A.B. de Haan
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Industrial Separation Processes
Thermal Unit Operations and Mechanical Unit Operations
Green solvents have emerged as promising green entrainers to substitute conventional entrainers in extractive distillation to separate azeotropic mixtures. However, the limited availability of thermodynamic data for green-solvent-containing mixtures continues to hinder their practical implementation in this process. This study is the first to report experimental vapor–liquid equilibrium (VLE) data for the n-hexane + ethanol azeotropic system containing the greener entrainer 1-butylpyrrolidin-2-one (NBP) alongside the benchmark entrainer 1-methylpyrrolidin-2-one (NMP). Using a Fischer Labodest VLE602 ebulliometer, VLE measurements were performed at pressures of 50.0 and 100.0 kPa and various entrainer-to-feed ratios (E/F). The reliability of the reported VLE data was tested and confirmed using the Van Ness thermodynamic consistency test. The results show that NBP enhances relative volatility and effectively eliminates the azeotrope, performing comparably to the benchmark entrainer NMP. The nonrandom-two-liquid (NRTL) model was utilized to regress the investigated VLE data and determine the optimum binary interaction parameters (BIPs). As a result, the NRTL model demonstrates good agreement with the experimental data. This thermodynamic modeling confirms the data’s reliability and suitability for process design, highlighting NBP’s potential as an environmentally friendly alternative entrainer in extractive distillation.
In this work, dimethyl isosorbide (DMI) and 1-butylpyrrolidin-2-one (NBP), as biobased and greener organic solvents, were used for the first time as entrainers in extractive distillation to separate a close-boiling mixture of methylcyclohexane and toluene. Vapor–liquid equilibrium (VLE) data were collected for pseudoternary mixtures consisting of methylcyclohexane and toluene in the presence of DMI and NBP at various entrainer-to-feed ratios (E/F) and pressures. The VLE measurements were conducted by using a Fischer Labodest VLE602 ebulliometer, and the thermodynamic consistency of the data was verified by using the Van Ness test. Both DMI and NBP were found to increase the relative volatility of methylcyclohexane to toluene, successfully eliminating close-boiling behavior. Compared to benchmark entrainers, both outperformed 1-methylpyrrolidin-2-one (NMP) and sulfolane under certain conditions. In comparison with other green entrainers, DMI and NBP showed similar performance to gamma-valerolactone (GVL) and Cyrene under specific conditions. The VLE data were accurately correlated by using the nonrandom two-liquid (NRTL) model.
Product and process design
Driving sustainable innovation
"Product and process design - driving sustainable innovation" is the 2nd edition of a comprehensive textbook for product and process design courses at BSc, MSc, EngD, and PhD level. It covers both heuristics based design methods as well as systems engineering approaches. It contains specific methods to co-design products and processes, so that both designs are better than when these designs are made separately. This integrated combination makes the book unique. For making designs that contribute to the Sustainable Development Goals of the United Nations specific methods are provided for the People, Planet, and Prosperity dimensions. This second edition of the book includes examples and exercises for each design method, which makes it very suitable for teaching purposes. The book is furthermore of interest to industrial process and product developers for many industry branches as it provides methods for design, modelling, and experimental validation for each innovation stage. It is also very useful for R&D managers as it provides guidelines for essential activities in each innovation stage (discovery, concept, feasibility, development, detailed engineering), leading to successful implementations of new processes and new products. Includes a major revision of all chapters with more examples and exercises and interactive options via website for quizzes. Provides training in process technology, sustainability, process design, scale-up and intensification.
Carbohydrates are the renewable feedstocks to produce 5-hydroxymethylfurfural (HMF) through hexose dehydration. Fructose is widely applied as the raw material in the formation of HMF due to its high rate and selectivity of conversion to HMF. In the HMF production process, the liquid-liquid extraction is essentially used to extract HMF from the reaction medium. The use of an ionic liquid (IL) and a deep eutectic solvent (DES) has been recognized to increase the yield of HMF by suppressing the formation of side products. The aim of this study is to systematically study the effect of fructose on the extraction performance of HMF in the water-1-ethyl-3-methylimidazolium tetrafluoroborate ([EMIM][BF4]) or choline chloride urea (ChCl-urea)-sodium chloride (NaCl) solution at 313.15 K and an atmospheric pressure of 0.1 MPa. Methyl isobutyl ketone was used as a selective extraction solvent. The separation factor and the distribution coefficient of HMF were obtained from liquid-liquid equilibrium (LLE) data to interpret the extraction performance. According to the results in this study, fructose had a minimal effect on the extraction performance of HMF. For the LLE system using [EMIM][BF4], the HMF distribution coefficient values showed comparable values to the LLE system without fructose. However, the separation factors decreased by around 1.1 times. Furthermore, fructose decreased the separation factors by around 1.3 times and distribution coefficients of HMF by around 1.1 times for the LLE system using ChCl-urea. A comparison of the IL and DES used indicated that HMF extraction from an aqueous DES (ChCl-urea) demonstrated a better extraction performance with the separation factor, and the HMF distribution coefficient values were 1.4 and 1.2 times higher than those for HMF extraction from an aqueous IL ([EMIM][BF4]), respectively. The experimental LLE data were correlated well using the non-random two-liquid model. The reliability of the experimental LLE data was also satisfactorily ascertained by the Hand and Othmer-Tobias correlations.
