Advanced Reaction Systems for Hydrogen Production

[EN] This PhD work started in March 2010 with the support of the University of the Basque Country (UPV/EHU) under the program named “Formación de Personal Investigador” at the Chemical and Environmental Engineering Department in the Faculty of Engineering of Bilbao. The major part of the Thesis work was carried out in the mentioned department, as a member of the Sustainable Process Engineering (SuPrEn) research group. In addition, this PhD Thesis includes the research work developed during a period of 6 months at the Institut für Mikrotechnik Mainz GmbH, IMM, in Germany. During the four years of the Thesis, conventional and microreactor systems were tested for several feedstocks renewable and non-renewable, gases and liquids through several reforming processes in order to produce hydrogen. For this purpose, new catalytic formulations which showed high activity, selectivity and stability were design. As a consequence, the PhD work performed allowed the publication of seven scientific articles in peer-reviewed journals. This PhD Thesis is divided into the following six chapters described below. The opportunity of this work is established on the basis of the transition period needed for moving from a petroleum based energy system to a renewable based new one. Consequently, the present global energy scenario was detailed in Chapter 1, and the role of hydrogen as a real alternative in the future energy system was justified based on several outlooks. Therefore, renewable and non-renewable hydrogen production routes were presented, explaining the corresponding benefits and drawbacks. Then, the raw materials used in this Thesis work were described and the most important issues regarding the processes and the characteristics of the catalytic formulations were explained. The introduction chapter finishes by introducing the concepts of decentralized production and process intensification with the use of microreactors. In addition, a small description of these innovative reaction systems and the benefits that entailed their use were also mentioned. In Chapter 2 the main objectives of this Thesis work are summarized. The development of advanced reaction systems for hydrogen rich mixtures production is the main objective. In addition, the use and comparison between two different reaction systems, (fixed bed reactor (FBR) and microreactor), the processing of renewable raw materials, the development of new, active, selective and stable catalytic formulations, and the optimization of the operating conditions were also established as additional partial objectives. Methane and natural gas (NG) steam reforming experimental results obtained when operated with microreactor and FBR systems are presented in Chapter 3. For these experiments nickel-based (Ni/Al2O3 and Ni/MgO) and noble metal-based (Pd/Al2O3 and Pt/Al2O3) catalysts were prepared by wet impregnation and their catalytic activity was measured at several temperatures, from 973 to 1073 K, different S/C ratios, from 1.0 to 2.0, and atmospheric pressure. The Weight Hourly Space Velocity (WHSV) was maintained constant in order to compare the catalytic activity in both reaction systems. The results obtained showed a better performance of the catalysts operating in microreactors. The Ni/MgO catalyst reached the highest hydrogen production yield at 1073 K and steam-to-carbon ratio (S/C) of 1.5 under Steam methane Reforming (SMR) conditions. In addition, this catalyst also showed good activity and stability under NG reforming at S/C=1.0 and 2.0. The Ni/Al2O3 catalyst also showed high activity and good stability and it was the catalyst reaching the highest methane conversion (72.9 %) and H2out/CH4in ratio (2.4) under SMR conditions at 1073 K and S/C=1.0. However, this catalyst suffered from deactivation when it was tested under NG reforming conditions. Regarding the activity measurements carried out with the noble metal-based catalysts in the microreactor systems, they suffered a very quick deactivation, probably because of the effects attributed to carbon deposition, which was detected by Scanning Electron Microscope (SEM). When the FBR was used no catalytic activity was measured with the catalysts under investigation, probably because they were operated at the same WHSV than the microreactors and these WHSVs were too high for FBR system. In Chapter 4 biogas reforming processes were studied. This chapter starts with an introduction explaining the properties of the biogas and the main production routes. Then, the experimental procedure carried out is detailed giving concrete information about the experimental set-up, defining the parameters measured, specifying the characteristics of the reactors used and describing the characterization techniques utilized. Each following section describes the results obtained from activity testing with the different catalysts prepared, which is subsequently summarized: Section 4.3: Biogas reforming processes using γ-Al2O3 based catalysts The activity results obtained by several Ni-based catalysts and a bimetallic Rh-Ni catalyst supported on magnesia or alumina modified with oxides like CeO2 and ZrO2 are presented in this section. In addition, an alumina-based commercial catalyst was tested in order to compare the activity results measured. Four different biogas reforming processes were studied using a FBR: dry reforming (DR), biogas steam reforming (BSR), biogas oxidative reforming (BOR) and tri-reforming (TR). For the BSR process different steam to carbon ratios (S/C) from 1.0 to 3.0, were tested. In the case of BOR process the oxygen-to-methane (O2/CH4) ratio was varied from 0.125 to 0.50. Finally, for TR processes different S/C ratios from 1.0 to 3.0, and O2/CH4 ratios of 0.25 and 0.50 were studied. Then, the catalysts which achieved high activity and stability were impregnated in a microreactor to explore the viability of process intensification. The operation with microreactors was carried out under the best experimental conditions measured in the FBR. In addition, the physicochemical characterization of the fresh and spent catalysts was carried out by Inductively Coupled Plasma Atomic Emission Spectroscopy (ICP-AES), N2 physisorption, H2 chemisorption, Temperature Programmed Reduction (TPR), SEM, X-ray Photoelectron Spectroscopy (XPS) and X-ray powder Diffraction (XRD). Operating with the FBR, conversions close to the ones predicted by thermodynamic calculations were obtained by most of the