COD removal from textile industry effluent: pilot plant studies

This work involved the treatment of industrial waste water from a nylon carpet printing plant. As dyeing of nylon is particularly difficult, acid dyes, fixing agents, thickeners, finishing agents, are required for successful colouration and cause major problems with the plant's effluent disposal in terms of chemical oxygen demand (COD). Granular activated carbon (GAC) Filtrasorb 400 was used to treat a simulated process plant effluent containing all the pollutants. Equilibrium isotherm experiments were established and experimental data obtained showed good empirical correlation with Langmuir isotherm theory. Column experimental data, in terms of COD were correlated using the bed depth service time (BDST) model. Solid phase loading in the columns were found to approach that in equilibrium studies indicating an efficient use of adsorbent. The results from the BDST model were then used to design a pilot adsorption rig at the plant. The performance of the pilot plant column were accurately predicted by scale-up from the bench scale columns. (C) 2001 Elsevier Science BN. All rights reserved.

TAP studies of ammonia decomposition over Ru and Ir catalysts

The Temporal Analysis of Products (TAP) technique has been used to investigate the mechanism involved in the catalytic decomposition of NH3 over a series of catalysts consisting of activated carbon supported Ru (promoted and non-promoted with Na) and over an activated carbon supported Ir. An extensive study of the role played by both the support and the promoter in the

The effects of temperature on the performance of electrochemical double layer capacitors

An electrochemical double layer capacitor test cell containing activated carbon xerogel electrodes and ionic liquid electrolyte was tested at 15, 25 and 40 OC to examine the effect of temperature on electrolyte resistance (RS) and equivalent series resistance (ESR) measured using impedance spectroscopy and capacitance using charge/discharge cycling. A commercial 10F capacitor was used as a comparison. Viscosity, ionic self-diffusion coefficients and differential scanning calorimetry measurements were used to provide an insight into the behaviour of the 1,2-dimethyl-3-propylimdazolium electrolyte. Both RS and ESR decreased with increasing temperature for both capacitors. Increasing the temperature also increased the capacitance for both the test cell and the commercial capacitor but proportionally more for the test cell. An increase in temperature decreased the ionic liquid electrolyte viscosity and increased the self diffusion coefficients of both the anion and the cation indicating an increase in dissociation and increase in ionic mobility.

Hysteretic adsorption and desorption of hydrogen by nanoporous metal-organic frameworks

Adsorption and desorption of hydrogen from nanoporous materials, such as activated carbon, is usually fully reversible. We have prepared nanoporous metal-organic framework materials with flexible linkers in which the pore openings, as characterized in the static structures, appear to be too small to allow H-2 to pass. We observe hysteresis in their adsorption and desorption kinetics above the supercritical temperature of H-2 that reflects the dynamical opening of the "windows" between pores. This behavior would allow H-2 to be adsorbed at high pressures but stored at lower pressures.

Removal of natural hormones in dairy farm wastewater using reactive and sorptive materials

The objective of this study was to examine the estrogen and androgen hormone removal efficiency of reactive (Connelly zero-valent iron (ZVI), Gotthart Maier ZVI) and sorptive (AquaSorb 101 granular activated carbon (GAC) and OrganoLoc PM-100 organo clay (OC)) materials from HPLC grade water and constructed wetland system (CWS) treated dairy farm wastewater. Batch test studies were performed and hormone concentration analysis carried out using highly sensitive reporter gene assays (RGAs). The results showed that hormonal interaction with these materials is selective for individual classes of hormones. Connelly ZVI and AquaSorb 101 GAC were more efficient in removing testosterone (Te) than 17?-estradiol (E2) and showed faster removal rates of estrogen and androgen than the other materials. Gotthart Maier ZVI was more efficient in removing E2 than Te. OrganoLoc PM-100 OC achieved the lowest final concentration of E2 equivalent (EEQ) and provided maximum removal of both estrogens and androgens.

