Valorisation of waste fractions from autohydrolysis of selected lignocellulosic materials

Non‐isothermal processing of lignocellulosic materials in aqueous media (autohydrolysis reaction) under mild conditions leads to solutions containing valuable chemicals (oligosaccharides, sugars and acetic acid) and other, undesired, compounds (belonging to the extractive and acid‐soluble lignin fractions) which have to be removed in further purification treatments. Liquors obtained by non‐isothermal autohydrolysis of Eucalyptus globulus wood and corncobs under a variety of operational conditions were extracted with ethyl acetate in order to remove non‐saccharide components, and the suitability of the fraction dissolved in the organic phase was assayed for possible utilisation as an antioxidant. The yield and antioxidant activity of ethyl acetate extracts (measured by the α,α‐diphenyl‐β‐picrylhydrazyl (DPPH) radical scavenging capacity) showed a strong dependence on the autohydrolysis conditions. The antioxidant activity of extracts obtained under selected operational conditions compared well with synthetic antioxidants. © 2003 Society of Chemical Industry     

Synthesis of Rice Processing Plants. I. Development of Simplified Models

This article, the first of three articles on the synthesis of rice processing plants, focuses on the development of simplified mathematical models necessary for use in optimizing rice processing plants. The second concentrates on the optimal synthesis of a rice plant and the third on the sensitivity of the optimization to uncertainty in model parameters. Existing models for rice processing unit operations are not suitable for flowsheet optimization and new models need to be developed to overcome numerical difficulties that occur in optimization applications, specifically in mixed integer nonlinear programming (MINLP) applications. Simplified models of the drying, cooling, and tempering units are developed. In addition head rice yield models, used as a quality indicator, energy consumption, and economic models were also developed. Naturally, the new models exhibit some mismatch with respect to the existing models from which they were developed. However, a sensitivity analysis, presented in Part III, has shown that the optimal flowsheet structure was not sensitive to a lack of fit between the simplified and complex models. The simplified models were found adequate to be appropriate for use at the synthesis stage.     

Nonstationary Simulation Model of Absorber with Falling Film of Suspension

A nonstationary model of SO₂ absorption from a gas phase to a countercurrent falling film of absorbing slurry was developed. Laminar, wavy and turbulent film structures were considered based on published information. Resistances to the mass transfer on the gas and the liquid sides of the interphase were considered, together with chemical reactions in the liquid phase. Relevant chemical equilibria in the liquid phase were modeled. Original experimental data on the neutralization reagent dissolution rate presented as a polydispersed two‐phase system of solids and on the rate of dissolved sulfite oxidation were used. The model was verified with experimental data from a laboratory‐scale falling‐film absorber using a single vertical tube under various geometrical and operating conditions, and a very good agreement was found with the experiment. Parametric sensitivity analysis showed the critical parts of the model.     

High-performance MIM capacitor using ALD high-k HfO/sub 2/-Al/sub 2/O/sub 3/ laminate dielectrics

For the first time, we successfully fabricated and demonstrated high performance metal-insulator-metal (MIM) capacitors with HfO/sub 2/-Al/sub 2/O/sub 3/ laminate dielectric using atomic layer deposition (ALD) technique. Our data indicates that the laminate MIM capacitor can provide high capacitance density of 12.8 fF//spl mu/m/sup 2/ from 10 kHz up to 20 GHz, very low leakage current of 3.2 /spl times/ 10/sup -8/ A/cm/sup 2/ at 3.3 V, small linear voltage coefficient of capacitance of 240 ppm/V together with quadratic one of 1830 ppm/V/sup 2/, temperature coefficient of capacitance of 182 ppm//spl deg/C, and high breakdown field of /spl sim/6 MV/cm as well as promising reliability. As a result, the HfO/sub 2/-Al/sub 2/O/sub 3/ laminate is a very promising candidate for next generation MIM capacitor for radio frequency and mixed signal integrated circuit applications.     

