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ChemEngineering, Volume 3, Issue 2 (June 2019)

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Cover Story (view full-size image) A commonly used reactor type is a fixed-bed reactor, which can be modeled with different levels of [...] Read more.
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Open AccessArticle
Simulation of Conjugate Heat Transfer in Thermal Processes with Open Source CFD
ChemEngineering 2019, 3(2), 59; https://doi.org/10.3390/chemengineering3020059
Received: 8 May 2019 / Revised: 29 May 2019 / Accepted: 29 May 2019 / Published: 6 June 2019
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Abstract
A verification and validation study was performed using the open source computational fluid dynamics software package OpenFOAM version 6-dev for conjugate heat transfer problems. The test cases had a growing complexity starting from a simple steady state problem over unsteady heat transfer to [...] Read more.
A verification and validation study was performed using the open source computational fluid dynamics software package OpenFOAM version 6-dev for conjugate heat transfer problems. The test cases had a growing complexity starting from a simple steady state problem over unsteady heat transfer to more realistic engineering applications. First, a fin effectiveness study was performed. Then, the external convection at pipes and internal pipe heat transfer were investigated. The validity of the techniques was shown for each test case by comparing the simulation results with experimental and analytic data available in the literature. Finally, a simplified shell-and-tube heat exchanger was simulated to demonstrate how these methods can be applied to plant scale engineering problems. Full article
(This article belongs to the Special Issue Progress in Thermal Process Engineering)
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Open AccessReview
Specifically Designed Ionic Liquids—Formulations, Physicochemical Properties, and Electrochemical Double Layer Storage Behavior
ChemEngineering 2019, 3(2), 58; https://doi.org/10.3390/chemengineering3020058
Received: 8 April 2019 / Revised: 16 May 2019 / Accepted: 31 May 2019 / Published: 3 June 2019
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Abstract
Two key features—non-volatility and non-flammability—make ionic liquids (ILs) very attractive for use as electrolyte solvents in advanced energy storage systems, such as supercapacitors and Li-ion batteries. Since most ILs possess high viscosity and are less prone to dissolving common electrolytic salts when compared [...] Read more.
Two key features—non-volatility and non-flammability—make ionic liquids (ILs) very attractive for use as electrolyte solvents in advanced energy storage systems, such as supercapacitors and Li-ion batteries. Since most ILs possess high viscosity and are less prone to dissolving common electrolytic salts when compared to traditional electrolytic solvents, they must be formulated with low viscosity thinner solvents to achieve desired ionic conductivity and dissolution of electrolyte salts in excess of 0.5 M concentration. In the past few years, our research group has synthesized several specifically designed ILs (mono-cationic, di-cationic, and zwitterionic) with bis(trifluoromethylsulfonyl)imide (TFSI) and dicyanamide (DCA) as counter anions. This article describes several electrolyte formulations to achieve superior electrolytic properties. The performance of a few representative IL-based electrolytes in supercapacitor coin cells is presented. Full article
(This article belongs to the Special Issue Advanced Ionic Liquid-Based Mixed Solvent Systems)
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Open AccessArticle
KLa Determination Using the Effectiveness-NTU Method: Application to Countercurrent Absorbers in Operation Using Viscous Solvents for VOCs Mass Transfer
ChemEngineering 2019, 3(2), 57; https://doi.org/10.3390/chemengineering3020057
Received: 4 February 2019 / Revised: 1 March 2019 / Accepted: 24 May 2019 / Published: 1 June 2019
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Abstract
In this study, the Effectiveness-NTU method, which is usually applied to heat exchanger design, was adapted to gas–liquid countercurrent absorbers to determine the overall mass transfer coefficient, KLa, of the apparatus in operation. It was demonstrated that the ε-NTU method could [...] Read more.
In this study, the Effectiveness-NTU method, which is usually applied to heat exchanger design, was adapted to gas–liquid countercurrent absorbers to determine the overall mass transfer coefficient, KLa, of the apparatus in operation. It was demonstrated that the ε-NTU method could be used to determine the KLa using the Henry coefficient of the solute to be transferred (HVOC), the gas flow-rate (QG), the liquid flow-rate (QL), the scrubber volume (V), and the effectiveness of the absorber (ε). These measures are calculated from the gaseous concentrations of the solute measured at the absorber inlet (CGin) and outlet (CGout), respectively. The ε-NTU method was validated from literature dedicated to the absorption of volatile organic compounds (VOCs) by heavy solvents. Therefore, this method could be a simple, robust, and reliable tool for the KLa determination of gas–liquid contactors in operation, despite the type of liquid used, i.e., water or viscous solvents. Full article
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Open AccessArticle
Parameter Estimation Strategies in Thermodynamics
ChemEngineering 2019, 3(2), 56; https://doi.org/10.3390/chemengineering3020056
Received: 26 February 2019 / Revised: 23 May 2019 / Accepted: 26 May 2019 / Published: 1 June 2019
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Abstract
Many thermodynamic models used in practice are at least partially empirical and thus require the determination of certain parameters using experimental data. However, due to the complexity of the models involved as well as the inhomogeneity of available data, a straightforward application of [...] Read more.
Many thermodynamic models used in practice are at least partially empirical and thus require the determination of certain parameters using experimental data. However, due to the complexity of the models involved as well as the inhomogeneity of available data, a straightforward application of basic methods often does not yield a satisfactory result. This work compares three different strategies for the numerical solution of parameter estimation problems, including errors both in the input and in the output variables. Additionally, the new idea to apply multi-criteria optimization techniques to parameter estimation problems is presented. Finally, strategies for the estimation and propagation of the model errors are discussed. Full article
(This article belongs to the Special Issue Progress in Thermal Process Engineering)
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Open AccessFeature PaperArticle
Investigation of Thermal Behavior of Layered Double Hydroxides Intercalated with Carboxymethylcellulose Aiming Bio-Carbon Based Nanocomposites
ChemEngineering 2019, 3(2), 55; https://doi.org/10.3390/chemengineering3020055
Received: 31 March 2019 / Revised: 17 May 2019 / Accepted: 27 May 2019 / Published: 1 June 2019
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Abstract
Carboxymethylcellulose (CMC), a polymer derived from biomass, was intercalated into layered double hydroxides (LDH) composed by M2+/Al3+ (M2Al-CMC, M = Mg or Zn) and evaluated as precursors for the preparation of biocarbon-based nanocomposites by pyrolysis. M2Al-CMC [...] Read more.
