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Industrial Chemistry Reactions: Kinetics, Mass Transfer and Industrial Reactor Design

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A special issue of Processes (ISSN 2227-9717). This special issue belongs to the section "Chemical Processes and Systems".

Deadline for manuscript submissions: closed (31 July 2021) | Viewed by 49133

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Prof. Dr. Elio Santacesaria

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CEO Eurochem Engineering LtD ex, University of Naples, 80131 Naples, Italy
Interests: kinetics; catalysis; reactor design and simulation; separation science
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Prof. Dr. Riccardo Tesser

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NICL—Department of Chemical Science, University of Naples Federico II, 80126 Naples, Italy
Interests: heterogenous catalysis; biomass transformation; green chemistry kinetics; mass transfer and industrial reactors
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Prof. Dr. Vincenzo Russo

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NICL—Department of Chemical Science, University of Naples Federico II, 80126 Naples, Italy
Interests: chemical reaction engineering; kinetics; catalysis; reactor; modeling
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Special Issue Information

Dear Colleagues,

The impressive progress of commercially available computers allows us nowadays to solve complicated mathematical problems in many scientific and technical fields. This revolution has reinvigorated chemical engineering science in all its compartments. More sophisticated approaches to catalysis, kinetics, reactor design and simulation have been developed thanks to the newly available powerful calculation methods. It is well known that many chemical reactions are of great interest for industrial processes and must be conducted on a large-scale in order to get needed information in thermodynamics, kinetics, and transport phenomena related to mass, energy, and momentum. For a reliable industrial-scale reactor design, all this information must be employed in appropriate equations and mathematical models that allow for accurate and reliable simulations for the purposes of scaling up. The aim of this proposed Special Issue is to collect worldwide contributions from experts in the field of industrial reactor design based on kinetic and mass-transfer studies. The following areas/sections will be covered by the call for original papers:

Kinetic studies for complex reaction schemes (multiphase systems)
Kinetics and mass transfer in multifunctional reactors
Reactions in mass-transfer dominated regime (fluid-solid and intraparticle diffusive limitations)
Kinetics and mass-transfer modeling with alternative approaches (ex. stochastic modeling)
Pilot plant and industrial size reactors simulation and scale-up based on kinetic studies (lab-to-plant approach)

Prof. Elio Santacesaria
Prof. Riccardo Tesser
Prof. Dr. Vincenzo Russo
Guest Editors

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Processes is an international peer-reviewed open access monthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2400 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

reactor design and simulation
kinetics of chemical reactions
complex reactions
multiphase systems
multi-functional reactors
transport phenomena

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Industrial Chemistry Reactions (3rd Edition): Kinetics, Mass and Heat Transfer in View of the Industrial Reactors Design in Processes (1 article)

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Editorial

Jump to: Research, Review

5 pages, 1364 KiB

Open AccessEditorial

Special Issue on “Industrial Chemistry Reactions: Kinetics, Mass Transfer and Industrial Reactor Design”

by Elio Santacesaria, Riccardo Tesser and Vincenzo Russo

Processes 2022, 10(2), 411; https://doi.org/10.3390/pr10020411 - 20 Feb 2022

Viewed by 1361

Abstract

The impressive developments in commercially available technologies, in terms of new equipment and faster computers, allow us to solve ever-more complicated chemical and technical issues within industrial chemistry and reaction engineering fields [...] Full article

(This article belongs to the Special Issue Industrial Chemistry Reactions: Kinetics, Mass Transfer and Industrial Reactor Design)

