25 nanopowder.     

Preparation of carbon aerogel microspheres by a simple-injection emulsification method

Carbon aerogel microspheres were successfully prepared using a simple-injection emulsification method, employing sol–gel polycondensation of a resorcinol–formaldehyde solution containing sodium carbonate as a catalyst. This process was followed by solvent exchange using acetone, supercritical drying with carbon dioxide and carbonization in a nitrogen atmosphere. The effect of curing time before starting injection, injection rate and agitation rate of continuous phase on the particle size and the porous properties of the carbon aerogel microspheres was investigated. Adsorption of phenol by using the prepared carbon aerogel microspheres was also examined. The diameter of carbon aerogel microspheres was controlled in the range of 20–55 μm by varying injection rate and agitation rate. The mean diameter of carbon aerogel microspheres decreased with increasing the injection rate and the agitation rate, whereas their mean diameter was independent of the curing time. The BET surface area and total pore volume of carbon aerogel microspheres increased with increasing the curing time. In contrast, their BET surface area and total pore volume decreased with increasing the injection rate and the agitation rate. The BET surface area, total pore volume, mesopore volume and micropore volume of the carbon aerogel microspheres with a mean diameter of 45 μm were 903 m²/g, 0.60 cm³/g, 0.31 cm³/g and 0.27 cm³/g, respectively. The phenol-adsorption capacity of these carbon aerogel microspheres was 29.3 mg phenol/g adsorbent.     

Comparison of electrochemical performances of LiFePO4/C composite materials by two preparation routes

This study reports on the preparation of LiFePO₄/C composite materials prepared by the hydrothermal and sol–gel processes for comparison. The synthesis condition on the hydrothermal process was performed at 170 °C for 19 h. The polystyrene (PS) polymer was used as a carbon source; the PS was added at a range of 0–5 wt.%. The temperature of the post-thermal process was set at 750–850 °C. The citric acid (denoted as CA) was used as the reducing agent and the carbon source in the sol–gel process. The temperatures of the sintering process were set at a range of 650–850 °C. The optimal sintering temperature was at 850 °C for 12 h in the hydrothermal process; the optimal carbon residue content was approximately 3.20 wt.%. It was revealed that the highest discharge capacity of LiFePO₄/C composites by the hydrothermal process at 0.1 C is 163 mAh g^?1. The optimal sintering temperature was found to be at 750 °C for the sol–gel process. The highest carbon content was approximately 11.94 wt.% as the molar ratio of CA is 1.0. The highest discharge capacity of LiFePO₄/C composites by the sol–gel process at 0.1 C was approximately 130.35 mAh g^?1.     

Flocculant-assisted synthesis of Fe2O3/carbon composites for superior lithium rechargeable batteries

High-performance iron oxide/carbon (Fe₂O₃/C) composites for lithium-ion batteries are synthesized by the combination of flocculant-assisted process and thermo-chemical treatment. Carboxymethylcellulose is used simultaneously as the flocculant and carbon source. This facile and scalable method lends itself to the fabrication of other metal oxide/carbon composites based on the flocculation mechanism. The lithium storage mechanism and cycling performance of Fe₂O₃/C composites are investigated by cyclic voltammetry and charge–discharge tests. As the rates increase from 50 to 1000 mA g^?1, the composites display high charge capacities of 834 mAh g^?1 for the first cycle at 50 mA g^?1 and 497 mAh g^?1 at 1000 mA g^?1 over 100 cycles. Excellent rate capability and cyclability are ascribed presumablely to the isolation and buffer functions of the conductive carbon matrix against particle aggregation and large volume variety upon cycling.     

Application of crack tip plasticity based fatigue model on high temperature alloy HAYNES® 282®

Confined crack tip plasticity model is employed to predict time independent fatigue crack growth rate (FCGR) behavior of HAYNES® 282® alloy at temperatures 1200F and 1400F. Crack growth tests were done in lab air, vacuum and steam environments at load ratios R = K_min/K_max ranging from 0.05 to 0.5. Calibrated model predicts average cyclic crack growth rate behavior of the material reasonably well. Predictions do not capture the accelerated fatigue crack growth rates observed in the data at low load levels. Such effects are believed to be caused by environmentally driven factors, which are not expected to be predicted by plasticity based models.     