Physical properties of a new Deep Eutectic Solvent based on lithium bis[(trifluoromethyl)sulfonyl]imide and N-methylacetamide as superionic suitable electrolyte for lithium ion batteries and electric double layer capacitors

Herein we present a study on the physical/chemical properties of a new Deep Eutectic Solvent (DES) based on N-methylacetamide (MAc) and lithium bis[(trifluoromethyl)sulfonyl]imide (LiTFSI). Due to its interesting properties, such as wide liquid-phase range from -60°C to 280°C, low vapor pressure, and high ionic conductivity up to 28.4mScm at 150°C and at x=1/4, this solution can be practically used as electrolyte for electrochemical storage systems such as electric double-layer capacitors (EDLCs) and/or lithium ion batteries (LiBs). Firstly, relationships between its transport properties (conductivity and viscosity) as a function of composition and temperature were discussed through Arrhenius' Law and Vogel-Tamman-Fulcher (VTF) equations, as well as by using the Walden classification. From this investigation, it appears that this complex electrolyte possesses a number of excellent transport properties, like a superionic character for example. Based on which, we then evaluated its electrochemical performances as electrolyte for EDLCs and LiBs applications by using activated carbon (AC) and lithium iron phosphate (LiFePO) electrodes, respectively. These results demonstrate that this electrolyte has a good compatibility with both electrodes (AC and LiFePO) in each testing cell driven also by excellent electrochemical properties in specific capacitance, rate and cycling performances, indicating that the LiTFSI/MAc DES can be a promising electrolyte for EDLCs and LiBs applications especially for those requiring high safety and stability. © 2013 Elsevier Ltd.

Comparative study on performances of trimethyl-sulfonium and trimethyl-ammonium based ionic liquids in molecular solvents as electrolyte for electrochemical double layer capacitors

The present work reports a comparative study on the performances of two bis[(trifluoromethyl)sulfonyl]imide-based protic (PIL) and aprotic (AIL) ionic liquids, namely, trimethyl-ammonium bis[(trifluoromethyl)sulfonyl]imide ([HN][TFSI], PIL) and trimethyl-sulfonium bis[(trifluoromethyl) sulfonyl]imide ([S][TFSI], AIL), as mixtures with three molecular solvents: gamma butyrolactone (?-BL), propylene carbonate (PC), and acetonitrile (ACN) as electrolytes for supercapacitor applications. After an analysis of their transport properties as a function of temperature, cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and galvanostatic charge-discharge measurements were conducted at 25 and -30 C to investigate the performance of these mixtures as electrolytes for supercapacitors using activated carbon as the electrode material. Surprisingly, for each solvent investigated, no significant differences were observed between the electrolytes based on the PIL and AIL in their electrochemical performance due to the presence or the absence of the labile proton. Furthermore, good specific capacitances were observed in the case of ?-BL-based electrolytes even at low temperature. Capacitances up to 131 and 80 F·g are observed for the case of the [S][TFSI] + ?-BL mixture at 25 and -30 C, respectively. This latter result is very promising particularly for the formulation of new environmentally friendly electrolytes within energy storage systems even at low temperatures. © 2013 American Chemical Society.

Physicochemical Investigation of Adiponitrile-Based Electrolytes for Electrical Double Layer Capacitor

An ether-functionalised cyclic sulfonium based ionic liquid as an electrolyte for electrochemical double layer capacitors

A novel cyclic sulfonium cation-based ionic liquid (IL) with an ether-group appendage and the bis{(trifluoromethyl)sulfonyl}imide anion was synthesised and developed for electrochemical double layer capacitor (EDLC) testing. The synthesis and chemical-physical characterisation of the ether-group containing IL is reported in parallel with a similarly sized alkyl-functionalised sulfonium IL. Results of the chemical-physical measurements demonstrate how important transport properties, i.e. viscosity and conductivity, can be promoted through the introduction of the ether-functionality without impeding thermal, chemical or electrochemical stability of the IL. Although the apparent transport properties are improved relative to the alkyl-functionalised analogue, the ether-functionalised sulfonium cation-based IL exhibits moderately high viscosity, and poorer conductivity, when compared to traditional EDLC electrolytes based on organic solvents (propylene carbonate and acetonitrile). Electrochemical testing of the ether-functionalised sulfonium IL was conducted using activated carbon composite electrodes to inspect the performance of the IL as a solvent-free electrolyte for EDLC application. Good cycling stability was achieved over the studied range and the performance was comparable to other solvent free,
IL-based EDLC systems. Nevertheless, limitations of the attainable performance are primarily the result of sluggish transport properties and a restricted operative voltage of the IL, thus highlighting key aspects of this field which require further attention.

