Composition Of Liquid Phase Research Articles

Hydrogen production and elemental migration during supercritical water gasification of food waste digestate

The rapid growth of food waste (FW) is a huge challenge on a global scale, and anaerobic digestion is one of the most commonly used methods to deal with food waste, and the increasing amount of food waste digestate (FWD) produced by anaerobic digestion also poses a huge challenge to waste management. This paper explores supercritical water gasification (SCWG) as a valuable and innovative strategy for the conversion of FWD into H2-rich syngas. The research focuses on analyzing the effects of reaction temperature and residence time on syngas production, gas composition, element migration (C, N and P) during the SCWG process. Experimental results show that as the reaction temperature increases from 400 °C to 500 °C, the total syngas yield increases significantly, from 2.4 mol/kg to 9.7 mol/kg, especially the yields of H2, CO2, and CH4. As the reaction temperature increases and the residence time increases, the migration of carbon from the solid and liquid phases to the gas phase accelerates with increasing temperature and residence time, resulting in a higher proportion of carbon in the gas phase. In terms of liquid phase composition, nitrogenous compounds are significantly converted into ammonium (NH4+-N) at higher temperatures. In addition, the organic phosphorus is observed transferring into inorganic phosphorus, which are mainly apatite. This study explores the scalability of SCWG and its potential for the production of clean fuels, thereby contributing to the sustainable management of FWD.

Thermophysical Properties of the Hydrogen Carrier System Based on Aqueous Solutions of Isopropanol or Acetone

One concept for the safe storage and transport of molecular hydrogen (H2) is the use of hydrogen carrier systems which can bind and release hydrogen in repeating cycles. In this context, the liquid system based on isopropanol and its dehydrogenated counterpart acetone is particularly interesting for applications in direct isopropanol fuel cells that are operated with an excess of water. For a comprehensive characterization of diluted aqueous solutions of isopropanol or acetone with technically relevant solute amount fractions between 0.02 and 0.08, their liquid density, liquid viscosity, and interfacial tension were investigated using various light scattering and conventional techniques as well as equilibrium molecular dynamics (EMD) simulations between (283 and 403) K. Polarization-difference Raman spectroscopy (PDRS) was used to monitor the liquid-phase composition during surface light scattering (SLS) experiments on viscosity and interfacial tension. For comparison purposes and to expand the database, capillary viscometry and dynamic light scattering (DLS) from bulk fluids with dispersed particles were also applied to determine the viscosity while the pendant-drop (PD) method allowed access to the interfacial tension. By adding isopropanol or acetone to water, density and, in particular, interfacial tension decrease significantly, while viscosity shows a pronounced increase. The behavior of viscosity and interfacial tension is closely related to the strong hydrogen bonding between the unlike mixture components and the pronounced enrichment of both solutes at the vapor–liquid interface, as revealed by EMD simulations. For an aqueous solution with an isopropanol amount fraction of 0.04, minor variations in interfacial tension and viscosity were found in the presence of pressurized H2 up to 7.5 MPa. Overall, the results from this study contribute to an extended database for diluted aqueous solutions of isopropanol or acetone, especially at temperatures above 323 K.

Versatility of the Templated Surface Assembly of Nanoparticles from Water-in-Oil Microemulsions in Equivalent Hybrid Nanostructured Films.

Water-in-oil microemulsions, as stable colloidal dispersions from quasi-ternary mixtures, have been used in diverse applications, including nanoreactors for confined chemical processes. Their use as soft templates not only includes nanomaterial synthesis but also the interfacial assembly of nanoparticles in hybrid nanostructures. Especially the hierarchical arrangement of different types of nanoparticles over a surface in filament networks constitutes an interesting bottom-up strategy for facile and tunable film coating. Herein, we demonstrate the versatility of this surface assembly from microemulsion dispersions. Transmission and Scanning Electron Microscopy, in addition to UV-Vis Transmittance Spectroscopy, proved the assembly tunability after solvent evaporation under different conditions: the nanostructured films can be formed over different surfaces, using different compositions of liquid phases, as well as with the incorporation of different nanoparticle materials while keeping equivalent surface functionalization. This offers the possibility of adapting different components and conditions for coating tuning on a larger scale with simple procedures.