catalysts tested. The Rh-Ni/Ce-Al2O3 catalyst obtained the highest hydrogen production yield in DR. In BSR process, the Ni/Ce-Al2O3 catalyst achieved the best activity results operating at S/C=1.0. In the case of BOR process, the Ni/Ce-Zr-Al2O3 catalyst showed the highest reactants conversion values operating at O2/CH4=0.25. Finally, in the TR process the Rh-Ni/Ce-Al2O3 catalyst obtained the best results operating at S/C=1.0 and O2/CH4=0.25. Therefore, these three catalysts were selected to be coated onto microchannels in order to test its performance under BOR and TR processes conditions. Although the operation using microreactors was carried out under considerably higher WHSV, similar conversions and yields as the ones measured in FBR were measured. Furthermore, attending to other measurements like Turnover Frequency (TOF) and Hydrogen Productivity (PROD), the values calculated for the catalysts tested in microreactors were one order of magnitude higher. Thus, due to the low dispersion degree measured by H2-chemisorption, the Ni/Ce-Al2O3 catalyst reached the highest TOF and PROD values. Section 4.4: Biogas reforming processes using Zeolites L based catalysts In this section three type of L zeolites, with different morphology and size, were synthesized and used as catalyst support. Then, for each type of L zeolite three nickel monometallic and their homologous Rh-Ni bimetallic catalysts were prepared by the wetness impregnation method. These catalysts were tested using the FBR under DR process and different conditions of BSR (S/C ratio of 1.0 and 2.0), BOR (O2/CH4 ratio of 0.25 and 0.50) and TR processes (at S/C=1.0 and O2/CH4=0.25). The characterization of these catalysts was also carried out by using the same techniques mentioned in the previous section. Very high methane and carbon dioxide conversion values were measured for almost all the catalysts under investigation. The experimental results evidenced the better catalytic behavior of the bimetallic catalysts as compared to the monometallic ones. Comparing the catalysts behavior with regards to their morphology, for the BSR process the Disc catalysts were the most active ones at the lowest S/C ratio tested. On the contrary, the Cylindrical (30–60 nm) catalysts were more active under BOR conditions at O2/CH4=0.25 and TR processes. By the contrary, the Cylindrical (1–3 µm) catalysts showed the worst activity results for both processes. Section 4.5: Biogas reforming processes using Na+ and Cs+ doped Zeolites LTL based catalysts A method for the synthesis of Linde Type L (LTL) zeolite under microwave-assisted hydrothermal conditions and its behavior as a support for heterogeneously catalyzed hydrogen production is described in this section. Then, rhodium and nickel-based bimetallic catalysts were prepared in order to be tested by DR process and BOR process at O2/CH4=0.25. Moreover, the characterization of the catalysts under investigation was also carried out. Higher activities were achieved by the catalysts prepared from the non-doped zeolites, Rh-Ni/D and Rh-Ni/N, as compared to the ones supported on Na+ and Cs+ exchanged supports. However, the differences between them were not very significant. In addition, the Na+ and Cs+ incorporation affected mainly to the Disc catalysts. Comparing the results obtained by these catalysts with the ones studied in the section 4.4, in general worst results were achieved under DR conditions and almost the same results when operated under BOR conditions. In Chapter 5 the ethylene glycol (EG) as feed for syngas production by steam reforming (SR) and oxidative steam reforming (OSR) was studied by using microchannel reactors. The product composition was determined at a S/C of 4.0, reaction temperatures between 625°C and 725°C, atmospheric pressure and Volume Hourly Space Velocities (VHSV) between 100 and 300 NL/(gcath). This work was divided in two sections. The first one corresponds to the introduction of the main and most promising EG production routes. Then, the new experimental procedure is detailed and the information about the experimental set-up and the measured parameters is described. The characterization was carried out using the same techniques as for the previous chapter. Then, the next sections correspond to the catalytic activity and catalysts characterization results. Section 5.3: xRh-cm and xRh-np catalysts for ethylene glycol reforming Initially, catalysts with different rhodium loading, from 1.0 to 5.0 wt. %, and supported on α-Al2O3 were prepared by two different preparation methods (conventional impregnation and separate nanoparticle synthesis). Then, the catalysts were compared regarding their measured activity and selectivity, as well as the characterization results obtained before and after the activity tests carried out. The samples prepared by a conventional impregnation method showed generally higher activity compared to catalysts prepared from Rh nanoparticles. By-product formation of species such as acetaldehyde, ethane and ethylene was detected, regardless if oxygen was added to the feed or not. Among the catalysts tested, the 2.5Rh-cm catalyst was considered the best one. Section 5.4: 2.5Rh-cm catalyst support modification with CeO2 and La2O3 In this part of the Chapter 5, the catalyst showing the best performance in the previous section, the 2.5Rh-Al2O3 catalyst, was selected in order to be improved. Therefore, new Rh based catalysts were designed using α-Al2O3 and being modified this support with different contents of CeO2 or La2O3 oxides. All the catalysts containing additives showed complete conversion and selectivities close to the equilibrium in both SR and OSR processes. In addition, for these catalysts the concentrations measured for the C2H4, CH4, CH3CHO and C2H6 by-products were very low. Finally, the 2.5Rh-20Ce catalyst was selected according to its catalytic activity and characterization results in order to run a stability test, which lasted more than 115 hours under stable operation. The last chapter, Chapter 6, summarizes the main conclusions achieved throughout this Thesis work. Although very high reactant conversions and rich hydrogen mixtures were obtained using a fixed bed reaction system, the use of microreactors improves the key issues, heat and mass transfer limitations, through which the reforming reactions are intensified. Therefore, they seem to be a very interesting and promising alternative for process intensification and decentralized production for remote application.

