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Lead oxide (PbO) formation can occur in Lead-Bismuth Eutectic (LBE)-cooled nuclear systems in case of oxygen ingress or temperature decrease of the coolant beyond the normal operation ranges. In the present work the formation of lead oxide in an actively cooled LBE flow is studied. Computational fluid dynamics (CFD) is used to predict the nucleation, growth and dissolution of PbO particles. Solid oxide particles are modeled as a pseudo-continuous phase, using the Kinetic Theory of Granular Flow (KTGF) to account for particle-flow interaction. The particle size distribution (PSD) is accounted for using Population Balance Equations/Models (PBE/PBM). The results obtained from the model are qualitatively in good agreement with experimental results obtained in the MEXICO loop at SCK·CEN. The calculated PSD reveals that the majority of the oxide particles are expected to be in the sub-micron range. Experimental results indicate that in the studied conditions PbO nucleates in the LBE bulk leading to suspended particles in the LBE flow.

Photocatalytic nanomaterials, using only light as the source of excitation, have been developed for the breakdown of volatile organic compounds (VOCs) in air for a long time. It is a tough challenge to immobilize these powder photocatalysts and prevent their entrainment with the gas stream. Conventional methods for making stable films typically require expensive deposition equipment and only allow the deposition of very thin layers with limited photocatalytic performance. The present work presents an alternative approach, using the combination of commercially available photocatalytic nanopowders and a polymer or inorganic sol–gel-based matrix. Analysis of the photocatalytic degradation of ethanol was studied for these layers on metallic substrates, proving a difference in photocatalytic activity for different types of stable layers. The sol–gel-based TiO2 layers showed an improved photocatalytic activity of the nanomaterials compared with the polymer TiO2 layers. In addition, the used preparation methods require only a limited amount of photocatalyst, little equipment, and allow easy upscaling.

Innovative gas-solid fluidized beds with process intensification capabilities are among the most promising alternatives for the current state of the art in the chemical industry. In the present work the advantages of such a reactor that sustains a rotating fluidized bed with gas-solid slip velocities much higher than those in conventional fluidized beds are illustrated computationally and experimentally. A Gas-Solid Vortex Reactor (GSVR) demonstration unit is designed to operate at typical biomass fast pyrolysis conditions targeting the production of chemicals and fuels from renewable feedstocks. For the demonstration unit preheated N 2 supplies the thermal energy required by the fast pyrolysis process but alternative sources can also be evaluated. A broad range of operation conditions in the 80 mm diameter and 15 mm height GSVR can be evaluated: N 2 mass flow rates of 5–10 g s −1 and biomass feed mass flow rates of 0.14–1.4 g s −1 . Particle-free and particulate flow experiments confirmed that the carrier gas is evenly distributed around the GSVR cylindrical chamber as anticipated by computational fluid dynamic simulations. The latter also supported the inclusion of a profiled bottom end wall and a diverging exhaust. Cold flow experiments with biomass confirmed that the GSVR sustains a rotating fluidized bed with average bed height of 10 mm and solids azimuthal velocities of 6–7 m s −1 .

Biomass fast pyrolysis has been considered one of the best alternatives for the thermal conversion of biomass into bio-oil. This work introduces a new reactor technology for biomass fast pyrolysis, the Gas-Solid Vortex Reactor (GSVR), to obtain high bio-oil yields. The GSVR was designed to decrease the residence time of the pyrolysis vapors; thus, the secondary cracking reactions are reduced, to enhance the segregation of the char and the unreacted biomass and to improve the heat transfer rate. Biomass fast pyrolysis experiments have been carried out for the first time in a Gas-Solid Vortex Reactor (GSVR) at 773 K, using softwood (pine) and hardwood (poplar) as feedstock. Char yields as low as 10 wt. % in the GSVR were comparable to those reported for the same feedstocks processed in conventional fluidized bed reactors. The yields of non-condensable gases in the range of 15–17 wt. % were significantly lower than those reported for other commonly used biomass fast pyrolysis reactors. Two-dimensional gas chromatography (GC × GC) revealed noticeable differences at the molecular level between the bio-oils from the GSVR and bio-oils from other reactors. The aromatics in the pine bio-oil consist almost entirely (85 wt. %) of guaiacols. For poplar bio-oils no predominant group of aromatics was found, but phenolics, syringols, and catechols were the most pronounced. The experimental results highlight the advantages of the GSVR for biomass pyrolysis, reaching stable operation in around 60 s, removing the formed char selectively during operation, and enabling fast entrainment of pyrolysis vapors. Results indicate a great potential for increasing yield and selectivity towards guaiacols in softwood (e.g., pine) bio-oil. Likewise, decreasing pyrolysis temperature could increase the yield of guaiacols and syringols in hardwood (e.g., poplar) bio-oil.