Experimental Study on the Impact of Sorption-Desorption on Nitrate Isotopes

Nitrate pollution is a global environmental problem, and mean nitrate levels have risen by an estimated 36% in global waterways since 1990. Tracing nitrate sources is important for water quality management, and nitrate isotopes (δ15N-NO3− and δ18O-NO3−) are commonly used for this purpose because of the different isotopic compositions of different sources. However, the impact of nitrate sorption on matrix and desorption from matrix on N and O isotopic composition of nitrate in liquid phase has not been well clarified. To explore the mechanism for the changes in nitrate concentration and isotopes in liquid phase during sorption and desorption, this study took a shale sample (enriched in clay minerals and commonly exposed in the Earth), conducted a series of laboratory experiments for nitrate sorption and desorption, and studied the impact of sorption and desorption on nitrate N and O isotopic composition in liquid phase. The results showed that the shale sample exhibited a rapid sorption and desorption rate for nitrate in the surface water samples, with the nitrate concentration in the solution decreasing from 14.3 mg/L to 4.1 mg/L within 5 min. The sorption data fit the Langmuir model better than that of the Freundlich model. The maximum possible sorption (Qmax) for the shale sample was estimated to be 46 μg/g. Preliminary laboratory experiments showed that changes in δ15N-NO3− values were not obvious, and changes in δ18O-NO3− values in liquid phase were minor during sorption and desorption of the shale sample, suggesting that nitrogen isotopic fractionation can be neglected, and the sorption of nitrate by the shale sample has a very limited impact on the distribution of nitrate isotopes in liquid phase. However, the impact of nitrate desorption on the nitrate isotopes in liquid phase depends on the isotopic composition of exchangeable nitrate in the solid phase, which may be related to antecedent water–rock interactions. This study provides important information for elucidating the evolution mechanism of nitrate and its isotopic compositions following sorption-desorption, and is conducive to revealing the nitrogen cycle law in the environment.

Effect of dissolved KOH and NaCl on the solubility of water in hydrogen: A Monte Carlo simulation study.

Vapor-Liquid Equilibria (VLE) of hydrogen (H2) and aqueous electrolyte (KOH and NaCl) solutions are central to numerous industrial applications such as alkaline electrolysis and underground hydrogen storage. Continuous fractional component Monte Carlo simulations are performed to compute the VLE of H2 and aqueous electrolyte solutions at 298-423K, 10-400bar, 0-8 molKOH/kg water, and 0-6 molNaCl/kg water. The densities and activities of water in aqueous KOH and NaCl solutions are accurately modeled (within 2% deviation from experiments) using the non-polarizable Madrid-2019 Na+/Cl- ion force fields for NaCl and the Madrid-Transport K+ and Delft Force Field of OH- for KOH, combined with the TIP4P/2005 water force field. A free energy correction (independent of pressure, salt type, and salt molality) is applied to the computed infinite dilution excess chemical potentials of H2 and water, resulting in accurate predictions (within 5% of experiments) for the solubilities of H2 in water and the saturated vapor pressures of water for a temperature range of 298-363K. The compositions of water and H2 are computed using an iterative scheme from the liquid phase excess chemical potentials and densities, in which the gas phase fugacities are computed using the GERG-2008 equation of state. For the first time, the VLE of H2 and aqueous KOH/NaCl systems are accurately captured with respect to experiments (i.e., for both the liquid and gas phase compositions) without compromising the liquid phase properties or performing any refitting of force fields.

Influence of Na-Al phosphate glass leachates in clays sorption behavior toward radionuclides

The article presents the results of the study of the sorption of 90Sr, 137Cs, 233U, 237Np, 239Pu,and 241Am radionuclides from model groundwater, model leachate of aluminophosphate glass and Na2HPO4 solutions of different concentrations on bentonite clays of Kamalinskoye (Krasnoyarsk Territory), Desyaty Khutor (Republic of Khakassia), and Dinozavrovoye (Republic of Kazakhstan) deposits. We determined that the presence of aluminophosphate glass leachate in the liquid phase reduced the sorption activity of the studied clays towards caesium. The distribution coefficients of strontium depend more on the clay properties than on the liquid phase composition. However, with increasing concentration of phosphate ion, we observed an increase in the strength of sorbed strontium retention by clay. The sorption of uranium, neptunium, plutonium and americium, increased in the presence of components leached from the aluminophosphate glass-like matrix, and the strength of their fixation by clay increased.