New (1R,4R)-2-arylidene-p-menthan-3-ones with a bridging ester group in the arylidene fragment. Synthesis and behavior in liquid-crystalline systems

(1R,4R)-2-(4-Hydroxybenzylidene)- and (1R,4R)-2-(4′-hydroxybiphenyl- 4-yl)methylene-p-menthan-3-ones were synthesized by condensation of (-)-menthone with O-tetrahydropyran-2-yl derivatives of 4-hydroxybenzaldehyde and 4′-hydroxy-4-formylbiphenyl, respectively, in a DMSO - base medium followed by the removal of the protective group. The reactions of these hydroxy derivatives with 4-alkylbenzoic, 4-alkyloxybenzoic, trans-4-alkylcyclohexane-4- carboxylic, and 4′-alkylbiphenyl-4-carboxylic acids afforded three series of new chiral esters. Compounds containing the arylidene moiety with three benzene rings were found to exhibit liquid-crystalline properties. The characteristic features of these compounds are discussed based on the results of studies by polarizing microscopy, differential scanning calorimetry, and small-angle X-ray scattering. It was found that the mesomorphic compounds under study can form a smectic A mesophase, twist grain boundary mesophases (TGBA), and blue phases in a wide temperature range. Upon dissolution of certain of chiral compounds in 4′-cyano-4-pentylbiphenyl, a rather high twisting power and the thermal stabilizing effect on mesophases were observed.

The application of STEM and in situ controlled dehydration to bacterial systems using ESEM.

Transmission imaging with an environmental scanning electron microscope (ESEM) (Wet STEM) is a recent development in the field of electron microscopy, combining the simple preparation inherent to ESEM work with an alternate form of contrast available through a STEM detector. Because the technique is relatively new, there is little information available on how best to apply this technique and which samples it is best suited for. This work is a description of the sample preparation and microscopy employed by the authors for imaging bacteria with Wet STEM (scanning transmission electron microscopy). Three different bacterial samples will be presented in this study: first, used as a model system, is Escherichia coli for which the contrast mechanisms of STEM are demonstrated along with the visual effects of a dehydration-induced collapse. This collapse, although clearly in some sense artifactual, is thought to lead to structurally meaningful morphological information. Second, Wet STEM is applied to two distinct bacterial systems to demonstrate the novel types of information accessible by this approach: the plastic-producing Cupriavidus necator along with wild-type and ΔmreC knockout mutants of Salmonella enterica serovar Typhimurium. Cupriavidus necator is shown to exhibit clear internal differences between bacteria with and without plastic granules, while the ΔmreC mutant of S. Typhimurium has an internal morphology distinct from that of the wild type.

