Intraparticle Diffusion Limitations Research Articles

Hard Template-Assisted Trans-Crystallization Synthesis of Hierarchically Porous Cu-SSZ-13 with Enhanced NH3-SCR Performance

Small porous Cu-SSZ-13 catalysts have recently been commercialized for the selective catalytic reduction of NOx with ammonia (NH3-SCR) on diesel vehicles. Unfortunately, the conventional Cu-SSZ-13 catalyst still confronts the challenge of diffusion limitations, which represent a major obstacle that reduces the catalyst’s SCR performance. Herein, a hierarchically porous SSZ-13 zeolite was synthesized via a trans-crystallization method assisted by the use of carbon black as a hard template in a short synthetic period, and the corresponding Cu-SSZ-13 catalysts with mesopores exhibited improved low-temperature activity and hydrothermal stability when compared with their microporous counterpart. A series of characterizations revealed that the mesopores are conducive to an increase in Cu loading while helping to stabilize the CHA structure and maintain the Cu species in their ionic form. More importantly, intra-particle diffusion limitations are reduced via the introduction of the mesopores owing to the shortened diffusion path inside the SSZ-13 zeolite, thus not only enhancing the active sites’ accessibility but also promoting the diffusion of the reactants and products. This work contributes to the design and synthesis of a high-performance Cu-SSZ-13 zeolite SCR catalyst for the removal of NOx emitted from diesel vehicles.

Intra-particle diffusion limitation for steam methane reforming over a Ni-based catalyst

This work aims to evaluate the diffusion limitation for the steam methane reforming process over spherical catalyst particles (Ni/α-Al2O). Numerical calculations based on a CFD model were conducted to determine the intrinsic and actual reaction rates. The CFD model was validated using experimental results, and good agreement was achieved. The effectiveness factor for the reaction rates was used to express the effect of diffusion limitation within the porous catalyst particle. The effectiveness factor was determined for a wide range of operational parameters, including a temperature range of 800–1300 K and a steam-to-methane ratio of 1–5. The analysis was performed for spherical catalyst particles with diameters up to 3.42 mm, and the effectiveness factor as a function of catalyst particle diameter, temperature, and steam-to-methane ratio was established. The results show that the effectiveness factor is inversely proportional to the diameter of the catalyst particle and that an increase in reaction temperature and steam-to-methane ratio leads to an increase in diffusion limitation. The limitations of the analysis are discussed and justified. The final expression for the effectiveness factor can be used in a pseudo-homogeneous steam methane reformer model where the effectiveness factor varies depending on the position in the packed bed.

Evaluation of the relevant mass and heat transfer phenomena in a packed bed membrane reactor for the direct conversion of CO2 to dimethyl ether

This study investigates the relevant heat and mass transfer phenomena occurring at the different scales in a packed bed (membrane) reactor for the direct conversion of CO2 to dimethyl ether (DME) via the implementation of 2D heterogeneous reactor models. Intra-particle diffusion limitations were found to be relevant for particle diameters larger than 1 mm and temperature above 220 ⁰C, such that the catalyst efficiency drops down to 50% and 5% for the Cu/ZnO/Al2O3 and the HZSM-5, respectively, in the most critical conditions (i.e., 270 ⁰C and Dp of 10 mm). A component-specific Thiele modulus-efficiency correlation was developed based on the results of the rigorous particle model to account for pore-diffusion limitations without having to solve a complex heterogeneous reactor model. This correlation shows the typical behavior reported in literature for power law kinetics and accurately predicts the reaction performance with deviation of less than 5% for values of the Thiele modulus lower than 2. In the packed bed membrane reactor (PBMR), the concentration polarization (CP) also showed to affect the reactor performance. The concentration of water at the surface of the membrane selective layer was found to be up to 64% lower than the concentration in the bulk phase, hindering the effectiveness of the membrane separation. To account for this phenomenon via a simplified approach, a Sherwood-type correlation was developed to determine a CP mass transfer coefficient, based on the results obtained via the rigorous 2D PBMR model. Such correlation showed to predict with high accuracy (i.e., errors lower than 5%) the effect of the CP on the PBMR performance. Differently from the pore diffusion and CP phenomena, the intra-particle heat transfer, the particle–fluid mass and heat transfer as well as the axial dispersion were found to have a negligible effect on the reactor behavior. Finally, given the relevant mass/heat transfer phenomena, this study proposes further reactor optimization strategies, such as the reduction of the zeolite loading in the bifunctional catalyst bed by ca. 90% with respect to what is reported in literature.