Účinek vysoceemisivních povlaků na radiační přenos tepla v parních krakovacích pecích není zdaleka znám. Chybí experimentální data popisující emisivní vlastnosti materiálů, které se používají v parních krakovacích pecích. Z tohoto důvodu se provádí měření spektrální normálové emisivity na zvýšených teplotách, přičemž se hodnotí emisivní vlastnosti žáruvzdorných šamotových cihel před a po depozici vysoceemisivního povlaku. Po nanesení povlaku s vysokou emisivitou na základní šamotový materiál se výrazně zvýší jeho emisivita. Provedené experimenty s parní krakovací jednotkou ukazují 5% snížení rychlosti spalování topného plynu po nanesení vysoceemisivního povlaku na žáruvzdorný materiál krakovací komory. Parametrické studie zabývající se účinkem emisivních vlastností reaktorové cívky a stěny pece na radiační přenos tepla ve spalovací komoře potvrzují, že pro přesné modelování chování povlaků s vysokou emisivitou je vyžadován jiný model než model šedého plynu. Přestože model šedého plynu postačuje k zachycení chování chladiče reaktorové cívky, je nezbytný jiný, nešedý model, který zobecňuje absorpci a opětovné vyzařování plynu ve spcifických spektrálních pásmech, aby mohl přesně zachytit výhody využití vysoceemisivního povlaku na stěně pece. The effect of high emissivity coatings on the radiative heat transfer in steam cracking furnaces is far from understood. To start, there is a lack of experimental data describing the emissive properties of the materials encountered in steam cracking furnaces. Therefore, spectral normal emissivity measurements are carried out, evaluating the emissive properties of refractory firebricks before and after applying a high emissivity coating at elevated temperatures. The emissive properties are enhanced significantly after applying a high emissivity coating. Pilot unit steam cracking experiments show a 5 % reduction in fuel gas firing rate after applying a high emissivity coating on the refractory of the cracking cells. A parametric study, showing the effect of reactor coil and furnace wall emissive properties on the radiative heat transfer inside a tube-in-box geometry, confirms that a non-gray gas model is required to accurately model the behavior of high emissivity coatings. Even though a gray gas model suffices to capture the heat sink behavior of a reactor coil, a non-gray gas model that is able to account for the absorption and re-emission in specific bands is necessary to accurately model the benefits of applying a high emissivity coating on the furnace wall.

The radiation and convection section of a steam cracker are thermally coupled. Optimization and design requires a coupled simulation of both sections. In this work a 1D model for the convection section, CONVEC-1D, is developed. Several models for the different heat transfer phenomena are implemented and evaluated. For flow boiling, an empirical and a mechanistic model are developed and compared for both single- and multicomponent hydrocarbon feeds. The latter is performing best over a wide range of operating conditions, taking into account the different two-phase flow regimes. The coupled iterative procedure is demonstrated for an n-pentane steam cracker convection section.

Lead-Bismuth Eutectic (LBE) is an interesting candidate as coolant for future Accelerator Driven Systems (ADS) and Generation IV (Gen. IV) nuclear power plants. A well-known issue of liquid metal coolants is the need for coolant chemistry control and continuous purification. This paper presents a purification strategy for control of the dissolved oxygen content in LBE by means of a LBE cold trap. Although cold traps have been explored in the past for Sodium Fast Reactors (SFR) and more recently for lead-lithium (PbLi), advances on cold trapping for LBE are lacking behind. Formation of lead oxide (PbO) is promoted in a non-isothermal purification device (cold trap) to lower the dissolved oxygen concentration present in the liquid metal. Attachment of PbO particles to the stainless steel filter material is observed and continuous growth of captured PbO consumes oxygen from the liquid metal melt. A long-term purification campaign of more than one month is presented to demonstrate the increase in cold trap effectiveness with loading.