The application of STEM and in situ controlled dehydration to bacterial systems using ESEM

Transmission imaging with an environmental scanning electron microscope (ESEM) (Wet STEM) is a recent development in the field of electron microscopy, combining the simple preparation inherent to ESEM work with an alternate form of contrast available through a STEM detector. Because the technique is relatively new, there is little information available on how best to apply this technique and which samples it is best suited for. This work is a description of the sample preparation and microscopy employed by the authors for imaging bacteria with Wet STEM (scanning transmission electron microscopy). Three different bacterial samples will be presented in this study: first, used as a model system, is Escherichia coli for which the contrast mechanisms of STEM are demonstrated along with the visual effects of a dehydration-induced collapse. This collapse, although clearly in some sense artifactual, is thought to lead to structurally meaningful morphological information. Second, Wet STEM is applied to two distinct bacterial systems to demonstrate the novel types of information accessible by this approach: the plastic-producing Cupriavidus necator along with wild-type and δmreC knockout mutants of Salmonella enterica serovar Typhimurium. Cupriavidus necator is shown to exhibit clear internal differences between bacteria with and without plastic granules, while the δmreC mutant of S. Typhimurium has an internal morphology distinct from that of the wild type. © 2012 Wiley Periodicals, Inc.

Luminescence functionalization of mesoporous silica with different morphologies and applications as drug delivery systems

Ordered mesoporous silica (MCM-41) particles with different morphologies were synthesized through a simple hydrothermal process. Then these silica particles were functionalized with luminescent YVO4:EU3+ layers via the Pechini sol-gel process. The obtained YVO4:Eu3+ and MCM-41 composites, which maintained the mesoporous structure of MCM-41 and the red luminescence property of YVO4:Eu3+ were investigated as drug delivery systems using ibuprofen (IBU) as model drug. The physicochemical properties of the samples were characterized by X-ray diffraction (XRD), Fourier transform-infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), N-2 adsorption, and photoluminescence (PL) spectra, respectively.

Investigation of facilitated ion-transfer reactions at high driving force by scanning electrochemical Microscopy

The kinetics of facilitated ion-transfer (FIT) reactions at high driving force across the water/1,2-dichloroethane (W/DCE) interface is investigated by scanning electrochemical microscopy (SECM). The transfers of lithium and sodium ions facilitated by dibenzo-18-crown-6 (DB18C6) across the polarized W/DCE interface are chosen as model systems because they have the largest potential range that can be controlled externally. By selecting the appropriate ratios of the reactant concentrations (Kr c(M)+/c(DB18C6)) and using nanopipets as the SECM tips, we obtained a series of rate constants (k(f)) at various driving forces (Delta(O)(W) phi(ML+)(0') - Es, Delta(O)(W) phi(ML+)(0') is the formal potential of facilitated ion transfer and Es is the potential applied externally at the substrate interface) based on a three-electrode system. The FIT rate constants k(f) are found to be dependent upon the driving force. When the driving force is low, the dependence of 1n k(f) on the driving force is linear with a transfer coefficient of about 0.3. It follows the classical Butler-Volmer theory and then reaches a maximum before it decreases again when we further increase the driving forces. This indicates that there exists an inverted region, and these behaviors have been explained by Marcus theory.

In situ scanning tunneling microscopy studies of nanometer size palladium particles on highly oriented pyrolytic graphite

A special electrodeposition process of palladium was studied by cyclic voltammetry, X-ray photoelectron spectroscopy (XPS) and in situ scanning tunneling microscopy (STM). A kind of palladium(IV) complex was attached to the highly oriented pyrolytic graphite (HOPG) electrode surface by electro-oxidation of palladium(II) complex first, and was then reduced to palladium particles. The surface complexes and particles of palladium were both characterized by in situ STM and XPS. The Pd particles are in the nanometer range of size and exhibit electrocatalytic activity towards the oxidation of hydrazine and hydroxylamine.

