New Catalysts for the Renewable Production of Monomers for Bioplastics

Terephthalic acid (PTA) is one of the monomers used for the synthesis of the polyester, polyethylene terephthalate (PET), that is used for the large-scale manufacture of synthetic fibers and plastic bottles. PTA is largely produced from the liquid-phase oxidation of petroleum-derived p-xylene (PX). However, there are now ongoing worldwide efforts exploring alternative routes for producing PTA from renewable, biomass resources.

In this thesis, I present a new route to PTA starting from the biomass-derived platform chemical, 5-hydroxymethylfurfural (HMF). This route utilizes new, selective Diels-Alder-dehydration reactions involving ethylene and is advantageous over the previously proposed Diels-Alder-dehydration route to PTA from HMF via 2,5-dimethylfuran (DMF) since the H₂ reduction of HMF to DMF is avoided. Specifically, oxidized derivatives of HMF are reacted as is, or after etherification-esterification with methanol, with ethylene over solid Lewis acid catalysts that do not contain strong Brønsted acids in order to synthesize intermediates of PTA and its equally important diester, dimethyl terephthalate (DMT). The partially oxidized HMF, 5-(hydroxymethyl)furoic acid (HMFA) is reacted with high pressure ethylene over a pure-silica molecular sieve catalyst containing framework tin (Sn-Beta) to produce the Diels-Alder-dehydration product, 4-(hydroxymethyl)benzoic acid (HMBA), with ~30% selectivity at ~20% yield. If HMFA is protected with methanol to form methyl 5-(methoxymethyl)furan-2-carboxylate (MMFC), MMFC can react with ethylene in the presence of a pure-silica molecular sieve containing framework zirconium (Zr-Beta) to produce methyl 4-(methoxymethyl)benzenecarboxylate (MMBC) with >70% selectivity at >20% yield. HMBA and MMBC can then be oxidized to produce PTA and DMT, respectively. When Lewis acid containing mesoporous silica (MCM-41) and amorphous silica, or Brønsted acid containing zeolites (Al-Beta), are used as catalysts, a significant decrease in selectivity/yield of the Diels-Alder-dehydration product is observed.

An investigation to elucidate the reaction network and side products in the conversion of MMFC to MMBC was performed, and the main side products are found to be methyl 4-formylcyclohexa-1,3-diene-1-carboxylate and the ethylene Diels-Alder adduct of this cyclohexadiene. These products presumably form by a different dehydration pathway of the MMFC/ethylene Diels-Alder adduct and should be included when determining the overall selectivity to PTA or DMT since, like MMBC, these compounds are precursors to PTA or DMT.

Fundamental physical and chemical information on the ethylene Diels-Alder-dehydration reactions catalyzed by the Lewis acid-containing molecular sieves was obtained. Madon-Boudart experiments using Zr-Beta as catalyst show that the reaction rates are limited by chemical kinetics only (physical transport limitations are not present), all the Zr⁴⁺ centers are incorporated into the framework of the molecular sieve, and the whole molecular sieve crystal is accessible for catalysis. Apparent activation energies using Zr-Beta are low, suggesting that the overall activation energy of the system may be determined by a collection of terms and is not the true activation energy of a single chemical step.

Upgrading Bio-Platform Molecules in the Gas-Phase: From Levulinic Acid to Bio-Chemicals

Levulinic acid (LA) is a polyfunctional molecule obtained from biomass. Because of its structure, the United States Department of energy classified LA as one of the top 12 building block chemicals. Typically, it is valorized through chemical reduction to γ-valerolactone (GVL). It is usually done with H2 in batch systems with high H2 pressures and noble metal catalysts, making it expensive and less applicable. Therefore, alternative approaches such as catalytic transfer hydrogenation (CTH) through the Meerwein–Ponndorf–Verley (MPV) reaction over heterogeneous catalysts have been studied. This uses organic molecules (alcohols) which act as a hydride transfer agent (H-donor), to reduce molecules containing carbonyl groups. Given the stability of the intermediate, reports have shown the batch liquid-phase CTH of levulinate esters with secondary alcohols, and remarkable results (GVL yield) have been obtained over ZrO2, given the need of a Lewis acid (LASites) and base pair for CTH. However, there were no reports of the continuous gas-phase CTH of levulinate esters. Therefore, high surface area ZrO2 was tested for gas-phase CTH of methyl levulinate (ML) using ethanol, methanol and isopropanol as H-donors. Under optimized conditions with ethanol (250 ℃), the reaction is selective towards GVL (yield 70%). However, heavy carbonaceous materials over the catalyst surface progressively blocked LASites changing the chemoselectivity. The in situ regeneration of the catalyst permitted a partial recovery of the LASites and an almost total recovery of the initial catalytic behavior, proving the deactivation reversible. Tests with methanol were not promising (ML conversion 35%, GVL yield 4%). As expected, using isopropanol provided complete conversion and a GVL yield of 80%. The reaction was also tested using bioethanol derived from agricultural waste. In addition, a preliminary study was performed for the hydrogenolysis of polyols to produce bioethanol, were Pd-Fe catalyst promoted the ethanol selective (37%) hydrogenolysis of glycerol.