Batchwise Leaching of Calcium from Demolished Concrete Fines in an Aqueous Ammonium Nitrate Solution: Part 1 Experimental Study

In this work, the dissolution step of the indirect mineral carbonation process was investigated; first, a process-relevant thermodynamic framework is introduced, and then, an extensive experimental campaign with aqueous ammonium nitrate (AN) as the solvent is presented. Steady-state experiments after 24 h of leaching under different solvent concentrations and cement dosing were studied, confirming the applicability of the developed thermodynamic framework and its mathematical description. Afterward, batch experiments were performed to study the kinetic leaching behavior from different particle sizes, at different temperatures, and under a variety of industrially relevant conditions. Smaller particles release more calcium faster than larger particles as their calcium content is higher, and they have more specific surface available and less intraparticle diffusion limitations. Between temperatures of 5 and 35 °C, a 20% increase in dissolution performance was observed, which is due to an increase in reaction kinetics and/or diffusivity. Experiments under industrially relevant conditions reveal that increasing both the AN concentration and the solid to liquid ratio increases the amount of calcium in solution but has contradicting effects on extraction efficiency. For the typical conditions of a solid to liquid ratio of 0.2 and an AN concentration of 0.5 M, about 32% of the available calcium was leached after 20 min, resulting in a calcium concentration of 0.065 M; thereafter, this leaching process slows down sharply. The knowledge developed in this work forms a solid foundation for future modeling and scaling up of the indirect mineral carbonation process.

The role of effectiveness factor on the modeling of methanol steam reforming over CuO/ZnO/Al2O3 catalyst in a multi-tubular reactor

A pseudo-homogeneous model for the methanol steam reforming process was developed based on reaction kinetics over a CuO/ZnO/Al 2 O 3 catalyst and non-adiabatic heat and mass transfer performances in a co-current packed-bed reactor. A Thiele modulus method and an intraparticle distribution method were applied for predicting the effectiveness factors for main reactions and providing insights into the diffusion-reaction process in a cylindrical catalyst pellet. The results of both methods are validated and show good agreements with the experimental data, but the intraparticle distribution method provides better predictions. Results indicate that increases in catalyst size and bulk fluid temperature amplify the impact of intraparticle diffusion limitations, showing a decrease in effectiveness factors. To satisfy the requirements of a high temperature polymer electrolyte membrane fuel cell stack, the optimized operating conditions, which bring the methanol and CO concentrations to less than 1 % vol in the reformate stream, are determined based on the simulation results. • One-dimensional pseudo-homogeneous model of a packed-bed methanol steam reformer. • Two methods to obtain approximate solutions of the catalytic effectiveness factor. • Validation of reaction kinetics and effectiveness factors with experimental data. • Effects of main operating parameters on the intraparticle heat and mass transfer. • Optimized conditions to obtain less than 1% of CH 3 OH and CO in reformate gas.

Studies into the kinetic compensation effects of Loy Yang Brown coal during gasification in a steam environment – A mechanistic view

This study aims to investigate the kinetic compensation effects (KCE) and gain insights into the mechanisms, during gasification of Loy Yang brown coal char with steam, in an in-situ fluidized bed gasification operation for two-particle size ranges (106–150 and 180–212 µm). The instantaneous rate of char gasification and CO, CO₂, and H₂ formation was measured by continuous monitoring of product gas composition through a quadrupole mass spectrometer. Gasification of the smaller particle size range (106–150 µm) in kinetics-controlled regime shows less importance of char-catalyzed element on the WGS reaction, as revealed by the apparent activation energy and apparent frequency factor for CO and CO₂ formation. However, the study of kinetic parameters of char consumption on gasification using coal char with larger particle sizes (180–212 µm) indicated the limitations of intraparticle diffusion. That potentially affects the CO₂ formation by catalyzed WGS through re-adsorption of CO on catalytic char surface at a higher conversion level (> 0.3) as revealed by the difference in the extent of KCE for CO and CO₂ formation. The difference in the extent of KCE for char consumption and H₂ formation for bigger particles indicates the intraparticle diffusion limitations also appear to affect the route of H₂ formation, i.e., significantly produced through adsorption on catalytical active site with less involving the carbon active sites on char surface.