Co-production of power and urea from coal with CO<Subscript>2</Subscript> capture: performance assessment

Coal-based power plants are largest emitter of CO₂ as a single sector. To use fossil fuels (including coal), CO₂ capture and storage is a visible option. But large energy requirement for this process and risk associated with storage of CO₂ demand alternative solutions including recycling of captured CO₂. In this paper, a co-production of power and urea is proposed using coal with captured CO₂. Detailed ASPEN Plus^® model is developed for this plant. As shift reaction for producing H₂ has significant effect on output parameters, analysis is done for two different values of shift reaction, i.e., 90 and 95 % conversion. Plant consumes substantial auxiliary power (~19 % for the base case). Auxiliary power becomes a minimum for about 25 % captured CO₂ utilization for 95 % shift conversion. An economy factor is also defined to estimate the economic advantage of utilizing captured CO₂. Results show that economic advantage is obtained for CO₂ utilization beyond ~5 % for 95 % water gas shift reaction and it is beyond ~10 % for a 90 % shift reaction.     

Highly enhanced and stable activity of defect-induced titania nanoparticles for solar light-driven CO2 reduction into CH4

Photocatalytic reduction of CO₂ to fuel offers an exciting opportunity for helping to solve current energy and global warming problems. Although a number of solar active catalysts have been reported, most of them suffer from low product yield, instability, and low quantum efficiency. Therefore, the design and fabrication of highly active photocatalysts remains an unmet challenge. In the current work we utilize hydrogen-doped, blue-colored reduced titania for photocatalytic conversion of CO₂ into methane (CH₄). The photocatalyst is obtained by exposure of TiO₂ to NaBH₄ at 350 °C for 0.5 h. Sensitized with Pt nanoparticles, the material promotes solar spectrum photoconversion of CO₂ to CH₄ with an apparent quantum yield of 12.40% and a time normalized CH₄ generation rate of 80.35 μmol g^?1 h^?1, which to the best of our knowledge is a record for photocatalytic-based CO₂ reduction. The material appears intrinsically stable, with no loss in sample performance over five 6 h cycles, with the sample heated in vacuum after each cycle.     

Experimental investigation of the influence of different leaking gases on the heat transfer in a HVMLI cryogenic tank after SCLIV

This paper presented an experimental investigation of the influence of different leaking gases on the heat transfer process in a high-vacuum-multilayer-insulation (HVMLI) cryogenic tank after sudden catastrophic loss of insulation vacuum (SCLIV). The experiments were conducted with the breakdown of the insulation vacuum with nitrogen, air, helium, oxygen, argon, carbon dioxide and the gas mixture of argon and carbon dioxide. The maximum value of the venting rate and heat flux could be ordered as following: CO₂ > O₂ > Ar > the gas mixture > He > Air > N₂, while the average value of the venting rate and heat flux could be ordered as following: O₂ > Ar > He > the gas mixture > CO₂ > Air > N₂. The temperature distribution indicated that phase change heat transfer happened in the insulation jacket after the five different gases including air, argon, the gas mixture of argon and carbon dioxide, oxygen and carbon dioxide were introduced into the insulation jacket.     

Microwave-assisted hydrothermal synthesis of zinc oxide particles starting from chloride precursor

Zinc oxide (ZnO) was synthesized using a microwave assisted hydrothermal (MAH) process based on chloride/urea/water solution and under 800 W irradiation for 5 min. In the bath, Zn²⁺ ions reacted with the complex carbonate and hydroxide ions to form zinc carbonate hydroxide hydrate (Zn₄CO₃(OH)₆·H₂O), and the conversion from Zn₄CO₃(OH)₆·H₂O to ZnO was synchronously achieved by a MAH process. The as-prepared ZnO has a sponge-like morphology. However, the initial sponge-like morphology of ZnO could change to a net-like structure after thermal treatment, and compact nano-scale ZnO particles were finally obtained when the period of thermal treatment increased to 30 min. Pure ZnO nanoparticles was obtained from calcination of loose sponge-like ZnO particles at 500 °C. The analysis of optical properties of these ZnO nanoparticles showed that the intensity of 393 nm emission increased with the calcination temperature because the defects were reduced and the crystallinity was improved.     

Porous liquids as solvents for the economical separation of carbon dioxide from methane

Current CO₂ separation technologies by liquid solvents suffer from either high regeneration costs or low selectivity/capacity of the solvent. Dispersing ca. 12.5 wt% CO₂-selective zeolite rho solid into the commercial CO₂ capture solvent Genosorb® converts it into a porous liquid with at least 2.5 times greater CO₂ capacity and CO₂/CH₄ selectivity compared to Genosorb® itself. This is predicted to result in more economical separation processes, particularly for biogas upgrading.     

