Gas-liquid Mass Transfer Research Articles

Exploring kinetics and mass transfer in photocatalytic CO2 reduction: Impact of photocatalyst loading and stirrer speed

CO2 photocatalytic reduction is a potential and promising technology to reduce the level of the greenhouse gas in the atmosphere but also as an alternative and renewable fuel resource. However, the products yield of the reaction is still low and the identification of the optimal operating conditions that affect the process are still needed to be determined. This study investigates the impact of key operational parameters, specifically photocatalyst concentration and stirring speed, on the photocatalytic reduction of CO2 in a slurry batch photoreactor utilizing synthesized TiO2. A simplified photocatalytic kinetic model, incorporating the radiation field within the photoreactor, was developed, considering mass transfer from liquid to gas phase for the primary detected reaction products (CO, CH4, and H2). The proposed models elucidate the influence of different operating conditions on product yields. Stirring speed, controlled by a magnetic stirrer, impacts the gas–liquid mass transfer rate. Increased liquid phase stirring speed ensures faster species transport to the gas phase, with a diminishing effect beyond 900 rpm. TiO2 photocatalyst mass concentration influences the available total active surface and irradiation absorbance in the photoreactor volume. Optimal product yields were observed at the lowest tested photocatalyst concentration (0.5 g · L-1), indicating improved irradiation distribution and reduced particle agglomeration, resulting in higher available active surface for the reaction. The calculation model successfully predicted product yields even with lower photocatalyst concentration of 0.25 g · L-1, with marginal increases in predicted yields. These findings provide valuable insights for scaling up and optimizing the CO2 photocatalytic reduction process, offering a foundation for future research.

Study on CO2 absorption by EmimCl-MEA deep eutectic solvent in microchannel

Carbon dioxide (CO2) is widely acknowledged as the primary contributor to the greenhouse effect. Microchannel reactors can be used for enhancing chemical processes, solving the problems of limited gas-liquid mass transfer, and have significant advantages in CO2 capture. In this study, the deep eutectic solvent (DES) prepared by mixing ionic liquid (1-ethyl-3-methylimidazolium chloride, EmimCl) and Ethanolamine (MEA) in a molar ratio of 1:1 was selected for CO2 capture in a microchannel. The structure and physical properties of the DES were investigated, and the effects of gas and liquid flow rates, water content, and CO2 concentration on the CO2 absorption properties were analyzed. The increase of the water content not only significantly reduces the viscosity of DES, but also improves the CO2 absorption performance. In addition, the CO2 absorption mechanism of this DES has been obtained by the NMR spectrum, showing that the absorption process is a rapid chemical absorption process between CO2 and MEA. The Cl- of EmimCl could stabilize the protonated amine and prevent it from further reacting with MEACO2-, furthermore increasing the CO2 absorption rate.

Gas-liquid mass transfer in microbubble column reactors

Microbubble column reactors (MBCRs) present great potential in gas-liquid reactions due to their superior mass transfer efficiency. In this work, an automated platform was built to investigate the effect of gas/liquid superficial velocity, and liquid viscosity on mass transfer performance. Compared to conventional bubble column reactors, MBCRs exhibit significantly enhanced mass transfer efficiency. The findings show that kLa initially increases, followed by a subsequent decrease with the increase of gas superficial velocity. This behavior is attributed to transitioning from a homogeneous to a heterogeneous regime as gas superficial velocity increases. The liquid viscosity has a dual effect on kLa within a homogeneous regime. However, the kL in MBCRs is smaller than that in conventional bubble column reactors due to the movement of large bubbles enhancing liquid turbulence. Moreover, a dimensionless correlation was developed integrating the Weber number to predict the mass transfer coefficient.