Processes requiring intensive interfacial momentum, mass and heat exchange between gases and particulate solids can be greatly enhanced by operating in a centrifugal field. This is realized in the Gas-Solid Vortex Reactor (GSVR) with centrifugal accelerations up to two orders of magnitude higher than the Earth's gravitational acceleration. Here, the flow patterns of two 1g-Geldart B-type particles are experimentally assessed, over the gas inlet velocity range 82–126 m s−1, in an 80 mm diameter and 15 mm height GSVR. The particles are monosized aluminum spheres of 0.5 mm diameter, and walnut shell in the sieve fraction 0.50–0.56 mm and aspect ratio 1.3 ± 0.2. Two dimensional Particle Image Velocimetry combined with Digital Image Analysis and pressure measurements revealed that periodic fluctuations in solids azimuthal and radial velocity between gas inlet slots are strongly related to the average solids azimuthal velocity and bed uniformity. Aluminum particles feature steeper changes in azimuthal velocity and more attenuated changes in radial velocity than walnut shell particles. Within the assessed gas inlet velocity range the solids bed of aluminum exhibits average azimuthal velocities and bed voidages 40–50% and ≈10% lower than those of walnut shell. The aerodynamic response time of the particles, i.e. ρsdp2/18μg, emerged as an important parameter to assess the influence of the carrier gas jet on the radial deflection of the particles and the interaction solids bed-outer wall. Too low aerodynamic response time relates to nonuniformity in bed voidage due to solids radial velocity fluctuations. Excessive aerodynamic response time indicates low solids azimuthal velocities due to solids bed-outer wall friction.

Vortex units are commonly considered for various single and multiphase applications due to their process intensification capabilities. The transition from gas‐only flow to gas–solid flow remains largely unexplored nonetheless. During this transition, primary flow phenomenon, jets, and secondary flow phenomena, counterflow and backflow, are substantially reduced, before a rotating solids bed is established. This transitional flow regime is referred to as the vortex suppression regime. In the present work, this flow transition is identified and validated through experimental and computational studies in two vortex units with a scale differing by a factor of 2, using spherical aluminum and alumina particles. This experimental data supports the proposed theoretical particle monolayer solids loading that allows estimation of vortex suppression regime solids capacity for any vortex unit. It is shown that the vortex suppression regime is established at a solids loading theoretically corresponding to a monolayer being formed in the unit for 1g‐Geldart D‐ and 1g‐Geldart B‐type particles. The model closely agrees with experimental vortex suppression range for both aluminum and alumina particles. The model, as well as the experimental data, shows that the flow suppression regime depends on unit dimensions, particle diameter, and particle density but is independent of gas flow rate. This combined study, based on experimental and computational data and on a theoretical model, reveals the vortex suppression to be one of the basic operational parameters to study flow in a vortex unit and that a simple monolayer model allows to estimate the needed solids loading for any vortex device to induce this flow transition.

A unique normalized radial pressure profile characterizes the bed of a gas‐solid vortex reactor over a range of particle densities and sizes, solid capacities, and gas flow rates: 950–1240 kg/m3, 1–2 mm, 2 kg to maximum solids capacity, and 0.4–0.8 Nm3/s (corresponding to gas injection velocities of 55–110 m/s), respectively. The combined momentum conservation equations of both gas and solid phases predict this pressure profile when accounting for the corresponding measured particle velocities. The pressure profiles for a given type of particles and a given solids loading but for different gas injection velocities merge into a single curve when normalizing the pressures with the pressure value downstream of the bed. The normalized—with respect to the overall pressure drop—pressure profiles for different gas injection velocities in particle‐free flow merge in a unique profile. © 2015 The Authors AIChE Journal published by Wiley Periodicals, Inc. on behalf of American Institute of Chemical Engineers AIChE J, 61: 4114–4125, 2015

Regime maps that predict the heavy hydrocarbon droplet impingement behavior on a heated wall (Weber number of the impinging droplet v/s wall temperature) are constructed based on CFD simulations using the Volume of Fluid model with the geo-reconstruct scheme. Based on the simulation results, maps are constructed for single-component droplets with a diameter of 50 and of 100 µm. The applied CFD model is validated by comparing these with regime maps available in literature, constructed based on experimental data for model liquids and liquid mixtures. The impingement regimes of Splash, Stick, Rebound and Breakup are well-predicted. Two distinct types of Splash (Splash with ligament formation and Splash with ring detachment) are reported for the first time. Using the validated CFD model, regime maps are constructed for multi-component heavy hydrocarbon droplets with a diameter of 50 and of 100 µm. Significant differences between the single-component and the multi-component droplet impact behavior are observed. Improved and new correlations for regime transitions, droplet stretching on the wall, droplet rebounding velocity and number of splashed droplets are derived based on energy balances. They are found to correlate well with CFD predictions.

