Green organic entrainers and natural deep eutectic solvents (NADESs) possessing high boiling points and decomposition temperatures, exhibit considerable potential as advanced materials for green entrainers in extractive distillation. However, there is a wide range of solvents to choose from and their properties are only rarely available for use in process design and simulation. The present study aims to assess the selection parameters and examine the performance of and select green organic entrainers and NADESs for the separation of the close boiling mixture methylcyclohexane-toluene. The evaluation carried out was based on selectivity and relative volatility values obtained by using predictive models. COSMO-RS (a unimolecular quantum chemical calculation) was employed to predict the selectivity at infinite dilution, while group contribution methods such as UNIFAC and modified UNIFAC (Dortmund) were used to predict the relative volatility. According to the calculated results, the selectivity appeared a more important selection parameter than the performance index. The relative volatility prediction using the UNIFAC and UNIFAC Dortmund methods exhibits comparable trends to the selectivity results derived from COSMO-RS. However, the use of UNIFAC and modified UNIFAC (Dortmund) in predicting the relative volatility of NADES containing mixtures is limited due to the absence of functional group parameters. This CAPE study reveals that, based on the calculated selectivity (using COSMO-RS) and relative volatility (using UNIFAC, and modified UNIFAC (Dortmund)), most of the proposed green organic entrainers and NADESs exhibit a higher or comparable selectivity and relative volatility as the benchmark entrainers. This confirms the potential of the evaluated green entrainers with higher selectivity and relative volatility to enhance the design of extractive distillation. Therefore, the cost, energy and water consumption, as well as CO2 emissions in the methylcyclohexane and toluene separation can be reduced.@en

The aim of this study is to introduce and showcase the applicability of the ‘Green-by-Design method’, a tool created by the cooperative Cosun that integrates different indicators involving economic, environmental, inherent safety and health aspects for comparative analysis at an early design stage. Two case studies are presented to exemplify the evaluation principles and steps considered along the ‘Green-by-Design method’: ethylene glycol production and fava bean protein isolate extraction. The results indicate that the ‘Green-by-Design method’ provides a comprehensive comparison of different design concepts, by combining various indicators into a single score, enabling sustainability to be an integral aspect in the decision-making during an early design phase.@en

"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.

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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.

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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.

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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.

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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.

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Product and Process Design: Driving Innovation is a comprehensive textbook for students and industrial professionals. It treats the combined design of innovative products and their innovative manufacturing processes, providing specific methods for BSc, MSc, PDEng and PhD courses. Students, industrial innovators and managers are guided through all design steps in all innovation stages (discovery, concept, feasibility, development, detailed engineering, and implementation) to successfully obtain novel products and their novel processes. 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.@en

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⁺.

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Different approaches that could be used for process intensification in liquid-liquid extraction and their wide applications in bio-based and chemical processes are described. An approach for process intensification in liquid-liquid extraction could be the use of new materials in the solvent system instead of the conventional organic solvents. These new materials include ionic liquids, deep eutectic solvents, polymers, modifiers, and supramolecular structures etc. that increase the extraction capability of the solvent system. The most known approach for process intensification is the development of novel extractors such as micromixers, microchannels, membrane extractors etc. that bring more effective and efficient extraction of products than the traditional extractors. Another approach is the use of external force such as ultrasound, microwave, centrifugal and electric field as a means of process intensification by increasing the extraction efficiency and selectivity in solvent extraction processes. Integration and hybrid separation methods also bring process intensification by means of combined operations, reduced energy consumption and capital investment. These methods include extractive fermentation, reactive extraction, extractive distillation, membrane extraction etc. All the above mentioned process intensification strategies are applied in liquid-liquid extraction of bio-based products, such as fermentation-based products, biofuels and platform chemicals, and significant improvements in extraction performance can be achieved.@en

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.

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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.

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Spray roasting of metal chloride solutions is frequently used in steel industries to recover pickling liquids. As spray roasting reactors are difficult to characterize experimentally, computational fluid dynamics simu- lations have been used to investigate reactor performance. These simulations require a particle formation model, which describes the particles size history including the characteristic effect of particle swelling. Based on available literature, different swelling models are compared by simulations of an industrial scale reactor. The influence of particle swelling is discussed. The results clearly indicate the necessity to investi- gate particle swelling, potential collision effects and fragmentation for sound simulation of spray roasting reactors.@en

The focus of this work is the extraction of the bio-based platform chemical 5-hydroxymethylfurfural (HMF) from aqueous solution. HMF is a promising molecule produced from hexoses and can serve as basis for numerous applications such as biofuels and bio-based polymers. The goal of this work is to improve the isolation of this valuable compound by means of a countercurrent extraction process. In a first step, equilibrium studies are carried out on the applied component system MIBK/HMF/water. Experiments show that no significant influence of HMF concentration and process temperature on the partition coefficients exists in the investigated ranges. Only by adding sodium chloride it is possible to increase the partition coefficient by a factor of about 2.5. Comparison with other organic solvents, such as ethyl acetate and 2-heptanone shows that MIBK has superior properties for HMF extraction since it yields high partition coefficients and has low solubility in water. Hence, it is used in the countercurrent extraction. The process intensified extraction column (PIEC) applied in our investigations has high extraction efficiency due to its optimized hydrodynamics, resulting in experimental yields of the extraction up to 99% of HMF@en