Enhanced CO2 absorption in amine-based carbon capture aided by coconut shell-derived nitrogen-doped biochar

The sluggish CO2 absorption kinetics and constrained CO2 absorption capacity diminish the practicality of using amine-based absorption for CO2 capture, impeding progress toward carbon neutrality goals. This study aims to develop a catalytic CO2 absorption process to promote CO2 absorption by introducing a solid base catalyst, namely, coconut shell-derived nitrogen-doped biochar (NBC), into an amine-based solution. The coconut shells were modified with urea and activated with KOH to prepare an NBC catalyst with improved basic characteristics. The findings showed that compared to non-catalytic absorption, the NBC catalyst increased the CO2 absorption amount, CO2 absorption rate, and absorption efficiency of the monoethanolamine (MEA) solution by 16.9 %, 43.4 %, and 13.1 %, respectively. The basic sites on the NBC surface provided extra electrons to motivate the formation of MEACOO- and HCO3-. NBC’s large surface area and porous structure also advanced the gas–liquid mass transfer, accelerating the CO2 absorption rate. Furthermore, the NBC exhibited excellent cyclic stability and facilitated the subsequent CO2 desorption process. This work develops a promising and practical approach to significantly improve the amine-based absorption and reuse of waste biomass resources for efficient CO2 capture.

Gas–Liquid Mass Transfer Intensification for Selective Alkyne Semi-Hydrogenation with an Advanced Elastic Catalytic Foam-Bed Reactor

The Elastic Catalytic Foam-bed Reactor (EcFR) technology was used to enhance a model catalytic hydrogenation reaction by improving gas–liquid mass transfer. This advanced technology is based on a column packed with a commercial elastomeric polyurethane open-cell foam, which also acts as a catalyst support. A simple and efficient crankshaft-inspired system applied in situ compression/relaxation movements to the foam bed. For the first time, the catalytic support parameters (i.e., porosity, tortuosity, characteristic length, etc.) underwent cyclic and controlled changes over time. These dynamic cycles have made it possible to intensify the transfer of gas to liquid at a constant energy level. The application chosen was the selective hydrogenation of phenylacetylene to styrene in an alcoholic solution using a palladium-based catalyst under hydrogen bubble conditions. The conversion observed with this EcFR at 1 Hz as cycle frequency was compared with that observed with a conventional Fixed Catalytic Foam-bed Reactor (FcFR).

Improved biological methanation using tubular foam-bed reactor

BackgroundPower-to-gas is the pivotal link between electricity and gas infrastructure, enabling the broader integration of renewable energy. Yet, enhancements are necessary for its full potential. In the biomethanation process, transferring H2 into the liquid phase is a rate-limiting step. To address this, we developed a novel tubular foam-bed reactor (TFBR) and investigated its performance at laboratory scale.ResultsA non-ionic polymeric surfactant (Pluronic® F-68) at 1.5% w/v was added to the TFBR’s culture medium to generate a stabilized liquid foam structure. This increased both the gas–liquid surface area and the bubble retention time. Within the tubing, cells predominantly traveled evenly suspended in the liquid phase or were entrapped in the thin liquid film of bubbles flowing inside the tube. Phase (I) of the experiment focused primarily on mesophilic (40 °C) operation of the tubular reactor, followed by phase (II), when Pluronic® F-68 was added. In phase (II), the TFBR exhibited 6.5-fold increase in biomethane production rate (MPR) to 15.1 (LCH4/LR/d)\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$({\ ext{L}}_{{\ ext{CH}}_{4}}\ ext{/}{\ ext{L}}_{\ ext{R}}\ ext{/d)}$$\\end{document}, with a CH4 concentration exceeding 90% (grid quality), suggesting improved H2 transfer. Transitioning to phase (III) with continuous operation at 55 °C, the MPR reached 29.7 LCH4/LR/d\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${\ ext{L}}_{{\ ext{CH}}_{4}}\ ext{/}{\ ext{L}}_{\ ext{R}}\ ext{/d}$$\\end{document} while maintaining the grid quality CH4. Despite, reduced gas–liquid solubility and gas–liquid mass transfer at higher temperatures, the twofold increase in MPR compared to phase (II) might be attributed to other factors, i.e., higher metabolic activity of the methanogenic archaea.To assess process robustness for phase (II) conditions, a partial H2 feeding regime (12 h 100% and 12 h 10% of the nominal feeding rate) was implemented. Results demonstrated a resilient MPR of approximately 14.8 LCH4/LR/d\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${\ ext{L}}_{{\ ext{CH}}_{4}}\ ext{/}{\ ext{L}}_{\ ext{R}}\ ext{/d}$$\\end{document} even with intermittent, low H2 concentration.ConclusionsOverall, the TFBR’s performance plant sets the course for an accelerated introduction of biomethanation technology for the storage of volatile renewable energy. Robust process performance, even under H2 starvation, underscores its reliability. Further steps towards an optimum operation regime and scale-up should be initiated. Additionally, the use of TFBR systems should be considered for biotechnological processes in which gas–liquid mass transfer is a limiting factor for achieving higher reaction rates.

