Periodic Operation with Modulation of Inlet Concentration and Flow Rate Part I: Nonisothermal Continuous Stirred-Tank Reactor

The nonlinear frequency response (NFR) method, which is an analytical, fast, and easy method for evaluating the performance of forced periodically operated chemical reactors, was used to investigate possible improvements to a nonisothermal continuous stirred tank reactor (CSTR) when inlet concentration and/or flow rate is periodically modulated. The product yield corresponding to periodic operation is defined, expressions for its estimation, based on the NFR method, are derived, and it is used to evaluate the performance improvements due to periodic operation. Part I considers the general nonisothermal case. In Part II, these results are applied to an adiabatic CSTR and used to evaluate possible improvements for the case of the hydrolysis reaction of acetic anhydride.This is the peer-reviewed version of the article: Daliborka Nikolić, Andreas Seidel‐Morgenstern, Menka Petkovska, Periodic Operation with Modulation of Inlet Concentration and Flow Rate. Part I: Nonisothermal Continuous Stirred‐Tank Reactor, Chemical Engineering & Technology, 2016, 39, 11, 2020-2028, [ https://doi.org/10.1002/ceat.201600185]The published version: [https://cer.ihtm.bg.ac.rs/handle/123456789/1889

Isolation of soybean protein P34 from oil bodies using hydrophobic interaction chromatography

<p>Abstract</p> <p>Background</p> <p>Soybeans play a prominent role in allergologic research due to the high incidence of allergic reactions. For detailed studies on specific proteins it is necessary to have access to a large amount of pure substance.</p> <p>Results</p> <p>In this contribution, a method for purifying soybean (<it>Glycine max</it>) protein P34 (also called Gly m Bd 30 K or Gly m 1) using hydrophobic interaction chromatography is presented. After screening experiments using 1 mL HiTrap columns, Butyl Sepharose 4 FF was selected for further systematic investigations. With this stationary phase, suitable operation conditions for two-step gradient elution using ammonium sulphate were determined experimentally. The separation conditions obtained in a small column could be scaled up successfully to column volumes of 7.5 and 75 mL, allowing for high product purities of almost 100% with a yield of 27% for the chromatographic separation step. Conditions could be simplified further using a onestep gradient, which gave comparable purification in a shorter process time. The identity of the purified protein was verified using in-gel digestion and mass spectrometry as well as immunological techniques.</p> <p>Conclusion</p> <p>With the technique presented it is possible to produce, within a short timeframe, pure P34, suitable for further studies where an example antigen is needed.</p

Parameter Identifiability of Artemisinin Synthesis using Design of Experiments

Artemisinin-based combination therapies are recommended by the World Health Organization to treat malaria, one of the most abundant infectious diseases in the world. Recently, a novel production route, which combines the extraction and the catalyzed chemical synthesis, has been shown to be a promising sustainable processing alternative [Triemer, 2018]. To exploit its mechanism, operational settings and limits, mathematical modeling might be beneficial when thorough system insight is required. In a first step, we consider the catalyzed synthesis step from dihydroartemisinic acid to artemisinin, and we show that only a subset of the parameters of the considered model is identifiable with the available sparse data using a singular value decomposition approach. In a second step, within the framework of design of experiments (DoE), we demonstrate the effect of additional experimental data to overcome the non-identifiability problem of the model parameters

Detailed Kinetic Model for the Reaction of Ethene to Propene on Ni/AlMCM-41

The Ni/AlMCM-41 was prepared and applied as the catalyst for the direct conversion of ethene to propene. Based on the results of the broad experimental study, two reaction networks were compared, one consisting of dimerization, isomerization and metathesis and a modified network suggesting the cracking of long-chain olefins. To correlate the experimentally obtained data, the classical Langmuir-Hinshelwood-Hougen-Watson model was applied for both reaction networks. The second network involving catalytic cracking offers a satisfying prediction of the observed product distributions

Optimal startup operation of simulated moving bed chromatographic processes

Abstract: SMB represents one of the widely established periodic adsorption processes and its periodic and nonlinear dynamics presents a significant challenge to the formulation and solution of the optimal startup issue. A multistage startup concept allowing to adjust operating conditions stage-wise is proposed. The startup problem is then formulated aiming at driving the system towards the reference cyclic steady state (CSS) in an optimum manner. A tailored decomposition algorithm is developed to tackle the resulting optimization problem and guarantee numerical tractability. The feasibility of the solution approach is demonstrated on a binary separation with nonlinear competitive isotherms. It is found that the new startup policy dramatically reduces transient time and desorbent consumption. The startup performance in terms of product concentration and purity is also evaluated quantitatively