Process Technology
An Introduction, 2nd Edition
The book provides a general overview about process technology. It focuses on the structure and development of production processes, main technological operations and some important aspects of process economics. For the technological operations the authors emphasize operating principles, reasons for application and available industrial equipment. • Design calculations are kept to a necessary minimum and well explained. • Provides a combination of theory supplemented by even more examples and case studies.
Deep eutectic solvent (DES) has demonstrated its ability to improve the yield and selectivity in the 5-hydroxymethylfurfural (HMF) production process. Liquid-liquid extraction is a beneficial process in HMF production to recover HMF from the reaction medium. In the present study, the effect of DES (choline chloride urea) on the liquid-liquid equilibria (LLE) of HMF-water-organic solvent (methyl isobutyl ketone (MIBK) or 2-pentanol) systems in the absence and presence of sodium chloride (NaCl) was investigated at 313.15 K and atmospheric pressure (0.1 MPa). The tie-lines of the multicomponent systems were measured using several analytical methods. According to the experimental results, the extraction performance decreased with an increase in DES concentration. However, the addition of 10 wt % NaCl into the HMF aqueous DES solution can induce stronger liquid-liquid phase splitting, enhancing the separation factors and distribution coefficients of HMF by around 2.7 and 1.6 times, respectively. Additionally, MIBK showed better extraction performance in the presence of DES and NaCl with the separation factors 2.6 times higher than those of 2-pentanol and the HMF distribution coefficients above 1.8. The LLE of the multicomponent systems were correlated well with the nonrandom two-liquid (NRTL) model.
HMF (5-hydroxymethylfurfural) is a well-known promising product from hexose dehydration used for production of biofuels and chemicals. Liquid-liquid extraction is an essential process in HMF production to recover HMF from reaction medium. One of the important parameters needed in the extraction process design is liquid-liquid equilibrium (LLE) data. Organic solvent (methyl isobutyl ketone or 2-pentanol) was applied as extraction solvent to induce phase separation and extract HMF from the aqueous solution in the presence of the ionic liquid [EMIM][BF4] (1-ethyl-3-methylimidazolium tetrafluoroborate) and NaCl (sodium chloride). The aim of this study is to investigate the effect of [EMIM][BF4] on the phase equilibria of methyl isobutyl ketone (MIBK) or 2-pentanol, HMF, water systems in the absence and presence of NaCl at 313.15 K and atmospheric pressure (0.1 MPa). The separation factor and the distribution coefficient of HMF were obtained for interpreting liquid-liquid extraction performance. The results indicated that the presence of [EMIM][BF4] caused negative effect on the LLE of organic solvent-HMF-water systems. The slope of tie-lines became more negative with increasing [EMIM][BF4] concentration, indicating lower HMF distribution coefficients and separation factors. However, the presence of NaCl in the HMF aqueous ionic liquid solution can enhance both the separation factor and the distribution coefficient making the HMF extraction more favourable with the HMF distribution coefficient values higher than 1 over the whole range of initial HMF concentrations. According to the results in the present study, MIBK was found superior as an extraction solvent for HMF in the presence of [EMIM][BF4] and NaCl exhibited from the better extraction performance with the separation factors 2.0 times higher than those of 2-pentanol. Furthermore, the NRTL activity coefficient model satisfactorily correlated all the experimental phase equilibrium data provided in this study. The RMSD (root mean square deviations) of the NRTL model were 0.97% and 0.63% for the investigated LLE systems with MIBK and 2-pentanol as solvent in the absence of NaCl, respectively. Whereas, the RMSD of the LLE systems containing NaCl were 0.28% for MIBK-HMF-water-[EMIM][BF4]-NaCl and 0.90% for 2-pentanol-HMF-water-[EMIM][BF4]-NaCl.