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Research

Jump to: Editorial, Review

11 pages, 1731 KiB

Open AccessFeature PaperArticle

Removal of Dissolved Oxygen from Water by Nitrogen Stripping Coupled with Vacuum Degassing in a Rotor–Stator Reactor

by Zemeng Zhao, Zhibang Liu, Yang Xiang, Moses Arowo and Lei Shao

Processes 2021, 9(8), 1354; https://doi.org/10.3390/pr9081354 - 01 Aug 2021

Cited by 5 | Viewed by 4107

Abstract

Oxygen is a harmful substance in many processes because it can bring out corrosion and oxidation of food. This study aimed to enhance the removal of dissolved oxygen (DO) from water by employing a novel rotor–stator reactor (RSR). The effectiveness of the nitrogen stripping coupled with vacuum degassing technique for the removal of DO from water in the RSR was investigated. The deoxygenation efficiency (η) and the mass transfer coefficient (K_La) were determined under various operating conditions for the rotational speed, liquid volumetric flow rate, gas volumetric flow rate, and vacuum degree. The nitrogen stripping coupled with vacuum degassing technique achieved values for η and K_La of 97.34% and 0.0882 s⁻¹, respectively, which are much higher than those achieved with the vacuum degassing technique alone (η = 89.95% and K_La = 0.0585 s⁻¹). A correlation to predict the K_La was established and the predicted K_La values were in agreement with the experimental values, with deviations generally within 20%. The results indicate that RSR is a promising deaerator thanks to its intensification of gas–liquid contact. Full article

(This article belongs to the Special Issue Industrial Chemistry Reactions: Kinetics, Mass Transfer and Industrial Reactor Design)

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21 pages, 3328 KiB

Open AccessFeature PaperArticle

Optimization of the Production of 1,1-Diethoxybutane by Simulated Moving Bed Reactor

by Jasper Spitters, Jonathan C. Gonçalves, Rui P. V. Faria and Alírio E. Rodrigues

Processes 2021, 9(2), 189; https://doi.org/10.3390/pr9020189 - 20 Jan 2021

Cited by 5 | Viewed by 1567

Abstract

Simulated moving bed technology is applied in the field of pharmaceutical, petrochemical and fine chemistry. It shows capability in separating multicomponent mixtures up to high purities. In this work, an attempt was made to optimize the production of 1,1-diethoxybutane (DEB), using the simulated moving bed technology. A fixed bed model is made with good agreement with experimental results. This fixed bed model was expanded to a simulated moving bed model. This model was used to determine the optimum conditions regarding the switching time and flowrates in each section. From this model, the optimum switching time was found to be 2.4 min, and the ratio of liquid flowrate over the solid flowrate in ^{Section 1}^{Section 2}^{Section 3} and ^{Section 4} of the SMBR was found to be 4.24, 1.77, 3.03 and 1.35, respectively. Under those conditions, the productivity was 19.8 kg DEB per liter of adsorbent per day, and the desorbent consumption was 6.1 L of ethanol per kg of DEB. The results were obtained with a minimum purity of the extract and raffinate of 97%. Full article

(This article belongs to the Special Issue Industrial Chemistry Reactions: Kinetics, Mass Transfer and Industrial Reactor Design)

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11 pages, 2900 KiB

Open AccessArticle

Transesterification Using Ultrasonic Spray of Triolein Containing CaO Particles into Methanol Vapor in a 3-Phase Reactor

