Polyurethane‐ and Polystyrene‐Supported 2,2,6,6‐Tetramethyl‐ piperidine‐1‐oxyl (TEMPO); Facile Preparation,Catalytic Oxidation and Application in a Membrane Reactor

In this contribution, the facile synthesis of two new polymer‐supported 2,2,6,6‐tetramethylpiperidine‐1‐oxyl (TEMPO) catalysts and their application in the catalytic oxidation of alcohols to carbonyl compounds are described. For attachment of the TEMPO group to the polymer an isocyanate functionalized polymer is chosen. This new approach facilitates the synthesis in comparison with previously existing methods which generally require deprotonation of TEMPO prior to reaction with the polymer. Following this approach, polyurethane (PU)‐ and polystyrene (PS)‐based TEMPO catalysts are prepared in a one‐step reaction from commercially available compounds. Both polymer‐supported catalysts showed promising yields for a variety of substrates using inorganic and/or organic co‐oxidants in biphasic and/or monophasic systems. The recyclability of the corresponding catalysts was studied in repetitive batch experiments using filtration or distillation depending on the support type. Furthermore, application of the homogeneous polyurethane‐supported TEMPO for the selective oxidation of benzyl alcohol in a continously operated membrane reactor is demonstrated.     

Medium‐Temperature Shift Catalysts for Hydrogen Purification in a Single‐Stage Reactor

Interest regarding the WGS process has grown significantly, because of the recent progression in fuel cells as a clean technology for power generation. Due to the large volume and cost of WGS conventional two‐stage reactors, and also problems related to pyrophoricity and lengthy reduction of customary catalysts, the current challenge is to develop more active and stable catalysts that convert CO in a single‐stage medium temperature shift (MTS, 280–360 °C) reactor, which is applicable in small‐scale fuel cells. Advanced and newly developed catalytic systems for hydrogen purification via MTS reactions are reviewed and discussed in this study. Pt‐based catalysts on reducible oxide supports, e.g., CeO₂ and TiO₂, have mainly been used for this reaction. It is known that ceria is the most applicable active and stable support and highly promising for MTS reactions, considering its high oxygen storage capacity and mobility of surface oxygen/hydroxyl groups. New studies investigate modified ceria, e.g., CeZr, to improve its catalytic properties.     

Asymmetric Homogeneous Hydrogenation in Flow using a Tube‐in‐Tube Reactor

In this update, the asymmetric homogeneous hydrogenation of a number of trisubstituted olefins utilizing the recently developed tube‐in‐tube gas‐liquid flow reactor is described. A number of chiral iridium‐ and rhodium‐based catalysts and other parameters such as pressure, solvent, temperature and catalyst loading were screened. The advantage of the flow set‐up for rapid screening and optimization of reaction parameters is illustrated. Furthermore, a comparative study using batch conditions aided in the optimization of the flow reaction set‐up. The set‐up was further modified to recycle the catalyst which prolonged catalytic activity.     

New Indenylidene‐Schiff Base‐Ruthenium Complexes for Cross‐Metathesis and Ring‐Closing Metathesis

We here report on the stability and catalytic activity of new indenylidene‐Schiff base‐ruthenium complexes 3a – f through representative cross‐metathesis (CM) and ring‐closing metathesis (RCM) reactions. Excellent activity of the new complexes was found for the two selected RCM reactions; prominent conversion was obtained compared to the commercial Hoveyda–Grubbs catalyst 2 . Moreover, excellent results were obtained for a standard CM reaction. Higher conversions were achieved with one of the indenylidene catalysts compared with Hoveyda–Grubbs catalyst. Unexpectedly, an isomerization reaction was observed during the CM reaction of allylbenzene. To the best of our knowledge, isomerization reactions in this model CM reaction in closed systems have never been described using first generation catalysts, including the Hoveyda–Grubbs catalyst. The first model CM reactions as well as the RCM reactions have been monitored using ¹H NMR. The course of the CM reaction of 3‐phenylprop‐1‐ene ( 8 ) and cis‐1,4‐diacetoxybut‐2‐ene ( 9 ) was monitored by GC. The isomerization reaction was studied by means of GC‐mass spectrometry and in situ IR spectroscopy. All catalysts were structurally characterized by means of ¹H, ¹³C, and ³¹P NMR spectroscopy.     

