Pressure filtration characteristics of enzymatically hydrolyzed biomass suspensions

Enzymatic hydrolysis of lignocellulosic polymers is likely to become one of the key technologies enabling industrial production of liquid biofuels and chemicals from lignocellulosic biomass. Certain types of enzymes are able to hydrolyze cellulose and hemicellulose polymers to shorter units and finally to sugar monomers. These monomeric sugars are environmentally acceptable carbon sources for the production of liquid biofuels, such as bioethanol, and other chemicals, such as organic acids. Liquid biofuels in particular have been shown to contribute to the reduction of net emissions of greenhouse gases. The solid residue of enzymatic hydrolysis is composed mainly of lignin and partially degraded fibers, while the liquid phase contains the produced sugars. It is usually necessary to separate these two phases at some point after the hydrolysis stage. Pressure filtration is an efficient technique for this separation. Solid-liquid separation of biomass suspensions is difficult, because biomass solids are able to retain high amounts of water, which cannot be readily liberated by mechanical separation techniques. Most importantly, the filter cakes formed from biomaterials are compressible, which ultimately means that the separation may not be much improved by increasing the filtration pressure. The use of filter aids can therefore facilitate the filtration significantly. On the other hand, the upstream process conditions have a major influence on the filtration process. This thesis investigates how enzymatic hydrolysis and related process conditions affect the filtration properties of a cardboard suspension. The experimental work consists of pressure filtration and characterization of hydrolysates. The study provides novel information about both issues, as the relationship between enzymatic hydrolysis conditions and subsequent filtration properties has so far not been considered in academic studies. The results of the work reveal that the final degree of hydrolysis is an important factor in the filtration stage. High hydrolysis yield generally increases the average specific cake resistance. Mixing during the hydrolysis stage resulted in undefined changes in the physical properties of the solid residue, causing a high filtration resistance when the mixing intensity was high. Theoretical processing of the mixing data led to an interesting observation: the average specific cake resistance was observed to be linearly proportional to the mixer shear stress. Another finding worth attention is that the size distributions of the solids did not change very dramatically during enzymatic hydrolysis. There was an observable size reduction during the first couple of hours, but after that the size reduction was minimal. Similarly, the size distribution of the suspended solids remained almost constant when the hydrolyzed suspension was subjected to intensive mixing. It was also found that the average specific cake resistance was successfully reduced by the use of filter aids. This reduction depended on the method of how the filter aids were applied. In order to obtain high filtration capacity, it is recommended to use the body feed mode, i.e. to mix the filter aid with the slurry prior to filtration. Regarding the quality of the filtrate, precoat filtration was observed to produce a clear filtrate with negligible suspended solids content, while the body feed filtrates were turbid, irrespective of which type of filter aid was used.

Utilization of steelmaking waste materials for production of calcium carbonate (CaCO3)