An integrated technology for the absorption and utilization of CO2 in alkanolamine solution for the preparation of BaCO3 in a high-gravity environment

In this study, an integrated technology is proposed for the absorption and utilization of CO2 in alkanolamine solution for the preparation of BaCO3 in a high gravity environment. The effects of absorbent type, high gravity factor, gas/liquid ratio, and initial BaCl2 concentration on the absorption rate and amount of CO2 and the preparation of BaCO3 are investigated. The results reveal that the absorption rate and amount of CO2 follow the order of ethyl alkanolamine (MEA) > diethanol amine (DEA) > N-methyldiethanolamine (MDEA), and thus MEA is the most effective absorbent for CO2 absorption. The absorption rate and amount of CO2 under high gravity are higher than that under normal gravity. Notably, the absorption rate at 75 min under high gravity is approximately 2 times that under normal gravity. This is because the centrifugal force resulting from the high-speed rotation of the packing can greatly increase gas-liquid mass transfer and micromixing. The particle size of BaCO3 prepared in the rotating packed bed is in the range of 57.2−89 nm, which is much smaller than that prepared in the bubbling reactor (>100.3 nm), and it also has higher purity (99.6 %) and larger specific surface area (14.119 m2/g). It is concluded that the high gravity technology has the potential to increase the absorption and utilization of CO2 in alkanolamine solution for the preparation of BaCO3. This study provides new insights into carbon emissions reduction and carbon utilization.

Mass transfer and bubble hydrodynamics in stirred tank with multiple properties fluid via a CFD‐PBM method

AbstractThe performance of a stirred bioreactor was evaluated in this study in terms of the bubble hydrodynamics and the mass transfer efficiency, using a non‐viscous Newtonian fluid of water, a viscous non‐Newtonian fluid of xanthan, and a viscous non‐Newtonian fluids of xanthan with dispersed soybean powder, respectively. The computational fluid dynamics–population balance model (CFD‐PBM) method coupled with the viscosity model and the mass transfer model is established to simulate the gas–liquid mass transfer process and bubble size distribution in the stirred bioreactor. The results demonstrate that the rheological properties of the fluid play an important role in determining the gas holdup, the mass transfer efficiency, and the bubble size distribution. Viscosity of the fluid exhibits a negative impact on gas–liquid mass transfer rate and gas holdup. Moreover, by properly adjusting the operating conditions such as the stirrer speed, it is possible to modulate the gas dispersion and mass transfer rate in the reactor.

Gas-liquid-soild triphasic continuous flow microreactor for improving homogeneous distribution of solid composites in heterogeneous photocatalytic degradation progress