Effects of Potassium and Manganese Promoters on Nitrogen-Doped Carbon Nanotube-Supported Iron Catalysts for CO2 Hydrogenation

Nitrogen-doped carbon nanotubes (NCNTs) were used as a support for iron (Fe) nanoparticles applied in carbon dioxide (CO₂) hydrogenation at 633 K and 25 bar (1 bar = 10⁵ Pa). The Fe/NCNT catalyst promoted with both potassium (K) and manganese (Mn) showed high performance in CO₂ hydrogenation, reaching 34.9% conversion with a gas hourly space velocity (GHSV) of 3.1 L·(g·h)⁻¹. Product selectivities were high for olefin products and low for short-chain alkanes for the K-promoted catalysts. When Fe/NCNT catalyst was promoted with both K and Mn, the catalytic activity was stable for 60 h of reaction time. The structural effect of the Mn promoter was demonstrated by X-ray diffraction (XRD), temperature-programmed reduction (TPR) with molecular hydrogen (H₂), and in situ X-ray absorption near-edge structure (XANES) analysis. The Mn promoter stabilized wüstite (FeO) as an intermediate and lowered the TPR onset temperature. Catalytic ammonia (NH₃) decomposition was used as an additional probe reaction for characterizing the promoter effects. The Fe/NCNT catalyst promoted with both K and Mn had the highest catalytic activity, and the Mn-promoted Fe/NCNT catalysts had the highest thermal stability under reducing conditions.     

Thermodynamic and kinetic studies for the adsorption of Hg(II) by nano-TiO2 from aqueous solution

Titanium dioxide nanocrystals were employed, for the first time, for the sorption of Hg(II) ions from aqueous solutions. The effects of varying parameters such as pH, temperature, initial metal concentration, and contact time on the adsorption process were examined. Adsorption equilibrium was established in 420 min and the maximum adsorption of Hg(II) on the TiO₂ was observed to occur at pH 8.0. The adsorption data correlated with Freundlich, Langmuir, Dubinin–Radushkevich (D–R), and Temkin isotherms. The Freundlich isotherm showed the best fit to the equilibrium data. The Pseudo-first order and pseudo-second-order kinetic models were studied to analyze the kinetic data. A second-order kinetic model fit the data with the (k₂ = 2.8126 × 10^?3 g mg^?1min^?1, 303 K). The intraparticle diffusion models were applied to ascertain the rate-controlling step. The thermodynamic parameters (ΔG°, ΔH°, and ΔS°) were calculated which showed an endothermic adsorption process. The equilibrium parameter (R_L) indicated that TiO₂ nanocrystals are useful for Hg(II) removal from aqueous solutions.     

An activated microporous carbon prepared from phenol-melamine-formaldehyde resin for lithium ion battery anode

Microporous carbon anode materials were prepared from phenol-melamine-formaldehyde resin by ZnCl₂ and KOH activation. The physicochemical properties of the obtained carbon materials were characterized by scanning electron microscope, X-ray diffraction, Brunauer–Emmett–Teller, and elemental analysis. The electrochemical properties of the microporous carbon as anode materials in lithium ion secondary batteries were evaluated. At a current density of 100 mA g^?1, the carbon without activation shows a first discharge capacity of 515 mAh g^?1. After activation, the capacity improved obviously. The first discharge capacity of the carbon prepared by ZnCl₂ and KOH activation was 1010 and 2085 mAh g^?1, respectively. The reversible capacity of the carbon prepared by KOH activation was still as high as 717 mAh g^?1 after 20 cycles, which was much better than that activated by ZnCl₂. These results demonstrated that it may be a promising candidate as an anode material for lithium ion secondary batteries.     

Carbon nanotube/chitosan/gold nanoparticles-based glucose biosensor prepared by a layer-by-layer technique

A new amperometric glucose biosensor was constructed, based on the immobilization of glucose oxidase (GOx) with cross-linking in the matrix of chitosan on a glassy carbon electrode, which was modified by layer-by-layer assembled carbon nanotube (CNT)/chitosan (CHIT)/gold nanoparticles (GNp) multilayer films. With the increasing of CNT/CHIT/GNp layers, the response current to H₂O₂ was changed regularly and the response current reached a maximum value when the number of CNT/CHIT/GNp layers was 8. The assembling process of multilayer films was simple to operate. With GOx as an enzyme model, a new glucose biosensor was fabricated. The excellent electocatalytic activity and special structure of the enzyme electrode resulted in good characteristics. The linear range was 6 × 10^? 6 ～ 5 × 10^? 3 M, with a detection limit of 3 × 10^? 6 M estimated at a signal-to-noise ratio of 3, fast response time (less than 6 s). Moreover, it exhibited good reproducibility and stability.     

