Comonomer sequence distribution in metallocene-based ethylene/1-butene (S-34) and ethylene/1-hexene (S-43) copolymers

Metallocene based polyethylenes were prepared by SMOPEC's "metallocene adduct" technology in a gas phase fluidized bed model reactor. The C-13-NMR spectra of ethylene/1-butene (S-34) and ethylene/1-hexene(S-43) copolymers were studied in a manner analogous to that established by Hsieh and Cheng. The comonomer sequence distributions of copolymer samples were obtained. The results show that these metallocene based copolymers contain a small amount of butene and hexene, and the EE and EEE sequences are dominant.

Biomass-derived Oxymethylene Ethers as Diesel Additives: A Thermodynamic Analysis

Conversion of biomass for production of liquid fuels can help in reducing the greenhouse gas (GHG) emissions which are predominantly generated by combustion of fossil fuels. Adding oxymethylene ethers (OMEs) in conventional diesel fuel has the potential to reduce soot formation during the combustion in a diesel engine. OMEs are downstream products of syngas, which can be generated by the gasification of biomass. In this research, a thermodynamic analysis has been conducted through development of data intensive process models of all the unit operations involved in production of OMEs from biomass. Based on the developed model, the key process parameters affecting the OMEs production including equivalence ratio, H2/CO ratio, and extra water flow rate were identified. This was followed by development of an optimal process design for high OMEs production. It was found that for a fluidized bed gasifier with heat capacity of 28 MW, the conditions for highest OMEs production are at an air amount of 317 tonne/day, at H2/CO ratio of 2.1, and without extra water injection. At this level, the total OMEs production is 55 tonne/day (13 tonne/day OME3 and 9 tonne/day OME4). This model would further be used in a techno-economic assessment study of the whole biomass conversion chain to determine the most attractive pathways.

Photocatalytic reactors for environmental remediation: A review

Research in the field of photocatalytic reactors in the past three decades has been an area of extensive and diverse activity with an extensive range of suspended and fixed film photocatalyst configurations being reported. The key considerations for photocatalytic reactors, however, remain the same; effective mass transfer of pollutants to the photocatalyst surface and effective deployments and illumination of the photocatalyst. Photocatalytic reactors have the potential versatility to be applied to the remediation of a range of water and gaseous effluents. Furthermore they have also been applied to the treatment of potable waters. The scale-up of photocatalytic reactors for waste and potable water treatment plants has also been demonstrated. Systems for the reduction of carbon dioxide to fuel products have also been reported. This paper considers the main photocatalytic reactor configurations that have been reported to date. 

Biomass fly ash incorporation in cement based materials

In recent years, pressures on global environment and energy security have led to an increasing demand on renewable energy sources, and diversification of Europe’s energy supply. Among these resources the biomass could exert an important role, since it is considered a renewable and CO2 neutral energy resource once the consumption rate is lower than the growth rate, and can potentially provide energy for heat, power and transports from the same installation. Currently, most of the biomass ash produced in industrial plants is either disposed of in landfill or recycled on agricultural fields or forest, and most times this goes on without any form of control. However, considering that the disposal cost of biomass ashes are raising, and that biomass ash volumes are increasing worldwide, a sustainable ash management has to be established. The main objective of the present study is the effect of biomass fly ashes in cement mortars and concretes in order to be used as a supplementary cementitious material. The wastes analyzed in the study were collected from the fluidized bed boilers and grate boilers available in the thermal power plants and paper pulp plants situated in Portugal. The physical as well as chemical characterisations of the biomass fly ashes were investigated. The cement was replaced by the biomass fly ashes in 10, 20 and 30% (weight %) in order to investigate the fresh properties as well as the hardened properties of biomass fly ash incorporated cement mortar and concrete formulations. Expansion reactions such as alkali silica reaction (ASR), sulphate attack (external and internal) were conducted in order to check the durability of the biomass fly ash incorporated cement mortars and concretes. Alternative applications such as incorporation in lime mortars and alkali activation of the biomass fly ashes were also attempted. The biomass fly ash particles were irregular in shape and fine in nature. The chemical characterization revealed that the biomass fly ashes were similar to a class C fly ash. The mortar results showed a good scope for biomass fly ashes as supplementary cementitious materials in lower dosages (<20%). The poor workability, concerns about the organic content, alkalis, chlorides and sulphates stand as the reasons for preventing the use of biomass fly ash in high content in the cement mortars. The results obtained from the durability tests have shown a clear reduction in expansion for the biomass fly ash mortars/concretes and the binder blend made with biomass fly ash (20%) and metakaolin (10%) inhibited the ASR reaction effectively. The biomass fly ash incorporation in lime mortars did not improve the mortar properties significantly though the carbonation was enhanced in the 15-20% incorporation. The biomass fly ash metakaolin blend worked well in the alkali activated complex binder application also. Portland cement free binders (with 30-40 MPa compressive strength) were obtained on the alkali activation of biomass fly ashes (60-80%) blended with metakaolin (20-40%).