HMF (5-hydroxymethylfurfural) is one of the bio renewable materials that can be used to produce a wide range of chemical products. In the HMF production process, yield and selectivity may be increased by liquid-liquid extraction of HMF using an organic solvent to prevent its degradation. Phase equilibrium data are required for rational design and optimal separation of HMF from the aqueous solution. In this study, liquid-liquid equilibrium (LLE) data of HMF, water, and methyl isobutyl ketone (MIBK) or 2-pentanol at 313.15 K (40 °C) and atmospheric pressure were measured and correlated using the NRTL and UNIQUAC models. The root mean square deviations (RMSD) of the NRTL and UNIQUAC models were 0.42% and 0.48% for the MIBK-HMF-water and 0.81% and 0.77% for the 2-pentanol-HMF-water system, respectively. The results indicated that higher distribution coefficients are achieved in the 2-pentanol-HMF-water system compared to the MIBK-HMF-water system. On the other hand, the separation ability of MIBK is better than that of 2-pentanol. In liquid-liquid extraction, not only a high distribution coefficient of HMF is important, but also a high separation factor is desirable to reduce the amount of co-extracted water. Therefore, in the present study the distribution coefficient of HMF from MIBK-HMF-water and the separation factor of the 2-pentanol-HMF-water system was improved by introducing a certain amount of salt into the aqueous solution. The salts examined in this study were based on the variety of cation (Na+, K+) and anion (Cl−, SO4 2−). The NRTL model was applied to correlate the LLE of organic solvent-HMF-water-salt systems, the results of which provided good agreement with the experimental data. The presence of salt can enhance the partitioning of HMF into the organic phase as well as the separation factor up to 2 times indicating the salting-out ability of the studied salts. The order of salting-out strength was NaCl > Na2SO4 > KCl > K2SO4 in which Cl− and Na+ demonstrated stronger salting-out ability than SO4 2− and K+.
Product and process design
Driving Innovation
The authors’ decades of innovation experience in industry, as well as in teaching BSc, MSc, and post-academic product and process design courses, thereby including the latest design publications, culminate in this book.
Provides training in process technology, sustainability, process design, scale-up and intensification. Readers will benefit from the authors' industrial experience in research, development, design, start-up, operation and de-bottlenecking. ...
The authors’ decades of innovation experience in industry, as well as in teaching BSc, MSc, and post-academic product and process design courses, thereby including the latest design publications, culminate in this book.
Provides training in process technology, sustainability, process design, scale-up and intensification. Readers will benefit from the authors' industrial experience in research, development, design, start-up, operation and de-bottlenecking.
The aim of this work was to investigate the productivity of continuous lactate fermentations at increased cell densities on simulated lignocellulosic hydrolyzate and wheat straw hydrolyzates using Ca(OH)2suspensions as base. To this end, a semi-automated membrane bioreactor prototype with external tubular membranes was designed and constructed. Long-term continuous fermentations were run in membrane bioreactor mode and compared to batch and continuous mode. Fouling of the membranes proved to be the major bottleneck in the process. The semi-automated membrane module switch elegantly circumvented this problem, allowing constant operating conditions throughout extended periods of time. Maximal productivities of 30.5 g kg−1.h−1could be reached in the prototype during 30.5 h combined with an average lactate concentration of 85.4 g kg−1and complete consumption of C5 and C6 carbohydrates. In this fermentation zone, the (liquid) residence time was 2.8 h. These numbers demonstrate significant performance improvements in comparison with batch and (regular) continuous conditions.
The separation of the close-boiling point mixture: toluene - methylcyclohexane can be carried out by extractive distillation using the ionic liquid 1-hexyl-3-methylimidazolium tetracyanoborate ([hmim][TCB]), reported as promising solvent for the separation of this mixture. However, the polar nature of ionic liquids causes the formation of two liquid phases which can be overcome with high solvent-to-feed ratios (S/F) resulting in high liquid phase viscosities that cause mass transfer limitations. Experiments in an extractive distillation pilot plant were performed with the objective of firstly exploring different operating conditions and secondly to compare the mass transfer efficiencies produced by [hmim][TCB] and the reference organic solvent N-methyl-2-pyrrolidone. Pure viscosity, density and surface tension data as well as ternary viscosity and density data of tolune - methylcyclohexane - [hmim][TCB] were measured to compute the mass transfer efficiency. From pilot plant experiments it was found that all the studied operating conditions did not form two-liquid phases. However, the high solvent-to-feed ratios increased the liquid phase viscosities and consequently the use of this ionic liquid produces Height Equivalent to a Theoretical Plates (HETPs) twice as high as the reference solvent NMP causing slightly lower top purities and a longer required distillation column for a required separation.