The steel industry produces, besides steel, also solid mineral by-products or slags, while it emits large quantities of carbon dioxide (CO2). Slags consist of various silicates and oxides which are formed in chemical reactions between the iron ore and the fluxing agents during the high temperature processing at the steel plant. Currently, these materials are recycled in the ironmaking processes, used as aggregates in construction, or landfilled as waste. The utilization rate of the steel slags can be increased by selectively extracting components from the mineral matrix. As an example, aqueous solutions of ammonium salts such as ammonium acetate, chloride and nitrate extract calcium quite selectively already at ambient temperature and pressure conditions. After the residual solids have been separated from the solution, calcium carbonate can be precipitated by feeding a CO2 flow through the solution. Precipitated calcium carbonate (PCC) is used in different applications as a filler material. Its largest consumer is the papermaking industry, which utilizes PCC because it enhances the optical properties of paper at a relatively low cost. Traditionally, PCC is manufactured from limestone, which is first calcined to calcium oxide, then slaked with water to calcium hydroxide and finally carbonated to PCC. This process emits large amounts of CO2, mainly because of the energy-intensive calcination step. This thesis presents research work on the scale-up of the above-mentioned ammonium salt based calcium extraction and carbonation method, named Slag2PCC. Extending the scope of the earlier studies, it is now shown that the parameters which mainly affect the calcium utilization efficiency are the solid-to-liquid ratio of steel slag and the ammonium salt solvent solution during extraction, the mean diameter of the slag particles, and the slag composition, especially the fractions of total calcium, silicon, vanadium and iron as well as the fraction of free calcium oxide. Regarding extraction kinetics, slag particle size, solid-to-liquid ratio and molar concentration of the solvent solution have the largest effect on the reaction rate. Solvent solution concentrations above 1 mol/L NH4Cl cause leaching of other elements besides calcium. Some of these such as iron and manganese result in solution coloring, which can be disadvantageous for the quality of the PCC product. Based on chemical composition analysis of the produced PCC samples, however, the product quality is mainly similar as in commercial products. Increasing the novelty of the work, other important parameters related to assessment of the PCC quality, such as particle size distribution and crystal morphology are studied as well. As in traditional PCC precipitation process, the ratio of calcium and carbonate ions controls the particle shape; a higher value for [Ca2+]/[CO32-] prefers precipitation of calcite polymorph, while vaterite forms when carbon species are present in excess. The third main polymorph, aragonite, is only formed at elevated temperatures, above 40-50 °C. In general, longer precipitation times cause transformation of vaterite to calcite or aragonite, but also result in particle agglomeration. The chemical equilibrium of ammonium and calcium ions and dissolved ammonia controlling the solution pH affects the particle sizes, too. Initial pH of 12-13 during the carbonation favors nonagglomerated particles with a diameter of 1 μm and smaller, while pH values of 9-10 generate more agglomerates of 10-20 μm. As a part of the research work, these findings are implemented in demonstrationscale experimental process setups. For the first time, the Slag2PCC technology is tested in scale of ~70 liters instead of laboratory scale only. Additionally, design of a setup of several hundreds of liters is discussed. For these purposes various process units such as inclined settlers and filters for solids separation, pumps and stirrers for material transfer and mixing as well as gas feeding equipment are dimensioned and developed. Overall emissions reduction of the current industrial processes and good product quality as the main targets, based on the performed partial life cycle assessment (LCA), it is most beneficial to utilize low concentration ammonium salt solutions for the Slag2PCC process. In this manner the post-treatment of the products does not require extensive use of washing and drying equipment, otherwise increasing the CO2 emissions of the process. The low solvent concentration Slag2PCC process causes negative CO2 emissions; thus, it can be seen as a carbon capture and utilization (CCU) method, which actually reduces the anthropogenic CO2 emissions compared to the alternative of not using the technology. Even if the amount of steel slag is too small for any substantial mitigation of global warming, the process can have both financial and environmental significance for individual steel manufacturers as a means to reduce the amounts of emitted CO2 and landfilled steel slag. Alternatively, it is possible to introduce the carbon dioxide directly into the mixture of steel slag and ammonium salt solution. The process would generate a 60-75% pure calcium carbonate mixture, the remaining 25-40% consisting of the residual steel slag. This calcium-rich material could be re-used in ironmaking as a fluxing agent instead of natural limestone. Even though this process option would require less process equipment compared to the Slag2PCC process, it still needs further studies regarding the practical usefulness of the products. Nevertheless, compared to several other CO2 emission reduction methods studied around the world, the within this thesis developed and studied processes have the advantage of existing markets for the produced materials, thus giving also a financial incentive for applying the technology in practice.

Modelling of ultrasound assisted mixing in Newtonian and non-Newtonian liquids

The purpose of this work is to obtain a better understanding of behaviour of possible ultrasound appliance on fluid media mixing. The research is done in the regard to Newtonian and non-Newtonian fluids. The process of ultrasound appliance on liquids is modelled in COMSOL Multiphysics software. The influence of ultrasound using is introduced as waveform equation. Turbulence modelling is fulfilled by the k-ε model in Newtonian fluid. The modeling of ultrasound assisted mixing in non-Newtonian fluids is based on the power law. To verify modelling results two practical methods are used: Particle Image Velocimetry and measurements of mixing time. Particle Image Velocimetry allows capturing of velocity flow field continuously and presents detailed depiction of liquid dynamics. The second way of verification is the comparison of mixing time of homogeneity. Experimentally achievement of mixing time is done by conductivity measurements. In modelling part mixing time is achieved by special module of COMSOL Multiphysics – the transport of diluted species. Both practical and modelling parts show similar radial mechanism of fluid flow under ultrasound appliance – from the horn tip fluid moves to the bottom and along the walls goes back. Velocity profiles are similar in modelling and experimental part in the case of Newtonian fluid. In the case of non-Newtonian fluid velocity profiles do not agree. The development track of ultrasound-assisted mixing modelling is presented in the thesis.