Carboxymethylcellulose (CMC), a polymer derived from biomass, was intercalated into layered double hydroxides (LDH) composed by M2+/Al3+ (M2Al-CMC, M = Mg or Zn) and evaluated as precursors for the preparation of biocarbon-based nanocomposites by pyrolysis. M2Al-CMC hybrids were obtained by coprecipitation and characterized by X ray diffraction (XRD), vibrational spectroscopies, chemical analysis, and thermal analysis coupled to mass spectrometry. Following, pyrolyzed materials obtained between 500–1000 °C were characterized by XRD, Raman spectroscopy, scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS). Above 600 °C, Raman spectra of all samples showed the presence of graphitic carbon, which plays a role in the degree of crystallinity of produced inorganic phases (for comparison purposes, M2Al-CO3 materials were investigated after calcination in the same experimental conditions). XRD patterns of Mg2Al-CMC pyrolyzed between 600–1000 °C showed poorly crystallized MgO and absence of spinel reflections, whereas for Zn2Al-CMC, it was observed well crystallized nanometric ZnO at 800 °C, and ZnAl2O4 and γ-Al2O3 phases at 1000 °C. Above 800 °C, the carbothermic reaction was noticed, transforming ZnO to zinc vapour. This study opens perspectives for nanocomposites preparation based on carbon and inorganic (mixed) oxides through precursors having organic-inorganic interactions at the nanoscale domain. Full article
(This article belongs to the Special Issue Advanced Applications of Layered Double Hydroxides)
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Open AccessArticle
Corrosion Behavior of a Carbon Network/Aluminum Matrix Porous Composite in Salinated and Acidic Environments
ChemEngineering 2019, 3(2), 54; https://doi.org/10.3390/chemengineering3020054
Received: 18 March 2019 / Revised: 11 May 2019 / Accepted: 24 May 2019 / Published: 1 June 2019
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Abstract
Through this work, a carbon network/aluminum matrix porous composite material was analyzed for its susceptibility to material degradation in sulfuric acid and seawater corrosive media. Simple potentiodynamic electrochemical testing was implemented, and from polarization curves, the Tafel coefficients and exchange current densities were [...] Read more.
Through this work, a carbon network/aluminum matrix porous composite material was analyzed for its susceptibility to material degradation in sulfuric acid and seawater corrosive media. Simple potentiodynamic electrochemical testing was implemented, and from polarization curves, the Tafel coefficients and exchange current densities were obtained for a comparative analysis. The pseudo exchange current densities for corrosion of the composite material were compared to those found for Al 1235 and 6061-T6. By relating the pseudo icorr of these materials in each environment, an understanding regarding the relative propensity to corrosion was determined. According to the recovered data, the composite had the lowest pseudo icorr in all corrosion systems and was consequently inferred the least likely to corrode. The factor that primarily contests this conclusion is the material’s relatively large exposed surface area. The existence of carbon along the grain boundaries in the C/Al composite improved its corrosion behavior. Further discussion concerning the implication of βc is offered. Electrochemical impedance spectroscopic (EIS) tests were performed in the frequency range from 0.001 Hz to 100 kHz. An immersion corrosion test was conducted to calculate the corrosion rate in different environments. Morphological observation on the corrosion surface was also carried out to evaluate the corrosion product deposition on each material. Full article
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Open AccessArticle
Effect of O3 Dose on the O3/UV Treatment Process for the Removal of Pharmaceuticals and Personal Care Products in Secondary Effluent
ChemEngineering 2019, 3(2), 53; https://doi.org/10.3390/chemengineering3020053
Received: 28 February 2019 / Revised: 10 May 2019 / Accepted: 27 May 2019 / Published: 1 June 2019
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Abstract
A municipal wastewater treatment plant (WWTP) is a melting pot of numerous pharmaceuticals and personal care products (PPCPs) together with many other substances. The removal of PPCPs using advanced oxidation processes within a WWTP is one way to reduce the amount of PPCPs [...] Read more.
A municipal wastewater treatment plant (WWTP) is a melting pot of numerous pharmaceuticals and personal care products (PPCPs) together with many other substances. The removal of PPCPs using advanced oxidation processes within a WWTP is one way to reduce the amount of PPCPs that potentially enter an aquatic environment. The aim of this study was to examine the effectiveness of the ozone (O3)/UV treatment process, especially, the effects of O3 dose and reaction time, on the removal of PPCPs in the secondary effluent of a WWTP. Experiments were conducted using a pilot-scale treatment process that consisted of two flow-through reactors connected in series. Each reactor was equipped with three 65 W lamps (UV65W). The experimental variables were ozone dosage (1, 2, 3, 4, and 6 mg L−1) and hydraulic retention time (HRT; 5 and 10 min). On the basis of the PPCP concentrations after O3/UV65W treatment and their limit of detection (LOD), 38 PPCPs detected in the secondary effluent were classified into 5 groups ranging from the category of “sensitive” to O3/UV65W or “unstable” in the O3/UV65W process to the category of “insensitive” to O3/UV65W or “very stable” in the O3/UV65W process. Full article
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Open AccessArticle
Synthetic Packed-Bed Generation for CFD Simulations: Blender vs. STAR-CCM+
ChemEngineering 2019, 3(2), 52; https://doi.org/10.3390/chemengineering3020052
Received: 8 April 2019 / Revised: 3 May 2019 / Accepted: 7 May 2019 / Published: 14 May 2019
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Abstract
A common reactor type in the chemical and process industry is the fixed-bed reactor. Accurate modeling can be achieved with particle-resolved computational fluid dynamic (CFD) simulations. However, the underlying bed morphology plays a paramount role. Synthetic bed-generation methods are much more flexible and [...] Read more.