Phase behavior of sodium and potassium salts in their aqueous solutions: Experiment and computational thermodynamics

AbstractWith the rapid development of the semiconductor industry, the demand for ultraclean and high‐purity electronic chemicals, especially ultrapure water as a general solvent for cleaning semiconductor chips, has increased dramatically. The distillation process is a good choice for large‐scale production of ultrapure water that can be used to clean semiconductor chips, but there is a lack of basic thermodynamic theory for removing ionic impurities. In this work, the temperature and vapor–liquid phase composition of sodium and potassium salts aqueous solutions at vapor–liquid equilibrium (VLE) were investigated by experiments. The microstructure of each inorganic salt aqueous solution was explored by molecular dynamics simulation and quantum chemical calculation, and the interaction between each ion and water molecule was analyzed. A volatilization mechanism of inorganic salts was proposed, and it was found that the volatilization of inorganic salts in an aqueous solution was affected by the strength of interaction between the dissociated anions and cations and water molecules. Finally, the conductor‐like screening model segment activity coefficient (COSMO‐SAC) model predicted the VLE values of inorganic salt aqueous solutions. The prediction at low concentrations (xs < 0.06) was in good agreement with the experimental data.

Method validation of an inductive measurement system (IMS) for nanoscale zero-valent iron (nZVI) particles determination in sand-packed columns

The purpose of this work was to develop and validate a rapid, non-destructive, real-time measurement system for nanoscale zero-valent iron (nZVI) particles determination in sand-packed columns. This aims to provide an approach to analyse for nZVI particle transport and nZVI induced contaminant degradation reactions in 1-dimensional aquifer experiments. The inductive measurement system (IMS) was developed and tested by measuring columns filled with varying portions of nZVI and sandy aquifer material. Method validation was conducted for this innovative approach in accordance with several guidelines in disciplinary areas. The linearity of ZVI concentration and measurement signal was confirmed. Calibration curves were determined to be linear over the range of 0.11–53.50 g/L for nZVI NANOFER STAR, 0.10–81.67 g/L for nZVI BASF 1, 0.12–58.26 g/L for nZVI Carbo-Iron, 0.12–69.70 g/L for nZVI NANOFER 25DS ORM, 0.12–50.69 g/L for nZVI NANOFER 25DS, and 0.21–1613.39 g/L for nZVI Höganäs 1* (dry). This method was determined to be sensitive in nZVI, accurate (101.63 % within-run recovery, 101.85 % between-run recovery covering 76 days), and precise (0.46 % repeatability RSD, 0.85 % intermediate precision RSD covering 76 days). LOQ was determined ranging from 0.10 to 0.21 g/L for nZVI used in experiments and regression through origins was selected as the calibration model. Quality control processes were performed to assure the reliability of the results and the long-term stability. Additional data processing steps allowed to compensate for measurement deviations resulting from different liquid phase compositions, e.g. dispersants used for nZVI suspensions. This method is now successfully validated in single-laboratory conditions.

Thermodynamic Characteristics and Selectivity of the Liquid-Phase Adsorption of Aromatic Compounds on Hypercrosslinked Polystyrene Networks with Ultimate-High Crosslinking Densities by Data of Liquid Chromatography.