Modulation of intercellular communication by differential regulation and heteromeric mixing of co-expressed connexins

Intercellular communication may be regulated by the differential expression of subunit gap junction proteins (connexins) which form channels with differing gating and permeability properties. Endothelial cells express three different connexins (connexin37, connexin40, and connexin43) in vivo. To study the differential regulation of expression and synthesis of connexin37 and connexin43, we used cultured bovine aortic endothelial cells which contain these two connexins in vitro. RNA blots demonstrated discordant expression of these two connexins during growth to confluency. RNA blots and immunoblots showed that levels of these connexins were modulated by treatment of cultures with transforming growth factor-ß1. To examine the potential ability of these connexins to form heteromeric channels (containing different connexins within the same hemi-channel), we stably transfected connexin43-containing normal rat kidney (NRK) cells with connexin37 or connexin40. In the transfected cells, both connexin proteins were abundantly produced and localized in identical distributions as detected by immunofluorescence. Double whole-cell patch-clamp studies showed that co-expressing cells exhibited unitary channel conductances and gating characteristics that could not be explained by hemi-channels formed of either connexin alone. These observations suggest that these connexins can readily mix with connexin43 to form heteromeric channels and that the intercellular communication between cells is determined not only by the properties of individual connexins, but also by the interactions of those connexins to form heteromeric channels with novel properties. Furthermore, modulation of levels of the co-expressed connexins during cell proliferation or by cytokines may alter the relative abundance of different heteromeric combinations.

Mixing in rotating drums

Tämän diplomityön tarkoitus on parantaa meesauunin toiminnallista tehokkuutta tehostamalla lämmönsiirtoa. Lämmönsiirron parantamiseksi kehitetään erilaisia nostinratkaisuja. Kokeita suoritetaan käyttäen eri sekoitinratkaisuja ja erilaisia prosessiparametreja. Työn kirjallisuusosassa esitetään meesauuni sekä rumpumaisten uunien toiminta. Työssä selvitetään myös sekoituksen analysointiin käytettäviä tapoja ja laskukaavoja. Kirjallisuusosassa keskitytään myös rummussa tapahtuviin fysikaalisiin ilmiöihin sekä erilaisten fluidien reologiaan. Työn kokeellisessa osassa käytettiin LUT Kemiantekniikalla suunniteltua pilot -kokoluokan rumpu-uunia, jolla kokeitaan suoritettiin, käyttäen erilaisia sekoitinratkaisuja ja sekoitusprosessiparametreja. Kokeissa käytettiin myös eri viskositeetin omaavia materiaaleja. Valitut materiaalit olivat vesi, CMC (karboksimetyyliselluloosa) ja kiinteä meesa. Kokeiden tuloksena löydettiin nostinratkaisuja, joilla sekoittumista ja lämmönsiirtoa pystytään parantamaan sekä pidentämään viipymäaikaa.

Cajá-flavored drinks: a proposal for mixed flavor beverages and a study of the consumer profile

Mixed flavor beverages represent a trend that is gaining the allegiance of potential fruit juice consumers. The present study proposed to prepare mixed flavor beverages and verify their consumer acceptance. Cajá beverage (sample A) was used as the standard. The other beverages were prepared by mixing the cajá-flavored product with other flavors: strawberry (B), pineapple (C), jabuticaba (D), mango (E) and cashew (F). The consumer profiles in the two regions studied were similar. Overall beverages B, A and F were the most accepted, with scores of 7.7, 6.4 and 6.2, respectively. Internal Preference Mapping showed that most of the consumers were located near beverages A, B and F, confirming the acceptance results. The consumers indicated appearance and flavor as the most appreciated characteristics in beverages A, B and F. Beverages A, B and F presented higher total soluble solids contents and viscosities than the other beverages. Consumer segmentation did not depend on the different levels of familiarity with the cajá flavor. Thus the preparation of mixed flavor beverages of cajá-strawberry and cajá-cashew is an excellent proposal because it presents flavors with good potential for marketing in different regions of Brazil.