A common reactor type in the chemical and process industry is the fixed-bed reactor. Accurate modeling can be achieved with particle-resolved computational fluid dynamic (CFD) simulations. However, the underlying bed morphology plays a paramount role. Synthetic bed-generation methods are much more flexible and faster than image-based approaches. In this study, we look critically at the two different bed generation methods: Discrete element method (DEM) (in the commercial software STAR-CCM+) and the rigid-body model (in the open-source software Blender). The two approaches are compared in terms of synthetically generated beds with experimental data of overall and radial porosity, particle orientation, as well as radial velocities. Both models show accurate agreement for the porosity. However, only Blender shows similar particle orientation than the experimental results. The main drawback of the DEM is the long calculation time and the shape approximation with composite particles. Full article
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Open AccessArticle
Overview of Water Shutoff Operations in Oil and Gas Wells; Chemical and Mechanical Solutions
ChemEngineering 2019, 3(2), 51; https://doi.org/10.3390/chemengineering3020051
Received: 23 January 2019 / Revised: 8 May 2019 / Accepted: 10 May 2019 / Published: 14 May 2019
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Abstract
This paper provides an integrated overview of the water shutoff operations, starting from the causes to the solutions. The paper begins with explaining the benefits of eliminating excessive water production. Then, the different types of water production and their properties are explained. The [...] Read more.
This paper provides an integrated overview of the water shutoff operations, starting from the causes to the solutions. The paper begins with explaining the benefits of eliminating excessive water production. Then, the different types of water production and their properties are explained. The paper also focuses in reviewing the disadvantages of producing unwanted water as well as the sources of it, followed by an explanation of the methodology for identifying the problem. Then, the chemical solutions for water shutoff are reviewed which are generally applied to solve the excessive unwanted water production in the reservoir or near the wellbore area. Finally, the paper illustrates the common mechanical solutions for water shutoff within the wellbore. The aim behind this paper is to provide a general description of identifying the unwanted water production sources and the common practices for water shutoff operations. Full article
(This article belongs to the Special Issue Contribution of Chemistry in Drilling Engineering Progress)
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Open AccessArticle
Experimental Study for HIx Concentration by Electro-Electrodialysis (EED) Cells in the Water Splitting Sulfur-Iodine Thermochemical Cycle
ChemEngineering 2019, 3(2), 50; https://doi.org/10.3390/chemengineering3020050
Received: 6 February 2019 / Revised: 5 May 2019 / Accepted: 8 May 2019 / Published: 12 May 2019
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Abstract
The efficiency of HI concentration/separation from a HIx solution, (mixture of HI/H2O/I2) represents a crucial factor in the sulfur-iodine thermochemical water splitting process for hydrogen production. In this paper, an experimental study on HI cathodic concentration in HI [...] Read more.
The efficiency of HI concentration/separation from a HIx solution, (mixture of HI/H2O/I2) represents a crucial factor in the sulfur-iodine thermochemical water splitting process for hydrogen production. In this paper, an experimental study on HI cathodic concentration in HIx solution using stacked electro-electrodialysis (EED) cells was carried out under the conditions of 1 atm and at three different temperature (25, 55 and 85 °C) and using a current density of 0.10 A/cm2. Results showed that an increase in HI concentration can be obtained under certain conditions. The apparent transport number (t+) in all the experiments was very close to 1, and the electro-osmosis coefficient (β) changed in a range of 1.08–1.16. The tests showed a detectable, though slow, increase in both the anodic iodine and cathodic hydriodic acid concentrations. Full article
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Open AccessArticle
Novel Photocatalytic NH3 Synthesis by NO3 Reduction over CuAg/TiO2
ChemEngineering 2019, 3(2), 49; https://doi.org/10.3390/chemengineering3020049
Received: 7 December 2018 / Revised: 26 April 2019 / Accepted: 5 May 2019 / Published: 8 May 2019
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Abstract
The highly effective reaction system was investigated for the photocatalytic ammonia synthesis from the reduction of nitrate ions by using the semiconductor photocatalyst, Cu and Ag doped on TiO2 (CuAg/TiO2) at room temperature under UV light irradiation (max. 352 nm). [...] Read more.
The highly effective reaction system was investigated for the photocatalytic ammonia synthesis from the reduction of nitrate ions by using the semiconductor photocatalyst, Cu and Ag doped on TiO2 (CuAg/TiO2) at room temperature under UV light irradiation (max. 352 nm). In this study, CuAg/TiO2 gave the high efficiency and the selectivity for the ammonia synthesis by the photoreduction of nitrate in the presence of methanol as a hole scavenger. For the evaluation of the photocatalytic activity over CuAg/TiO2, various TiO2 samples, such as standard TiO2, Cu/TiO2, and Ag/TiO2, were evaluated in the same procedure. The chemical properties were investigated by XRD, TEM, XPS, PL, and DRS. We examined the optimum conditions for the experimental factors and the important issues, including the effect of the molar ratio of Cu and Ag onto TiO2, the optimization of the CuAg amount loaded on TiO2, the influence of the loading amount of the catalyst on the reduction of nitrate ions, the exploration of the optimum hole scavenger, and the reusability of the optimum photocatalyst. The very efficient conversion of nitrate ions (95%) and the highest selectivity (86%) were achieved in the reaction with the optimum conditions. Here, we reported the process that nitrate ions can efficiently be reduced, and ammonia can be selectively synthesized over CuAg/TiO2. Full article
(This article belongs to the Special Issue Advances in Metal-Based Catalysts)
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Open AccessArticle
Lattice-Boltzmann Simulation and Experimental Validation of a Microfluidic T-Junction for Slug Flow Generation
ChemEngineering 2019, 3(2), 48; https://doi.org/10.3390/chemengineering3020048
Received: 24 January 2019 / Revised: 4 April 2019 / Accepted: 23 April 2019 / Published: 5 May 2019
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Abstract
We investigate the interaction of two immiscible fluids in a head-on device geometry, where both fluids are streaming opposite to each other. The simulations are based on the two-dimensional (2D) lattice Boltzmann method (LBM) using the Rothman and Keller (RK) model. We validate [...] Read more.