Forced periodic reactor operation with simultaneous modulation of two inputs: Nonlinear frequency response analysis and experimental demonstration

The classical design of continuously operated chemical reactors assumes that they are operated in a steady-state which is usually optimized and maintained by using appropriate control systems. Nevertheless, it has been known for quite some time that, in some cases, better performance can be achieved by applying a periodic regime exploiting forced modulations of one or more inputs to the reactor [1,2]. Finding out whether, at which conditions and to which extent periodic operation can be superior to the optimal steady-state is difficult. One approach that can be used is an approximate, analytical method called nonlinear frequency response (NFR) method [3]. The NFR method is based on the concept of higher order frequency response functions (FRFs) and applicable for weakly nonlinear systems [3]. Frequency response of a weakly nonlinear system, in addition to the basic harmonic, contains a non-periodic (DC) term and, theoretically, an infinite sequence of higher harmonics. The DC component of the output is responsible for the average performance of the periodically operated reactor, and its sign and value define whether, and to which extent, the periodic operation leads to process improvement. Using the NFR method, this DC component can be approximately estimated from a single asymmetrical second order FRF (for modulation of a single input) or from several single input and cross- asymmetrical second order FRFs (for multiple-input modulation). For the case of multiple modulated inputs, the optimal phase difference between the modulated inputs, which is an essential parameter, can be directly determined [4,5]. Promising parameters to be periodically modulated separately or simultaneously are clearly the reactant inlet concentrations, the flow-rates and the feed temperatures. We used the NFR method in order to identify forced periodic conditions under which the acetic acid anhydride hydrolysis (chosen as a test reaction) can be favorably performed in a CSTR. Based on the results of the theoretical analysis, experimental investigations were performed using a lab-scale reactor exposed to two fluctuating inlet streams (water and acetic anhydride) with adjustable flow-rates, which enables modulation of the inlet reactant concentrations or/and total flow-rates in a flexible manner. The concentration of the acetic acid formed is measured in the reactor online and used to monitor the process dynamics. Averaged values of the product outlet stream serve to validate the mean values predicted by NFR analysis and to evaluate the potential of this flexible forcing strategy

Evaluation of possible improvements of forced periodically operated reactor in which methanol synthesis takes place – based on the Nonlinear Frequency Response analysis

The continuous industrial chemical processes are typically designed through steady-state conditions. Nevertheless, there is evidence that processes can be intensified by applying optimized forced periodic operation. Possible improvements in reactor performances caused by the implementation of forced periodic operation (FPO) can be successfully evaluated by applying a nonlinear frequency response (NFR) analysis, before experimental investigation. In this study, we will present the results of two case studies based on heterogeneously catalyzed methanol synthesis in a continuous stirred tank reactor (CSTR). The first is an isothermal case, and the second is a more complicated and more realistic, non-isothermal case.This is a paper for 15th International Conference on Applied Energy (ICAE2023), Dec. 3-7, 2023, Doha, Qata

Corrigendum to ‘‘Alumino-mesostructured Ni catalysts for the direct conversion of ethene to propene” [J. Catal. 305 (2013) 154–168]

Ni/MCM-41 and Ni/AlMCM-41 were synthesized at different Si/Al ratios and tested in the direct conversion of ethene to propene (ETP-reaction). It was intended to evaluate the effect of modifying the catalyst acidity on the ETP-reaction rather than optimizing its performance. All catalysts were characterized by powder XRD, N2-physisorption, 29Si and 27Al MAS NMR, TEM, NH3-TPD, pyridine-DRITFS, H2-TPR, and TPO. Ni/MCM-41 showed low catalytic activity due to its low acidity. Ni/AlMCM-41 catalyst with a Si/Al ratio of 60 had high catalytic activity. Characterization results revealed that the catalyst structure does not have effect on the catalytic activity. Al could be incorporated into the MCM-41 framework up to Si/Al ratio of 16. Two different Ni-composites on the surface of the MCM-41 and AlMCM-41 were observed. Deeper characterization is required to know the Ni state. Important deactivation was observed at 450 °C. The nature of the carbonaceous species and reaction mechanism require deeper characterization