Optimal Control of the Primary Drying Stage of Freeze Drying of Solutions in Vials Using Variational Calculus

The problem of operating freeze drying of pharmaceutical products in vials placed in trays of a freeze dryer to remove free water (in frozen state) at a minimum time was formulated as an optimal control problem. Two different types of freeze dryer designs were considered. In type I freeze dryer design, upper and lower plate temperatures were controlled together, while in type II freeze dryer design, upper and lower plate temperatures were controlled independently. The heat input to the material being dried and the drying chamber pressure were considered as control variables. Constraints were placed on the system state variables by the melting and scorch temperatures during primary drying stage. Necessary conditions of optimality for the primary drying stage of freeze drying process in vials are derived and presented. Furthermore, an approach for constructing the optimal control policies that would minimize the drying time for the primary drying stage was given. In order to analyze optimal control policy for the primary drying stage of the freeze-drying process in vials, a rigorous multi-dimensional unsteady state mathematical model was used. The theoretical approach presented in this work was applied in the freeze drying of skim milk. Significant reductions in the drying times of primary drying stage of freeze drying process in vials were obtained, as compared to the drying times obtained from conventional operational policies.     

Start-up and steady-state results of a full-scale UASB reactor treating malting wastewater.

An Imhoff tank was reconstructed into a 250 m3 UASB reactor in order to treat a malting plant wastewater. The UASB was inoculated with sludge from an anaerobic lagoon used for slaughterhouse wastewater treatment. After two months of operation the reactor achieved full load with an HRT of 17 h, a COD removal higher than 80% and a biogas production of 300 m3/day (77% average methane content), with an organic loading rate of 3.6 kgCOD/m3.d (0.24 kgCOD/kgVSS.d). A yield coefficient of 0.09 gVSS/gCODrem was found from a mass balance. The fat present in the inoculated sludge (48 mg/gSSV) did not affect the start up performance. Sludge from the inoculum with high content of fat (270 mg/gSSV), was separated by flotation in the first week of operation. The COD removal efficiency was scarcely influenced by the reactor operation temperature (17-25 degrees C).     

Optimised anaerobic treatment of house-sorted biodegradable waste and slaughterhouse waste in a high loaded half technical scale digester.

Anaerobic co-digestion of organic wastes from households, slaughterhouses and meat processing industries was optimised in a half technical scale plant. The plant was operated for 130 days using two different substrates under organic loading rates of 10 and 12 kgCOD.m(-3).d(-1). Since the substrates were rich in fat and protein components (TKN: 12 g.kg(-1) the treatment was challenging. The process was monitored on-line and in the laboratory. It was demonstrated that an intensive and stable co-digestion of partly hydrolysed organic waste and protein rich slaughterhouse waste can be achieved in the balance of inconsistent pH and buffering NH4-N. In the first experimental period the reduction of the substrate COD was almost complete in an overall stable process (COD reduction >82%). In the second period methane productivity increased, but certain intermediate products accumulated constantly. Process design options for a second digestion phase for advanced degradation were investigated. Potential causes for slow and reduced propionic and valeric acid degradation were assessed. Recommendations for full-scale process implementation can be made from the experimental results reported. The highly loaded and stable codigestion of these substrates may be a good technical and economic treatment alternative.     

Spinel Phase Relations in the Fe3O4–CuFe2O4 System

Phase equilibria involving spinel solid solutions, delafossite, and hematite in the Fe–Cu–O system are studied by emf measurements in solid-electrolyte galvanic cells. The results demonstrate that, above 1250 K, Fe₃O₄ and CuFe₂O₄ form a continuous series of solid solutions. At lower temperatures, the solid solution disproportionates with the formation of delafossite and Fe₂O₃, and two spinel solid solutions appear: one based on Fe₃O₄ and the other based on Cu₂FeO₄. The compositions of the spinel phases in equilibrium with delafossite and Fe₂O₃ are determined in the range 1100–1250 K.