We investigate the interaction of two immiscible fluids in a head-on device geometry, where both fluids are streaming opposite to each other. The simulations are based on the two-dimensional (2D) lattice Boltzmann method (LBM) using the Rothman and Keller (RK) model. We validate the LBM code with several benchmarks such as the bubble test, static contact angle, and layered flow. For the first time, we simulate a head-on device by forcing periodicity and a volume force to induce the flow. From low to high flow rates, three main flow patterns are observed in the head-on device, which are dripping-squeezing, jetting-shearing, and threading. In the squeezing regime, the flow is steady and the droplets are equal. The jetting-shearing flow is not as stable as dripping-squeezing. Moreover, the formation of droplets is shifted downstream into the main channel. The last flow form is threading, in which the immiscible fluids flow parallel downstream to the outlet. In contrast to other studies, we select larger microfluidic channels with 1-mm channel width to achieve relatively high volumetric fluxes as used in chemical synthesis reactors. Consequently, the capillary number of the flow regimes is smaller than 10−5. In conclusion, the simulation compares well to experimental data. Full article
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Open AccessArticle
Ionic Liquid Hydrogel Composite Membranes (IL-HCMs)
ChemEngineering 2019, 3(2), 47; https://doi.org/10.3390/chemengineering3020047
Received: 19 February 2019 / Revised: 24 April 2019 / Accepted: 26 April 2019 / Published: 5 May 2019
Cited by 1 | Viewed by 511 | PDF Full-text (1786 KB) | HTML Full-text | XML Full-text
Abstract
In this work, novel hydrogel composites membranes comprising [2-(Methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide as monomer, N,N-methylene bisacrylamide as cross-linker, and 1-butyl-3-methylimidazolium hexafluorophosphate as ionic liquid additive, have been developed. Ionic liquid hydrogel composite membranes (IL-HCMs) were tested for membrane contactors applications, aiming to reduce surface hydrophobicity [...] Read more.
In this work, novel hydrogel composites membranes comprising [2-(Methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide as monomer, N,N-methylene bisacrylamide as cross-linker, and 1-butyl-3-methylimidazolium hexafluorophosphate as ionic liquid additive, have been developed. Ionic liquid hydrogel composite membranes (IL-HCMs) were tested for membrane contactors applications, aiming to reduce surface hydrophobicity of the polypropylene support, to reduce wetting tendency due to interaction with hydrophobic foulants, while affecting salts rejection in desalination operation, because of the entrapment of ILs inside the porous mesh-like structure of the gel layer. Transmembrane flux comparable to the sole polypropylene support was observed for IL content > 1 wt.%. Furthermore, all IL membranes presented a larger rejection to sodium chloride than the PP support or the composites without ionic liquid inside. Although the overall transmembrane flux of IL-HCMs developed in this work is comparable with that of state of the art MD membranes, this study demonstrated that the strong hydrophilic hydrogel layer, with C.A. < 50° for IL content larger than 1 wt.%, serves as a stabilization coating, by providing the new media between the feed and the hydrophobic membrane surface, thus potentially controlling the diffusion of hydrophobic foulant molecules. This would result in a decrease in the membrane wetting and fouling aptitude. Full article
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Open AccessArticle
Unusual Regularities of Propylene Carbonate Obtained by Propylene Oxide Carboxylation in the Presence of ZnBr2/Et4N+Br System
ChemEngineering 2019, 3(2), 46; https://doi.org/10.3390/chemengineering3020046
Received: 11 February 2019 / Revised: 23 April 2019 / Accepted: 28 April 2019 / Published: 4 May 2019
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Abstract
The aim of the work was to study the unusual regularities of propylene carbonate prepared by carboxylation of propylene oxide in the presence of the catalytic system ZnBr2/Et4N+Br. Using the kinetic method, a long induction [...] Read more.
The aim of the work was to study the unusual regularities of propylene carbonate prepared by carboxylation of propylene oxide in the presence of the catalytic system ZnBr2/Et4N+Br. Using the kinetic method, a long induction period was detected, followed by the rapid formation of propylene carbonate in a quantitative yield, where the maximum turnover frequency (TOF) values reached 21,658 h−1. The regularities of the influence of the main process parameters on the induction period duration and the reaction rate were established. Based on the results obtained and considering the literature, assumptions about the mechanism of the process were proposed and ways for its further study were outlined. Full article
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Open AccessArticle
Simulation for the Performance and Economic Evaluation of Conventional Activated Sludge Process Replacing by Sequencing Batch Reactor Technology in a Petroleum Refinery Wastewater Treatment Plant
ChemEngineering 2019, 3(2), 45; https://doi.org/10.3390/chemengineering3020045
Received: 14 March 2019 / Revised: 16 April 2019 / Accepted: 29 April 2019 / Published: 3 May 2019
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Abstract
Treatment of the petroleum refinery wastewater containing complex chemicals using biological processes is usually challenging because of the inhibition and/or toxicity of these matters when they serve as microbial substrates. In addition, performance modeling and cost evaluation of processes are essential for designing, [...] Read more.