Optimization of Fischer‐Tropsch Process in a Fixed‐Bed Reactor Using Non‐uniform Catalysts

Optimization of Fischer‐Tropsch (FT) process in a fixed‐bed reactor is carried out using non‐uniform catalysts. The C₅⁺ yield of the reactions is maximized utilizing a combination of non‐uniform catalysts across the bed. A 1D heterogeneous model is developed to simulate the bed containing uniform and non‐uniform catalysts. It is found that the egg‐shell and surface‐layered catalysts result in higher C₅⁺ yield. Moreover, effects of cooling temperature are studied. Genetic Algorithm (GA) and Successive Quadratic Programming (SQP) methods are applied. Feed and cooling temperature are selected as decision variables together with distribution of non‐uniform catalysts along the bed. The optimization result shows 14.47 % increase in the C₅⁺ yield with respect to the base condition.     

A preliminary evaluation of a continuous‐flow reactor for liquid–liquid–solid phase‐transfer catalyzed synthesis of n‐butyl phenyl ether

This study evaluates the feasibility of using a continuous‐flow stirred vessel reactor (CFSVR) to synthesize n‐butyl phenyl ether (ROPh) from n‐butyl bromide (RBr) and sodium phenolate (NaOPh) by liquid–liquid–solid phase‐transfer catalysis (triphase catalysis). The factors affecting the preparation of triphase catalysts, the etherification reaction in a batch reactor, and the performance in a CFSVR were investigated. The kinetic study with a batch reactor indicated that when the initial concentration of NaOPh or RBr was high, the conversion of RBr would depend on the initial concentration of both RBr and NaOPh. The reaction can be represented by a pseudo‐first‐order kinetic model when the concentration of NaOPh is in proper excess to that of RBr, and the apparent activation energy is 87.8 kJ mol^?1. When the etherification reaction was carried out in the CFSVR, the catalyst particles did not flow out of the reactor, even at a high agitation speed. The conversion of RBr in the CFSVR was, as predicted, lower than that in the batch reactor, but was higher than the theoretical value because the dispersed phase is not completely mixed. Copyright © 2004 Society of Chemical Industry     

Immobilization and activation of vanadium(III) and titanium(III) single‐site catalysts for ethylene polymerization using MgCl2‐based supports

Significant increases in the activity of vanadium(III) amidinate catalysts for ethylene polymerization have been obtained by immobilization on a MgCl₂‐based support prepared by reaction of AlEt₃ with a MgCl₂/ethanol adduct. Catalyst immobilization and activation on this type of support prevents the rapid decay in activity observed under homogeneous polymerization conditions with unsupported catalysts. Stable polymerization activity is also observed with analogous titanium(III) complexes. Polyethylene with narrow molecular weight distribution and spherical particle morphology is obtained without reactor fouling. Copyright © 2005 Society of Chemical Industry     

CO2 methanation: Optimal start‐up control of a fixed‐bed reactor for power‐to‐gas applications

Utilizing volatile renewable energy sources (e.g., solar, wind) for chemical production systems requires a deeper understanding of their dynamic operation modes. Taking the example of a methanation reactor in the context of power‐to‐gas applications, a dynamic optimization approach is used to identify control trajectories for a time optimal reactor start‐up avoiding distinct hot spot formation. For the optimization, we develop a dynamic, two‐dimensional model of a fixed‐bed tube reactor for carbon dioxide methanation which is based on the reaction scheme of the underlying exothermic Sabatier reaction mechanism. While controlling dynamic hot spot formation inside the catalyst bed, we prove the applicability of our methodology and investigate the feasibility of dynamic carbon dioxide methanation. © 2016 American Institute of Chemical Engineers AIChE J, 63: 23–31, 2017     

TPD‐TG‐MS Investigations of the Catalytic Conversion of Glycerol over MOx‐Al2O3‐PO4 Catalysts

