Continuous-flow Packed-bed Reactor Research Articles

Continuous kinetics of 2-hydroxyisobutryic acid esterification using solid acid granular and monolithic activated carbon catalysts

Kinetics of 2-hydroxyisobutyric acid (2-HIBA) esterification with ethanol was studied using sulfonated carbon catalysts in granular (sGAC) and monolith (sACM) forms in a continuous flow packed bed reactor. 2-HIBA is a potential biobased carboxylic acid and its ester a sustainably produced industrial solvent. The catalyst monolith form, made from renewable carbon, offers significantly higher space time yields and conversions, yet little kinetic data or models are available for its use, especially under non-ideal conditions. The effect of ethanol/2-HIBA molar ratio (44, 10, 3.6 and 1.5) at different liquid residence times (3–9 min) was investigated using sGAC. Kinetics of sACM esterifications were investigated at a molar ratio of 3.6 by varying the residence time (2–7 min) and compared with the sGAC. The sACM displayed higher ester yields, acid conversions, and significantly higher reaction rates and space–time-yields (2.1–2.8 ×) compared to the sGAC due to higher surface area to volume ratio. The sACM reaction rates and turnover frequency were comparable to solid acid resins and sulfated silica and zirconia. Pseudo-homogeneous, Eley-Rideal and Langmuir-Hinshelwood models were applied to fit the kinetic data, and the reaction system parameters were obtained through regression analysis. The LH dual active site model resulted in the lowest mean relative error for both 2-HIBA and ester concentration residuals. Adsorption/desorption equilibrium constants for 2-HIBA, ethanol, and ester, were higher compared to water suggesting hydrophobic regions in the sGAC/sACM. Estimation of the external and internal mass transfer criteria indicated negligible effects of mass transfer. With further development sACM and the kinetic model can be used for reactor design of continuous esterification processes using solid acid monolith catalysts.

In situ growth of iron incorporated Ni3S2 nanosheet on nickel foam in mediating electron transfer to peroxymonosulfate for pollutant abatement

Catalytic oxidation of organic pollutants is a well-known and effective technique for pollutant abatement. Unfortunately, this method is significantly hindered in practical applications by the low efficiency and difficult recovery of the catalysts in a powdery form. Herein, a three-dimensional (3D) framework of Fe-incorporated Ni3S2 nanosheets in-situ grown on Ni foam (Fe-Ni3S2@NF) was fabricated by a facile two-step hydrothermal process and applied to trigger peroxymonosulfate (PMS) oxidation of organic compounds in water. A homogeneous growth environment enabled the uniform and scalable growth of Fe-Ni3S2 nanosheets on the Ni foam. Fe-Ni3S2@NF possessed outstanding activity and durability in activating PMS, as it effectively facilitated electron transfer from organic pollutants to PMS. Fe-Ni3S2@NF initially supplied electrons to PMS, causing the catalyst to undergo oxidation, and subsequently accepted electrons from organic compounds, returning to its initial state. The introduction of Fe into the Ni3S2 lattice enhanced electrical conductivity, promoting mediated electron transfer between PMS and organic compounds. The 3D conductive Ni foam provided an ideal platform for the nucleation and growth of Fe-Ni3S2, accelerating pollutant abatement due to its porous structure and high conductivity. Furthermore, its monolithic nature simplified the catalyst recycling process. A continuous flow packed-bed reactor by encapsulating Fe-Ni3S2@NF catalyst achieved complete pollutant abatement with continuous operation for 240 h, highlighting its immense potential for practical environmental remediation. This study presents a facile synthesis method for creating a novel type of monolithic catalyst with high activity and durability for decontamination through Fenton-like processes.

Energy-efficient and eco-friendly continuous production of 5-CMF in a UV-ultrasound irradiated catalytic packed bed reactor: heterogeneous kinetics, reactor simulation and LCA analysis

An energy-efficient heterogeneous catalytic (Smopex-101 and TiO2) continuous flow packed bed reactor employing synergistic effects of UV-ultrasound (US) irradiations for the environmentally sustainable synthesis of high purity 5-CMF.