Treatment of the petroleum refinery wastewater containing complex chemicals using biological processes is usually challenging because of the inhibition and/or toxicity of these matters when they serve as microbial substrates. In addition, performance modeling and cost evaluation of processes are essential for designing, construction, and forecasting future economic requirements of the petroleum refinery wastewater treatment plants (PRWWTPs). In this study, the performance and economics of conventional activated sludge (CAS) process replacing by sequencing batch reactor (SBR) technology in a two train PRWWTP were evaluated using simulation. The final treated effluent characteristics for the PRWWTPs containing CAS + CAS and SBR + CAS processes under steady state conditions were studied and evolution of the main parameters of the final effluent during the 30 days of simulation for these plants were investigated. Finally, the total project construction, operation labor, maintenance, material, chemical, energy, and amortization costs of these plants were estimated and compared. Results demonstrated that the project construction cost of PRWWTP containing CAS + CAS processes was lower than that of PRWWTP containing SBR + CAS processes and the energy and amortization costs for both plants were higher in comparison with the operation, maintenance, material, and chemical costs. Note that this study is a computer simulation and drawing general conclusions only on the basis of computer simulation may be insufficient. Full article
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Open AccessReview
Flexibility Options for Absorption and Distillation to Adapt to Raw Material Supply and Product Demand Uncertainties: A Review
ChemEngineering 2019, 3(2), 44; https://doi.org/10.3390/chemengineering3020044
Received: 25 February 2019 / Revised: 8 April 2019 / Accepted: 29 April 2019 / Published: 3 May 2019
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Abstract
The chemical industry has to deal with increasing uncertainties regarding the boundary conditions of their production processes. On the one hand, uncertainties affect the availability, quality, and prizes of raw material and energy. On the other hand, the demand side is affected by [...] Read more.
The chemical industry has to deal with increasing uncertainties regarding the boundary conditions of their production processes. On the one hand, uncertainties affect the availability, quality, and prizes of raw material and energy. On the other hand, the demand side is affected by increasing volatilities in product demand and increasing requirements for product variety. These changing boundary conditions lead to higher needs for flexibility in production processes of the chemical industry. Within this article technical solutions for an enhancement of different forms of flexibility are presented for production concepts and apparatus concepts, respectively. The latter focuses on unit operations for the separation of gas–liquid mixtures. This includes a review regarding transformable, modular production processes and a classification of their field of application. Additionally, concepts for named unit operations on different scales are presented and discussed. The presented concepts are also classified with respect to the different types of flexibility. Full article
(This article belongs to the Special Issue Progress in Thermal Process Engineering)
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Open AccessArticle
Reactive Extraction of Lactic Acid, Formic Acid and Acetic Acid from Aqueous Solutions with Tri-n-octylamine/1-Octanol/n-Undecane
ChemEngineering 2019, 3(2), 43; https://doi.org/10.3390/chemengineering3020043
Received: 19 February 2019 / Revised: 16 April 2019 / Accepted: 19 April 2019 / Published: 30 April 2019
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Abstract
The present work develops the basics for the isolation of lactic acid, acetic acid and formic acid from a single as well as a mixed feed stream, as is present, for example, in fermentation broth for lactic acid production. Modelling of the phase [...] Read more.
The present work develops the basics for the isolation of lactic acid, acetic acid and formic acid from a single as well as a mixed feed stream, as is present, for example, in fermentation broth for lactic acid production. Modelling of the phase equilibria data is performed using the law of mass action and shows that the acids are extracted according to their pka value, where formic acid is preferably extracted in comparison to lactic and acetic acid. Back-extraction was performed by 1 M NaHCO3 solution and shows the same tendency regarding the pka value. Based on lactic acid, the solvent phase composition, consisting of tri-n-octylamine/1-octanol/n-undecane, was optimized in terms of the distribution coefficient. The data clearly indicate that, compared to physical extraction, mass transfer can be massively enhanced by reactive extraction. With increasing tri-n-octylamine and 1-octanol concentration, the equilibrium constant increases. However, even when mass transfer increases, tri-n-octylamine concentrations above 40 wt%, lead to third phase formation, which needs to be prevented for technical application. The presented data are the basis for the transfer to liquid membrane permeation, which enables the handling of emulsion tending systems. Full article
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Open AccessArticle
Vapor Pressure Mapping of Ionic Liquids and Low-Volatility Fluids Using Graded Isothermal Thermogravimetric Analysis
ChemEngineering 2019, 3(2), 42; https://doi.org/10.3390/chemengineering3020042
Received: 21 December 2018 / Revised: 20 March 2019 / Accepted: 17 April 2019 / Published: 20 April 2019
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Abstract
One of the hallmarks of ionic liquids (ILs) and a critical part of their sustainable implementation is their low volatility, although statements in this regard are frequently made in the absence of a critical evaluation. Although it is generally accepted that conventional ILs [...] Read more.
One of the hallmarks of ionic liquids (ILs) and a critical part of their sustainable implementation is their low volatility, although statements in this regard are frequently made in the absence of a critical evaluation. Although it is generally accepted that conventional ILs exhibit significantly reduced vapor pressures relative to common organic solvents, glib statements about ILs having zero volatility can no longer be abided, even if a concrete temperature-dependent vapor pressure, Pvap(T), framework for placement of IL performance has not yet been established. In this communication, Pvap(T) values of 30 illustrative low-volatility fluids—including representative imidazolium-, ammonium-, and pyrrolidinium-based aprotic ILs; examples of protic, polymeric, and di-cationic ILs; as well as deep eutectic solvents (DESs) and glycols—were determined using a simple, convenient, and reproducible isothermal thermogravimetric method. Guided by this “vapor pressure map”, observed trends can be discussed in terms of anion basicity, cation geometry, alkane chain length, hydrogen bonding strength, and van der Waals forces, providing a context for the placement of theoretical and experimental vapor pressures gleaned in future IL and DES studies. Full article
(This article belongs to the Special Issue Advanced Ionic Liquid-Based Mixed Solvent Systems)
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Open AccessArticle
Nanohybrid Layered Double Hydroxides Used to Remove Several Dyes from Water
ChemEngineering 2019, 3(2), 41; https://doi.org/10.3390/chemengineering3020041
Received: 10 February 2019 / Revised: 9 April 2019 / Accepted: 14 April 2019 / Published: 19 April 2019
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Abstract
For the preparation and characterization of several layer double hydroxides (LDH) with inorganic interlayer anions (carbonate and nitrate) and nanohybrids, two organo-LDHs were studied in detail. The dodecylbenzene sulfonate (DBS) was used as an organic interlayer anion to modify the hydrophilic nature of [...] Read more.