The catalytic performance of bifunctional catalysts, MO_x‐Al₂O₃‐PO₄, that contain acidic centers and different transition metal oxide components were evaluated in the gas‐phase dehydration of glycerol using the TPD‐TG‐MS technique and a continuous flow reactor experiment. The initial catalytic activity and selectivity to acrolein and acetol significantly depends on the acidity and the type of transition metal oxide. The higher the total acidity, the higher the acrolein selectivity in the order W > Mo > Cu > V~ Fe ~Cr > Ce. On the other hand, Mn‐, Cr‐, and Fe‐containing catalysts favor the formation of products of oxidative C‐C cleavage. TPD‐TG‐MS investigations of catalysts loaded with glycerol are useful tools for fast‐screening of initial activities of catalysts in the gas‐phase dehydration of glycerol.     

Thermal and catalytic upgrading of a biomass‐derived oil in a dual reaction system

The thermal and catalytic upgrsding of bio‐oil to liquid fuels was studied at atmospheric pressure in a dual reactor system over HZSM‐5, silica‐alumina and a mixed catalyst containing HZSM‐5 and silica‐alumina. This bio‐oil was produced by the rapid thermal processing of the maple wood. In this work, the intent was to improve the catalyst life. Therefore, the first reactor containing no catalyst facilitated thermal cracking of blo‐oil whereas the second reactor containing the desired catalyst upgraded the thermally cracked products. The effects of process variables such as reaction temperature (350°C to 410°C), space velocity (1.8 to 7.2 h^?1) and catalyst type on the amounts and quality of organic liquid product (OLP) were investigated, In the case of HZSM‐5 catalyst, the yield of OLP was maximum at 27.2 wt% whereas the selectivity for aromatic hydrocarbons was maximum at 83 wt%. The selectivities towards aromatics and aliphatic hydrocarbons were highest for mixed and silica‐alumina catalysts, respectively. In all catalyst cases, maximum OLP was produced at an optimum reaction temperature of 370°C in both reactors, and at higher space velocity. The gaseous product consisted of CO and CO₂, and C₁‐C₆ hydrocarbons, which amounted to about 20 to 30 wt% of bio‐oil. The catalysts were deactivated due to coking and were regenerated to achieve their original activity.     

Hydrierung von p‐Nitrophenol zu p‐Aminophenol als Testreaktion für die katalytische Aktivität von Pt‐Trägerkatalysatoren

The hydrogenation of p‐nitrophenol (PNP) to p‐aminophenol (PAP) using NaBH₄ as a reducing agent was studied as a test reaction for determining the catalytic activity of supported Pt catalysts. The initial reaction rate, which is accessible within less than 10 minutes via online UV‐vis spectroscopy at room temperature, ambient pressure and in water as a solvent, was used as measure for the catalytic activity. For three Pt catalysts supported on porous SiO₂, porous glass and Al₂O₃, respectively, significant differences in the catalytic activity were observed. However, especially in case of very active catalysts, limitations of the reaction by internal or external mass transfer have to be considered.     

A Microfluidic Approach to the Rapid Screening of Palladium‐Catalysed Aminocarbonylation Reactions

The evaluation and selection of the most appropriate catalyst for a chemical transformation is an important process in many areas of synthetic chemistry. Conventional catalyst screening involving batch reactor systems can be both time‐consuming and expensive, resulting in a large number of individual chemical reactions. Continuous flow microfluidic reactors are increasingly viewed as a powerful alternative format for reacting and processing larger numbers of small‐scale reactions in a rapid, more controlled and safer fashion. In this study we demonstrate the use of a planar glass microfluidic reactor for performing the three‐component palladium‐catalysed aminocarbonylation reaction of iodobenzene, benzylamine and carbon monoxide to form N‐benzylbenzamide, and screen a series of palladium catalysts over a range of temperatures. N‐Benzylbenzamide product yields for this reaction were found to be highly dependent on the nature of the catalyst and reaction temperature. The majority of catalysts gave good to high yields under typical flow conditions at high temperatures (150 °C), however the palladium(II) chloride‐Xantphos complex [PdCl₂(Xantphos)] proved to be far superior as a catalyst at lower temperatures (75–120 °C). The utilised method was found to be an efficent and reliable way for screening a large number of palladium‐catalysed carbonylation reactions and may prove useful in screening other gas/liquid phase reactions.     