Valorization of solid wastes from cellulose and paper industry

This thesis reports in detail studies of industrial solid wastes valorization as alternative raw materials. All tested wastes are classified as non-hazardous and are generated in the pulp and paper process, including primary sludge, dregs, grits, lime mud and bottom ash (this generated in a process that occurs in parallel to the production of cellulose, whose aim is the production of energy to supply the plant through the combustion of forest biomass in fluidized bed). A detailed general characterization was performed at each waste and according to their characteristics, they were selected some applications in materials with potential use, specifically in Fibercement, Bituminous Mixture for regularization layer and industrial mortars (rendering mortars and cementitious-adhesive). After decided to application each waste was specifically tested to proceed the setting up of formulations containing different content of waste in replacement of the raw conventional material. As an isolated case, the bottom ash was tested not only as an alternative raw material for construction materials, but also it was tested for its use in fluidized bed in which the waste is generated as raw material. Both dregs and bottom ash had undergone special treatment to make possible to obtain a better quality of waste in order do not compromise the final product characteristics and process. The dregs were tested in bituminous mixtures as received and also washed (on the laboratory scale to remove soluble salts) and bottom ash were washed and screened in industrial scale (for removal of soluble salts, especially chlorides and coarse fraction particles elimination - particles larger than 1 mm size). The remaining residues form used in such as received avoiding additional costs. The results indicated potential and some limitations for each application to the use of these wastes as alternative raw material, but in some cases, the benefits in relation to valorization overlap with its limitations in both aspects, environmental and economic.

Economical and operational optimization of CALB immobilization on MP1000 for amidation of olein fatty acids with ethanolamine

Dissertação de Mestrado , Engenharia Biológica, Faculdade de Engenharia de Recursos Naturais, Universidade do Algarve, 2008

Low-Carbon Cement with Waste Oil-Cracking Catalyst Incorporation

The present paper shows preliminary results of an ongoing project which one of the goals is to investigate the viability of using waste FCC catalyst (wFCC), originated from Portuguese oil refinery, to produce low carbon blended cements. For this purpose, four blended cements were produced by substituting cement CEM I 42.5R up to 20% (w/w) by waste FCC catalyst. Initial and final setting times, consistency of standard paste, soundness and compressive strengths after 2, 7 and 28 days were measured. It was observed that the wFCC blended cements developed similar strength, at 28 days, compared to the reference cement, CEM I 42.5R. Moreover, cements with waste FCC catalyst incorporation up to 15% w/w meet European Standard EN 197-1 specifications for CEM II/A type cement, in the 42.5R strength class.

Low-carbon cement with waste oil-craking catalyst incorporation

The present paper shows preliminary results of an ongoing project which one of the goals is to investigate the viability of using waste FCC catalyst (wFCC), originated from Portuguese oil refinery, to produce low carbon blended cements. For this purpose, four blended cements were produced by substituting cement CEM I 42.5R up to 20% (w/w) by waste FCC catalyst. Initial and final setting times, consistency of standard paste, soundness and compressive strengths after 2, 7 and 28 days were measured. It was observed that the wFCC blended cements developed similar strength, at 28 days, compared to the reference cement, CEM I 42.5R. Moreover, cements with waste FCC catalyst incorporation up to 15% w/w meet European Standard EN 197-1 specifications for CEM II/A type cement, in the 42.5R strength class.

Simulação de um processo de pirólise rápida de biomassa

Mestrado em Engenharia Química - Ramo Optimização Energética na Indústria Química

Cr(N,C) diffusion coating formation on pre-nitrocarburised H13 tool steel

The microstructural processes of Cr(N,C) coating formation by thermoreactive deposition and diffusion (TRD) on pre-nitrocarburised H13 tool steel were studied. Both nitrocarburising and TRD were performed in fluidized bed furnaces at 570 °C. During TRD, chromium was transferred from chromium powder in the fluidized bed, to the nitrocarburised substrates by gas-phase reactions initiated by reaction of HCl gas with the chromium. Addition of 30% H2 to the input inert gas was found to increase the rate of coating formation, although hydrogen reduction resulted in rapid loss of nitrogen to the surface. The reason for the increased rate of coating formation could not be established without further investigation, although several possible explanations have been proposed. It was found that porosity and the formation of an iron nitride ‘cover layer’ during nitrocarburising were the biggest influences on the microstructure of the Cr(N,C) coating. Microstructural characterization of the coatings was performed by scanning electron microscopy (SEM), X-ray diffraction (XRD) and glow discharge optical emission spectroscopy (GDOES).