For the preparation and characterization of several layer double hydroxides (LDH) with inorganic interlayer anions (carbonate and nitrate) and nanohybrids, two organo-LDHs were studied in detail. The dodecylbenzene sulfonate (DBS) was used as an organic interlayer anion to modify the hydrophilic nature of the interlayer. The aim of the modification of the layered double hydroxides (LDH) was to change the hydrophilic character of the interlayer to hydrophobic with the purpose of improving its ability to adsorb several (anionic and cationic) dyes from water. These compounds have been used as adsorbents of amaranth (Am), diamine green B (DGB) and brilliant green (BG) dyes. Adsorption tests were conducted using variable pH values, contact times and initial dye concentrations (adsorption isotherms) to identify the optimum conditions for the intended purpose. Adsorbents and adsorption products were characterized by several physicochemical techniques. The results of the adsorption tests showed that the organo-LDH nanohybrids could be efficient adsorbents in the removal of studied dyes from water. Thus, it can be concluded that nanohybrids studied in this work might act as suitable supports in the design of adsorbents for the removal of a wide spectrum of dyes with the aim of reducing the adverse effects on water resources. Full article
(This article belongs to the Special Issue Advanced Applications of Layered Double Hydroxides)
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Open AccessArticle
Use of Calcined Dolomite as Chemical Precipitant in the Simultaneous Removal of Ammonium and Phosphate from Synthetic Wastewater and from Agricultural Sludge
ChemEngineering 2019, 3(2), 40; https://doi.org/10.3390/chemengineering3020040
Received: 28 March 2019 / Revised: 12 April 2019 / Accepted: 16 April 2019 / Published: 18 April 2019
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Abstract
Phosphorus as phosphate and nitrogen as ammonium or nitrate are the main nutrients in wastewaters and agricultural sludges. They runoff easily to waterways and cause eutrophication in water bodies. However, ammonium and phosphate could be precipitated simultaneously and used as recycled nutrients. In [...] Read more.
Phosphorus as phosphate and nitrogen as ammonium or nitrate are the main nutrients in wastewaters and agricultural sludges. They runoff easily to waterways and cause eutrophication in water bodies. However, ammonium and phosphate could be precipitated simultaneously and used as recycled nutrients. In this research, dolomite calcined at 650 °C, 750 °C, or 950 °C and commercial MgO were used as precipitants in simultaneous phosphate and ammonium removal from synthetic (NH4)2HPO4 solution and agricultural sludge. Calcination at 750 °C was the preferred option as dolomite was decomposed to MgO and CaCO3 for optimal struvite precipitation. Molar ratios of 1.1–1.6:1–2:2 (Mg:P:N) were employed in the experiments. Very robust ammonium removal was obtained with MgO (57%), dolomite 650 °C and dolomite 750 °C (75%). MgO removed almost all phosphate, while dolomite 650 °C removed 65%, and dolomite 750 °C removed 60% (70% from agricultural sludge). Some part of the phosphate was adsorbed, most likely by CaCO3, during dolomite precipitation. Struvite was the only identified reaction product in all samples after 24 h of precipitation. Calcined dolomite had great potential in ammonium and phosphate precipitation from both synthetic waters and agricultural sludges and the precipitates could be used as recycled fertilizers. Full article
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Open AccessArticle
Ion-Liquid Based Supercapacitors with Inner Gate Diode-Like Separators
ChemEngineering 2019, 3(2), 39; https://doi.org/10.3390/chemengineering3020039
Received: 11 March 2019 / Revised: 6 April 2019 / Accepted: 9 April 2019 / Published: 14 April 2019
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Abstract
In order to minimize unintentional discharge, supercapacitors are interfaced with a membrane that separates the anode from the cathode—this membrane is called the separator. We focus here on separators, which are structured as electronic diode-like. We call an electrically structured separator “the gate”. [...] Read more.
In order to minimize unintentional discharge, supercapacitors are interfaced with a membrane that separates the anode from the cathode—this membrane is called the separator. We focus here on separators, which are structured as electronic diode-like. We call an electrically structured separator “the gate”. Through experiments, it was demonstrated that ionic liquid-filled supercapacitors, which were interfaced with gated separators exhibited a substantial capacitance (C) increase and reduction in the equivalent series resistance (ESR) compared to cells with ordinary separators. These two attributes help to increase the energy, which is stored in a cell, since for a given cell’s voltage, the dissipated energy on the cell, UR = V2/4(ESR) and the stored energy, UC = CV2/2, would increase. These were indeed ionic diodes since the order of the diode layout mattered—the diode-like structures exhibited maximum capacitance when their p-side faced the auxiliary electrode. Full article
(This article belongs to the Special Issue Advanced Functional Low-dimensional Materials and Their Applications)
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Open AccessArticle
The Formation of Layered Double Hydroxide Phases in the Coprecipitation Syntheses of [Ni0.80Co0.15](1−x)/0.95Alx(OH)2(anionn)x/n (x = 0–0.2, n = 1, 2)
ChemEngineering 2019, 3(2), 38; https://doi.org/10.3390/chemengineering3020038
Received: 17 January 2019 / Revised: 20 March 2019 / Accepted: 28 March 2019 / Published: 9 April 2019
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Abstract
This study investigates the synthesis of [Ni0.80Co0.15](1−x)/0.95Alx(OH)2 (x = 0–0.2) materials by coprecipitation to understand the formation of layered double hydroxide (LDH) phases as influenced by Al content and synthesis route. [...] Read more.
