Enhancing cation exchange capacity of chars through ozonation

The use of ozone to increase the cation exchange capacity (CEC) of two chars produced from pyrolysis of Douglas fir (Pseudotsuga menziessii) and a control bituminous coal activated carbon (AC) is reported. Chars were produced from the wood fraction of Douglas fir (DFWC) and the bark (DFBC) at 500 °C using an auger driven reactor with a nitrogen sweep gas under mild vacuum. Five ozone treatment times, ranging from 5 min to 60 min, were investigated. The initial properties of each char were found to differ significantly from the other samples in terms of surface area, proximate composition, and elemental composition. DFWC did not show significant mass loss or temperature variation during ozone treatment; however, after 1 h of oxidation both DFBC and AC samples resulted in 20% and 30% mass loss, respectively, and reactor temperatures in excess of 60 °C. Analysis of the pore size distribution of each treatment shows that ozone treatment did not significantly affect small micropores after 30 min of treatment for any material, but did reduce the apparent surface area of mesopores. Increases in carboxylic groups were identified with ozone treatment and found to correlate strongly with changes in measured CEC. The formation of lactone was found to correlate positively with reactor temperature during oxidation. These results indicate that the properties of chars, including surface area, pore structure, and chemical composition, as well as reactor conditions strongly affect the ozone oxidation of chars.     

Experimental evidence of a relationship between monomer plasma residence time and carboxyl group retention in acrylic acid plasma polymers

Decreasing carboxyl retention in deposits from the glow region of an acrylic acid plasma was measured by X-ray photoelectron spectroscopy and chemical derivatisation as the collection distance from the monomer vapour inlet was increased. Volatilisation of plasma polymerised acrylic acid was detected after trifluoroethanol derivatisation; this is correlated with evaporation of low molecular weight components observed previously.     

Purification of Ellagic Acid by UF Membranes

Ellagic acid (2, 3, 7, 8‐tetrahydroxy(1)benzopyrano(5, 4, 3‐cde)(1)benzopyran‐5, 10‐dione) was selected as a model pollutant which is present in the tannic fraction of cork processing wastewater. The ultrafiltration of aqueous ellagic acid solutions through three membranes was studied in tangential UF laboratory equipment. Two of the membranes were polyethersulfone (Biomax10K and Biomax5K, with MWCO of 10000 and 5000 Da, respectively), and the third made of regenerated cellulose (Ultracel5K, with MWCO of 5000 Da). The water hydraulic permeability was evaluated for each membrane. The evolution of the permeate flow rate with processing time was followed, and the influence of the main operating variables (feed flow rate, trans‐membrane pressure and nature of the membranes) on the permeate flux was also established. According to the hypothesis of the film theory, the intrinsic and apparent rejection coefficients, as well as the mass transfer coefficients, were also determined, and the values obtained were discussed as a function of the operating conditions used.     

Formation of Ketoacids in Ozonated Drinking Water

Three ketoacids; glyoxylic acid, pyruvic acid and ketomalonic acid, were identified in ozonated drinking waters and fulvic acid solutions using gas chromatography-mass spectrometry. It was found that the concentrations of ketoacids were much higher than those of aldehydes in ozonated waters. The significance of ketoacids in finished drinking waters is discussed.     

Study of the Catalytic Ozonation of Humic Substances in Water and Their Ozonation Byproducts

It is shown that using transition metals, especially Mn(II) and Ag(I), during ozonation of humic substances in water allows important reductions in the content of organic matter. Characterization of the organic compounds resulting from ozonation was made by concentrating the sample through liquid-liquid extraction or derivation with PFBOA.HCl, along with the GC/MS and GC/ECD techniques. In total, 110 different organic compounds were identified using GC/MS; mainly carboxylic acids, aromatics, hydrocarbons, aldehydes, ketones, and furan-carboxylic acids. The percentages of elimination or formation levels reached during ozonation are discussed.     

GC/MS characterization of effluents front the ozone bleaching of eucalypt kraft pulps

Concerns regarding the possible environmental effects of organochlorine by‐products from bleaching of pulp with chlorine‐based compounds have led to the pulp and paper industry developing new bleaching sequences. Ozone, oxygen and hydrogen peroxide are the main reagents in these Totally Chlorine Free (TCF) bleaching processes.