Possibilidades e limitações no uso da temperatura em cromatografia líquida de fase reversa

High-temperature liquid chromatography (HTLC) is a technique that presents a series of advantages in liquid phase separations, such as: reduced analysis time, reduced pressure drop, reduced asymmetry factors, modified retentions, controlled selectivities, better efficiencies and improved detectivities, as well as permitting green chromatography. The practical limitations that relate to instrumentation and to stationary phase instability are being resolved and this technique is now ready to be applied for routine determinations.

Caracterização reológica das diferentes fases de extrato de inulina de raízes de chicória, obtidas por abaixamento de temperatura

Inulin is a functional food ingredient, generally employed as sugar or fat substitute in food systems. This ingredient can be found in several vegetal products, including chicory roots. As the solubility of inulin is susceptible to temperature changes, the product suffers a fractionalization resulting in two phases when cooled, originating a precipitated phase, more viscose, and a liquid phase, of lesser viscosity. The study of rheological properties of different phases of inulin extract is important for equipment designing, such as mixer and bombs. In this work, rheological behavior at three different temperatures (25; 40 and 50 ºC) was determined for liquid and precipitated phases of inulin liquid extract, extracted from chicory roots by hot water diffusion and cooled at two different temperatures (8 and -10 ºC), suffering phases separation. The precipitated phase was analyzed in two conditions: pure and with the addition of microencapsulating agents (maltodextrin and hydrolized starch). All of them presented a linear behavior, similar to that of the Plastics of Bingham. Some of them, however, were not an adequate fit to this model.

Dynamic transitions in a three dimensional associating lattice gas model

The aggregation of interacting Brownian particles in sheared concentrated suspensions is an important issue in colloid and soft matter science per se. Also, it serves as a model to understand biochemical reactions occurring in vivo where both crowding and shear play an important role. We present an effective medium approach within the Smoluchowski equation with shear which allows one to calculate the encounter kinetics through a potential barrier under shear at arbitrary colloid concentrations. Experiments on a model colloidal system in simple shear flow support the validity of the model in the concentration range considered. By generalizing Kramers' rate theory to the presence of shear and collective hydrodynamics, our model explains the significant increase in the shear-induced reaction-limited aggregation kinetics upon increasing the colloid concentration.

High performance magnetic separation of gold nanoparticles for catalytic oxidation of alcohols

We present the magnetic separation approach to facilitate the recovery of gold nanoparticle (AuNP) catalysts. The use of magnetically recoverable supports for the immobilization of AuNPs instead of traditional oxides, polymers or carbon based solids guarantees facile, clean, fast and efficient separation of the catalyst at the end of the reaction cycle. Magnetic separation can be considered an environmentally benign separation approach, since it minimizes the use of auxiliary substances and energy for achieving catalyst recovery. The catalyst preparation is based on the immobilization of Au(3+) on the surface of core-shell silica-coated magnetite nanoparticles, followed by metal reduction using two different methods. AuNPs were prepared by thermal reduction in air and by hydrogen reduction at mild temperature. Interestingly, the mean particle size of the supported AuNPs was similar (ca. 5.9 nm), but the polydispersity of the samples is quite different. The catalytic activity of both catalysts in the aerobic oxidation of alcohols was investigated and a distinct selectivity for benzyl alcohol oxidation was observed.

Dynamic transitions in a two dimensional associating lattice gas model

Using Monte Carlo simulations we investigate some new aspects of the phase diagram and the behavior of the diffusion coefficient in an associating lattice gas (ALG) model on different regions of the phase diagram. The ALG model combines a two dimensional lattice gas where particles interact through a soft core potential and orientational degrees of freedom. The competition between soft core potential and directional attractive forces results in a high density liquid phase, a low density liquid phase, and a gas phase. Besides anomalies in the behavior of the density with the temperature at constant pressure and of the diffusion coefficient with density at constant temperature are also found. The two liquid phases are separated by a coexistence line that ends in a bicritical point. The low density liquid phase is separated from the gas phase by a coexistence line that ends in tricritical point. The bicritical and tricritical points are linked by a critical lambda-line. The high density liquid phase and the fluid phases are separated by a second critical tau-line. We then investigate how the diffusion coefficient behaves on different regions of the chemical potential-temperature phase diagram. We find that diffusivity undergoes two types of dynamic transitions: a fragile-to-strong transition when the critical lambda-line is crossed by decreasing the temperature at a constant chemical potential; and a strong-to-strong transition when the critical tau-line is crossed by decreasing the temperature at a constant chemical potential.