The homogeneous distribution of solid composites in continuous flow photocatalytic progress is difficult due to the settle and clog in capillary. To overcome this challenge, a gas–liquid-soild triphasic continuous flow photoreactor was designed and used for heterogeneous photocatalytic degradation of antibiotics wastewater. In this work, take Bi2WO6 as photocatalyst, photocatalytic degradation of ofloxacin wastewater was studied systematically under different operational parameters and flow characteristics. The photocatalytic degradation performance of flow photoreactor was superior to batch counterpart, especially in later stage of reaction. The apparent reaction rate constants (k) of flow photoreactor was about 1.6 times that of batch counterpart. The gas–liquid mass transfer coefficient of flow photoreactor was more than 25 times that of batch photoreactor. Moreover, the influence mechanism of gas fraction, flow rate and tube diameter on photocatalytic degradation performance was investigated under various continuous flow conditions. Higher gas fraction, faster flow rate and smaller tube diameter were beneficial to improve photocatalytic degradation performance due to the enhancement of irradiation transmission and intensification of mass transfer. Therefore, the results of this work provided a guideline for the application of gas–liquid-soild triphasic continuous flow photocatalytic degradation technology in the future.

Numerical study of structural optimization for improving gas-liquid flow and microalgae carbon fixation rate in air-lift photobioreactors

In this paper, the gas-liquid flow pattern and CO2 dissolution transport process of microalgae solution in an air-lift photobioreactor (PBR) are investigated by numerical simulations. In order to promote the gas-liquid mass transfer efficiency to enhance the carbon fixation, we propose different optimization schemes for the structure. Firstly, a two-phase flow model and a mass transfer model are employed to investigate the fluid flow characteristics. The flow state is evaluated by velocity in light direction, turbulent kinetic energy (TKE), gas hold-up and CO2 mass transfer coefficient. The results show that the gas flow rate of 0.2 V/V/min is the optimum value for the inlet. Secondly, CO2 mass transfer and carbon fixation rates are analyzed for different inlet CO2 volume fractions. With the increase of CO2 volume fraction, the carbon fixation rate first increases and then decreases, the highest fixation rate reaching 2.21 × 10−4 mol m−3 s−1 at 6 %. Finally, based on numerical simulations, three optimized structures with different spacing of baffles are proposed and evaluated the performance in comparison with the original. The results show that the gas distribution and CO2 mass transfer are significantly improved, with the one-sided baffle structure is the best. In summary, this study provides a new and useful reference to evaluate the gas-liquid mixing and improve the microalgae carbon fixation rate.

Gas-liquid flow and mass transfer characteristics in improved heart-shaped structure microreactor

The gas-liquid two-phase flow and mass transfer characteristics in heart-shaped structure microreactor were visually investigated in an Advanced Flow Reactor (AFR). Three various flow patterns were observed in the experiment: Taylor-bubble flow, Taylor-flow, and unstable broken flow. The experiment observed that the bubbles only broke steadily under the action of the first heart-shaped unit obstacle; while in the latter heart-shaped units, the larger bubbles would break resulting in the unstable broken flow. The efficiency of CO2 absorption increases as the gas-liquid two-phase flow rate ratio decreases and the solution concentration rises. The volume mass transfer coefficient increases with the increase of the gas-liquid two-phase flow rate ratio and the solution concentration. The absorption efficiency and mass transfer coefficient in channel 2 with two rows of heart-shaped units is greater than channel 1 with one row of heart-shaped units. Additionally, there exists an optimal performance ratio for reactor under the appropriate gas-liquid flow rate ratio.

CFD simulation and experimental study of CO2 absorption in a rotating packed bed

The rotating packed bed (RPB), a process intensification equipment, has been widely studied and applied to chemical engineering processes such as gas absorption, nanomaterial preparation, and polymer devolatilization. In this study, we presented a typical RPB model to study the intensification mechanism of high gravity on gas-liquid mass transfer. Based on this, three-dimensional computational fluid dynamics (CFD) simulations and experiments of CO2 physical absorption were conducted to investigate the gas-liquid mass transfer characteristics in the RPB. The predicted and experimental values of CO2 saturation rates of the liquid phase showed good agreement, and the errors were within ± 15 % under various operating conditions. Moreover, detailed flow field and mass transfer information that are difficult to measure experimentally, such as the distribution of CO2 mass fraction in the liquid, liquid holdup, turbulent kinetic energy dissipation rate, and gas-liquid interfacial area, were analyzed by CFD simulation results. These results provide a solid foundation for the further development and application of RPB.