This study delves into the thermodynamics of liquid-phase adsorption on hypercrosslinked polystyrene networks (HPSNs), widely recognized for their distinct structure and properties. Despite the considerable progress in HPSN synthesis and characterization, gaps persist regarding the chromatographic retention mechanism, thermodynamics of adsorption, and their impact on the adsorption selectivity, especially in the case of networks with ultra-high crosslinking densities (up to 500%). Utilizing high-performance liquid chromatography (HPLC), we have explored, for the first time, the thermodynamic intricacies of liquid-phase adsorption onto HPSNs crosslinked in the entire range of the crosslinking degree from 100 to 500%. Our findings reveal the dependences of thermodynamic characteristics and selectivity of adsorption on the crosslinking degree, textural features, and liquid-phase composition in the region of extremely low adsorbent surface coverages (Henry's range). We have detected that, in the case of HPSNs, the dependence of the thermodynamic characteristics of adsorption on the liquid-phase composition is different than for classical HPLC stationary phases. Moreover, we scrutinize the impact of the molecular structure of the studied aromatic compounds on the thermodynamic characteristics and selectivity of the liquid-phase adsorption on HPSNs. Investigating liquid-phase adsorption selectivity, we demonstrate the pivotal role of π-π interactions in separating aromatic compounds on HPSNs. Eventually, we unveil that the thermodynamic characteristics of adsorption peculiarly depend on the crosslinking degree due to the profound impact of the crosslinking on the electronic density in benzene rings in HPSNs, whereas the separation throughput peaks for the polymer with a 500% crosslinking degree, attributed to its exceptionally rigid network structure, moderate swelling and micropore volume, and minimum specific surface area.

A LOGICAL AND MATHEMATICAL MODEL OF THE PHASE EQUILIBRIUM MODELING AND ITS APPLICATION AS A TECHNOLOGICAL INNOVATION BY EXAMPLE OF THE TRIGLYCERIDE MATERIALS TRANSFORMATION INTO FATTY ACID ESTERS

This study was conducted in order to create a logical and mathematical model for the production of fatty acid esters from triglyceride raw materials, based on methods adapted to appropriate systems and ultimately aimed at solving problems of improving the quality of products, creating flexible technological schemes focused on a variety of raw materials and products, without time-consuming and lengthy experiments. The logical-mathematical model is based on the UNIFAC calculation model in a modified form, which provides data calculation adequate to the experiment. The modified UNIFAC model is confirmed by a set of experimental data, the calculation of technological parameters shows acceptability in predicting the optimal technological conditions of the processes used. The possibility of achieving compliance with the calculated experimental data is shown by examples of using the model in solving problems during the development of multi-stage extraction of free fatty acids from triglyceride raw materials when evaluating the composition of raw materials and liquid phases in extraction systems at different stages of the extraction process, as well as the obtained products using the gas chromatography method. The generalized data are presented in the form of a logical and mathematical model that describes the system of using the calculated data necessary for the production process. The logical-mathematical model takes into account several alternative variants of the technology, includes criteria by which the choice of a variant of the technological process takes place. The results obtained represent an important stage in the development of digital production technologies and experience in the development of technological innovations. The above model becomes the basis for transferring the technology of transformation of triglyceride raw materials into fatty acid esters to an innovative level, which lays the foundation for creating a cyber-physical system combining the work of a process engineer and a digital system.

Liquid-liquid phase of imidazolium-based ionic liquids in n-butyl acetate + n-butanol mixtures: Experimental measurements, quality testing, phase stability, thermodynamic modeling

The ester n-butyl acetate is an important chemical compound produced by esterification with n-butanol and used as solvent for pigments, vegetable oils and fats, and in the production of varnishes, coatings, waxes and resins. This work investigated the use of ionic liquids (ILs) as solvents in separation processes involving these substances. The ionic liquid 1-butyl-3-methylimidazolium chloride ([BMIM][Cl]) was synthesized, while 1-ethyl-3-methylimidazolium ethyl sulfate ([EMIM][EtSO4]) and 1-ethyl-3-methylimidazolium tetrafluoroborate ([EMIM][BF4]) were purchased. The liquid–liquid equilibrium (LLE) was analyzed based on the experimental measurements (binodal curve, tie-lines), σ-profiles analysis (COSMOTherm), experimental data quality tests, phase stability and thermodynamic modeling with NRTL for the n-butyl acetate + n-butanol + IL ([BMIM][Cl], [EMIM][EtSO4], [EMIM][BF4]) systems at 298.15 K and 101.3 kPa. Experimental results indicated that the studied systems had the LLE phase behavior of type I. Experiments and calculations showed that [EMIM][EtSO4] and [BMIM][Cl] had the best capacities to separate the azeotrope n-butanol and n-butyl acetate. All systems showed separation factors values higher than unity. Low deviations, in the compositions of both liquid phases, indicate that the NRTL model was able to analyze the phase stability and model the phase behavior of the n-butyl acetate + n-butanol + IL systems using gamma-gamma approach.