Hydrogen adsorption on functionalized nanoporous activated carbons

There is considerable interest in hydrogen adsorption on carbon nanotubes and porous carbons as a method of storage for transport and related energy applications. This investigation has involved a systematic investigation of the role of functional groups and porous structure characteristics in determining the hydrogen adsorption characteristics of porous carbons. Suites of carbons were prepared with a wide range of nitrogen and oxygen contents and types of functional groups to investigate their effect on hydrogen adsorption. The porous structures of the carbons were characterized by nitrogen (77 K) and carbon dioxide (273 K) adsorption methods. Hydrogen adsorption isotherms were studied at 77 K and pressure up to 100 kPa. All the isotherms were Type I in the IUPAC classification scheme. Hydrogen isobars indicated that the adsorption of hydrogen is very temperature dependent with little or no hydrogen adsorption above 195 K. The isosteric enthalpies of adsorption at zero surface coverage were obtained using a virial equation, while the values at various surface coverages were obtained from the van't Hoff isochore. The values were in the range 3.9-5.2 kJ mol(-1) for the carbons studied. The thermodynamics of the adsorption process are discussed in relation to temperature limitations for hydrogen storage applications. The maximum amounts of hydrogen adsorbed correlated with the micropore volume obtained from extrapolation of the Dubinin-Radushkevich equation for carbon dioxide adsorption. Functional groups have a small detrimental effect on hydrogen adsorption, and this is related to decreased adsorbate-adsorbent and increased adsorbate-adsorbate interactions.

Adsorption of aqueous metal ions on oxygen and nitrogen functionalized nanoporous activated carbons

In this study, the adsorption characteristics of two series of oxygen and nitrogen functionalized activated carbons were investigated. These series were a low nitrogen content(similar to 1 wt % daf) carbon series derived from coconut shell and a high nitrogen content (similar to 8 wt % daf) carbon series derived from polyacrylonitrile. In both series, the oxygen contents were varied over the range similar to 2-22 wt % daf. The porous structures of the functionalized activated carbons were characterized using N-2 (77 K) and CO2 (273 K) adsorption. Only minor changes in the porous structure were observed in both series. This allowed the effect of changes in functional group concentrations on metal ion adsorption to be studied without major influences due to differences in porous structure characteristics. The surface group characteristics were examined by Fourier transform infrared (FTIR) spectroscopy, acid/base titrations, and measurement of the point of zero charge (pH(PZC)). The adsorption of aqueous metal ion species, M2+(aq), on acidic oxygen functional group sites mainly involves an ion exchange mechanism. The ratios of protons displaced to the amount of M2+(aq) metal species adsorbed have a linear relationship for the carbons with pH(PZC) <= 4.15. Hydrolysis of metal species in solution may affect the adsorption of metal ion species and displacement of protons. In the case of basic carbons, both protons and metal ions are adsorbed on the carbons. The complex nature of competitive adsorption between the proton and metal ion species and the amphoteric character of carbon surfaces are discussed in relation to the mechanism of adsorption.

Adsorption of metal ions on nitrogen surface functional groups in activated carbons