Effect of surfactant on dynamics and gas-liquid mass transfer for single carbon dioxide bubbles

In carbonation reaction, the impact of surfactants on the movement and mass transfer behavior of carbon dioxide bubbles were crucial for the production of high-quality silicon dioxide products. The study employed the Matlab image processing system to investigate the shapes, motion velocities, and rise path of single carbon dioxide bubbles within varying concentrations of cetyltrimethyl ammonium bromide (CTAB) solutions. This exploration aimed to elucidate the effect of CTAB on the movement and mass transfer coefficient (MTRC) of single carbon dioxide bubbles. Alterations in the CTAB solution concentration and bubble sizes significantly influenced the mass transfer and movement characteristics of single carbon dioxide bubbles. The conclusion was drawn through the computation of the MTRC of single carbon dioxide bubbles in deionized water and CTAB solutions: the addition of CTAB significantly reduced the mass transfer efficiency of carbon dioxide in deionized water, with the MTRC of CTAB solutions decreasing as the solution concentration increased. Utilizing the stagnant cap model, it can be concluded that CTAB's reduction of the MTRC of carbon dioxide was attributed to the high viscosity of the medium, low bubble velocity, stable flow conditions, and intensified adsorption degree of CTAB molecules at the gas-liquid interface. According to the significant periodic trajectories of single carbon dioxide bubbles in the stable range, the correlation between the trajectories of compressible bubbles in surfactant solution and mass transfer in liquid phase was established, and the previous method based on rigid sphere model was modified. The paper proposed the mechanism of CTAB's influence on single carbon dioxide bubbles, offering crucial theoretical insights into the industrial application of surfactants in the carbonation process for producing silicon dioxide.

The fundamental role of pH in CH4 bioconversion into polyhydroxybutyrate in mixed methanotrophic cultures

Climate change and plastic pollution are likely the most relevant challenges for the environment in the 21st century. Developing cost-effective technologies for the bioconversion of methane (CH4) into polyhydroxyalkanoates (PHAs) could simultaneously mitigate CH4 emissions and boost the commercialization of biodegradable polymers. Despite the fact that the role of temperature, nitrogen deprivation, CH4:O2 ratio or micronutrients availability on the PHA accumulation capacity of methanotrophs has been carefully explored, there is still a need for optimization of the CH4-to-PHA bioconversion process prior to becoming a feasible platform in future biorefineries. In this study, the influence of different cultivation broth pH values (5.5, 7, 8.5 and 10) on bacterial biomass growth, CH4 bioconversion rate, PHA accumulation capacity and bacterial community structure was investigated in a stirred tank bioreactor under nitrogen deprivation conditions. Higher CH4 elimination rates were obtained at increasing pH, with a maximum value of 50.4 ± 2.7 g CH4·m−3·h−1 observed at pH 8.5. This was likely mediated by an increased ionic strength in the mineral medium, which enhanced the gas-liquid mass transfer. Interestingly, higher PHB accumulations were observed at decreasing pH, with the highest PHB contents recorded at a pH 5.5 (43.7 ± 3.4 %w·w−1). The strong selective pressure of low pH towards the growth of Type II methanotrophic bacteria could explain this finding. The genus Methylocystis increased its abundance from 34 % up to 85 and 90 % at pH 5.5 and 7, respectively. On the contrary, Methylocystis was less abundant in the community enriched at pH 8.5 (14 %). The accumulation of intracellular PHB as energy and carbon storage material allowed the maintenance of high CH4 biodegradation rates during 48 h after complete nitrogen deprivation. The results here obtained demonstrated for the first time a crucial and multifactorial role of pH on the bioconversion performance of CH4 into PHA.

