This paper reports the results of an investigation of industrial requirements for thermodynamic and transport properties carried out during the years 2019–2020. It is a follow-up of a similar investigation performed and published 10 years ago by the Working Party (WP) of Thermodynamics and Transport Properties of European Federation of Chemical Engineering (EFCE).1 The main goal was to investigate the advances in this area over the past 10 years, to identify the limitations that still exist, and to propose future R&D directions that will address the industrial needs. An updated questionnaire, with two new categories, namely, digitalization and comparison to previous survey/changes over the past 10 years, was sent to a broad number of experts in companies with a diverse activity spectrum, in oil and gas, chemicals, pharmaceuticals/biotechnology, food, chemical/mechanical engineering, consultancy, and power generation, among others, and in software suppliers and contract research laboratories. Very comprehensive answers were received by 37 companies, mostly from Europe (operating globally), but answers were also provided by companies in the USA and Japan. The response rate was about 60%, compared to 47% in the year 2010. The paper is written in such a way that both the majority and minority points of view are presented, and although the discussion is focused on needs and challenges, the benefits of thermodynamics and success stories are also reported. The results of the survey are thematically structured and cover changes, challenges, and further needs for a number of areas of interest such as data, models, systems, properties, and computational aspects (molecular simulation, algorithms and standards, and digitalization). Education and collaboration are discussed and recommendations on the future research activities are also outlined. In addition, a few initiatives, books, and reviews published in the past decade are briefly discussed. It is a long paper and, to provide the reader with a more complete understanding of the survey, many (anonymous) quotations (indicated with “...” and italics) from the industrial colleagues who have participated in the survey are provided. To help disseminate the specific information of interest only to particular industrial sectors, the paper has been written in such a way that the individual sections can also be read independently of each other.

A detailed kinetic model for the lignin oxidation chemistry is presented. It is based mainly on the mechanisms and kinetics presented in the literature. Parameters that could not be found in the literature were regressed against the experimental data obtained from oxidation experiments with softwood kraft lignin. In addition to the detailed model for the chemistry, acid-base equilibrium reactions and gas-liquid mass transfer were modeled. Most of the experimental observations could be reproduced with the developed model. The reasons behind the behavior of guaiacyl and condensed phenols are discussed. The reaction routes affecting lignin solubilization and chemical consumption are presented. Model-ing of acid-base equilibria proved to be important because acid-base pairs of reactants react differently. Carbon dioxide buffers the pH and in this way affects the chemical reactions through the pH. A similar model could also be developed for other lignin treatments; for example, waste water purification or chemicals production in new biorefinery concepts. The developed reaction scheme will be used as a part of oxygen delignification model.

A kinetic analysis is presented for the homogeneous degradation of galactoglucomannan (GGM) in hot water extraction conditions. In the experiments used for constructing the kinetic model, GGM extracted from spruce wood meal was treated at temperatures from 150 to 170 °C and in buffered pH 3.8−4.2. The hydrolysis of glycosidic bonds in GGM was modeled as a random process which is catalyzed by hydrogen ions. The real hydrogen ion concentration at the reaction temperatures was estimated. The Arrhenius equation was used to describe the temperature dependence of the hydrolysis rate and an activation energy of 102 kJ/mol was obtained for the reaction. The presented model predicts accurately the evolution of the molecular weight distribution with lower computational load than other similar models.

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Advanced analysis methods have been developed to follow the reactions of lignin during alkaline oxygen delignification conditions more comprehensively than before. This aim was attained by monitoring both the lignin macromolecule and the dissolved reaction products. Softwood (SW) and hardwood (HW) kraft spent liquor lignins were studied as substrates under various reaction conditions. The decrease in the contents of different types of free phenolic hydroxyl groups and the concurrent formation of carboxylic acids was followed by 31P NMR of the phosphitylated products. In addition, the formation of acidic degradation products with low molecular weight was determined by capillary zone electrophoresis (CE). This way, it was possible to distinguish the carboxylic acids bound to the lignin macromolecule from the cleaved reaction products, even if they partly co-precipitated during sample preparation. Peak deconvolution was applied to get information on syringyl type phenolic structures and on C(5) condensed guaiacyl structures in hardwood lignin. Pyrolysis-GC/MS was applied to provide additional information about the distribution of guaiacyl/syringyl/p-hydroxyphenyl (G/S/H) type lignin subunits, as well as changes in the phenylpropane side chain.

In this article, a phenomenological model is proposed for alkali impregnation and hot water extraction of wood. Elementary reaction kinetics, ion exchange (IE) equilibrium, and mass transfer rates are considered in the model. IE is a consequence of the dissociation of the covalently bound uronic acid and phenolic groups in the wood fiber wall (FW). Due to this effect, the molality of cations is higher in the FW liquid than in the liquid external to the FW, whereas the opposite is true for anions. For the development of kinetic models under the participation of hydroxyl and hydrogen ions, the estimation of their molalities in these two liquid phases is crucial because of their ubiquitous presence in chemical reactions. This study applies a recently developed physicochemical modeling environment in which alkali impregnation and hot water extraction processes are considered. The simulations revealed that the IE effect is significant and affects the chemical reaction kinetics in both processes in focus. Furthermore, the IE effect does not remain constant but varies as a function of treatment time.

This work introduces a phenomena-based model for delignification in the kraft pulping process. The solubilization of lignin is described as a set of chemical reactions representing the entire chemistry of lignin degradation as well as dissolution of the degraded lignin. For modeling, reaction mechanisms and reactions kinetics derived mainly from the literature were used. Each reaction was simulated separately and then combined for the overall degradation. The model was validated with experimental results from pine wood meal pulping under a wide range of reaction parameters. The experimental data presented a good fit with the model. With the aid of the model, the structure and the amount of wood components, in fibers and black liquor, can be determined at any pulping stage. Several engineering parameters can be computed from the detailed chemical composition of liquor and wood or chemical pulp. These include, e.g., kappa number, brightness, yield, active alkali, effective alkali, sulfidity, and higher heating value.

Thermodynamics is the science of the interactions between energy and matter. It was formalized in the late 19th century and remains an essential piece in solving many technological challenges that society faces today. Yet, it is often considered complex and challenging, perhaps because it is often taught within a rigid mathematical framework, without highlighting the extensive range of applications and the tools that it offers for understanding and elaborating a sustainable future. The authors of this paper have performed an industrial survey (Kontogeorgis et al., Ind. Eng. Chem. Res., 2021, 60, 13, 4987-5013), which pointed out that thermodynamics is indeed a cornerstone of many processes in a large range of industries, but that as of today, many questions and needs remain unanswered. Some missing answers are caused by a lack of knowledge of the existing tools (educational issue), some by the unavailability of models, parameters or by the lack of transferability of the concepts from one system to another. In other cases, simply, no generally accepted approach exists, and fundamental research is required for understanding the phenomena. In all cases, data are needed, either to understand, develop, or validate the models. Specific recent examples of applied thermodynamics research relevant to industrial practice are discussed. This manuscript aims not only at promoting research but also at encouraging highly trained professionals to engage in education, laboratory work, fundamental developments, and/or model validation. Such professionals should find positions both in academia and in industry, as well as with software vendors. Collaboration between academia, industry, and software vendors is essential in order to foster new developments and serve the goals of sustainable development and circular economy.