Orbital multicriticality in spin-gapped quasi-one-dimensional antiferromagnets

Motivated by the quasi-one-dimensional antiferromagnet CaV(2)O(4), we explore spin-orbital systems in which the spin modes are gapped but orbitals are near a macroscopically degenerate classical transition. Within a simplified model we show that gapless orbital liquid phases possessing power-law correlations may occur without the strict condition of a continuous orbital symmetry. For the model proposed for CaV(2)O(4), we find that an orbital phase with coexisting order parameters emerges from a multicritical point. The effective orbital model consists of zigzag-coupled transverse field Ising chains. The corresponding global phase diagram is constructed using field theory methods and analyzed near the multicritical point with the aid of an exact solution of a zigzag XXZ model.

Microstructural characterization of as-cast Cr-Si alloys

This work presents results of microstructural characterization of as-cast Cr-Si alloys. The alloys were prepared by arc melting pure Cr (min. 99.996%) and Si (min. 99.998%) powder mixtures under argon atmosphere in a water-cooled copper crucible with nonconsumable tungsten electrode and titanium getter. The phases were identified by scanning electron microscopy (SEM), using the back-scattered electron (BSE) image mode and X-ray diffraction (XRD). The results confirm the currently accepted Cr-Si phase diagram in terms of the invariant reactions and solid phases present in this system. Small corrections are proposed for the compositions of the liquid phase in the following reactions: (i) L double left right arrow Cr-ss+Cr3Si, from 15 to 16 at.% Si; (ii) L+alpha Cr5Si3 double left right arrow CrSi, from 51 at.% Si to slightly above 53 at.% Si; (iii) L double left right arrow CrSi+CrSi2, from 56 to slightly above 57 at.% Si; (iv) L double left right arrow CrSi2+Si, from 82 to slightly above 85 at.% Si. (c) 2006 Elsevier Inc. All rights reserved.

Spontaneous infiltrations of compound systems of Y(2)O(3), Sm(2)O(3), RE(2)O(3), Al(2)O(3) and AIN in SiC ceramics

Silicon carbide ceramics (SiC) are used in different applications in the engineering area due to the excellent properties, mainly in high temperatures. They are usually obtained by liquid-phase sintering enabling to form volatile products and, consequently, defects. The present work aims at studying the obtention of SiC ceramics by spontaneous infiltration using a eutectic composition of the Al(2)O(3)/Y(2)O(3), AIN/Y(2)O(3), Al(2)O(3)/Sm(2)O(3), AlN/Sm(2)O(3), Al(2)O(3)/RE(2)O(3) and AlN/RE(2)O(3) Systems. RE(2)O(3) is the concentrate of the rare-earth oxide obtained from Xenotime ore. Infiltration tests were carried out in argon atmosphere, graphite crucibles, in several temperatures near the melting point of each system, varying from 2.5 to 60 min. It was observed that Al(2)O(3)/Y(2)O(3), Al(2)O(3)/SM(2)O(3), AlN/SM(2)O(3) and Al(2)O(3)/RE(2)O(3) systems do not infiltrate appropriately and the AlN/Y(2)O(3) and AlN/RE(2)O(3) systems infiltrated spontaneously more than 20 mm; however, the first one presented a higher degree of infiltration, approximately 97%. (C) 2009 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Toughened ZrO2 ceramics sintered with a La2O3-rich glass as additive

In this study, the influence of the glass addition and sintering parameters on the densification and mechanical properties of tetragonal zirconia polycrystals (3Y-TZP) ceramics were evaluated. High-purity tetragonal ZrO2 powder and La2O3-rich glass were used as starting powders. Two compositions based on ZrO2 and containing 5wt.% and 10wt.% of La2O3-rich glass were studied in this work. The starting powders were mixed/milled by planetary milling, dried at 90 degrees C for 24 h, sieved through a 60 mesh screen and uniaxially cold pressed under 80 MPa. The samples were sintered in air at 1200 degrees C, 1300 degrees C, 1400 degrees C for 60 min and at 1450 degrees C for 120 min, with heating and cooling rates of 10 degrees C/min. Sintered samples were characterized by relative density, X-ray diffraction (XRD) and scanningelectron microscopy (SEM). Hardness and fracture toughness were obtained by Vickers indentation method. Dense sintered samples were obtained for all conditions. Furthermore, only tetragonal-ZrO2 was identified as crystalline phase in sintered samples, independently of the conditions studied. Samples sintered at 1300 degrees C for 60 min presented the optimal mechanical properties with hardness and fracture toughness values near to 12 GPa and 8.5 MPa m(1/2) respectively. (c) 2007 Elsevier B.V, All rights reserved.