Fresh meat quality of pigs fed diets with different fatty acid profiles and supplemented with red wine solids

Abstract Three groups of pigs were fed three different diets, namely a diet rich in saturated fatty acids (palm oil-based, PO), a polyunsaturated fatty acid (PUFA)-rich diet (corn oil-based, CO), and a PUFA-rich diet (corn oil-based) supplemented with red wine solids (RWS), which was added to the diet (CO+RWS) in order to assess the protective effect on the oxidative status of the pork meat. The addition of corn oil favourably modulates the FAs profile of the backfat, and to a lesser extent of the intramuscular fat of semimembranosus muscle, without causing adverse effects on the meat quality or on its oxidative stability. Moreover, these parameters were not affected by the addition of the RWS in the CO+RWS diet.

Phonon spectra and thermodynamic properties of rare gas solids based on empirical and semi-empirical (ab initio) two-body potentials : a comparative study /

We study the phonon dispersion, cohesive and thermal properties of raxe gas solids Ne, Ar, Kr, and Xe, using a variety of potentials obtained from different approaches; such as, fitting to crystal properties, purely ab initio calculations for molecules and dimers or ab initio calculations for solid crystalline phase, a combination of ab initio calculations and fitting to either gas phase data or sohd state properties. We explore whether potentials derived with a certain approaxih have any obvious benefit over the others in reproducing the solid state properties. In particular, we study phonon dispersion, isothermal ajid adiabatic bulk moduli, thermal expansion, and elastic (shear) constants as a function of temperatiue. Anharmonic effects on thermal expansion, specific heat, and bulk moduli have been studied using A^ perturbation theory in the high temperature limit using the neaxest-neighbor central force (nncf) model as developed by Shukla and MacDonald [4]. In our study, we find that potentials based on fitting to the crystal properties have some advantage, particularly for Kr and Xe, in terms of reproducing the thermodynamic properties over an extended range of temperatiures, but agreement with the phonon frequencies with the measured values is not guaranteed. For the lighter element Ne, the LJ potential which is based on fitting to the gas phase data produces best results for the thermodynamic properties; however, the Eggenberger potential for Ne, where the potential is based on combining ab initio quantum chemical calculations and molecular dynamics simulations, produces results that have better agreement with the measured dispersion, and elastic (shear) values. For At, the Morse-type potential, which is based on M0ller-Plesset perturbation theory to fourth order (MP4) ab initio calculations, yields the best results for the thermodynamic properties, elastic (shear) constants, and the phonon dispersion curves.

Application of [Lambda] to the fourth perturbation theory in calculating the equation of state of rare gas solids and fcc metals

We have calculated the thermodynamic properties of monatomic fcc crystals from the high temperature limit of the Helmholtz free energy. This equation of state included the static and vibrational energy components. The latter contribution was calculated to order A4 of perturbation theory, for a range of crystal volumes, in which a nearest neighbour central force model was used. We have calculated the lattice constant, the coefficient of volume expansion, the specific heat at constant volume and at constant pressure, the adiabatic and the isothermal bulk modulus, and the Gruneisen parameter, for two of the rare gas solids, Xe and Kr, and for the fcc metals Cu, Ag, Au, Al, and Pb. The LennardJones and the Morse potential were each used to represent the atomic interactions for the rare gas solids, and only the Morse potential was used for the fcc metals. The thermodynamic properties obtained from the A4 equation of state with the Lennard-Jones potential, seem to be in reasonable agreement with experiment for temperatures up to about threequarters of the melting temperature. However, for the higher temperatures, the results are less than satisfactory. For Xe and Kr, the thermodynamic properties calculated from the A2 equation of state with the Morse potential, are qualitatively similar to the A 2 results obtained with the Lennard-Jones potential, however, the properties obtained from the A4 equation of state are in good agreement with experiment, since the contribution from the A4 terms seem to be small. The lattice contribution to the thermal properties of the fcc metals was calculated from the A4 equation of state, and these results produced a slight improvement over the properties calculated from the A2 equation of state. In order to compare the calculated specific heats and bulk moduli results with experiment~ the electronic contribution to thermal properties was taken into account~ by using the free electron model. We found that the results varied significantly with the value chosen for the number of free electrons per atom.