Measurement of the mass transfer coefficient at workpiece surfaces in heat treatment furnaces

The mass (e.g. carbon) transfer coefficient at a workpiece surface is an important kinetic factor to control the heat treatment process of the workpiece and to evaluate heat treatment equipment. The coefficient can be calculated from the carbon concentration at the surface of a sample carburized in a carburizing furnace for a given time. Two common measurement methods which use a thin plate and employ a component as samples respectively are evaluated and compared for sensitivity and uncertainty. The comparison shows that the use of a component produces higher measurement precision and also has the advantage in measuring the carbon transfer coefficients at different treated positions. This method is then extended and discussed methodologically. Also two equations are proposed to calculate the carbon transfer coefficient and its uncertainty, respectively. This method is also applied to measure the carbon transfer coefficient in a fluidized bed heat treatment furnace.

A novel approach for real mass transformation from V2O5 particles to nanorods

A solid-state, mass-quantity transformation from V2O5 powders to nanorods has been realized via a two-step approach. The nanorods were formed through a controlled nanoscale growth from the nanocrystalline V2O5 phase created by a ball milling treatment. The nanorods grow along the [010] direction and are dominated by {001} surfaces. Surface energy minimization and surface diffusion play important roles in their growth mechanism. Real large quantity production can be achieved when the annealing process is conducted in a fluidized bed which can treat large quantities of the milled materials at once. The crystal orientation of nanorods provides an improved cycling stability for lithium intercalation.

Pretreatment of seawater for biodegradable organic content removal using membrane bioreactor

Reverse osmosis (RO) is currently one of the most prevalent methods used for seawater desalination. During the past four decades, the research anddevelopment has reduced the energy consumption from about 20 to 4 kWh/m3, while improvements in membrane science has led to a 20-fold increase in the specific membrane flux. Nevertheless, research is still underway to reduce the operation and maintenance problems and thus improve the performance of RO systems. The most important maintenance problem associated with RO operation is the membrane fouling, especially biological fouling (biofouling). This work focuses on the aspects to eliminate biofouling in RO membranes, by adopting a proper pretreatment system. The experimental results revealed that fluidized bed biological granular activated carbon, at 15 min empty bed contact time (with dissolved organic carbon, DOC concentration of 6–8 mg/L) can be utilized effectively to remove nearly 100% biodegradable DOC from seawater. Continuous experiments of membrane bioreactor (MBR) have been conducted concomitantly to gain insight into the long-term effects of MBR on biodegradable organic content removal and biofouling control. The results show that MBR system produced better effluent with 78% DOC removal and quasi-total biodegradable DOC removal. Dissolved oxygen was not a limiting factor for the DOC degradation. Short-term experimental runs were conducted with RO membrane using both pretreated and non-pretreated seawater. The results showed that filtrate from MBR yielded the highest permeate flux improvement, which was approximately 300% compared with non-pretreated seawater.

Characterization and tribological performance of Cu-based intermetallic layers

Fluidized bed reactor chemical vapor deposition (FBR-CVD) has been used to enrich the surface of oxygen free high conductivity (OFHC) copper with titanium, silicon and aluminum. This technique enables the production of coherent and adherent intermetallic surface layers of uniform thickness and high hardness. The characterization of the coatings was performed using backscatter scanning electron microscopy (BS-SEM), X-ray diffraction (XRD), glow discharge optical emission spectroscopy (GDOES) and micro-hardness. The tribological properties of the coatings in dry sliding contact with steel were evaluated by pin-on-disc wear testing.

Computational simulation of the influence of inert particles on incomplete combustion of methane at a low air factor

It is well known that the gas–solid system plays a significant role in many industrial processes. It is a complex physical and chemical process, generally consisting of heat transfer, mass transfer, species diffusion, and chemical reactions. In this paper, the reaction of methane with air at a low air factor and the gas flow in a fluidized bed with 0.1 mm solid particles are computationally simulated to enable the study of the effect of the inert particles on the species diffusion and the chemical reactions. The reaction of methane and air is modeled by a two-step reaction mechanism that produces a continuous fluid phase composed of six gases (CH₄, CO, O₂, CO₂, H₂O, and N₂) and discrete solid particles in the reactor. The simulation results are compared with experiment and show that the finite rate model and the eddy dissipation model can well describe the reactions of gases in high-density gas–solid systems. The distribution of each gas and the particle behaviors are analyzed for incomplete combustion at different concentrations of loaded solid particles. The inert particles change the reactions by enhancing both the chemical kinetics and the species diffusion dynamics.