As large floor-fired furnaces have many applications in refinery and (petro-) chemical units and about 80% of heat transfer in these furnaces is by radiation, the accurate description of radiative heat transfer is of the most importance for accurate design and optimization. However, the impact of using different radiation models in coupled furnace/reactor simulations has never been evaluated before. Therefore, coupled furnace/reactor simulations of an industrial naphtha cracking furnace with a 130 kt/a capacity have been conducted. Computational fluid dynamics simulations were performed for the furnace side, while the one-dimensional reactor model COILSIM1D was used for the reactor simulations. The Adiabatic, P-1, discrete ordinates model (DOM), and discrete transfer radiation model (DTRM) were evaluated for modeling the radiative heat transfer. The results with DOM and DTRM are very similar both on the furnace and the reactor sides. The flue gas temperature using DOM is higher than when using the P-1 radiation model, resulting in higher incident radiation. Comparing the simulated results of all radiation models to the industrial product yields and run lengths shows that DOM and DTRM outperform the others. As DOM has a broader application range than DTRM, and because the current implementation of DTRM in FLUENT/14.0 cannot be run in parallel yet, DOM is the recommended radiation model for run length simulations of steam cracking furnaces.

The process intensification possibilities of a gas–solid vortex reactor have been studied for biomass fast pyrolysis using a combination of experiments (particle image velocimetry) and non-reactive and reactive three-dimensional computational fluid dynamics simulations. High centrifugal forces (greater than 30g) are obtainable, which allows for much higher slip velocities (>5 m s–1) and more intense heat and mass transfer between phases, which could result in higher selectivities of, for example, bio-oil production. Additionally, the dense yet fluid nature of the bed allows for a relatively small pressure drop across the bed (∼104 Pa). For the reactive simulations, bio-oil yields of up to 70 wt % are achieved, which is higher than reported in conventional fluidized beds across the literature. Convective heat transfer coefficients between gas and solid in the range of 600–700 W m–2 K–1 are observed, significantly higher than those obtained in competitive reactor technologies. This is partly explained by reducing undesirable gas–char contact times as a result of preferred segregation of unwanted char particles toward the exhaust. Experimentally, systematic char entrainment under simultaneous biomass–char operation suggested possible process intensification and a so-called “self-cleaning” tendency of vortex reactors.

In a Gas–Solid Vortex Reactor (GSVR), also referred to as a Rotating Fluidized Bed in Static Geometry, a fluidized bed is generated in a centrifugal field by introducing the gas via tangential inlet slots to the reactor chamber. Better heat and mass transfer are observed, making this a promising reactor type for Process Intensification. Developing GSVRs on industrial scale requires, amongst other, a good insight and understanding of the hydrodynamics of the granular flow. In the present work experiments are performed over a wide range of operating conditions in a cold flow pilot-scale set-up. The set-up has a diameter of 0.54 m, a length of 0.1 m and 36 tangential inlet slots of 2 mm. Different materials with solids density between 950–1800 kg/m3 and particle diameters of 1–2 mm, at varying gas injection velocities from 55 to 110 m/s are tested between minimum and maximum solids capacities. All these operating conditions are used to follow the change of granular flow by performing PIV. The rotating fluidized bed can change from a smoothly rotating, densely fluidized bed to a highly bubbling rotating fluidized bed depending on the operating conditions. Bubbling diminishes with increasing solids density and particle diameter. Experimental measurements of azimuthal particle velocity fields in a GSVR are for the first time reported. Azimuthal solids velocity is found to decrease with higher solids density and larger particle diameter. The critical minimum fluidization velocity, that is the minimum velocity at which the complete bed is fluidized, is calculated and the centrifugal bed behavior is mapped in terms of a dimensionless radial gas velocity and a dimensionless particle diameter, as conventionally done for gravitational beds.

Coke formation in the convection section of a steam cracker occurs when heavy feeds are cracked. This work presents CFD simulations of coke formation in the mixture superheater tubes in the convection section of a steam cracker. The hydrocarbon feed used for the simulations is a gas condensate. Eleven representative chemical species are selected, based on their boiling points, to mimic the entire range of feed components. The liquid–vapor spray flow in the mixture superheater tube is simulated based on an Eulerian–Lagrangian approach using ANSYS FLUENT 13.0. Evaporation of multicomponent droplets suspended in the vapor phase or deposited on a tube wall is considered. The mixture superheater tubes make three horizontal passes (11.3 m long and 0.077 m diameter) through the convection section. The droplet–wall interaction model considers ‘Splash’, ‘Rebound induced breakup’, ‘Rebound’ and ‘Stick’. The amount of liquid deposited on the mixture superheater tube wall is obtained by simulating the spray flow. The amount of coke formed from the liquid deposited on a wall is based on the phase separation model of (Wiehe, 1993). Industrial & Engineering Chemistry Research 32, 2447–2454. Spatial variations of the coke layer formed in the mixture superheater tubes as a function of outer tube wall temperatures and initial droplet diameter are presented. For outer tube wall temperatures lower than the boiling point of the highest-boiling species in the feed a 1 mm thick coke layer is formed over a period of 1 month. For outer tube wall temperatures higher than the boiling point of the highest boiling component in the feed no coke is formed in the mixture superheater tubes. This work provides guidelines to minimize the extent of coke formation in the steam cracker convection section when a heavy feed is cracked. It also provides possible remedies to completely eliminate the coking problem when cracking heavy feeds.

