Evaluation of catalytic pyrolysis of cassava rhizome by principal component analysis

Rhizome of cassava plants (Manihot esculenta Crantz) was catalytically pyrolysed at 500 °C using analytical pyrolysis–gas chromatography/mass spectrometry (Py–GC/MS) method in order to investigate the relative effect of various catalysts on pyrolysis products. Selected catalysts expected to affect bio-oil properties were used in this study. These include zeolites and related materials (ZSM-5, Al-MCM-41 and Al-MSU-F type), metal oxides (zinc oxide, zirconium (IV) oxide, cerium (IV) oxide and copper chromite) catalysts, proprietary commercial catalysts (Criterion-534 and alumina-stabilised ceria-MI-575) and natural catalysts (slate, char and ashes derived from char and biomass). The pyrolysis product distributions were monitored using models in principal components analysis (PCA) technique. The results showed that the zeolites, proprietary commercial catalysts, copper chromite and biomass-derived ash were selective to the reduction of most oxygenated lignin derivatives. The use of ZSM-5, Criterion-534 and Al-MSU-F catalysts enhanced the formation of aromatic hydrocarbons and phenols. No single catalyst was found to selectively reduce all carbonyl products. Instead, most of the carbonyl compounds containing hydroxyl group were reduced by zeolite and related materials, proprietary catalysts and copper chromite. The PCA model for carboxylic acids showed that zeolite ZSM-5 and Al-MSU-F tend to produce significant amounts of acetic and formic acids.

Catalytic pyrolysis of agricultural residues for bio-oil production

Agricultural residues from Thailand, namely stalk and rhizome of cassava plants, were employed as raw materials for bio-oil production via fast pyrolysis technology. There were two main objectives of this project. The first one was to determine the optimum pyrolysis temperature for maximising the organics yield and to investigate the properties of the bio-oils produced. To achieve this objective, pyrolysis experiments were conducted using a bench-scale (150 g/h) reactor system, followed by bio-oil analysis. It was found that the reactor bed temperature that could give the highest organics yield for both materials was 490±15ºC. At all temperatures studied, the rhizome gave about 2-4% higher organics yields than the stalk. The bio-oil derived from the rhizome had lower oxygen content, higher calorific value and better stability, thus indicating better quality than that produced from the stalk. The second objective was to improve the bio-oil properties in terms of heating value, viscosity and storage stability by the incorporation of catalyst into the pyrolysis process. Catalytic pyrolysis was initially performed in a micro-scale reactor to screen a large number of catalysts. Subsequently, seven catalysts were selected for experiments with larger-scale (150 g/h) pyrolysis unit. The catalysts were zeolite and related materials (ZSM-5, Al-MCM-41 and Al-MSU-F), commercial catalysts (Criterion-534 and MI-575), copper chromite and ash. Additionally, the combination of two catalysts in series was investigated. These were Criterion-534/ZSM-5 and Al-MSU-F/ZSM-5. The results showed that all catalysts could improve the bio-oils properties as they enhanced cracking and deoxygenation reactions and in some cases such as ZSM-5, Criterion-534 and Criterion-534/ZSM-5, valuable chemicals like hydrocarbons and light phenols were produced. The highest concentration of these compounds was obtained with Criterion-534/ZSM-5.