Tunable HMF hydrogenation to furan diols in a flow reactor using Ru/C as catalyst

• The hydrogenation of HMF to furan diols was studied and optimized in flow reactor. • The commercial Ru/C was an efficient catalyst for the BHMF and BHMTHF synthesis. • The highest BHMF and BHMTHF yields were ascertained only tuning the contact time. • The catalyst was stable up to 6 h and easily reactivable through acetone washing. • Internal mass transfer limitations occurred and affected the overall reaction rate. 5-hydroxymethylfurfural (HMF), accessible from various feedstocks, represents an important renewable platform-chemical, precursor for valuable biofuels and bio-based chemicals. In this work, the continuous hydrogenation of an aqueous solution of HMF to give strategic monomers, 2,5-bis(hydroxymethyl)furan (BHMF) and 2,5-bis(hydroxymethyl)tetrahydrofuran (BHMTHF) was investigated in a continuous flow reactor adopting a commercial Ru/C (5 wt%) as catalyst. The influence of the main process variables on products yield and selectivity was studied and optimized. The highest BHMF and BHMTHF yields of 87.9 and 93.7 mol%, respectively, were achieved by tuning the catalyst contact time, keeping all other variables constant (temperature, pressure, hydrogen flow rate, initial HMF concentration). Intraparticle diffusion limitation for hydrogen and HMF was shown to occur at some of the tested conditions by performing the HMF hydrogenation with different catalyst particle sizes, confirmed by calculations. Constant catalyst activity was observed up to 6 h time-on-stream and then gradually reduced. Fresh and spent catalyst characterization showed no significant sintering and negligible leaching of ruthenium during time-on-stream. A decrease of the specific surface area was observed, mainly due to humin deposition which is likely the reason for catalyst deactivation. Catalyst performance could be restored to initial values by a thorough washing of the catalyst.

Adsorption and regeneration on iron-activated biochar for removal of microcystin-LR

Novel iron activated biochars (FA-BCs) were prepared via simultaneous pyrolysis and activation of FeCl3-pretreated bermudagrass (BG) for removing microcystin-LR (MC-LR) in aqueous solution. Compared to the raw BC (without activation), the surface area and adsorption capacity of FA-BC at iron impregnation ratio of 2 (2 g FeCl3/g BG) were enhanced from 86 m2/g and 0.76 mg/g to 835 m2/g and 9.00 mg/g. Moreover, FA-BC possessed various iron oxides at its surface which provided the catalytic capacity for regeneration of MC-LR spent FA-BC and magnetic separation after the MC-LR adsorption. Possible mechanisms for the MC-LR adsorption onto FA-BC would include electrostatic attraction, π+-π, hydrogen bond, and hydrophobic interactions. The detailed adsorption studies indicated mainly chemisorption and intra-particle diffusion limitation would participate in the adsorption process. The thermal regeneration at 300 °C kept high regeneration efficiency (99–100%) for the MC-LR spent FA-BC during four cycles of adsorption-regeneration. In addition, the high regeneration efficiency (close to 100%) was also achieved by persulfate oxidation-driven regeneration. FA-BC also exhibited high adsorption capacity for the MC-LR from the real lake water to meet the MC-LR concentration below 1 μg/L as a safe guideline suggested by WHO.

Selective dehydration of glycerol on copper based catalysts

Glycerol is produced in large quantities as a byproduct of biodiesel, and among others hydroxyacetone (acetol) is an important commodity obtained from glycerol. Metallic Cu has been identified as active site for the dehydration of glycerol to hydroxyacetone and acid and metal sites are known to influence the catalytic performance. In this study, dehydration of glycerol over 5 wt.% copper supported on γ-Al2O3, ZrO2 and SiO2 was investigated. Catalysts were characterized by N2 physisorption, H2-TPR, NH3-TPD, N2O chemisorption, XPS, XRD, FTIR of pyridine adsorption. Cu/ZrO2 exhibited the highest hydroxyacetone yield at 20 % of glycerol conversion and the highest apparent reaction rate. The superior activity of Cu/ZrO2 was attributed to the highly acidic, both Lewis and Brönsted acidic, nature of the support and positive roles of the interfacial sites. The Weisz-Prater (WP) criterion was applied to confirm the absence of intraparticle diffusion limitations. It was assumed spherical particles and first order reaction. The WP value obtained in the worst scenario was less than 0.3 ensuring no diffusion limitation. Complementary DFT study indicates that both glycerol and hydroxyacetone interact significantly stronger on Cu/γ-Al2O3 and Cu/ZrO2 compared to metallic Cu, suggesting that the active sites are at the interface of Cu particles and the acidic support.