Covalent organic framework crystallization using a continuous flow packed-bed reactor

Covalent organic frameworks were crystallized directly in flow, resulting in a substantial decrease in required synthesis and processing time for a diverse class of nanomaterials.

Treatment of the insensitive munitions compound, 3-nitro-1,2,4-triazol-5-one (NTO), in flow-through columns packed with zero-valent iron.

The need for effective technologies to remediate the insensitive munitions compound 3-nitro-1,2,4-triazol-5-one (NTO) is emerging due to the increasing use by the US Army and environmental concerns about the toxicity and aqueous mobility of NTO. Reductive treatment is essential for the complete degradation of NTO to environmentally safe products. The objective of this study is to investigate the feasibility of applying zero-valent iron (ZVI) in a continuous-flow packed bed reactor as an effective NTO remediation technology. The ZVI-packed columns treated an acidic influent (pH 3.0) or a circumneutral influent (pH 6.0) for 6months (ca. 11,000 pore volumes, PVs). Both columns effectively reduced NTO to the amine product, 3-amino-1,2,4-triazol-5-one (ATO). The column treating the pH-3.0 influent exhibited prolonged longevity in reducing NTO, treating 11-fold more PVs than the column treating pH-6.0 influent until the breakthrough point (defined as when 85% of NTO was removed). The exhausted columns (defined as when only 10% of NTO was removed) regained the NTO reducing capacity by reactivation using 1M HCl, fully removing NTO. After the experiment, solid-phase analysis of the packed-bed material showed that ZVI was oxidized to iron (oxyhydr)oxide minerals such as magnetite, lepidocrocite, and goethite during NTO treatment. This is the first report on the reduction of NTO and the concomitant oxidation of ZVI in continuous-flow column experiments. The evidence indicates that treatment in a ZVI-packed bed reactor is an effective approach for the removal of NTO.

Kinetic Study of 4-Chlorophenol Biodegradation by Acclimated Sludge in a Packed Bed Reactor

In this study, batch experiments were conducted to evaluate the degradation of 4-CP using acclimated sludge. The Monod and Haldane models were employed to fit the specific growth rate with various initial 4-CP concentrations of 67–412 mg/L in the batch experiments. Haldane kinetics showed a better fit to experimental results than Monod kinetics. The kinetic parameters were obtained from a comparison of Monod and Haldane kinetics with batch experimental data. The values of μm and KS were found to be 0.691 d−1 and 5.62 mg/L, respectively, for Monod kinetics. In contrast, the values of μm, KS, and KI were 1.30 d−1, 8.38 mg/L, and 279.4 mg/L, respectively, for Haldane kinetics. The kinetic parameters in Haldane kinetics were used as input parameters for the kinetic model system of the packed bed reactor (PBR). The continuous flow PBR was conducted to validate the kinetic model system. The model-simulated results agreed well with experimental data in the PBR performance operation. At the steady-state stage, the removal efficiency of 4-CP was 70.8–96.1%, while the hydraulic retention time (HRT) was 2.5 to 12.4 h. The corresponding removal of 4-CP was assessed to be 94.6 and 96.1% when the inlet 4-CP loading rate was increased from 0.11 to 0.51 kg/m3-d. The approaches of kinetic models and experiments presented in this study can be applied to design a PBR for 4-CP treatment in wastewater from the effluents of various industries.

Bioremediation of bisphenol A found in industrial wastewater using Trametes versicolor (TV) laccase nanoemulsion-based bead organogel in packed bed reactor.