Membrane reactor immobilized with palladium‐loaded polymer nanogel for continuous‐flow Suzuki coupling reaction

A catalytic membrane reactor, which was immobilized with palladium‐loaded nanogel particles (NPs), was developed for continuous‐flow Suzuki coupling reaction. Palladium‐loaded membranes were prepared by immobilization of NPs, adsorption of palladium ions, and reduction into palladium(0). The presence of palladium in the membrane was confirmed by the scanning electron microscopy; palladium aggregation was not observed. The catalytic activity of the membrane reactor in continuous‐flow Suzuki coupling reaction was approximately double that of a comparable reactor in which palladium ions were directly adsorbed onto an aminated membrane. This was attributed to the formation of small palladium particles. The reusability in the continuous‐flow system was higher than that in a batch system, and the palladium‐loaded membrane reactor had high long‐term stability. © 2014 American Institute of Chemical Engineers AIChE J, 61: 582–589, 2015     

Preparation of sorbitol from D‐glucose hydrogenation in gas–liquid–solid three‐phase flow airlift loop reactor

A new process for D ‐glucose hydrogenation in 50 wt% aqueous solution, into sorbitol in a 1.5 m³ gas–liquid–solid three‐phase flow airlift loop reactor (ALR) over Raney Nickel catalysts has been developed. Five main factors affecting the reaction time and molar yield to sorbitol, including reaction temperature (T_R), reaction pressure (P_R), pH, hydrogen gas flowrate (Q_g) and content of active hydrogen, were investigated and optimized. The average reaction time and molar yield were 70 min and 98.6% under the optimum operating conditions, respectively. The efficiencies of preparation of sorbitol between the gas–liquid–solid three‐phase flow ALR and stirred tank reactor (STR) under the same operating conditions were compared. Copyright © 2004 Society of Chemical Industry     

Co‐current and Countercurrent Configurations for a Membrane Dual Type Methanol Reactor

A dynamic model for a membrane dual‐type methanol reactor was developed in the presence of catalyst deactivation. This reactor is a shell and tube type where the first reactor is cooled with cooling water and the second one with feed synthesis gas. In this reactor system, the wall of the tubes in the gas‐cooled reactor is covered with a palladium‐silver membrane which is only permeable to hydrogen. Hydrogen can penetrate from the feed synthesis gas side into the reaction side due to the hydrogen partial pressure driving force. Hydrogen permeation through the membrane shifts the reaction towards the product side according to the thermodynamic equilibrium. Moreover, the performance of the reactor was investigated when the reaction gas side and feed gas side streams are continuously either co‐current or countercurrent. Comparison between co‐current and countercurrent mode in terms of temperature, activity, methanol production rate as well as permeation rate of hydrogen through the membrane shows that the reactor in co‐current configuration operates with lower conversion and also lower permeation rate of hydrogen but with longer catalyst life than does the reactor in countercurrent configuration.     

Promoted Fe2O3‐Al2O3‐CuO Chromium‐Free Catalysts for High‐Temperature Water‐Gas Shift Reaction

Promoted Fe₂O₃‐Al₂O₃‐CuO (FAC) chromium‐free catalysts were prepared for high‐temperature water‐gas shift reactions and characterized by X‐ray diffraction (XRD), Brunauer‐Emmett‐Teller method (BET), temperature‐programmed reduction (TPR), and transmission electron microscopy (TEM) techniques. The catalytic results revealed that among the investigated promoted catalysts with Ce, La, Zn, Y, and Mn as promoters, the Mn‐promoted sample showed higher activity compared to the other promoted catalysts. Increasing the Mn content improved the surface area and catalytic activity. The FAC catalyst promoted with a high Mn content exhibited maximum activity and relatively high stability in high‐temperature water‐gas shift reaction.     