Iron-activated bermudagrass-derived biochar for adsorption of aqueous sulfamethoxazole: Effects of iron impregnation ratio on biochar properties, adsorption, and regeneration

This work focused on the impacts of FeCl3 impregnation ratio on the properties of FeCl3-activated bermudagrass (BG)-derived biochars (IA-BCs), adsorption of sulfamethoxazole (SMX) onto IA-BCs and regeneration of SMX-spent IA-BC. Compared with the control BC (85.82 m2/g), IA-BCs made via pyrolysis with FeCl3 to BG mass ratio between 1 and 3 (1–3 g FeCl3/g BG) resulted in significantly enhancing surface area (1014–1035 m2/g), hydrophobicity, Fe content in IA-BCs (3.87–7.27%), and graphitized carbon. The properties of IA-BCs supported magnetic separation and higher adsorption (32–265 mg SMX/g BC) than the control BC (6–14 mg SMX/g BC) at various pH. Adsorption experiments indicated various adsorption mechanisms between SMX and IA-BCs via π-π EDA, hydrophobic interactions, and hydrogen bond with intraparticle diffusion limitation. The adsorption was also found to be spontaneous and exothermic. The IA-BC made at FeCl3 to BG mass ratio of 2 (IA-BC2.0) showed the maximum adsorption capacity for SMX (253 mg SMX/g BC) calculated from Langmuir isotherm model. Additionally, both NaOH desorption and thermal oxidation showed effective regeneration of SMX-saturated IA-BC2.0 over multiple cycles. After three cycles of adsorption-regeneration, 64% and 62% of regeneration efficiencies were still achieved under thermal treatment at 300 °C and desorption with 0.1 M NaOH solution, respectively, indicating a cost-efficient adsorbent for the elimination of SMX in water.

Ultrasound-acid modified Merremia vitifolia biomass for the biosorption of herbicide 2,4-D from aqueous solution.

In this work, a biosorbent was prepared by the ultrasound-acid treatment of Merremia vitifolia plant and tested for the removal of 2,4-dichlorophenoxyacetic acid (2,4-D), a phenoxy herbicide. Optimal values of five batch biosorption parameters namely stirring speed, contact time, biosorbent dosage, initial pH and initial adsorbate concentration were experimentally obtained in sequential manner for an enhanced biosorption capacity. The kinetics of the biosorption of 2,4-D were best described by the pseudo first order kinetic model (R2 = 0.99) and the biosorption equilibrium data were successfully fitted to the Langmuir adsorption isotherm (R2 = 0.99) with a maximum biosorption capacity of 66.93 mg g-1. The mechanism of biosorption was investigated using two intraparticle diffusion models (Weber and Boyd), Dubinin-Radushkevich isotherm model and electrostatic interactions. The presence of intraparticle and film diffusion limitations for the biosorption was confirmed along with the physical and chemical nature of the biosorption. The thermodynamic parameters of the biosorption were calculated using the equilibrium data obtained at four different temperatures. The entropy change for biosorption was found to be negative indicating the decreased randomness at the interface. Desorption studies were carried out using different solvents and the percentages of desorption were compared.

Model Analysis of the Effects of Active Phase Distribution at the Pellet Scale in Catalytic Reactors for the Direct Dimethyl Ether Synthesis

The direct synthesis of dimethyl ether (DME) from syngas is an exothermic process, which requires two different catalyst functions in the same reactor: methanol (MeOH) synthesis and dehydration to DME. The two functions can be intimately mixed in hybrid pellets, located on separated pellets or coupled in core@shell-engineered pellets. In this work, a multitubular fixed-bed reactor, loaded with the catalyst configurations mentioned above, has been investigated by mathematical modeling. It is shown that the different spatial distribution of the active phases has a drastic impact on reactor performance. Using the mechanical mixture of separated pellets, the DME yield is hindered by intraparticle diffusion limitations. The hybrid catalyst, minimizing the diffusion length between methanol synthesis and dehydration catalyst functions, provides better DME yield performances but higher hotspot temperatures and can suffer from deactivation issues due to the detrimental interaction between the two catalytic functions. The MeOH@DME configuration, which allows for a limited contact between the catalyst active phases, guarantees DME yields comparable to those of hybrid pellets while moderating the hotspot temperature.