A DIFFERENTIAL SCANNING CALORIMETRY STUDY OF PLASMA IRRADIATION GRAFTING OF NASCENT POLYETHYLENE REACTOR POWDER

The melting behavior of poly(methyl methacrylate)-grafted nascent polyethylene reactor powder by plasma irradiation was studied by differential scanning calorimetry (DSC). The grafting yield ranged hom 11 to 190%. Grafting was found to lower both melting point and heat of fusion during the first run of DSC determination. The heat of fusion was used to calculate the apparent grafting yield of the samples. There was little strain induced by plasma-irradiated grafting on the surface of the polyethylene crystals. A method to determine the covalent grafting yield in the graft copolymer systems was developed. (C) 1995 John Wiley & Sons, Inc.

SCANNING ACOUSTIC MICROSCOPE FOR CHARACTERIZATION OF ARTERIAL PLAQUE

Unstable arterial plaque is likely the key component of atherosclerosis, a disease which is responsible for two-thirds of heart attacks and strokes, leading to approximately 1 million deaths in the United States. Ultrasound imaging is able to detect plaque but as of yet is not able to distinguish unstable plaque from stable plaque. In this work a scanning acoustic microscope (SAM) was implemented and validated as tool to measure the acoustic properties of a sample. The goal for the SAM is to be able to provide quantitative measurements of the acoustic properties of different plaque types, to understand the physical basis by which plaque may be identified acoustically. The SAM consists of a spherically focused transducer which operates in pulse-echo mode and is scanned in a 2D raster pattern over a sample. A plane wave analysis is presented which allows the impedance, attenuation and phase velocity of a sample to be de- termined from measurements of the echoes from the front and back of the sample. After the measurements, the attenuation and phase velocity were analysed to ensure that they were consistent with causality. The backscatter coefficient of the samples was obtained using the technique outlined by Chen et al [8]. The transducer used here was able to determine acoustic properties from 10-40 MHz. The results for the impedance, attenuation and phase velocity were validated for high and low-density polyethylene against published results. The plane wave approximation was validated by measuring the properties throughout the focal region and throughout a range of incidence angles from the transducer. The SAM was used to characterize a set of recipes for tissue-mimicking phantoms which demonstrate indepen- dent control over the impedance, attenuation, phase velocity and backscatter coefficient. An initial feasibility study on a human artery was performed.

Component Neural Systems for the Creation of Emotional Memories during Free Viewing of a Complex, Real-World Event.

To investigate the neural systems that contribute to the formation of complex, self-relevant emotional memories, dedicated fans of rival college basketball teams watched a competitive game while undergoing functional magnetic resonance imaging (fMRI). During a subsequent recognition memory task, participants were shown video clips depicting plays of the game, stemming either from previously-viewed game segments (targets) or from non-viewed portions of the same game (foils). After an old-new judgment, participants provided emotional valence and intensity ratings of the clips. A data driven approach was first used to decompose the fMRI signal acquired during free viewing of the game into spatially independent components. Correlations were then calculated between the identified components and post-scanning emotion ratings for successfully encoded targets. Two components were correlated with intensity ratings, including temporal lobe regions implicated in memory and emotional functions, such as the hippocampus and amygdala, as well as a midline fronto-cingulo-parietal network implicated in social cognition and self-relevant processing. These data were supported by a general linear model analysis, which revealed additional valence effects in fronto-striatal-insular regions when plays were divided into positive and negative events according to the fan's perspective. Overall, these findings contribute to our understanding of how emotional factors impact distributed neural systems to successfully encode dynamic, personally-relevant event sequences.

Differential scanning calorimetry in life science: thermodynamics, stability, molecular recognition and application in drug design

All biological phenomena depend on molecular recognition, which is either intermolecular like in ligand binding to a macromolecule or intramolecular like in protein folding. As a result, understanding the relationship between the structure of proteins and the energetics of their stability and binding with others (bio)molecules is a very interesting point in biochemistry and biotechnology. It is essential to the engineering of stable proteins and to the structure-based design of pharmaceutical ligands. The parameter generally used to characterize the stability of a system (the folded and unfolded state of the protein for example) is the equilibrium constant (K) or the free energy (deltaG(o)), which is the sum of enthalpic (deltaH(o)) and entropic (deltaS(o)) terms. These parameters are temperature dependent through the heat capacity change (deltaCp). The thermodynamic parameters deltaH(o) and deltaCp can be derived from spectroscopic experiments, using the van't Hoff method, or measured directly using calorimetry. Along with isothermal titration calorimetry (ITC), differential scanning calorimetry (DSC) is a powerful method, less described than ITC, for measuring directly the thermodynamic parameters which characterize biomolecules. In this article, we summarize the principal thermodynamics parameters, describe the DSC approach and review some systems to which it has been applied. DSC is much used for the study of the stability and the folding of biomolecules, but it can also be applied in order to understand biomolecular interactions and can thus be an interesting technique in the process of drug design.