The phase behavior of Isopropanol/Water/NaCl mixtures at atmospheric pressure and temperatures from 294.15 K up to the boiling point

Branched-chain higher alcohols (BCHAs) have potential applications in the preparation of biofuels as they have properties similar to those of gasoline. Isopropanol is the simplest member of the BCHA family and is produced by either a catalytic process or fermentation of biomass. Regardless of the process, the isopropanol is produced as a component of a mixture with water content as high as 80%; therefore, purification is needed to produce fuel-grade isopropanol. Azeotropic and heteroazeotropic distillation are currently used to purify the isopropanol but they are carbon-intensive and costly. The addition of NaCl to an isopropanol/water mixture has two effects: could trigger a liquid–liquid phase split; and increases the relative volatility of the alcohol. These effects could potentially be used as the departure for the design of low-carbon and less expensive purification operations.The phase behavior of isopropanol/water/NaCl mixtures was experimentally mapped at temperatures up to the boiling point at atmospheric pressure. The liquid–solid, liquid–liquid, liquid–liquid–solid, liquid–vapor, liquid–liquid–vapor, liquid–liquid–solid–vapor and liquid–solid–vapor regions were experimentally detected and located in the phase diagram. The equilibrium compositions within the liquid–liquid, liquid–vapor and liquid–liquid–solid–vapor regions were measured. Three well-known methods were employed to assess the reliability of the measured liquid–liquid phase compositions. The temperatures and the composition of the vapor phase in the liquid–liquid–vapor region were also experimentally measured. The collected experimental data was used to construct the phase diagram of isopropanol/water/NaCl mixtures at 5, 10 and 20 wt% NaCl content, at atmospheric pressure, and temperatures from 294.15 K to the boiling point.

Unraveling symbiotic microbial communities, metabolomics and volatilomics profiles of kombucha from diverse regions in China

Kombucha is a natural fermented beverage (mixed system). This study aimed to unravel the signatures of kombucha in China to achieve tailor-made microbial consortium. Here, biochemical parameters, microbiome, metabolite production and volatile profile were comprehensively compared and characterized across four regions (AH, HN, SD, SX), both commonalities and distinctions were highlighted. The findings revealed that yeast species yeast Starmerella, Zygosaccharomyces, Dekkera, Pichia and bacterium Komagataeibacter, Gluconobacter were the most common microbes. Additionally, the composition, distribution and stability of microbial composition in liquid phase were superior to those in biofilm. The species diversity, differences, marker and association were analyzed across four areas. Metabolite profiles revealed a total of 163 bioactive compounds (23 flavonoids, 13 phenols), and 68 differential metabolites were screened and identified. Moreover, the metabolic pathways of phenylpropanoids biosynthesis were closely linked with the highest number of metabolites, followed by flavonoid biosynthesis. Sixty-five volatile compounds (23 esters) were identified. Finally, the correlation analysis among the microbial composition and volatile and functional metabolites showed that Komagataeibacter, Gluconolactone, Zygosacchaaromycess, Starmerella and Dekkera seemed closely related to bioactive compounds, especially Komagataeibacter displayed positive correlations with 1-hexadecanol, 5-keto-D-gluconate, L-malic acid, 6-aminohexanoate, Starmerella contributed greatly to gluconolactone, thymidine, anabasine, 2-isopropylmalic acid. Additionally, Candida was related to β-damascenone and α-terpineol, and Arachnomyces and Butyricicoccus showed the consistency of associations with specific esters and alcohols. These findings provided crucial information for creating a stable synthetic microbial community structure, shedding light on fostering stable kombucha and related functional beverages.