Intraparticle diffusion model to determine the intrinsic kinetics of ethyl levulinate synthesis promoted by Amberlyst-15

Levulinic acid and its esters are considered very versatile chemical compounds used for a wide range of derivatives. Traditionally ethyl levulinate is synthesized in batch reactors, using homogeneous catalysts (H2SO4, H3PO4). Several investigations were reported on solid acid catalysts, as zeolites, sulfated oxides, sulfonic ion-exchange resins. Amberlyst-15 showed high potentials: to design a continuous reactor, it is necessary to investigate the stability of the catalyst and the kinetics of the reaction. In the present work, we demonstrated that the resin is stable for more than 5 days. Kinetic and mass transfer phenomena were studied, evaluating the partition and take-up of the used resin when put in contact with reactants and products. Two different samples of Amberlyst-15 were used, characterized by different size, demonstrating that bigger particles lead to higher intraparticle diffusion limitations.

Electro-Fenton Regeneration of Activated Carbon Fibers for the Removal of Pharmaceutical Residues

Introduction The electro-Fenton process is based on in-situ production of the Fenton’s reagent in order to continuously generate hydroxyl radicals in the bulk solution [1]. It is also possible to promote the generation of additional powerful oxidant species by using anode material with high oxygen evolution overpotential. Therefore, such electrochemical advanced oxidation process (EAOP) is able to degrade a large range of organic pollutants [1]. However, energy efficiency of EAOPs is strongly affected by mass transport limitations during the treatment of low concentrations of pollutants such as pharmaceutical residues. In fact, a large amount of hydroxyl radicals are wasted in parasitic reactions such as hydroxyl radical dimerization. The combination of adsorption and electro-Fenton processes aims at overcoming this drawback. Adsorption on activated carbon fibers (ACFs) is used for pre-concentration of organic pollutants. Then, ACFs can be directly used as cathode during the electro-Fenton process for desorption, degradation and mineralization of organic compounds as well as for regeneration of ACFs for additional adsorption steps [2]. The possibility to easily regenerate ACFs improve the cost-effectiveness of this material, which presents more suitable characterisitcs than grain or powder activated carbon (e.g. low intra-particle diffusion limitation leading to fast adsorption kinetics, narrow pore size distribution leading to selective adsorption of micropollutants). This innovative strategy was applied for the removal of pharmaceutical residues. Scale-up from batch to continuous filtration reactor was investigated. Material and methods A first set of experiments was performed in batch reactor for both adsorption and electro-Fenton processes, by using clofibric acid and ofloxacin as model pharmaceutical residues. Design parameters (e.g. anode material: boron-doped diamond (BDD) or TiOx) and operational parameters (current density, treatment time) were optimized for improving regeneration efficiency and mineralization of pharmaceutical residues. Regeneration efficiency was assessed by comparing the adsorption capacity of regenerated ACFs and pristine ACFs. Mineralization rate of desorbed organic compounds was measured by total organic carbon analysis. Biodegradability and acute toxicity (Microtox®) of the solution was also assessed. ACFs were characterized by scanning electron microscopy, Hg porosimetry, and Raman spectroscopy. Then, the study was focused on the design, implementation and optimization of this combined process in a single continuous filtration reactor and using a real effluent. Results and discussion Batch experiments using clofibric acid as model pollutant were performed in order to better understand the influence of critical design and operational parameters. The efficiency of the process was discussed as regards to (i) desorption of organic compounds and regeneration efficiency, (ii) degradation and mineralization of organic compounds and (iii) stability of ACFs for several successive adsorption/regeneration cycles. By using BDD as anode and a current density of 21 mA cm-2, it was observed that increasing the treatment time from 3 to 6 h strongly improved the regeneration effectiveness from 45 to 75%. Further increasing the treatment time to 9 h did not show significant positive effect because of the lower availability of a portion of adsorbed compounds within the ACF porosity. Besides, dividing the current density by a factor of 2.5 (8 mA cm-2) only reduced the regeneration efficiency from 75 to 64%, indicating that low current density might be more cost-effective. Using TiOx instead of BDD anode also only reduced the regeneration efficiency from 64 to 60%. TiOx is a new promising electrode material that is much less expensive than BDD. Therefore, using TiOx anode was considered as a more cost-effective configuration. A great advantage of this process is also that >80% of organic compounds desorbed from ACF were mineralized, thus avoiding the production of a toxic effluent. Regeneration efficiency was then assessed during 10 cycles of adsorption/regeneration without significant decrease due to the protection of the ACF surface by the cathodic polarization effect. Finally, this treatment strategy was implemented in a continuous filtration reactor where both adsorption and electro-Fenton regeneration could take place sequentially. Process efficiency for treating a real effluent was assessed by comparing breakthrough curves of pristine and regenerated filters. The development of this technology is currently focused on point-of-use filters for domestic applications (about 5 liters per day) as well as on industrial wastewater treatment (pilot-scale unit able to treat 10-20 liters per hour).