Adsorption of Cr(VI) from aqueous solution by hydrous zirconium oxide

A type of ZrO₂·nH₂O was synthesized and its Cr(VI) removal potential was investigated in this study. The kinetic study, adsorption isotherm, pH effect, thermodynamic study and desorption were examined in batch experiments. The kinetic process was described by a pseudo-second-order rate model very well. The Cr(VI) adsorption tended to increase with a decrease of pH. The adsorption data fitted well to the Langmuir model. The adsorption capacity increased from 61 to 66 mg g^?1 when the temperature was increased from 298 to 338 K. The positive values of both ΔH° and ΔS° suggest an endothermic reaction and increase in randomness at the solid–liquid interface during the adsorption. ΔG° values obtained were negative indicating a spontaneous adsorption process. The effective desorption of Cr(VI) on ZrO₂·nH₂O could be achieved using distilled water at pH 12.     

Toughening effect of short carbon fibers in the ZrB2–ZrSi2 ceramic composites

The toughening effect of the short carbon fibers in the ZrB₂–ZrSi₂ ceramic composites were investigated, where the ZrB₂–ZrSi₂ ceramics without carbon fibers were used as the reference. The mechanical properties were evaluated by means of flexural and SENB tests, respectively. The microstructure was characterized by SEM equipped with EDS. The results found that the short carbon fibers were uniformly incorporated in the ZrB₂–ZrSi₂ matrix and the relative density was about 97.92%. The flexural strength of short carbon fiber-reinforced ZrB₂–ZrSi₂ composites is 437 MPa; the fracture toughness and the work of fracture are 6.89 MPa m^1/2 and 259 J/m², respectively, which increased significantly in comparing with composites without fibers. The microstructure analysis revealed that the improved fracture toughness could be attributed to the fiber bridging, the fiber–matrix interface debonding and the fiber pullout, which consumed more fracture energy during the fracture process.     

Effect of carbon content and calcination temperature on the electrochemical performance of lithium iron phosphate/carbon composites as cathode materials for lithium-ion batteries

Lithium iron phosphate/carbon (LiFePO₄/C) composites were prepared by a convenient method with water-soluble phenol-formaldehyde resin as the carbon precursor. The morphology, crystalline structure, thermal stability, and composition of as-prepared LiFePO₄/C composites were investigated by scanning electron microscopy, X-ray diffraction, thermogravimetric analysis, and Raman spectrometry. Their electrochemical performance was examined based on cyclic voltammogram with a LAND battery testing system while the effect of carbon content and calcination temperature was highlighted. Results show that carbon content and calcination temperature dramatically influence the discharge capacities and rate performance of LiFePO₄/C composites. The optimal calcination temperature is 700 °C, and the optimal carbon content (mass fraction) is 8.7%. The LiFePO₄/C composite prepared under the optimal conditions exhibits an initial room temperature discharge capacity of 150.2 mA h g^?1 at a 0.2 C rate and a constant discharge capacity of about 105.7 mA h g^?1 at a 20.0 C rate after 50 cycles, showing promising potential as a novel cathode material for lithium ion batteries.     

Experimental study on the CO2 laser cutting of carbon fiber reinforced plastic composite

Promotion of massive application of carbon fiber reinforced plastics (CFRPs) in the industry can be accomplished by using faster and more flexible technologies such as laser cutting. The anisotropic and heterogeneous features of the CFRP make laser processing very challenging.A comprehensive study on the cut performance of a CO₂ laser to process sheets (3 mm thick) of a CFRP composite is presented. A high-beam quality CO₂ laser has been used in order to ascertain the capabilities of CO₂ laser cutting machines, widely used in metalworking applications, on the machining of this material. On the other hand, the influence of processing parameters, in both CW and pulsed mode, on the cut quality was studied.Cuts with a minimum heat affected zone, about 540 μm, were achieved using a high-beam quality CO₂ laser working in pulsed mode. In consequence, the CFRP strength remains practically unaffected compared to more conventional mechanical machining.