This study investigates the synthesis of [Ni0.80Co0.15](1−x)/0.95Alx(OH)2 (x = 0–0.2) materials by coprecipitation to understand the formation of layered double hydroxide (LDH) phases as influenced by Al content and synthesis route. Two routes were compared: the first method dissolved all the metal reagents into one solution before addition into the reaction vessel, while the second dissolved Al into a separate NaOH solution before simultaneous addition of the Ni/Co and Al solutions into the reaction vessel. The synthesized materials were characterized by Scanning Electron Microscopy, X-ray Diffraction, Inductively Coupled Plasma-Optical Emissions Spectroscopy and Thermogravimetric Analysis to understand the formation of LDH phases as influenced by Al content and synthesis method. It was found that as Al content increased, the amount of LDH phase present increased as well. No significant difference in LDH phase presence was observed for the two synthesis methods, but the morphologies of the particles were different. The method containing all the metals in one solution produced small particles, likely due to the continuous nucleation of Al(OH)3 disrupting particle growth. The method containing the separate Al in NaOH solution matched the morphology of the material with no Al, which is known to form desired large spherical particles under continuously stirring tank reactor synthesis conditions. Full article
(This article belongs to the Special Issue Advanced Applications of Layered Double Hydroxides)
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Open AccessArticle
Few-Layer Graphene from Mechanical Exfoliation of Graphite-Based Materials: Structure-Dependent Characteristics
ChemEngineering 2019, 3(2), 37; https://doi.org/10.3390/chemengineering3020037
Received: 19 February 2019 / Revised: 15 March 2019 / Accepted: 1 April 2019 / Published: 7 April 2019
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Abstract
We present a high-scale method to produce few-layer graphene (FLG) based on the mechanical exfoliation of graphite and compare the obtained FLG with the one reported earlier arising from pencil lead ablation. Several elements were modified and improved in the new approach. The [...] Read more.
We present a high-scale method to produce few-layer graphene (FLG) based on the mechanical exfoliation of graphite and compare the obtained FLG with the one reported earlier arising from pencil lead ablation. Several elements were modified and improved in the new approach. The purification and the ablation set-up were simplified, and the morphology of the FLG was modified and improved in view of some applications. The morphology-dependent properties of FLGs, lead-FLG, and graphite-FLG as conductive layers and in nanocomposites were investigated. The newly obtained FLG had a higher aspect ratio (high lateral size vs thickness/higher 2D aspect), which is reflected by enhanced transparency–conductivity features of the layer (film) and elongation-at-break behavior of the polymer composites. On the contrary, the nanocomposite containing lead-FLG showed, for instance, excellent gas barrier properties due to the multi-step structure of the lead-FLG flakes. Such structure exhibited less 2D and more 3D character, which can be highly suitable for applications where the presence of active/reactive edges is beneficial, e.g., in catalysis or supercapacitors’ electrodes. Nuclear reaction analysis was employed to investigate the morphology of graphite-FLG film. Full article
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Open AccessArticle
On the Impact of the Dynamics of Heat Transfer of the Thermal Machine Working Fluid and Heat Sources on the Shape of the Boundary of the Set of Realizable Regimes
ChemEngineering 2019, 3(2), 36; https://doi.org/10.3390/chemengineering3020036
Received: 9 November 2018 / Revised: 14 March 2019 / Accepted: 2 April 2019 / Published: 5 April 2019
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Abstract
From the point of view of finite time thermodynamics, the performance boundaries of thermal machines are considered, taking into account the irreversibility of the heat exchange processes of the working fluid with hot and cold sources. We show how the dynamics of heat [...] Read more.
From the point of view of finite time thermodynamics, the performance boundaries of thermal machines are considered, taking into account the irreversibility of the heat exchange processes of the working fluid with hot and cold sources. We show how the dynamics of heat exchange affects the shape of the optimal cycle of a heat engine and its performance, in particular, energy conversion efficiency in the maximum power mode. This energy conversion efficiency can depend only on the ratio of the heat transfer coefficients to the sources, or not depend on them at all. A class of dynamic functions corresponding to “natural” requirements is introduced and it is shown that, for any dynamics from this class, the optimal cycle consists of two isotherms and two adiabats, not only for the maximum power problem, but also for the problem of maximum energy conversion efficiency at a given power. Examples are given for calculating the parameters of the optimal cycle for the cases when the heat transfer coefficient to the cold source is arbitrarily large, and for dynamics in the form of a linear phenomenological (Fourier heat transfer) law. Full article
(This article belongs to the Special Issue Advanced Heat Exchangers for Waste Heat Recovery Applications)
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Open AccessArticle
Synthesis of Uniform Mesoporous Zeolite ZSM-5 Catalyst for Friedel-Crafts Acylation
ChemEngineering 2019, 3(2), 35; https://doi.org/10.3390/chemengineering3020035
Received: 4 March 2019 / Revised: 29 March 2019 / Accepted: 31 March 2019 / Published: 4 April 2019
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Abstract
This work highlights how the treatment of ZSM-5 (parent Zeolite Socony Mobil–5, Si/Al = 23) with different surfactant templates and alkaline solution, improved the catalytic performance in the Friedel-Crafts acylation of anisole with a propionic anhydride to obtain p-methoxypropiophenone. The modified microporous to [...] Read more.