by Ravisut Vitidsant, Satoshi Kodama and Hidetoshi Sekiguchi

Processes 2021, 9(1), 181; https://doi.org/10.3390/pr9010181 - 19 Jan 2021

Cited by 2 | Viewed by 2181

Abstract

Ultrasonic spraying was used in a three-phase reactor to produce small droplets of triolein mixed with CaO as a solid catalyst at temperatures above the boiling point of methanol for enhancement of the transesterification of triolein. Droplets fell in the methanol countercurrent flow and were collected at the bottom of the reactor, followed by circulation to the ultrasonic spray system. The experimental parameters included triolein flow rates of 2.5–9.0 mL/min, reaction temperatures of 70–100 °C, and catalyst contents of 1.0–7.0 wt%. The methanol feed rate was set to be constant. The results suggested that the enhancement was successful after using the three-phase reactor by generating a high contact surface area for the droplets, which was a key factor for determining the performance. Comparing the results with conventional transesterification in the liquid phase using the same CaO at 60 °C, the three-phase reactor produced a methyl ester yield 2–5% higher during the 60 min trial period. However, the yield became lower after 60 min because the mass transfer of methanol to the droplets was limited. The transesterification kinetics were estimated based on the experimental data—assuming a first-order reaction—and the results indicated a range of the rate constant, an apparent activation energy, and a pre-exponential factor of 1.21–3.70 × 10⁻² min⁻¹, 36.1 kJ mol⁻¹, and 64.9 min⁻¹, respectively, suggesting that the three-phase reactor was effective for fast transesterification at the initial stage. Full article

(This article belongs to the Special Issue Industrial Chemistry Reactions: Kinetics, Mass Transfer and Industrial Reactor Design)

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16 pages, 5862 KiB

Open AccessArticle

Development of Carbonization and a Relatively High-Temperature Halogenation Process for the Removal of Radionuclides from Spent Ion Exchange Resins

by Hee-Chul Yang, Hyeon-Oh Park, Kyu-Tae Park, Sung-Jun Kim, Hyung-Ju Kim, Hee-Chul Eun and Keunyoung Lee

Processes 2021, 9(1), 96; https://doi.org/10.3390/pr9010096 - 05 Jan 2021

Cited by 4 | Viewed by 2098

Abstract

This study investigated a two-step thermochemical treatment process consisting of carbonization and halogenation for the removal of radionuclides from spent cation-exchange resin (CER). Based on a thermal analysis of cation-exchange resins, we propose a two-step thermochemical treatment process involving the conversion of spent CER into pyrocarbon and then the removal of radioactive elements from the carbonized CER by converting them volatile halides at very high temperatures. The proposed process mainly consists of a carbonization and halogenation reactor, a UHC (unburned hydrocarbon) combustor, and wet scrubber. A step-by-step experimental and numerical optimization study was conducted with the carbonization and halogenation reactor and the UHC combustor. The optimum operating conditions could be established based on the results of a thermal analysis of the CER, a nonisothermal kinetic analysis, a numerical modeling study of a plug flow reactor (PFR)-type combustor, and a thermodynamic equilibrium analysis of a system consisting of a mix of carbonized CER and halogenation gas. The results of this study present detailed design of a novel multifunctional reactor and operating conditions of a bench-scale carbonization and halogenation process. Basic performance tests using CER doped with nonradioactive Co and Cs, indicated as Cs-137/134 and Co-60/58, were conducted under the optimized conditions. The results of these tests showed that the novel thermochemical process proposed in this study is a viable process that effectively removes radioactive elements from spent CER. Full article

(This article belongs to the Special Issue Industrial Chemistry Reactions: Kinetics, Mass Transfer and Industrial Reactor Design)

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14 pages, 3290 KiB

Open AccessArticle

Study of Deactivation in Suzuki Reaction of Polymer-Stabilized Pd Nanocatalysts

by Linda Nikoshvili, Elena S. Bakhvalova, Alexey V. Bykov, Alexander I. Sidorov, Alexander L. Vasiliev, Valentina G. Matveeva, Mikhail G. Sulman, Valentin N. Sapunov and Lioubov Kiwi-Minsker

Processes 2020, 8(12), 1653; https://doi.org/10.3390/pr8121653 - 15 Dec 2020

Cited by 11 | Viewed by 2333

Abstract

This work is addressed to the phenomenon of catalyst deactivation taking place during the repeated uses in the reaction of Suzuki-Miyaura (S-M) cross-coupling, which is widely applied in industry for C-C bond formation. Ligandless catalysts based on Pd(0) NPs supported on hyper-cross-linked polystyrene (HPS) of two types (non-functionalized and bearing tertiary amino groups) were studied in a model S-M reaction between 4-bromoanisole and phenylboronic acid. Synthesized catalysts were shown to be highly active under mild reaction conditions. HPS allows stabilization of Pd(0) NPs and prevents their agglomeration and detectable Pd leaching. However, the loss of catalytic activity was observed during recycling. The deactivation issue was assigned to the hydrophobic nature of non-functionalized HPS, which allowed a strong adsorption of cross-coupling product during the catalyst separation procedure. A thorough washing of Pd/HPS catalyst by hydrophobic solvent was found to improve to the big extent the observed catalytic activity, while the replacement of non-functionalized HPS by a one containing amino groups increased the catalyst stability at the expense of their activity. Full article