Ionic liquids (ILs) can replace conventional solvents in separation processes, such as extractive distillation (ED), because of their ability to selectively separate azeotropic/close boiling mixtures. Four case studies were selected: ethanol/water (1-ethyl-3-methylimidazolium dicyanamide, [emim][N(CN)2], and ethylene glycol, EG), 1-hexene/n-hexane (no suitable IL found), methylcyclohexane/toluene (1-hexyl-3-methylimidazolium tetracyanoborate, [hmim][B(CN)4], and N-methyl-2-pyrrolidone, NMP), and ethylbenzene/styrene (4-methyl-N-butylpyridinium tetrafluoroborate, [4-mebupy][BF4], and sulfolane). Pilot plant experiments proved that the developed models for ED could well describe the experimental results.

Conceptual processes were designed for the ED of three case studies. The ethanol/water process with [emim][N(CN)2] reduced the energy requirements with 16 % compared to the process with EG, provided that proper heat integration is implemented. The methylcyclohexane (MCH)/toluene process with [hmim][B(CN)4] required about 50 % less energy with heat integration than the conventional process with NMP with heat integration.

The IL [4-mebupy][BF4] reduced the energy requirement most compared to the conventional distillation for the ethylbenzene/styrene process (43.2 %), which is 5 % lower than with extractive distillation with sulfolane. However, the capital expenditures were about 23 % higher than for the sulfolane process. It can be concluded from the total annual costs that all studied ED processes outperform the current distillation process to obtain high purity styrene, but that ILs do not perform better than sulfolane.

The general conclusion of these four examples is that only in some special cases ILs can be more advantageously applied than conventional solvents in extractive distillation. The key performance points for ED are a high selectivity and high capacity, next to the solvent recovery and heat integration.@en

Enantioseparation through liquid extraction technology is an emerging field, e.g., enantioseparations of amino acids (and derivatives thereof), amino alcohols, amines, and carboxylic acids have been reported. Often, when a new selector is developed, the versatility of substrate scope is investigated. From an industrial point of view, the problem is typically approached the other way around, and for a target racemate, a selector needs to be found in order to accomplish the desired enantioseparation. This study presents such a screening approach for the separation of the enantiomers of DL-¿-methyl phenylglycine amide (DL-¿-MPGA), a model amide racemate with high industrial relevance. Chiral selectors that were reported for other classes of racemates were investigated, i.e., several macrocyclic selectors and Pd-BINAP complexes. It appeared very challenging to obtain both high extraction yields and good enantioselectivity for most selectors, but Pd-BINAP-based selectors performed well, with enantioselectivities up to 7.4 with an extraction yield of the desired enantiomer of 95.8%. These high enantioselectivities were obtained using dichloromethane as solvent. Using less volatile chlorobenzene or 1-chloropentane, reasonable selectivities of up to 1.7 were measured, making these the best alternative solvents for dichloromethane. Chirality 27:123¿130, 2015@en

Solvent impregnated resins (SIRs) were evaluated for the recovery of pyridine derivatives from an aqueous waste-stream containing also acetic acid and succinonitrile. For this purpose, a new solvent was developed, synthesized and impregnated in Amberlite XAD4. Sorption studies were used to determine the capacity, selectivity and the mass-transfer rate. A high capacity of 21 g 4-yanopyridine (CP) per kg SIR was found, with very high selectivity toward CP over the other solutes of at least 570. A modified Langmuir equation could describe the equilibrium sorption isotherm. Both the linear driving force model and a Fickian diffusion model were evaluated. The Fick-model described both regeneration and loading best. The CP-diffusivity through the solvent phase was estimated at 6.53 10 13 ± 2.5% m2 s 1. The model was validated using fixed-bed column experiments. The R2 values for this model ranged between 0.94 at a flow rate of 5 mL/min and 0.99 at a flow rate of 1 mL/min during the loading cycle. Due to mass-transfer limitations the breakthrough profiles were broad and breakthrough occurred after 5 or 23 bed volumes, for flow rates of 5 and 1 mL/min, respectively. Both acetic acid and succinonitrile broke through immediately due to the very high CP-selectivity of the SIR.@en

Solventimpregnatedresinsarepromisingfortheremovalofpolarorganiccompoundsfromaqueous streams, buthavelowmass-transferrates. Athoroughunderstandingofthephenomenaoccurringinside the oresofthesolventimpregnatedresinisthereforerequired.Inthisstudyamathematicalmodelwas developed todescribethesimultaneousdiffusionandreaction.Thediffusionwasdescribedusingthe Maxwell¿Stefanapproachtowardsmulti-componentdiffusionandincludedthevolume-expansionof the organicphase.Themodelwasvalidatedusingexperimentaldatafromtheliteratureonthe extractionofphenolbyCyanex923impregnatedinmacro-porouspolypropylene.Themodeldescribed the experimentaldataasfunctionoftemperatureandinitialconcentrationaccuratelywithan R240.96 and aregressedreactionrateconstantwithaconfidence intervalof 76%. Analysisofthemodelresults revealedthatmulti-componenteffectsasdescribedbytheMaxwell¿Stefanmodelwereoflimited importance whereasthevolumeexpansionwasessentialtoaccuratelydescribetheexperimentaldata.@en