Bisphenol A (BPA) is one of the toxic chemicals, which is widely used for manufacturing epoxy, polyester resin, and polycarbonates. These materials are extensively used in manufacturing of reusable bottles, baby bottles, dental sealants, various medical devices, and so forth. Moreover, canned and packaged foods are sources of bisphenol A, which is unknowingly consumed by many people worldwide. Its endocrine disrupting and teratogenic properties impose potential risk to the wildlife and human health. BPA has been linked to reproductive, metabolic, and immunity disorders in humans. Regardless of BPA ban in reusable and baby bottles, annually, 15 billion pounds of BPA still being produced. BPA pollution and its cleanup are major challenges. Therefore, it is essential to develop a suitable strategy to bioremediate BPA. The Trametes versicolor (TV) laccase-based nanoemulsion calcium alginate bead organogel was able to transform 94% of BPA within 2h of treatment. Organogel showed 60% of BPA removal from actual industrial wastewater in packed bed batch reactor and 67% of BPA removal in continuous flow packed bed reactor. The biological oxygen demand (BOD) of treated industrial effluent was 14 mg/L, which is very much less than untreated effluent's BOD, which was 48 mg/L. The chemical oxygen demand of industrial effluent was 1240 mg/ml, and treated effluent was 248 mg/L, respectively. Hence, application of nanoemulsion-based organogel in packed bed reactor found to be a potential candidate for the bioremediation of industrial effluent containing BPA. PRACTITIONER POINTS: The TV laccase-based nanoemulsion calcium alginate bead organogel was able to transform 94% of BPA. Organogel showed 67% of BPA removal from industrial wastewater in continuous flow packed bed reactor. The nanoemulsion-based organogel in packed bed reactor found to be potential candidate for the bioremediation of industrial effluent containing BPA.

Heterogeneous metallaphotoredox catalysis in a continuous-flow packed-bed reactor.

Metallaphotoredox catalysis is a powerful and versatile synthetic platform that enables cross-couplings under mild conditions without the need for noble metals. Its growing adoption in drug discovery has translated into an increased interest in sustainable and scalable reaction conditions. Here, we report a continuous-flow approach to metallaphotoredox catalysis using a heterogeneous catalyst that combines the function of a photo- and a nickel catalyst in a single material. The catalyst is embedded in a packed-bed reactor to combine reaction and (catalyst) separation in one step. The use of a packed bed simplifies the translation of optimized batch reaction conditions to continuous flow, as the only components present in the reaction mixture are the substrate and a base. The metallaphotoredox cross-coupling of sulfinates with aryl halides was used as a model system. The catalyst was shown to be stable, with a very low decrease of the yield (≈1% per day) during a continuous experiment over seven days, and to be effective for C–O arylations when carboxylic acids are used as nucleophile instead of sulfinates.

Mathematical modeling of a continuous-flow packed-bed reactor with immobilized lipase for kinetic resolution of (R,S)-2-pentanol.

In this study, the kinetic resolution of (R,S)-2-pentanol via transesterification to achieve S-2-pentanol, a key intermediate required in the synthesis of anti-Alzheimer drugs, was investigated in continuous-flow packed-bed reactors. The effects of residence time, substrate concentration, and operation time of the enzyme were investigated. Under steady state conditions, 50% conversion and enantiomeric excess of the substrate (ee S >99% were achieved at a residence time of 0.04 min. Productivity of the continuous-flow process (1.341 mmol/min/g)was about 4 times higher than that of the corresponding batch process (0.363 mmol/min/g). In addition, the mathematical modeling of the packed-bed reactor was conductedusing an axial dispersion model. Ping Pong Bi Bi kinetics was used in this model. Design parameters were determined and the developed equations were solved using an algorithm for solving boundary value problems for ordinary differential equations by collocation (bvp4c) using MATLAB. The results, obtained from the model, fitted the experimental data very well.).

Continuous production of a chiral amine in a packed bed reactor with co-immobilized amine dehydrogenase and formate dehydrogenase

A continuous flow packed bed reactor system was developed for the asymmetric reductive amination of 5-methyl-2-hexanone with a chimeric amine dehydrogenase (AmDH) and the formate dehydrogenase (FDH) from Candida boidinii. Both enzymes were co-immobilized onto the Nuvia® IMAC resin from Bio-Rad which employs the well-established binding chemistry between 6xHis-tagged proteins and immobilized Ni2+. Binding was robust under reaction conditions and continuous operation in a packed-bed flow column for more than five days was achieved. At 40 °C, conversion of 20 mM 5-methyl-2-hexanone ranged between 19 and 48%, with volumetric productivities between 443 and 107 g/L·day. The apparent biocatalyst half-life was 159 h and the absence of both internal and external mass transfer limitations was confirmed. Conversion was limited by modest competitive product inhibition of (R)-amine on ketone and an excess of enzyme over cofactor concentration, which precludes the use of Michaelis-Menten kinetics and results in a rate decrease of 80% compared to conditions where [S] ≫ [E]. The relationship between flow rate, conversion, and productivity was examined, with important lessons for reaction engineering. The reported work represents the first stable application of AmDHs in a continuous flow reactor for the production of chiral amines.