Characterisation of freeze-dried wafers and solvent evaporated films as potential drug delivery systems to mucosal surfaces

Freeze-dried (lyophilised) wafers and solvent cast films from sodium alginate (ALG) and sodium carboxymethylcellulose (CMC) have been developed as potential drug delivery systems for mucosal surfaces including wounds. The wafers (ALG, CMC) and films (CMC) were prepared by freeze-drying and drying in air (solvent evaporation) respectively, aqueous gels of the polymers containing paracetamol as a model drug. Microscopic architecture was examined using scanning electron microscopy, hydration characteristics with confocal laser scanning microscopy and dynamic vapour sorption. Texture analysis was employed to investigate mechanical characteristics of the wafers during compression. Differential scanning calorimetry was used to investigate polymorphic changes of paracetamol occurring during formulation of the wafers and films. The porous freeze-dried wafers exhibited higher drug loading and water absorption capacity than the corresponding solvent evaporated films. Moisture absorption, ease of hydration and mechanical behaviour were affected by the polymer and drug concentration. Two polymorphs of paracetamol were observed in the wafers and films, due to partial conversion of the original monoclinic to the orthorhombic polymorph during the formulation process. The results showed the potential of employing the freeze-dried wafers and solvent evaporated films in diverse mucosal applications due to their ease of hydration and based on different physical mechanical properties exhibited by both type of formulations.

An investigation into the subambient behavior of aqueous mannitol solutions using differential scanning calorimetry, cold stage microscopy, and X-ray diffractometry

The subambient behavior of aqueous mannitol solutions is of considerable relevance to the preparation of freeze dried formulations. In this investigation the properties of 3% w/v mannitol solutions were investigated using differential scanning calorimetry (DSC), cold stage microscopy (CSM), and X-ray diffraction (XRD) to identify the thermal transitions and structural transformations undergone by this system. It was found that on cooling from ambient the system formed ice at circa -20°C while a further exotherm was seen at approximately -30°C. Upon reheating an endotherm was seen at circa -30°C followed immediately by an exotherm at circa -25°C. Temperature cycling indicated that the thermal transitions observed upon reheating were not reversible. Modulated temperature DSC (MTDSC) indicated that the transitions observed upon reheating corresponded to a glass transition immediately followed by recrystallization, XRD data showed that recrystallization was into the ß form. Annealing at -35°C for 40 min prior to cooling and reheating resulted in a maximum enthalpy being observed for the reheating exotherm. It is concluded that on cooling 3% w/v aqueous mannitol solutions an amorphous phase is formed that subsequently recrystallises into the ß form. The study has also shown that DSC, CSM, and XRD are useful complementary techniques for the study of frozen systems

Differential Scanning Calorimetry Study and Computer Modeling of b a Phase Transformation in Ti-6Al-4V Alloy

The relationship between heat-treatment parameters and microstructure in titanium alloys has so far been mainly studied empirically, using characterization techniques such as microscopy. Calculation and modeling of the kinetics of phase transformation have not yet been widely used for these alloys. Differential scanning calorimetry (DSC) has been widely used for the study of a variety of phase transformations. There has been much work done on the calculation and modeling of the kinetics of phase transformations for different systems based on the results from DSC study. In the present work, the kinetics of the transformation in a Ti-6Al-4V titanium alloy were studied using DSC, at continuous cooling conditions with constant cooling rates of 5 °C, 10 °C, 20 °C, 30 °C, 40 °C, and 50 °C/min. The results from calorimetry were then used to trace and model the transformation kinetics in continuous cooling conditions. Based on suitably interpreted DSC results, continuous cooling–transformation (CCT) diagrams were calculated with lines of isotransformed fraction. The kinetics of transformation were modeled using the Johnson–Mehl–Avrami (JMA) theory and by applying the "concept of additivity." The JMA kinetic parameters were derived. Good agreement between the calculated and experimental transformed fractions is demonstrated. Using the derived kinetic parameters, the transformation in a Ti-6Al-4V alloy can be described for any cooling path and condition. An interpretation of the results from the point of view of activation energy for nucleation is also presented.