Nanobubbles produced by nanopores to probe gas-liquid mass transfer characteristics

HypothesisThis study tested the hypothesis of how the nanopore size of membranes and how the surface charge of nanobubbles responds to its pinch-off from the nanopore. This study also tested the hypothesis that nanobubbles that remain in solution after production may increase the dissolved oxygen content in water. ExperimentsThe effect of membrane pore size, hydrodynamic conditions (gas and liquid flow rates), and physicochemical parameters (pH and temperature) on volumetric mass transfer coefficient (kLa) for oxygen nanobubbles formed by the nanopore diffusion technique was investigated. This study experimentally determined the kLa by carefully removing the dissolved oxygen by nitrogen purging from nanobubble suspension to examine the sole contribution of nanobubble dissolution in water to the reaeration. ResultsScaling estimates indicate that the nanobubble pinch-off radius and nanopore radius have a power-law correlation and that nanobubble size declines with the nanopore size. This is in line with our experimental results. The surface charge of nanobubbles delays its pinch-off at the gas-liquid interface. Nanobubbles offered 3-4 times higher kLa than microbubbles. Standard oxygen transfer efficiency in water was found to be 78%, significantly higher than that in microbubbles. However, dissolving stable nanobubbles in water does not considerably increase dissolved oxygen levels.

Simulation of a Multistaggered Baffle Scrubber to Enhance the Efficiency of Simultaneous Desulfurization and Denitrification.

In this study, we conduct simulation research on simultaneous desulfurization and denitrification in a multistaggered baffle spray scrubber. By employing two-phase flow simulations within the Euler-Lagrange framework and calculating the gas-liquid mass transfer rate with user-defined functions, we comprehensively analyzed the effects of various operational parameters. Initially, we validated our simulation model by comparing the simulation results with experimental data. Under conditions of a 0.2 mm droplet diameter, a liquid-to-gas ratio (L/G) of 12 L/m3, and a gas flow rate of 5 CMM using a full cone nozzle, the simulation indicated a desulfurization efficiency of 99.90 versus 99.84% obtained experimentally and a denitrification efficiency of 92.01 versus 90.67% obtained experimentally. This comparison confirmed the reliability of the simulation model. Our findings indicate that a droplet size of 2 mm is optimal, enhancing the desulfurization efficiency from 99.90 to 99.98% and the denitrification efficiency from 92.01 to 99.76%. However, when the droplet size exceeds 2 mm, efficiencies marginally decrease. Increasing the liquid-to-gas ratio to 16 L/m3 further improves desulfurization and denitrification efficiencies to 99.98 and 99.80%, respectively. In contrast, higher inlet flue gas flow rates reduce these efficiencies, with a decline observed from 100% to as low as 93.90% for denitrification with 2 mm droplets. Additionally, the use of a swirl cone nozzle, compared to full or hollow cone nozzles, better disperses droplets, enhancing the gas-liquid contact and achieving efficiencies of 99.99% for desulfurization and 99.81% for denitrification with 2 mm droplets. These insights are valuable for optimizing operational conditions in industrial-scale spray scrubbers, significantly contributing to mitigating the environmental impacts of industrial emissions.

Development of a 10-litre pilot scale micro-nano bubble (MNB)-enhanced photocatalytic system for wastewater treatment

ABSTRACT A 10-litre pilot scale micro-nano bubble (MNB)-enhanced photocatalytic degradation system was developed using ZnO as the photocatalyst and salicylic acid (SA) as the model pollutant. The effectiveness of the MNB/ZnO/UV system was systematically compared with those of MNB, UV, MNB/UV, MNB/ZnO and ZnO/UV degradation systems. The effects of process parameters, including catalyst dosage, pollutant concentration, air-intake rate, pH and salt content on the degradation of SA, were comprehensively investigated. Optimum performance was obtained at neutral conditions with a catalyst dosage of 0.3 g/L and an air-intake rate of 0.1 L/min. For the degradation of SA, a kinetic constant of 0.04126/min was achieved in the MNB/ZnO/UV system, which is 4.5 times greater than that obtained in the conventional ZnO/UV system. The substantial increase in the degradation rate can be attributed to that the air MNB not only enhanced the gas-liquid mass transfer efficiency but also elevated the concentration of dissolved oxygen. A 10-litre pilot scale MNB/ZnO/UV system was successfully applied to the purification of lake water and river water, demonstrating great application potential for wastewater treatment.