Lipase-mediated hydrolysis of hempseed oil in a packed-bed reactor and in-line purification of PUFA as mono- and diacylglycerols

Mono- and diacylglycerols (MAG and DAG, respectively) of polyunsaturated fatty acids (PUFA) are raising an increasing interest as novel non-ionic food emulsifiers owing to the recognized health-promoting effects of PUFA. We here reported on the lipase-catalyzed hydrolysis of hempseed oil in a homogeneous medium based on oil and t-BuOH/water carried out in a continuous flow packed-bed reactor (PBR). The biotransformation was carried out by feeding the reaction mixture upwards the PBR at varying flow rates through a peristaltic pump. The system was coupled in-line with a second glass column filled with an ion-exchange resin to retain hydrolyzed free fatty acids (FFA), thus allowing the straightforward purification of the glyceride component. A mixture of MAG and DAG (yield 40%, 620mg) composed of linoleic and α-linolenic acid (82%) and oleic acid (16%) was obtained in less than 2h. The lipase-based PBR was used for 10 cycles without any loss of activity.

Continuous Flow Bioamination of Ketones in Organic Solvents at Controlled Water Activity using Immobilized ω-Transaminases.

Compared with biocatalysis in aqueous media, the use of enzymes in neat organic solvents enables increased solubility of hydrophobic substrates and can lead to more favorable thermodynamic equilibria, avoidance of possible hydrolytic side reactions and easier product recovery. ω‐Transaminases from Arthrobacter sp. (AsR−ωTA) and Chromobacterium violaceum (Cv−ωTA) were immobilized on controlled porosity glass metal‐ion affinity beads (EziG) and applied in neat organic solvents for the amination of 1‐phenoxypropan‐2‐one with 2‐propylamine. The reaction system was investigated in terms of type of carrier material, organic solvents and reaction temperature. Optimal conditions were found with more hydrophobic carrier materials and toluene as reaction solvent. The system's water activity (aw) was controlled via salt hydrate pairs during both the biocatalyst immobilization step and the progress of the reaction in different non‐polar solvents. Notably, the two immobilized ωTAs displayed different optimal values of aw, namely 0.7 for EziG3−AsR−ωTA and 0.2 for EziG3−Cv−ωTA. In general, high catalytic activity was observed in various organic solvents even when a high substrate concentration (450–550 mM) and only one equivalent of 2‐propylamine were applied. Under batch conditions, a chemical turnover (TTN) above 13000 was obtained over four subsequent reaction cycles with the same batch of EziG‐immobilized ωTA. Finally, the applicability of the immobilized biocatalyst in neat organic solvents was further demonstrated in a continuous flow packed‐bed reactor. The flow reactor showed excellent performance without observable loss of enzymatic catalytic activity over several days of operation. In general, ca. 70% conversion was obtained in 72 hours using a 1.82 mL flow reactor and toluene as flow solvent, thus affording a space‐time yield of 1.99 g L−1 h−1. Conversion reached above 90% when the reaction was run up to 120 hours.

FAST Hydrogenations as a Continuous Platform for Green Aromatic Nitroreductions

A continuous-flow packed-bed catalytic reactor has been developed for hydrogenation of aromatic nitrobenzoic acids in water to produce the corresponding anilines. These hydrogenations are green, more efficient, less consumptive, and safer than the conventional ­reduction process. Various industrially important aromatic amines have been produced in excellent yields and with high throughput. The optimized continuous-flow reduction process produces no detectable genotoxic intermediates, unlike the corresponding batch reduction. The reactor is modular in design and can be scaled up to produce several kilograms of product per day without extensive redesign.

Catalytic Production of Glucose-Galactose Syrup from Greek Yogurt Acid Whey in a Continuous-Flow Reactor.