This work highlights how the treatment of ZSM-5 (parent Zeolite Socony Mobil–5, Si/Al = 23) with different surfactant templates and alkaline solution, improved the catalytic performance in the Friedel-Crafts acylation of anisole with a propionic anhydride to obtain p-methoxypropiophenone. The modified microporous to mesoporous zeolite catalysts were characterized using different analytical techniques, including X-ray diffraction (XRD), nitrogen porosimetry, Fourier-transform infrared spectroscopy (FT-IR), temperature-programmed desorption (ammonia-TPD) and field emission scanning electron microscopy (FE-SEM) to analyze the crystallographic structure, surface acidity, surface area, porosity, morphology, and particle size. The results showed that the formed mesoporous zeolite by NaOH solution had smaller mesopores (ca. 3.7 nm) as compared to the mesoporous zeolites obtained by surfactant templates, such as, CTAB (ca. 14.9 nm), TPAOH (ca. 11.1 nm) and mixture of CTAB/TPAOH (ca. 15.2 nm). The catalytic acylation reaction was conducted in a batch glass reactor at various temperatures and the products were analyzed using off-line gas chromatography–mass spectrometry (GC-MS). It was found that the activity of treated ZSM-5 with mixed surfactant templates (CTAB/TPAOH) exhibited enhanced selectivity towards the main product (p-methoxypropiophenone) by a factor 1.7 or higher than unmodified ZSM-5 due to its increased surface area by 1.5 times and enhanced acid sites. Full article
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Open AccessArticle
Design Considerations of a Simplified Multiple Dividing Wall Column Pilot Plant
ChemEngineering 2019, 3(2), 34; https://doi.org/10.3390/chemengineering3020034
Received: 22 February 2019 / Revised: 28 March 2019 / Accepted: 30 March 2019 / Published: 3 April 2019
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Abstract
This contribution elaborates the design considerations of a simplified version of a four-product multiple dividing wall column in pilot plant scale that will be built at Ulm University. This will be the first realization of a multiple dividing wall column worldwide. A detailed [...] Read more.
This contribution elaborates the design considerations of a simplified version of a four-product multiple dividing wall column in pilot plant scale that will be built at Ulm University. This will be the first realization of a multiple dividing wall column worldwide. A detailed simulation approach, starting from the initialization by Vmin-method, is presented to obtain a feasible design of the column, taking into account the constraints of the operation within a university environment. The operating point was found by simulation studies, using the integrated optimization tool of AspenPlus© V10. It is shown that an NQ-curve can be applied on simplified multiple dividing wall columns. Based on the determined operating point, the thermodynamic and the fluid dynamic design of the pilot plant are discussed in detail. It is shown that the designed column can be operated to obtain all products with a purity of at least 98 mol%. Full article
(This article belongs to the Special Issue Progress in Thermal Process Engineering)
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Open AccessArticle
Photocatalytic Reduction of Hexavalent Chromium with Nanosized TiO2 in Presence of Formic Acid
ChemEngineering 2019, 3(2), 33; https://doi.org/10.3390/chemengineering3020033
Received: 5 February 2019 / Revised: 12 March 2019 / Accepted: 29 March 2019 / Published: 2 April 2019
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Abstract
Nanosized titanium dioxide (TiO2) nanoparticles were used for the photocatalytic reduction of hexavalent chromium in the presence of formic acid. The photoreduction of Cr(VI) in the absence of formic acid was quite slow. When formic acid was added in the chromium [...] Read more.
Nanosized titanium dioxide (TiO2) nanoparticles were used for the photocatalytic reduction of hexavalent chromium in the presence of formic acid. The photoreduction of Cr(VI) in the absence of formic acid was quite slow. When formic acid was added in the chromium solution as the hole scavenger, a rapid photocatalytic reduction of Cr(VI) was observed, owing to the consumption of hole and the acceleration of the oxidation reaction. Furthermore, three commercial TiO2 nanoparticles (AEROXIDE® P25; Ishihara Sangyo ST-01; FUJIFILM Wako Pure Chemical Corp.) were evaluated for the photoactivity of reduction of Cr(VI). Full article
(This article belongs to the Special Issue TiO2 Nanoparticles: Synthesis and Applications)
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Open AccessArticle
CFD Design of Hydrogenation Reactor for Transformation of Levulinic Acid to γ-Valerolactone (GVL) by using High Boiling Point Organic Fluids
ChemEngineering 2019, 3(2), 32; https://doi.org/10.3390/chemengineering3020032
Received: 29 December 2018 / Revised: 8 March 2019 / Accepted: 21 March 2019 / Published: 27 March 2019
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Abstract
Levulinic acid (LA) has been ranked as one of the “Top 10” building blocks for future bio-refineries as proposed by the US Department of Energy. It is considered one of the most important platform molecules for the production of fine chemicals and fuels [...] Read more.
Levulinic acid (LA) has been ranked as one of the “Top 10” building blocks for future bio-refineries as proposed by the US Department of Energy. It is considered one of the most important platform molecules for the production of fine chemicals and fuels based on its compatibility with existing processes, market economics, and industrial ability to serve as a platform for the synthesis of important derivatives. Hydrogenation of LA to produce γ-valerolactone (GVL) is an active area of research due to the potential of GVL to be used as a biofuel in its own right and for its subsequent transformation into hydrocarbon fuels. This paper contains a new design for a simple, cost effective, and safe hydrogenation reactor for the transformation of levulinic acid to γ-valerolactone (GVL) by utilizing high boiling point organic fluid. The hydrogenation reactor is composed of a heating source—organic fluid (called “DOWTHERM A” or “thermex”) and the catalytic reactor. The advantages of high boiling temperature fluids, along with advances in hydrocracking and reforming technologies driven by the oil and gas industries, make the organic concept more suitable and safer (water coming in contact with liquid metal is well understood in the metallurgical industry to be a steam explosion hazard) for heating the hydrogenation reactor. COMSOL multi-physics software version 4.3b was applied in this work and simultaneously solves the continuity, Navier-Stokes (fluid flow), energy (heat transfer), and diffusion with chemical reaction kinetics equations. It was shown that the heat flux supplied by the DOWTHERM A organic fluid could provide the necessary heat flux required for maintaining the hydrogenation process. It was found that the mass fractions of hydrogen and levulinic acid decreased along the reactor axis. The GVL mass fraction increased along the reactor axis. Full article
(This article belongs to the Special Issue Advances in Bio-Fuels Production)
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