A commercially available coconut-shell-derived active carbon was oxidized with nitric acid, and both the original and oxidized active carbons were treated with ammonia at 1073 K to incorporate nitrogen functional groups into the carbon. An active carbon with very high nitrogen content (similar to9.4 wt % daf) was also prepared from a nitrogen-rich precursor, polyacrylonitrile (PAN). These nitrogen-rich carbons had points of zero charge (pH(pzc)) similar to H-type active carbons. X-ray absorption near-edge structure (XANES) spectroscopy, Fourier transform infrared (FTIR) spectroscopy, and temperature-programmed desorption (TPD) were used to characterize the nitrogen functional groups in the carbons. The nitrogen functional groups present on the carbon surface were pyridinic, pyrrolic (or indolic), and pyridonic structures. The adsorption of transition metal cations Cd2+, Ni2+, and Cu2+ from aqueous solution on the suite of active carbons showed that adsorption was markedly higher for carbons with nitrogen functional groups present on the surface than for carbons with similar pH(pzc) values. In contrast, the adsorption characteristics of Ca2+ from aqueous solution were similar for all the carbons studied. Flow microcalorimetry (FMC) studies showed that the enthalpies of adsorption of Cd2+(aq) on the active carbons with high nitrogen contents were much higher than for nitric acid oxidized carbons studied previously, which also had enhanced adsorption characteristics for metal ion species. The enthalpies of adsorption of Cu2+ were similar to those obtained for Cd2+ for specific active carbons. The nitrogen functional groups in the carbons act as surface coordination sites for the adsorption of transition metal ions from aqueous solution. The adsorption characteristics of these carbons are compared with those of oxidized carbons.

Alkali Activated Fuel Ash and Slag Mixes:Optimization Study from Mortars to Concrete Building Blocks

Alkali activated binders, based on ash and slag, also known as geopolymers, can play a key role in reducing the carbon footprint of the construction sector by replacing ordinary Portland cement in some concretes. Since 1970s, research effort has been ongoing in many research institutions. In this study, pulverized fuel ash (PFA) from a UK power plant, ground granulated blast furnace slag (GGBS) and combinations of the two have been investigated as geopolymer binders for concrete applications. Activators used were sodium hydroxide and sodium silicate solutions. Mortars with sand/binder ratio of 2.75 with several PFA and GGBS combinations have been mixed and tested. The optimization of alkali dosage (defined as the Na2O/binder mass ratio) and modulus (defined as the Na2O/SiO2 mass ratio) resulted in strengths in excess of 70 MPa for tested mortars. Setting time and workability have been considered for the identification of the best combination of PFA/GGBS and alkali activator dosage for different precast concrete products. Geopolymer concrete building blocks have been replicated in laboratory and a real scale factory trial has been successfully carried out. Ongoing microstructural characterization is aiming to identify reaction products arising from PFA/GGBS combinations.

Chloride induced corrosion of steel in alkali activated slag concretes

Alkali activated slag (AAS) is an alternative cementitious material. Sodium silicate solution is usually used to activate ground granulated blast furnace slag to produce AAS. As a consequence, the pore solution chemistry of AAS differs from that of Portland cement (PC). Although AAS offers many advantages over PC, such as higher strength, superior resistance to acid and sulphate environments and lower embodied carbon due to 100% PC replacement, there is a need to assess its performance against chloride induced corrosion duo to its different pore solution chemistry. For PC systems, resistivity measurement, as a type of nondestructive test, is usually used to evaluate its chloride diffusivity and the corrosion rate of the embedded steel. However, due to the different pore solution chemistry present in the different AAS systems, the application of this test in AAS concretes would be questionable as the resistivity of concrete is highly dependent on its conductivity of the pore solution. Therefore, a study was carried out using twelve AAS concretes mixes, the results of which are reported in this paper. The AAS mixes were designed with alkali concentration of 4%, 6% and 8% (Na₂O% of the mass of slag) and modulus (Ms) of sodium silicate solution of 0.75, 1.00, 1.50 and 2.00. A PC concrete with the same binder content as the AAS concretes was also studied as a reference. The chloride diffusion coefficient was determined using a non-steady state chloride diffusion test (NT BUILD 443). The resistivity of the concretes before the diffusion test was also measured. Macrocell corrosion current (corrosion rate) for steel rods embedded in the concretes was measured whilst subjecting the concretes to a cyclic chloride ponding regime (1 day ponded with salt solution and 6 days drying). The results showed that the AAS concretes had lower chloride diffusivity with associated higher resistivity than the PC concrete. The measured corrosion rate was also lower for the AAS concretes. However, unlike the PC, in which a higher resistivity yields a lower diffusivity and corrosion rate, there was no relationship apparent between the resistivity and either the diffusivity or the corrosion rate of steel for the AAS concretes. This is assigned to the variation of the pore solution composition of the AAS concretes. This also means that resistivity measurements cannot be depended on for assessing the chloride induced corrosion resistance of AAS concretes.