The hydrolysis of lactose in aqueous solutions and dairy waste streams was studied using Amberlyst 70 as a heterogeneous acid catalyst in a continuous-flow packed-bed reactor. The catalyst was stable during hydrolysis of an aqueous lactose feed but deactivated owing to mineral poisoning when the dairy waste Greek yogurt acid whey (GAW) was used as the feedstock. A catalyst deactivation model was developed and showed that the deactivation of the Amberlyst 70 catalyst was proportional to the amounts of cations, urea and amino acids flowing through the catalyst bed. The Amberlyst 70 catalyst was regenerable with an aqueous acid regeneration treatment. Based on the experimental data, a rigorous technoeconomic analysis was performed for the production of glucose-galactose syrup (GGS) via lactose hydrolysis of GAW using three different catalysts. This approach shows that the GGS produced from GAW could become a valuable revenue stream for Greek yogurt manufacturers.

Highly efficient production of chiral amines in batch and continuous flow by immobilized ω-transaminases on controlled porosity glass metal-ion affinity carrier

In this study, two stereocomplementary ω-transaminases from Arthrobacter sp. (AsR-ωTA) and Chromobacterium violaceum (Cv-ωTA) were immobilized via iron cation affinity binding onto polymer-coated controlled porosity glass beads (EziG™). The immobilization procedure was studied with different types of carrier materials and immobilization buffers of varying compositions, concentrations, pHs and cofactor (PLP) concentrations. Notably, concentrations of PLP above 0.1 mM were correlated with a dramatic decrease of the immobilization yield. The highest catalytic activity, along with quantitative immobilization, was obtained in MOPS buffer (100 mM, pH 8.0, PLP 0.1 mM, incubation time 2 h). Leaching of the immobilized enzyme was not observed within 3 days of incubation. EziG-immobilized AsR-ωTA and Cv-ωTA retained elevated activity when tested for the kinetic resolution of rac-α-methylbenzylamine (rac-α-MBA) in single batch experiments. Recycling studies demonstrated that immobilized EziG3-AsR-ωTA could be recycled for at least 16 consecutive cycles (15 min per cycle) and always affording quantitative conversion (TON ca. 14,400). Finally, the kinetic resolution of rac-α-MBA with EziG3-AsR-ωTA was tested in a continuous flow packed-bed reactor (157 μL reactor volume), which produced more than 5 g of (S)-α-MBA (>49% conversion, >99% ee) in 96 h with no detectable loss of catalytic activity. The calculated TON was more than 110,000 along with a space-time yield of 335 g L−1 h−1.

Correlation between synthesis pH, structure and Cu/MgO/Al2O3 heterogeneous catalyst activity and selectivity in CO2 hydrogenation to methanol

Cu/MgO/Al2O3 catalysts were synthesized by a co-precipitation preparation method, varying pH, while their catalytic performance was evaluated in a continuous-flow packed-bed reactor to relate the catalytic material activity, selectivity and stability with its surface structure. The major reaction products were methanol and water with CO as a sole process by-product. Alkaline synthesis conditions (pH = 8) positively affected CO2 conversion and CH3OH yield (< 250 °C), as CuO and Cu2O phases were present, since Cu2+ was only partially reduced. The hydrogen consumption variation also indicated that these different Cu species changed the interaction with magnesium and alumina. An increase in active basic sites was ascribed to the formation of spinel CuAl2O4 and MgAl2O4. Alongside with H2 TPD, XRD and SEM data suggested that a higher precursor solution pH enhanced the dispersion of CuO, enlarged Cu and BET areas, and improved the adsorption of H2. The XPS profiles of fresh, pre-treated and spent heterogeneous catalysts indicated that the dispersed copper moieties were reduced (to Cu0 or Cu+) during CO2 hydrogenation. CO2 turnover was consistent with metallic atom distribution, derived from N2O measurements. A maximum TOF of 13.2 × 10–4 s–1 was obtained over the catalyst, prepared at the pH of 8, whereas a minimum TOF of 5.5 × 10–4 s–1 corresponded to the pH of 5. A volcano plot-type shape of the productivity and basicity versus pH was observed as well, as the highest methanol productivity was attained using the precipitation pH of 8 (200 °C operation).