In this study, eucalypt kraft pulps from a variety of Australian wood sources were subjected to bleaching sequences comprising oxygen, ozone and hydrogen peroxide/alkali extraction stages. The aqueous liquid effluents from each stage were analyzed by GC/MS for aldehydes, ketones, alcohols, carboxylic acids and other by‐products. Pentafluorobenzyl oxime derivatives of the aldehydes and ketones were analyzed by electron impact GC/MS. The major carbonyl compounds detected were formaldehyde, glyoxal, dimethylglyoxal and acetone. An homologous series of n‐aldehydes corresponding to cleavage of ω‐3, 6, 9 and 12 unsaturated fatty acids also was detected. Aromatic aldehydes were identified in the oxygen stage and high consistency ozone stages, but not in any medium consistency ozone or post‐ozone bleach stages. In all stages a series of saturated alkyl carboxylic acids from formic to octacosanoic acid was detected. Formic and acetic acids were present in the highest yield. Only trace quantities of unsaturated fatty acids were detected. Details of these and other compounds detected are discussed.     

Improved Anaerobic Process Efficiency Using Mesophilic and Thermophilic Elutriated Phased Treatment

An innovative anaerobic digestion elutriated phased treatment (ADEPT) has been evaluated at mesophilic (M-ADEPT) (35°C) and thermophilic (T-ADEPT) (55°C) temperatures in which the organic loading rate (OLR) was increased until reactor failure (pH<5.5). Single-stage continuously stirred tank reactors (CSTRs) at both temperatures were also operated as controls (M-CSTR for 35°C and T-CSTR for 55°C). The T-CSTR failed at an OLR of 7.4 g volatile solid (VS)/L?day and the M-CSTR at an OLR of 10 g VS/L?day while the M-ADEPT continued until an OLR of 18 g VS/L?day and the T-ADEPT reached an OLR of 24 g VS/L?day before system failure. The T-CSTR produced the poorest effluent quality as manifested by high propionate concentrations (1,500–2,500 mg/L) while both M-ADEPT and T-ADEPT produced much better quality of effluent with propionate concentrations below 100 mg/L. Thus it appears that the T-ADEPT design may solve effluent quality problems associated with normally high propionate concentrations produced during thermophilic anaerobic digestion. Superior effluent quality, reduced reactor volume requirements, more stable methanogenesis due to the extended solids retention time, and uncoupling of the methanogen wasting from the refractory sludge wasting process resulted in stable and efficient processing at both temperatures for the innovative ADEPT design. Because the higher amounts of volatile fatty acids produced in the acid elutriation phase of the ADEPT system can be a favorable carbon source for biological nutrient removal in wastewater treatment plants, this positive aspect should be considered in future applications of the ADEPT system.     

Modeling Water and Sulfuric Acid Transport through Coated Cement Concrete

The behavior of coated cement concrete in water and sulfuric acid was investigated over a three-year period. Two epoxy-based coatings were selected and cylindrical concrete specimens were coated and used in this investigation. The concrete-to-coating mass transfer coefficient ratio varied from 8 to 10. The penetration of liquids through bulk coating materials and coated concrete with and without holidays (pinholes) was studied. The mass change of the specimens was measured at regular intervals and a total of 64 coated specimens were tested. Coated concrete specimens with and without holidays had different performance with long-term immersion in deionized (DI) water and 3% sulfuric acid. Mass transfer models were developed using film and bulk concepts and were used to predict the increase in mass in coated concrete in nonreactive DI water and reactive 3% sulfuric acid solutions. The mass transfer model parameters for various solution-coating combinations were obtained from experiment data. The parameters of the effect of holiday size on the liquid transport process were also identified based on the experiment results.     

Prediction of sugars and acids in Chinese rice wine by mid-infrared spectroscopy

The use of Fourier transform mid-infrared spectroscopy (FT-MIR) for the rapid determination of sugars and acids in Chinese rice wine was presented in this study. Calibration models were developed by partial least squares regression (PLSR) for eleven parameters related to sugar content and acidity—namely, total sugar, non-sugar solid, glucose, maltose, isomaltotriose, isomaltose, panose, total acid, amino acid nitrogen, pH and lactic acid. In the calibration step, most of the parameters were accurately determined, obtaining regression coefficients of calibration (r_cal) ranging from 0.821 to 0.991. In validation, regression coefficients of validation (r_val) obtained for most parameters were higher than 0.85. Unsatisfactory predictions were obtained for isomaltotriose and isomaltose with r_val being 0.488 and 0.716, respectively. The residual predictive deviation (RPD) values were also higher than or close to 2.0 for all the parameters except for isomaltose and isomaltotriose. Overall, the results indicate that MIR spectroscopy can be applied to the quality determination of Chinese rice wine.