High-pressure vapor-liquid equilibrium measurements of methane + water mixtures by nuclear magnetic resonance spectroscopy

The vapor-liquid equilibrium (VLE) of methane + water mixtures has been studied with nuclear magnetic resonance (NMR) spectroscopy. This work had two primary goals. The first goal was to develop methods that broaden the utility of NMR spectroscopy for VLE measurements. In this regard, we report a method by which the liquid-phase and vapor-phase compositions are measured in separate experiments by adjusting the height of the liquid phase in the sample tube. We also report a method for hastening phase equilibration by adding glass beads to the sample and repeatedly inverting the sample tube. The second goal of this work was to collect VLE data on a challenging mixture with real-world importance. Mixtures of methane + water are a useful test case because of their challenging characteristics, including the widely differing vapor pressures of the two components. One use for accurate VLE data on methane + water mixtures is to better predict the formation of harmful liquid phases in natural gas pipelines. Herein we utilize 1H NMR spectroscopy to measure the VLE of methane + water mixtures at temperatures of 299.73, 307.98, and 323.25 K, and pressures ranging from 0.69 MPa to 13.89 MPa. Experiments were carried out with a 600 MHz spectrometer. Mixtures were prepared and equilibrated in a high-pressure zirconia sample tube with an integrated needle valve. NMR-based VLE measurements on the liquid phase are in good agreement with available literature data and with Henry's Law predictions at low pressures. However, the commonly used GERG-2008 model for natural gas systems deviates dramatically from the experimental data for the liquid phase. NMR-based VLE measurements on the vapor-phase resulted in measured water concentrations that are systematically lower than available literature data and models. This systematic offset is likely caused by peak overlap in the NMR spectra.

Novel Double Hybrid-Type Bone Cements Based on Calcium Phosphates, Chitosan and Citrus Pectin.

In this work, the influence of the liquid phase composition on the physicochemical properties of double hybrid-type bone substitutes was investigated. The solid phase of obtained biomicroconcretes was composed of highly reactive α-tricalcium phosphate powder (α-TCP) and hybrid hydroxyapatite/chitosan granules (HA/CTS). Various combinations of disodium phosphate (Na2HPO4) solution and citrus pectin gel were used as liquid phases. The novelty of this study is the development of double-hybrid materials with a dual setting system. The double hybrid phenomenon is due to the interactions between polycationic polymer (chitosan in hybrid granules) and polyanionic polymer (citrus pectin). The chemical and phase composition (FTIR, XRD), setting times (Gillmore needles), injectability, mechanical strength, microstructure (SEM) and chemical stability in vitro were studied. The setting times of obtained materials ranged from 4.5 to 30.5 min for initial and from 7.5 to 55.5 min for final setting times. The compressive strength varied from 5.75 to 13.24 MPa. By incorporating citrus pectin into the liquid phase of the materials, not only did it enhance their physicochemical properties, but it also resulted in the development of fully injectable materials featuring a dual setting system. It has been shown that the properties of materials can be controlled by using the appropriate ratio of citrus pectin in the liquid phase.

Effects of the different phase change materials on heat dissipation performances of the ternary polymer Li-ion battery pack in hot climate

To improve the heat dissipation performance of the Ternary Polymer Li-ion Batteries(TPLBs) in hot climate, a heat dissipation method including different PCMs (Paraffin, 10% GNP + Paraffin, 10% EG + CPCM) was established, and orthogonal test and fuzzy grey correlation analysis method were applied to investigate the heat dissipation effects of the TPLBP in hot climate. The results shown that the TPBP with 10% EG CPCM is of heat dissipation characteristics and thermal security (namely the temperature difference is less than 5K), it makes sure the safety operation of new energy vehicles under 3C in hot climate. And the fuzzy grey correlation values between the thermal conductivity λ of the PCM and the time τ0 of melting point appearance of the PCM in the TPLBP is of a maximum value of 0.5660, and the fuzzy grey correlation values between the discharge current I and the time τ0 of melting point appearance of the PCM in the TPLBP is of a minimum value of 0.3386. Therefore, the discharge current I has the greatest effect on the liquid phase composition ω of PCM, but also has the least effect on the time τ0 of melting point appearance of the PCM in the TPLBP.

Thermodynamic Study of the Electric Field Effect on Liquid-Vapor Mixture at Equilibrium: An Analysis on a Water-Ethanol Mixture.