(This article belongs to the Special Issue Industrial Chemistry Reactions: Kinetics, Mass Transfer and Industrial Reactor Design)

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26 pages, 6571 KiB

Open AccessArticle

Numerical Study on Bubble Rising in Complex Channels Saturated with Liquid Using a Phase-Field Lattice-Boltzmann Method

by Kang Yu, Yumei Yong and Chao Yang

Processes 2020, 8(12), 1608; https://doi.org/10.3390/pr8121608 - 07 Dec 2020

Cited by 7 | Viewed by 2879

Abstract

Packed bed reactors have been widely applied in industrial production, such as for catalytic hydrogenation. Numerical simulations are essential for the design and scale-up of packed beds, especially direct numerical simulation (DNS) methods, such as the lattice-Boltzmann method (LBM), which are the focus of future researches. However, the large density difference between gas and liquid in packed beds often leads to numerical instability near phase interface when using LBM. In this paper, a lattice-Boltzmann (LB) model based on diffuse-interface phase-field is employed to simulate bubble rising in complex channels saturated with liquid, while the numerical problems caused by large liquid-to-gas density ratio are solved. Among them, the channel boundaries are constructed with regularly arranged circles and semicircles, and the bubbles pass through the channels accompanied by deformation, breakup, and coalescence behaviors. The phase-field LB model is found to exhibit good numerical stability and accuracy in handing the problem of the bubbles rising through the high-density liquid. The effects of channel structures, gas-liquid physical properties, and operating conditions on bubble deformation, motion velocity, and drag coefficient are simulated in detail. Moreover, different flow patterns are distinguished according to bubble behavior and are found to be associated with channel structure parameters, gravity Reynolds number (Re_Gr), and Eötvös number (Eo). Full article

(This article belongs to the Special Issue Industrial Chemistry Reactions: Kinetics, Mass Transfer and Industrial Reactor Design)

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16 pages, 3261 KiB

Open AccessArticle

A Robust Method for the Estimation of Kinetic Parameters for Systems Including Slow and Rapid Reactions—From Differential-Algebraic Model to Differential Model

by Tapio Salmi, Esko Tirronen, Johan Wärnå, Jyri-Pekka Mikkola, Dmitry Murzin and Valerie Eta

Processes 2020, 8(12), 1552; https://doi.org/10.3390/pr8121552 - 27 Nov 2020

Cited by 1 | Viewed by 1758

Abstract

Reliable estimation of kinetic parameters in chemical systems comprising both slow and rapid reaction steps and rapidly reacting intermediate species is a difficult differential-algebraic problem. Consequently, any conventional approach easily leads to serious convergence and stability problems during the parameter estimation. A robust method is proposed to surmount this dilemma: the system of ordinary differential equations and nonlinear algebraic equations is converted to ordinary differential equations, which are solved in-situ during the parameter estimation. The approach was illustrated with two generic examples and an example from green chemistry: synthesis of dimethyl carbonate from carbon dioxide and methanol. Full article

(This article belongs to the Special Issue Industrial Chemistry Reactions: Kinetics, Mass Transfer and Industrial Reactor Design)