Computation of effectiveness factor for methanol steam reforming over Cu/ZnO/Al2O3 catalyst pellet

A mathematical model was developed for a diffusion–reaction process in a spherical catalyst pellet contained in a heterogeneous packed bed reactor. The model developed was solved to predict the effectiveness factor and also to perform sensitivity analysis for steam reforming of methanol on Cu/ZnO/Al2O3 catalyst a source of hydrogen fuel. The method of orthogonal collocation was used to solve the resulting differential equation. At temperature below 473 K the effect on intra-particle diffusion limitation is reduced to the minimum indicated by the effectiveness factor being almost equal to one but as the temperature increases above 473 K there is considerable increase in the diffusion limitation effect. The effects of thermal conductivity, diffusion coefficient, catalyst size and surface temperature on effectiveness factor for the reaction process were also considered. Result indicates that catalyst size of 1.623,, times ,,10^{ - 4} m eliminates the effect of intra-particle diffusion resistance in the pellet. The variation of effectiveness factor with Thiele modulus, showing the asymptotic values, using power law and Langmuir–Hinshelwood–Hougen–Watson (LHHW) kinetics, was predicted. The two reaction kinetics had almost the same magnitude of effectiveness factor at different Thiele modulus which indicates that they can adequately predict the reaction process.

Experimental study of low-rank coals using simultaneous thermal analysis (TG–DTA) techniques under air conditions and radiation level characterization

Simultaneous thermal analysis (TG–DTA) of low-rank coals from different annual periods (2015 and 2018) which originate from Kolubara and Nikola Tesla A (TENT A) coal-fired power plants was studied to identify their combustion characteristics and self-ignition risks. In order to investigate kinetics of thermo-oxidative degradation, model-free models including the Friedman and Kissinger–Akahira–Sunose methods were applied. In accordance with obtained kinetic results, numerical optimization of combustion process was implemented. Homogeneous and heterogeneous types of ignition were identified for the tested coals, and factors that affect their occurrence are the used heating rate and volatile matter content. From thermal susceptibility graph, it was found that the tested coals expand in a wide range of self-ignition risk, depending on their coal rank. The youngest coal (TENT A (2018)) has the largest propensity to self-ignite among high-ranking coals. It was found that less tendency of 2018 coals to show true isokinetic temperature in comparison with 2015 coals is a consequence of intraparticle diffusion limitations, and change of char properties, at higher conversion values. Gamma spectrometry analysis of coals showed that higher concentration of 40K radionuclide (which is in mineral composition) may contribute through its deposition on available sites, decreasing surface area for reaction with oxidizing species.

Beyond the effectiveness factor: Multi-step reactions with intraparticle diffusion limitations

Though common in many industrial chemical processes, multi-step reactions occurring within porous catalyst particles provide significant challenges to previously established modeling frameworks. In this work, a system of reaction-diffusion equations is solved analytically via eigenanalysis. The intraparticle concentration profiles are integrated over the particle volume to obtain effectiveness factors for each reacting species, referred to herein as a multi-step effectiveness vector (MEV). The MEV solution is tested for the case of uniform flow past a stationary catalyst particle with a state-of-the-art, multi-step reaction scheme for fluid catalytic cracking (FCC). Outputs from particle-resolved direct numerical simulation (DNS) are compared to outputs from ordinary differentials with effective reaction closures coming from the MEV solution, the classic single-step effectiveness factor (SEF) (R. Aris, “The mathematical theory of diffusion and reaction in permeable catalysts: The theory of the steady state,” Oxford University Press, 1975), and utilizing the intrinsic rates as-is. When compared to DNS, the MEV solution shows excellent agreement for the formation of all species and quantitatively captures the intraparticle concentration profiles. By contrast, the intrinsic treatment shows an over-prediction for product formation and the SEF treatment shows mixed levels of accuracy that depend upon the reaction coupling. Specifically, the SEF treatment accurately characterizes product formation if the kinetic scheme is weakly coupled but shows significant departure if stronger coupling is present. The computational cost associated with the MEV solution is associated with eigendecomposition of the Thiele matrix, an N×N matrix where N is the number of reacting components. Overall, the method is shown to be relatively easy to implement and may significantly enhance the fidelity of chemical reactor simulations that employ multi-step reaction schemes.