An evaluation of thermal plasmas in pyrometallurgy

The development of reliable, high powered plasma generators has resulted in many plasma processes being proposed as alternatives to existing pyrometallurgical technologies. This work evaluates the advantages and disadvantages of plasma systems by reviewing plasma generators, their integration with reactors and the process economics. Many plasma systems were shown to be technically and economically superior to existing technologies, but some of the plasma system advantages quoted in the literature were found to be impractical because of other system constraints. Process applications were limited by the power inputs available from plasma generators compared to AC electric furnaces. A series of trials were conducted where chromite and steelplant baghouse dusts were smelted in the Tetronics' 2.0 MW transferred arc/open bath reactor to confirm the operating characteristics of the plasma system and its economics. Chromite smelting was technical superior to submerged arc furnace technology, but the economics were unfavourable because of the limited power available from the water-cooled plasma torch and the high electrical energy consumption. A DC graphite electrode plasma furnace using preheated and prereduced chromite concentrates will compete economically with the submerged arc furnace. Ni, Cr and Mo were economically recovered from high alloy content steelplant dusts for recycling. Five Electric Arc Furnace dusts were smelted to produce a non-toxic residue and recover the contained zinc to an enriched zinc oxide product for recycling. It should be possible to condense the zinc vapour directly in a zinc splash condenser to increase the value of the product. Because of the limited power available from plasma generators, plasma processes will be most suitable for treating high and medium value materials such as Au, Pt, Mo, Ni, Ti, V, Cr etc at small production rates, heating metals in tundishes and ladles and remelting superalloy scrap. The treatment of environmentally hazardous waste materials is a particularly interesting application because of the additional financial incentives. Non-transferred arc plasma generators will be used for air and gas preheating in blast furnaces to reduce metallurgical coke consumptions.

Geochemical composition of sulfide and oxide minerals from ODP Sites 193-1188 and 193-1189, PACMANUS field

Ocean Drilling Program (ODP) Leg 193 recovered core from the active PACMANUS hydrothermal field (eastern Manus Basin, Papua New Guinea) that provided an excellent opportunity to study mineralization related to a seafloor hydrothermal system hosted by felsic volcanic rocks. The purpose of this work is to provide a data set of mineral chemistry of the sulfide-oxide mineralization and associated gold occurrence in samples drilled at Sites 1188 and 1189. PACMANUS consists of five active vent sites, namely Rogers Ruins, Roman Ruins, Satanic Mills, Tsukushi, and Snowcap. In this work two sites were studied: Snowcap and Roman Ruins. Snowcap is situated in a water depth of 1670 meters below sea level [mbsl], covers a knoll of dacite-rhyodacite lava, and is characterized by low-temperature diffuse venting. Roman Ruin lies in a water depth of 1693-1710 mbsl, is 150 m across, and contains numerous large, active and inactive, columnar chimneys. Sulfide mineralogy at the Roman Ruins site is dominated by pyrite with lesser amounts of chalcopyrite, sphalerite, pyrrhotite, marcasite, and galena. Sulfide minerals are relatively rare at Snow Cap. These are dominated by pyrite with minor chalcopyrite and sphalerite and traces of pyrrhotite. Native gold has been found in a single sample from Hole 1189B (Roman Ruins). Oxide minerals are represented by Ti magnetite, magnetite, ilmenite, hercynite (Fe spinel), and less abundant Al-Mg rich chromite (average = 10.6 wt% Al2O3 and 5.8 wt% MgO), Fe-Ti oxides, and a single occurrence of pyrophanite (Mn Ti O3). Oxide mineralization is more developed at Snowcap, whereas sulfide minerals are more extensive and show better development at Roman Ruins. The mineralogy was obtained mainly by a detailed optical microscopy study. Oxide mineral identifications were confirmed by X-ray diffraction, and mineral chemistry was determined by electron probe microanalyses.

Caracterização termo-mecânica de interconectores metálicos recobertos com filmes de LaCrO3

The cells unitaria of the solid oxide fuel cell are separated by means of interconnects, which serve as electrical contact between the cells. Lanthanum Chromite (LaCrO3) has been the most common material used as interconnect in solid oxide fuel cells. Reducing the operating temperature around 800 º C of cells to solid oxide fuel make possibilite the use of metallic interconnects as an alternative to ceramic LaCrO3. Metallic interconnects have advantages over ceramic interconnects such as high thermal conductivity, electricity, good ductility, low cost, good physical and mechanical properties. In this work evaluate the thermo-mechanical properties of the metallic substrate and coated metallic substrate with the ceramic LaCrO3 film via spray-pyrolysis, in order to demonstrate the feasibility of using this material as a component of a fuel cell solid oxide. The materials were characterized by X-ray diffraction, oxidation behavior, mechanical strength, optical microscopy (OM) and scanning electron microscopy (SEM). The X-ray diffraction proved the formation phase of the LaCrO3 on the metallic substrate and the identification of the phases formed after the oxidative test and mechanical strength at high temperature. The oxidation behavior showed the increased oxidation resistance of the coated metallic substrate. It was noted that the mechanical resistance to bending of the coated metallic substrate only increases at room temperature. The optical microscopy (OM) has provided an assessment of both the metallic substrate and the LaCrO3 film deposited on the metal substrate that, in comparison with the micrographs obtained from SEM. The SEM one proved the formation of Cr2O3 layer on the metallic substrate and stability of LaCrO3 film after oxidative test, it can also observe the displacement of the ceramic LaCrO3 film after of mechanical testing and mapping of the main elements as chromium, manganese, oxygen, lanthanum in samples after the thermo-mechanical tests.