In this paper, the effect of electric fields on phase equilibria through polarization is investigated. A relation is derived for the chemical potential of a system, where the electric field is localized over a liquid phase mixture in equilibrium with a vapor phase mixture. This relation is then applied to a water-ethanol mixture to explore the effect of polarization-based electric fields on the liquid phase composition. It is observed that the quadratic dependence on electric field strength produces little effect below field strengths of approx. 10 MV/m. However, above this field strength, the mole fraction of water in the liquid phase grows rapidly, increasing by a factor of 8 for a water vapor phase fraction of 0.2 and a field strength of 500 MV/m, which approaches the dielectric breakdown strength of water. Nonetheless, this field strength could be achievable with microfluidic experimental setups.

Unsupervised crystallization monitoring with NIR Spatially Resolved Spectroscopy combined with Principal Component Analysis

ATR-FTIR and NIR spectroscopies are widely deployed to monitor the liquid phase composition during crystallization. However, information about the solid phase is also essential for the crystallization process control. We propose in this study to implement Spatially Resolved Spectroscopy (SRS) based on the near-infrared spectral range, to collect relevant data related to both physical and chemical aspects of suspensions during seeded cooling crystallizations of an industrial organic compound. Different batch crystallizations with varying experimental conditions were carried out and monitored. Principal Component Analysis (PCA) was applied and score trajectories were analyzed over time. This data mining method enabled to differentiate batches according to their initial composition and to detect a secondary nucleation mechanism.

Steady state population balance modelling of precipitation processes: Nucleation, growth and size-dependent agglomeration

In this work a numerical methodology to solve the steady state Population Balance Equation (PBE) is developed. Three crystallisation mechanisms are included, namely: nucleation, size-independent growth and size-dependent loose agglomeration. The numerical method is based on the discretisation of the crystal size as distributed variable. In order to describe the loose agglomeration, the numerical methodology solves two PBE: one including the nucleation and growth mechanisms and one accounting for the agglomeration process. From the first PBE, liquid phase composition, supersaturation, developed crystal surface and Crystallite Size Distribution (CSD) are obtained. Similarly, the second PBE leads to the Agglomerate Size Distribution (ASD). The study of the size-dependant agglomeration kernel induces an additional numerical difficulty due to the dependency of both PBE and agglomeration kernel on the particle size. An accelerated fixed point algorithm based on the crossed secant method is adapted to overcome the difficulty and accurately solve the agglomeration PBE. The oxalic precipitation of uranium is simulated using this numerical methodology. First, the experimental results of a reference case are compared with the numerical predictions in terms of particle size distribution, mean size, mass fraction and moments. Then, the operating conditions are varied in order to test the algorithm robustness and performances. In all cases, the crossed secant method ensures the size-dependent agglomeration PBE solution and properly predicts the ASD. The developed numerical methodology predicts the mean particle size under the experimental uncertainty in a reasonable computation time and number of iterations.

Pyrolysis of LignoBoost lignin in ZnCl2-KCl-NaCl molten salt media: Insights into process-pyrolysis oil yield and composition relations

Depolymerization of lignin by pyrolysis has been identified as a viable route to produce renewable fuels and biobased platform chemicals. Herein we report the pyrolysis of LignoBoost lignin in a molten salt consisting of ZnCl2-KCl-NaCl (60:20:20 mol ratio) in a g-scale reactor set-up with a focus on the liquid phase yields and composition. The effects of relevant process parameters such as temperature (250–450 °C), reaction time (10–50 min), and N2 flow rate (10–30 mL min−1) on the product yields were elucidated using design of experiments. The highest bio-oil yield was 47.1 wt% (450 °C, 10 min) and the yield of organics in the bio-oil at this condition was 24 wt% (on lignin intake), the remainder being water. The latter is considerably higher than found for an experiment at similar conditions without salt (16 wt%). Temperature and reaction time were shown to have the largest effects on bio-oil yield. Prolonged reaction times resulted in higher amounts of gas phase components (H2, CO2) and water, and a reduced amount of solid products. Statistical analyses and validation experiments showed that the experimental product yields are in good agreement with the predicted values from the model. The properties and molecular composition of the liquid products were determined using various analytical techniques and reveal that the presence of a molten salt during pyrolysis has a positive influence on the composition of the liquid phase like a higher level of depolymerization and higher selectivity to aromatic and phenolic monomers compared to thermal pyrolysis.