Catalytic Oxidative Dehydrogenation of n‐Butane on Gallium Nitride‐Containing Titanosilicate Catalyst

GaN‐containing titanosilicate catalysts were used for the first time for the oxidative dehydrogenation (ODH) of n‐butane at a relatively low reaction temperature (460 °C). Commercially available GaN powder with a wurtzite crystal structure showed superior reactivity and stability for the ODH of n‐butane. The catalytic property of GaN catalyst for ODH strongly depends on the GaN particle size. The effects of the GaN weight percentage and GaN particle size on the catalytic performance are investigated in a fixed bed reactor. Based on the physicochemical properties of the catalyst characterized via TEM, DLS, N₂ adsorption‐desorption, XRF, O₂‐TPD, XRD, XPS, and in‐situ FTIR, the textural and structural properties of catalyst were obtained. The catalytic results reveal that the presence of GaN increases the activity of the catalysts, indicating that GaN can be used as a new active phase for the ODH of n‐butane. XRD, XPS, O₂‐TPD, DLS, TEM, and in‐situ FTIR results show that activated O species exist on the surface of the GaN catalyst and enhance the catalytic performance with a decreasing GaN particle size, suggesting that smaller GaN particles possess a remarkable capability to activate O species in O₂ and C‐H bonds in light alkanes.     

Modeling of Slug Velocity and Pressure Drop in Gas‐Liquid‐Liquid Slug Flow

Gas‐liquid‐liquid slug flow in a capillary reactor is a promising new concept that allows one to incorporate gas‐liquid reaction, liquid‐liquid extraction, and facile catalyst separation in a single unit. In order to assess the performance of a gas‐liquid‐liquid slug flow reactor, it is necessary to predict the slug velocity and pressure drop to ascertain residence times and reaction rates. New empirical models for velocity and pressure drop were developed based on existing models for two‐phase gas‐liquid and liquid‐liquid slug flows, and these were validated experimentally.     

Enhancement of Methanol Production in a Membrane Dual‐Type Reactor

In this study, a dynamic model for a membrane dual‐type methanol reactor was developed in the presence of long term catalyst deactivation. The proposed model is used to compare the performance of a membrane dual‐type methanol reactor with a conventional dual‐type methanol reactor. A conventional dual‐type methanol reactor is a shell and tube heat exchanger reactor in which the first reactor is cooled with cooling water and the second one is cooled with synthesis gas. In a membrane dual‐type reactor, the wall of the tubes in the gas‐cooled conventional reactor is covered with a palladium‐silver membrane, which is only permeable to hydrogen. Hydrogen can penetrate from the feed synthesis gas side into the reaction side due to the hydrogen partial pressure driving force. Hydrogen permeation through the membrane shifts the reaction towards the product side according to the thermodynamic equilibrium. The proposed dynamic model was validated against measured daily process data of a methanol plant recorded for a period of four years and a good agreement was achieved. The simulation results show that there is a favorable profile of temperature and activity of the membrane dual‐type reactor relative to single and conventional dual‐type reactor systems. Therefore, the performance of methanol reactor systems improves when a membrane is used in a conventional dual‐type methanol reactor.     

Model‐Aided Design of a Three‐Phase Gas‐Lift Reactor for Oxidation Accompanied by Catalyst Reversible Deactivation

A mathematical model of a three‐phase gas‐lift reactor (GLR) is developed to aid the design of a target reactor for simultaneous substrate catalytic oxidation in riser and a deactivated reactivation catalyst in the downcomer section of the multifunctional reactor. In the GLR model, the hydrodynamics of a real GLR and the kinetics of glucose oxidation by air over a palladium catalyst are incorporated. The GLR model searches for the optimal geometry of the target reactor. With regard to the GLR optimal geometry, the reactor productivity is maximal for given input operational conditions. An algorithm of the GLR model is presented together with simulation results of the target GLR and with insight into the parametric sensitivity of the model. Effects of the reaction components concentrations and the gas‐phase superficial velocity on the location of the target reactor optimal geometry and on the reactor productivity are discussed.