Infiltration of Al2O3/Y2O3 mix into SiC ceramic preforms

Silicon carbide ceramics are very interesting materials to engineering applications because of their properties. These ceramics are produced by liquid phase sintering (LPS), where elevated temperature and time are necessary, and generally form volatile products that promote defects and damage their mechanical properties. In this work was studied the infiltration process to produce SiC ceramics, using shorter time and temperature than LPS, thereby reducing the undesirable chemical reactions. SiC powder was pressed at 300 MPa and pre-sintered at 1550 degrees C for 30 min. Unidirectional and spontaneous infiltration of this preform by Al2O3/Y2O3 liquid was done at 1850 degrees C for 5, 10, 30 and 60 min. The kinetics of infiltration was studied, and the infiltration equilibrium happened when the liquid infiltrated 12 mm into perform. The microstructures show grains of the SiC surrounded by infiltrated additives. The hardness and fracture toughness are similar to conventional SiC ceramics obtained by LPS. (c) 2007 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Strength improvement of LPS-SiC ceramics by oxidation treatment

In this work, SiC ceramics were liquid phase sintered (LPS), using AIN-Y(2)O(3) as additives, and oxidized at 1400 degrees C in air for up to 120 h. Oxidation was monitored by the weight gain of the samples as function of exposition time and temperature. A parabolic growth of the oxidation layer has been observed and the coefficient of the growth rate has been determined by relating the weight gain and the surface area. The effect of oxidation on strength has been determined by 4-point bending tests. Phase analysis by Xray diffraction and microstructural observation by scanning electron microscopy indicated the formation of a uniform and dense oxidation layer. The elimination of surface flaws and pores and the generation of compressive stresses in the surface resulted in a strength increase of the oxidized samples. (C) 2009 Published by Elsevier Ltd.

AnSBBR Applied to a Personal Care Industry Wastewater Treatment: Effects of Fill Time, Volume Treated Per Cycle, and Organic Load

A study was performed regarding the effect of the relation between fill time, volume treated per cycle, and influent concentration at different applied organic loadings on the stability and efficiency of an anaerobic sequencing batch reactor containing immobilized biomass on polyurethane foam with recirculation of the liquid phase (AnSBBR) applied to the treatment of wastewater from a personal care industry. Total cycle length of the reactor was 8 h (480 min). Fill times were 10 min in the batch operation, 4 h in the fed-batch operation, and a 10-min batch followed by a 4-h fed batch in the mixed operation. Settling time was not necessary since the biomass was immobilized and decant time was 10 min. Volume of liquid medium in the reactor was 2.5 L, whereas volume treated per cycle ranged from 0.88 to 2.5 L in accordance with fill time. Influent concentration varied from 300 to 1,425 mg COD/L, resulting in an applied volumetric organic load of 0.9 and 1.5 g COD/L.d. Recirculation flow rate was 20 L/h, and the reactor was maintained at 30 A degrees C. Values of organic matter removal efficiency of filtered effluent samples were below 71% in the batch operations and above 74% in the operations of fed batch followed by batch. Feeding wastewater during part of the operational cycle was beneficial to the system, as it resulted in indirect control over the conversion of substrate into intermediates that would negatively interfere with the biochemical reactions regarding the degradation of organic matter. As a result, the average substrate consumption increased, leading to higher organic removal efficiencies in the fed-batch operations.

Effect of impeller type and stirring frequency on the behavior of an AnSBBR in the treatment of low-strength wastewater

The influence of impeller type and stirring frequency on the performance of a mechanically stirred anaerobic sequencing batch reactor containing immobilized biomass on an inert support (AnSBBR - Anaerobic Sequencing Batch Biofilm Reactor) was evaluated. The biomass was immobilized on polyurethane foam cubes placed in a stainless-steel basket inside a glass cylinder. Each 8-h batch run consisted of three stages: feed (10 min), reaction (460 min) and discharge (10 min) at 30 degrees C. Experiments were performed with four impeller types, i.e., helical, flat-blade, inclined-blade and curved-blade turbines, at stirring frequencies ranging from 100 to 1100 rpm. Synthetic wastewater was used in all experiments with an organic-matter concentration of 530 +/- 37 mg/L measured as chemical oxygen demand (COD). The reactor achieved an organic-matter removal efficiency of around 87% under all investigated conditions. Analysis of the four impeller types and the investigated stirring frequencies showed that mass transfer in the liquid phase was affected not only by the applied stirring frequency but also by the agitation mode imposed by each impeller type. The best reactor performance at all stirring frequencies was obtained when agitation was provided by the flat-blade turbine impeller. (C) 2010 Elsevier Ltd. All rights reserved.