Biomass Derivative Valorization Using Nano Core-Shell Magnetic Materials Based on Keggin-Heteropolyacids: Levulinic Acid Esterification Kinetic Study with N-Butanol

Magnetic materials based on Keggin heteropolyacids immobilized on mesoporous silica-coated magnetite particles with a core-shell structure were synthesized. The activity of the catalyst was studied in the esterification reaction of levulinic acid with n-butanol, and its kinetics was studied by the systematic variation of several reaction parameters, such as stirring speed, catalyst loading, molar ratio of reactants, and temperature. It was also seen that the reaction was free from any external mass transfer as well as intraparticle diffusion limitations and was intrinsically kinetically controlled. A second-order kinetic equation was found to be consistent with the experimental data. Also, an experimental activation energy of 17 kcal/mol was found. A solvent-free condition for this reaction has also added the green chemistry perception to the reaction. In addition, the resulting catalyst can be used repeatedly without significant decrease in activity.

Pore diffusion effects on catalyst effectiveness and selectivity of cobalt based Fischer-Tropsch catalyst

Abstract In this study we investigate performance characteristics (catalyst effectiveness, CH4 selectivity, and hydrocarbon product distribution) of with a highly active Co/Re/Al2O3 catalyst particle for Fischer-Tropsch synthesis. In numerical simulations we utilize kinetic parameters for CO consumption rate, CH4 formation rate and hydrocarbon formation rates (C2+ hydrocarbons) determined from experiments with this catalyst to study effects of catalyst activity, catalyst particle shape (sphere, slab, solid and hollow cylinder), size (i.e. diffusion length), catalyst distribution (uniform vs. eggshell type distribution for a spherical particle) and process conditions (temperature, pressure, syngas composition and conversion level) on the catalyst performance. With increase in Thiele modulus (i.e. particle size at a fixed set of process conditions) we observe increasing H2/CO ratio profile towards the center of the particle resulting in increase of local and average CH4 selectivity. The goal is to find conditions which allow one to use sufficiently large particles to reduce pressure drop, while avoiding negative influence of diffusional limitations on selectivity and activity. For each catalyst particle shape we determined values of Thiele modulus, i.e. characteristic length of diffusion, corresponding to the upper limit of the kinetic region, and investigated how it changes with operating conditions. We found that simultaneous increase of pressure and the use of syngas with H2/CO feed ratio of 1.4–1.7 is the best strategy for mitigating the negative impact of intraparticle diffusional limitations on CH4 selectivity. For a spherical particle of 1 mm in diameter, one can achieve CH4 selectivity of 5.6% with catalyst effectiveness factor of 1.07 at the reactor inlet by operating at 50 bar, 473 K and H2/CO = 1.4.

Multicomponent inverse modeling of supercritical fluid extraction of carotenoids, chlorophyll A, ergosterol and lipids from microalgae

The fundamentals of analyte extractable fraction, solubility, partitioning and mass transfer resistance in supercritical fluid extraction were studied using inverse modeling. These phenomena are essential for understanding, predicting and optimizing the supercritical fluid extraction process. Carotenoids, chlorophyll A, ergosterol and total lipids were extracted from the microalgae Chlorella sp. The analytes were measured continuously in-line and on-line using UV/Vis absorption spectroscopy measurements and by evaporative light scattering detection. Various pressures, temperatures, flow rates and fractions of ethanol as a co-solvent were evaluated. The extractable fraction of carotenoids, chlorophyll A and total lipids were dependent on the co-solvent fraction in the extraction phase. The additional amount that could be extracted by using more co-solvent followed a normal distribution, indicating that analytes should not simply be categorized into weakly or strongly bound. The characteristics of diminishing extraction rates over time was accounted for by analyte partitioning rather than intra-particle diffusion limitations.