CO2 sequestration by ammonia-enhanced phosphogypsum mineral carbonation: Development and optimization of reaction kinetic model

Comparing of existing kinetic models for direct mineral carbonation by solid waste, an optimized kinetic model was developed to depict the relationship between phosphogypsum carbonation ratio and reaction time. Based on the optimized model, the reaction mechanism of CO2 sequestration by ammonia-enhanced phosphogypsum mineral carbonation was analyzed. The experimental results show that, under specific conditions, including an ammonia ratio of 2.3, room temperature (25 °C), a liquid–solid ratio of 5:1, a gas flow rate of 200 mL/min, and a rotational speed of 500 rpm, phosphogypsum achieved its peak carbonation efficiency of 91 % within 30 min. The optimized model fitting curve has a high consistency with the experimental data, and the average R2 value is 0.991. The process of ammonia-enhanced phosphogypsum mineral carbonation comprises three distinct sub-processes. It is consisted of mass transfer in gas–liquid interface and solid–liquid interface, respectively, and product layer diffusion. Among them, the gas–liquid mass transfer is identified as the rate-controlling step in the mineral carbonation process. The present study provides a basis for the operation optimization and large-scale utilization of phosphogypsum mineral carbonation.

Continuous Cu/keto-ABNO catalyzed aerobic oxidation of ethyl lactate to ethyl pyruvate in a micro-packed bed reactor: Process optimization and reaction kinetics

Pyruvic acid and its esters are increasingly utilized as precursors for synthesizing antioxidations or dietary supplement in the pharmaceutical industry. The selectivity of oxidation step holds paramount importance in the synthesis route. In this study, a continuous micro-packed bed reactor platform is developed to determine the kinetic parameters of Cu/keto-ABNO catalyzed aerobic ethyl lactate (EL) oxidation. Initially, various operating parameters including types of nitroxyl radical, phase ratio, pressure and temperature were systematically studied to reveal their effect on the oxidation performance. The Cu/keto-ABNO catalyzed aerobic oxidation method can efficiently transform EL to ethyl pyruvate (EP) without hydrolysis. Comparing the aerobic oxidation performances in batch reactors, the reaction time was shortened to 1/15 and the space time yield was increased by 6 times in micro-packed bed reactors, which is due to the enhanced gas–liquid mass transfer. Finally, the kinetic parameters of this reaction were promptly determined and the supplementary validation experiments were conducted to confirm the applicability and accuracy of the kinetic model.

Catalytic cycloaddition of CO2 to epoxidized methyl oleate over a HBimCl-NbCl5/HCMC: Physicochemical, mass transfer and kinetic investigation

The cycloaddition of CO2 to epoxidized molecules is an ecofriendly strategy for synthesizing aliphatic carbonates. In this study, heterogeneous catalytic synthesis of carbonated methyl oleate was performed. Influences of reaction parameters such as reaction temperature (403.15–443.15 K), pressure (1–3 MPa), concentration of functional groups (1.22–2.88 mol·L−1) and catalyst loading (0.025–0.042 g·mL−1) on the kinetics were evaluated. Gas-liquid mass transfer of CO2 in the methylated oleic acid system was investigated, and a mathematical model was developed. The dissolution of CO2 was found to be exothermic, and the dissolution capacity decreases with increasing temperature and decreasing pressure. The solubility of CO2 follows an order of methylated form > epoxidized form > carbonated form. A high conversion rate (68.45 %) of epoxides was achieved in 6 h at 443.15 K and 3 MPa with a catalyst loading of 0.042 g·mL−1. These results show a potential route for synthesizing aliphatic carbonates by combining methyl oleate with CO2.