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16 pages, 4199 KiB

Open AccessArticle

Design and Development of Novel Continuous Flow Stirred Multiphase Reactor: Liquid–Liquid–Liquid Phase Transfer Catalysed Synthesis of Guaiacol Glycidyl Ether

by Nikhil H. Margi and Ganapati D. Yadav

Processes 2020, 8(10), 1271; https://doi.org/10.3390/pr8101271 - 10 Oct 2020

Cited by 3 | Viewed by 2882

Abstract

Phase transfer catalysed (PTC) reactions are used in several pharmaceutical and fine chemical industrial processes. We have developed a novel stirred tank reactor (Yadav reactor) to conduct batch and continuous liquid–liquid–liquid (L-L-L) PTC reactions. The reactor had a provision of using three independent stirrers for each phase, thereby having complete control over the rate of mass transfer across the two interfaces. In the continuous mode of operation, the top and bottom phases were continuously fed into the reactor while the middle phase was used as a batch. All three stirrers were used independently, thereby having independent control of mass transfer resistances. The reactor in a batch mode showed higher conversion and selectivity compared to a conventional batch reactor. L-L-L PTC reaction in the continuous mode was successfully performed without loss of the middle catalyst phase and with steady conversion and selectivity. The reaction of guaiacol with epichlorohydrin was conducted as a model reaction, with a 76% conversion of epichlorohydrin, 85% selectivity of guaiacol glycidyl ether, and the middle catalyst phase was stable throughout the process. Full article

(This article belongs to the Special Issue Industrial Chemistry Reactions: Kinetics, Mass Transfer and Industrial Reactor Design)

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23 pages, 8907 KiB

Open AccessFeature PaperArticle

Soybean Oil Epoxidation: Kinetics of the Epoxide Ring Opening Reactions

by Elio Santacesaria, Rosa Turco, Vincenzo Russo, Riccardo Tesser and Martino Di Serio

Processes 2020, 8(9), 1134; https://doi.org/10.3390/pr8091134 - 11 Sep 2020

Cited by 21 | Viewed by 5000

Abstract

The epoxide ring opening reaction (ROR) can be considered as the most important side reaction occurring in the epoxidation of soybean oil reaction network. This reaction consistently reduces the selectivity to epoxidized soybean oil (ESBO). The reaction is also important for producing polyols and lubricants. In this work, the reaction was studied in different operative conditions to evaluate the effect on ROR rate respectively: (i) The Bronsted acidity of the mineral acid (H₂SO₄ or H₃PO₄), used as catalyst for promoting the oxidation with hydrogen peroxide of formic to performic acid, that is, the reactant in the epoxide formation; (ii) the concentration of the nucleophilic agents, normally present during the ESBO synthesis like HCOOH, HCOOOH, H₂O, H₂O₂; (iii) the stirring rate that changes the oil–water interface area and affects the mass transfer rate; (iv) the adopted temperature. Many different kinetic runs were made in different operative conditions, starting from an already epoxidized soybean oil. On the basis of these runs two different reaction mechanisms were hypothesized, one promoted by the Bronsted acidity mainly occurring at the oil–water interface and one promoted by the nucleophilic agents, in particular by formic acid. As it will be seen, the kinetic laws corresponding to the two mentioned mechanisms are quite different and this explain the divergent data reported in the literature on this subject. All the kinetic runs were correctly interpreted with a new developed biphasic kinetic model. Full article

(This article belongs to the Special Issue Industrial Chemistry Reactions: Kinetics, Mass Transfer and Industrial Reactor Design)

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10 pages, 869 KiB

Open AccessFeature PaperEditor’s ChoiceArticle

Hydrogenation of Trans,Trans-Muconic Acid to Bio-Adipic Acid: Mechanism Identification and Kinetic Modelling