Rapid, highly efficient and stable catalytic hydrodechlorination of chlorophenols over novel Pd/CNTs-Ni foam composite catalyst in continuous-flow

A novel Pd/CNTs-Ni foam composite catalyst was developed for catalytic hydrodechlorination of chlorophenols by using CNTs-Ni foam as support. Characterizations including FESEM, TEM/HRTEM, HAADF-STEM and element mapping revel that the composite catalyst with 2 wt.% Pd loading possesses high porous micro-network structure and high dispersed active Pd nanoparticles (5.81 nm) on CNTs surface. The HDC of chlorophenols over Pd/CNTs-Ni foam composite catalyst has been studied in continuous-flow packed bed reactor. This packed bed reactor system with Pd/CNTs-Ni foam composite catalyst, presented the very short reaction cycle (22–74 s), high efficiency (dechlorination > 99.95%) and excellent catalytic stability during HDC in continuous-flow, making it to be a promising candidate for the HDC of wastewater containing highly toxic chlorinated organic pollutants and other Pd catalyzed hydrogenation reactions.

Production of galacto-oligosaccharides from whey permeate using β-galactosidase immobilized on functionalized glass beads

The conversion of whey permeates to galacto-oligosaccharides (GOS) was studied by the enzymatic action of β-galactosidase from Aspergillus oryzae in a continuous flow packed-bed reactor. A novel method of enzyme immobilization involving covalent immobilization of β-galactosidase on 3-aminopropyl triethoxysilane(3-APTES)-modified glass beads was developed by the cross-linking method. The pH and temperature dependence of the enzymatic efficiency of the glass bead-immobilized enzyme was compared with that of the free enzyme. Increased pH and thermal stabilities were observed for the immobilized enzyme versus the free enzyme. The reusability of the enzyme immobilized packed-bed reactor was studied and only about 4.6% of GOS yield was lost after eight reuses. Repeated cycle reactions were also carried out to improve the formation of GOS. The results showed that the GOS formation increased and a maximum GOS yield of 39.3% with 56.4% lactose conversion was obtained after the 2nd cycle of passing.

Synthesis of Geraniol Esters in a Continuous-Flow Packed-Bed Reactor of Immobilized Lipase: Optimization of Process Parameters and Kinetic Modeling.

With increasing demand for perfumes, flavors, beverages, and pharmaceuticals, the various associated industries are resorting to different approaches to enhance yields of desired compounds. The use of fixed-bed biocatalytic reactors in some of the processes for making fine chemicals will be of great value because the reaction times could be reduced substantially as well as high conversion and yields obtained. In the current study, a continuous-flow packed-bed reactor of immobilized Candida antarctica lipase B (Novozym 435) was employed for synthesis of various geraniol esters. Optimization of process parameters such as biocatalyst screening, effect of solvent, mole ratio, temperature and acyl donors was studied in a continuous-flow packed-bed reactor. Maximum conversion of ~87% of geranyl propionate was achieved in 15min residence time at 70°C using geraniol and propionic acid with a 1:1mol ratio. Novozym 435 was found to be the most active and stable biocatalyst among all tested. Ternary complex mechanism with propionic acid inhibition was found to fit the data.

Aerobic Oxidation of Diverse Primary Alcohols to Carboxylic Acids with a Heterogeneous Pd–Bi–Te/C (PBT/C) Catalyst

Heterogeneous catalytic aerobic oxidation methods represent a near-ideal approach for the conversion of primary alcohols to carboxylic acids. Here, we report that a heterogeneous catalyst composed of Pd, Bi, and Te supported on activated carbon is highly effective for the oxidation of diverse benzylic and aliphatic primary alcohols, including 5-(hydroxymethyl)furfural (HMF) and substrates bearing heterocycles and other important functional groups. In many cases, the desired carboxylic acid product is obtained in >90% yield. Additionally, the catalyst has been demonstrated in a continuous-flow packed-bed reactor for the oxidation of benzyl alcohol, achieving near-quantitative yield while undergoing over 30 000 turnovers.