Molecular dynamics calculation of mean square displacement in alkali metals and rare gas solids and comparison with lattice dynamics

Molec ul ar dynamics calculations of the mean sq ua re displacement have been carried out for the alkali metals Na, K and Cs and for an fcc nearest neighbour Lennard-Jones model applicable to rare gas solids. The computations for the alkalis were done for several temperatures for temperature vol ume a swell as for the the ze r 0 pressure ze ro zero pressure volume corresponding to each temperature. In the fcc case, results were obtained for a wide range of both the temperature and density. Lattice dynamics calculations of the harmonic and the lowe s t order anharmonic (cubic and quartic) contributions to the mean square displacement were performed for the same potential models as in the molecular dynamics calculations. The Brillouin zone sums arising in the harmonic and the quartic terms were computed for very large numbers of points in q-space, and were extrapolated to obtain results ful converged with respect to the number of points in the Brillouin zone.An excellent agreement between the lattice dynamics results was observed molecular dynamics and in the case of all the alkali metals, e~ept for the zero pressure case of CSt where the difference is about 15 % near the melting temperature. It was concluded that for the alkalis, the lowest order perturbation theory works well even at temperat ures close to the melting temperat ure. For the fcc nearest neighbour model it was found that the number of particles (256) used for the molecular dynamics calculations, produces a result which is somewhere between 10 and 20 % smaller than the value converged with respect to the number of particles. However, the general temperature dependence of the mean square displacement is the same in molecular dynamics and lattice dynamics for all temperatures at the highest densities examined, while at higher volumes and high temperatures the results diverge. This indicates the importance of the higher order (eg. ~* ) perturbation theory contributions in these cases.

Pharmacometrics of neuromuscular blocking agents in anesthetized patients and animals : impact of dose and intravascular mixing phase

Thèse numérisée par la Division de la gestion de documents et des archives de l'Université de Montréal

Z-scan and Degenerate Four Wave Mixing Studies in Certain Photonic Materials

International School of Photonics, Cochin University of Science & Technology

Mathematical Modelling of the Dynamics of Granular Materials in a Rotating Cylinder

The current study is aimed at the development of a theoretical simulation tool based on Discrete Element Method (DEM) to 'interpret granular dynamics of solid bed in the cross section of the horizontal rotating cylinder at the microscopic level and subsequently apply this model to establish the transition behaviour, mixing and segregation.The simulation of the granular motion developed in this work is based on solving Newton's equation of motion for each particle in the granular bed subjected to the collisional forces, external forces and boundary forces. At every instant of time, the forces are tracked and the positions velocities and accelarations of each partcle is The software code for this simulation is written in VISUAL FORTRAN 90 After checking the validity of the code with special tests, it is used to investigate the transition behaviour of granular solids motion in the cross section of a rotating cylinder for various rotational speeds and fill fraction.This work is hence directed towards a theoretical investigation based on Discrete Element Method (DEM) of the motion of granular solids in the radial direction of the horizontal cylinder to elucidate the relationship between the operating parameters of the rotating cylinder geometry and physical properties ofthe granular solid.The operating parameters of the rotating cylinder include the various rotational velocities of the cylinder and volumetric fill. The physical properties of the granular solids include particle sizes, densities, stiffness coefficients, and coefficient of friction Further the work highlights the fundamental basis for the important phenomena of the system namely; (i) the different modes of solids motion observed in a transverse crosssection of the rotating cylinder for various rotational speeds, (ii) the radial mixing of the granular solid in terms of active layer depth (iii) rate coefficient of mixing as well as the transition behaviour in terms of the bed turnover time and rotational speed and (iv) the segregation mechanisms resulting from differences in the size and density of particles.The transition behaviour involving its six different modes of motion of the granular solid bed is quantified in terms of Froude number and the results obtained are validated with experimental and theoretical results reported in the literature The transition from slumping to rolling mode is quantified using the bed turnover time and a linear relationship is established between the bed turn over time and the inverse of the rotational speed of the cylinder as predicted by Davidson et al. [2000]. The effect of the rotational speed, fill fraction and coefficient of friction on the dynamic angle of repose are presented and discussed. The variation of active layer depth with respect to fill fraction and rotational speed have been investigated. The results obtained through simulation are compared with the experimental results reported by Van Puyvelde et. at. [2000] and Ding et at. [2002].The theoretical model has been further extended, to study the rmxmg and segregation in the transverse direction for different particle sizes and their size ratios. The effect of fill fraction and rotational speed on the transverse mixing behaviour is presented in the form of a mixing index and mixing kinetics curve. The segregation pattern obtained by the simulation of the granular solid bed with respect to the rotational speed of the cylinder is presented both in graphical and numerical forms. The segregation behaviour of the granular solid bed with respect to particle size, density and volume fraction of particle size has been investigated. Several important macro parameters characterising segregation such as mixing index, percolation index and segregation index have been derived from the simulation tool based on first principles developed in this work.