Síntese e caracterização de espinélios a base de Cu, Fe e Cr para pigmentos cerâmicos

Inorganic pigment comprises a host lattice, which is part of the chromophore component (usually a transition metal cation) and possible components modifiers, which stabilize, add or restate the properties pigments. Among the materials with spinel, ferrites, and the chromite stand out, because they have broad technological importance in the area of materials, applicability, pigments, catalytic hydrogenation, thin film, ceramic tiles, among others. The present work, pigments containing CuFe2O4, CuCr2O4,e CuFeCrO4, were synthesized by a method that makes use of gelatin as organic precursor using their application to ceramic pigments. The pigments were characterized by X-ray diffraction (XRD), Infrared spectroscopy, scanning electron microscopy (SEM) spectroscopy in the UV-visible and Colorimetry. The results confirmed the feasibility of the synthetic route used, with respect to powders synthesized, there is the formation of spinel phase from 500°C, with an increase in crystallinity and the formation of other phases. The pigments were shown to be crystalline and the desired phases were obtained. The copper chromite have hues ranging from green to black according to the calcination temperature, while the copper chromite doped with iron had brownish. The ferrites showed copper color and darker brown to black, which may indicate an interesting factor because of the importance of black pigment

Estudo termo-mecânico de interconector metálico recoberto com filme de La0,8Ca0,2CrO3 e de interconector cerâmico de La0,8Sr0,2Cr0,92Co0,08O3 para PaCOS

Doped lanthanum chromite ( LaCrO3 ) has been the most common material used as interconnect in solid oxide fuel cells for high temperature ( SOFC-HT ) that enabling the stack of SOFCs. The reduction of the operating temperature, to around 800 º C, of solid oxide fuel cells enabled the use of metallic interconnects as an alternative to ceramic LaCrO3, From the practical point of view, to be a strong candidate for interconnect the material must have good physical and mechanical properties such as resistance to oxidizing and reducing environments, easy manufacture and appropriate thermo-mechanical properties. Thus, a study on the physic-mechanical interconnects La0,8Sr0,2Cr0,92Co0,08O3 ceramics for SOFC -AT obtained by the method of combustion , as well as thermo-mechanical properties of metallic interconnects (AISI 444) covered with La0,8Ca0,2CrO3 by deposition technique by spray-pyrolysis fuel cells for intermediate temperature (IT-SOFCs). The La0,8Sr0,2Cr0,92Co0,08O3 was characterized by X -ray diffraction(XRD) , density and porosity , Vickers hardness (HV) , the flexural strength at room temperature and 900 °C and scanning electron microscopy (SEM). The X -ray diffraction confirmed the phase formation and LaCrO3 and CoCr2O4, in order 6 GPa hardness and mechanical strength at room temperature was 62 MPa ceramic Interconnector. The coated metal interconnects La0,8Ca0,2CrO3 passed the identification by XRD after deposition of the film after the oxidation test. The oxidative behavior showed increased resistance to oxidation of the metal substrate covered by La0,8Ca0,2CrO3 In flexural strength of the coated metal substrate, it was noticed only in the increased room temperature. The a SEM analysis proved the formation of Cr2O3 and (Cr,Mn)3O4 layers on metal substrate and confirmed the stability of the ceramic La0,8 Ca0,2CrO3 film after oxidative test