by Alessandro Rosengart, Carlo Pirola and Sofia Capelli

Processes 2020, 8(8), 929; https://doi.org/10.3390/pr8080929 - 02 Aug 2020

Cited by 3 | Viewed by 3343

Abstract

The hydrogenation of trans,trans-muconic acid was investigated on a Pt/C 5% (wt) catalyst in a batch slurry reactor at constant hydrogen pressure (4 bar) and temperature (323, 333 and 343 K), with the purpose of developing a kinetic model able to predict conversions and product distributions. A dual-site Langmuir–Hinshelwood–Hougen–Watson (LHHW) model with hydrogen dissociation provided good fitting of the experimental data. The model parameters were regressed by robust numerical methods to overcome the computational challenges of the model parameters’ collinearity. Different reaction mechanisms were tested; the best model involved two subsequent hydrogenation steps. The first step yielded from trans,trans-muconic acid a monounsaturated intermediate (trans-2-hexenedioic acid), which was further hydrogenated to adipic acid in the second step. The intermediate was subjected to an equilibrium isomerization with cis-2-hexenedioic acid. The activation energy values and the rate constants were calculated for the reactions, providing the first reference for trans,trans-muconic acid hydrogenation. Full article

(This article belongs to the Special Issue Industrial Chemistry Reactions: Kinetics, Mass Transfer and Industrial Reactor Design)

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12 pages, 2235 KiB

Open AccessArticle

Modification of Conventional Sugar Juice Evaporation Process for Increasing Energy Efficiency and Decreasing Sucrose Inversion Loss

by Somchart Chantasiriwan

Processes 2020, 8(7), 765; https://doi.org/10.3390/pr8070765 - 30 Jun 2020

Cited by 3 | Viewed by 12388

Abstract

The evaporation process, boiler, and turbine are the main components of the cogeneration system of the sugar factory. In the conventional process, the evaporator requires extracted steam from the turbine, and bled vapor from the evaporator is supplied to the juice heater and the pan stage. The evaporation process may be modified by using extracted steam for the heating duty in the pan stage. This paper is aimed at the investigation of the effects of this process modification. Mathematical models of the conventional and modified processes were developed for this purpose. It was found that, under the conditions that the total evaporator area is 13,000 m², and the inlet juice flow rate is 125 kg/s, the optimum modified evaporation process requires extracted steam at a pressure of 157.0 kPa. Under the condition that the fuel consumption rate is 21 kg/s, the cogeneration system that uses the optimum modified evaporation process yields 2.3% more power output than the cogeneration system that uses a non-optimum conventional cogeneration process. Furthermore, sugar inversion loss of the optimum modified process is found to be 63% lower than that of the non-optimum conventional process. Full article

(This article belongs to the Special Issue Industrial Chemistry Reactions: Kinetics, Mass Transfer and Industrial Reactor Design)

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Review

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35 pages, 5681 KiB

Open AccessFeature PaperReview

Revisiting the Role of Mass and Heat Transfer in Gas–Solid Catalytic Reactions

by Riccardo Tesser and Elio Santacesaria

Processes 2020, 8(12), 1599; https://doi.org/10.3390/pr8121599 - 04 Dec 2020

Cited by 9 | Viewed by 4980

Abstract

The tremendous progress in the computing power of modern computers has in the last 20 years favored the use of numerical methods for solving complex problems in the field of chemical kinetics and of reactor simulations considering also the effect of mass and heat transfer. Many classical textbooks dealing with the topic have, therefore, become quite obsolete. The present work is a review of the role that heat and mass transfer have in the kinetic studies of gas–solid catalytic reactions. The scope was to collect in a relatively short document the necessary knowledge for a correct simulation of gas–solid catalytic reactors. The first part of the review deals with the most reliable approach to the description of the heat and mass transfer outside and inside a single catalytic particle. Some different examples of calculations allow for an easier understanding of the described methods. The second part of the review is related to the heat and mass transfer in packed bed reactors, considering the macroscopic gradients that derive from the solution of mass and energy balances on the whole reactor. Moreover, in this second part, some examples of calculations, applied to chemical reactions of industrial interest, are reported for a better understanding of the systems studied. Full article

(This article belongs to the Special Issue Industrial Chemistry Reactions: Kinetics, Mass Transfer and Industrial Reactor Design)

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