An industrial project was developed to optimize the biodiesel production from crude palm oil. This process was developed for a one ton scale application on the palm oil production facility in equatorial Africa, to be used on the plantation to provide fuel for the fleet of the company. Because of the specific conditions (crude palm oil as starting material, application in technologically difficult conditions), it was essential for the developed procedure to be robust and simple, and to use minimum amounts of chemicals. The process was optimised on lab-scale in 2005 and 2006, scaled up in the following year, and is since then successfully applied as intended on the palm oil plantation. The produced biodiesel is used pure, without mixing with diesel fuel and without additives. After several years of continuous use, no negative effects were noticed on the engines. The process efficiency and durability are therefore confirmed.

Liquid lead-bismuth eutectic (LBE) is an important candidate to become the primary coolant of future, generation IV, nuclear fast reactors and Accelerator Driven System (ADS) concepts. One of the main challenges with the use of LBE as a coolant is to avoid its oxidation which results in solid lead oxide (PbO) precipitation. The chemical equilibria governing PbO formation are well understood. However, insufficient kinetic information is currently available for the development of LBE-based nuclear technology. Here, we report the results of experiments in which the nucleation, growth and dissolution of PbO in LBE during temperature cycling are measured by monitoring dissolved oxygen using potentiometric oxygen sensors. The metastable region, above which PbO nucleation can occur, has been determined under conditions relevant for the operation of LBE cooled nuclear systems and was found to be independent of setup geometry and thus thought to be widely applicable. A kinetic model to describe formation and dissolution of PbO particles in LBE is proposed, based on Classical Nucleation Theory (CNT) combined with mass transfer limited growth and dissolution. This model can accurately predict the experimentally observed changes in oxygen concentration due to nucleation, growth and dissolution of PbO, using the effective interfacial energy of a PbO nucleus in LBE as a fitting parameter. The results are invaluable to evaluate the consequences of oxygen ingress in LBE cooled nuclear systems under normal operating and accidental conditions and form the basis for the development of cold trap technology to avoid PbO formation in the primary reactor circuit.

The feasibility of performing the SO2/NOx adsorption process in a gas-solid vortex reactor (GSVR) is examined and compared with the more traditional riser technology. The multiphase reacting flow is modeled using the Eulerian-Eulerian two-fluid model. Models of nonreacting flows were validated using data from a bench-scale experimental setup. The GSVR has the potential to significantly improved heat/mass transfer between phases, as compared to more conventional fluidization technologies. Process intensification opportunities are investigated. The model predicts continuous removal efficiencies greater than 99% for SO2 and approximately 80% for NOx. The gas-solid slip velocity and convective mass transfer coefficient for the riser were 0.2-0.5 and 0.06-0.12 m/s, respectively, whereas the values for the GSVR were 6-7 and 1.0-1.1 m/s, respectively. This order of magnitude increase in the external mass transfer coefficient highlights the potential intensification opportunities provided by the GSVR.

The hydrodynamic behavior of dispersed gas–solid flow is simulated for an industrial-scale Fluid Catalytic Cracking (FCC) riser using the multi-fluid approach, with complementary information from the Kinetic Theory of Granular Flow (KTGF) for the transport coefficients of the solid phase. A continuous Particle Diameter Distribution (PDD) is considered for the solid phase catalyst. The three-dimensional gas–solid flow is considered to be non-isothermal and turbulent. The hydrodynamics of the riser reactor is coupled to a 12-lump FCC kinetic model to predict the influence of a polydisperse distribution on gas–solid reactive flow. The kinetic model involves lumped species consisting of paraffins, naphthenes, aromatic rings, and aromatic substituent groups in medium and heavy fuel oil fractions and includes the effect of aromatic ring adsorption and catalyst deactivation due to coke formation. In this study, a Computational Fluid Dynamics (CFD) model using the Eulerian–Eulerian multi-fluid approach and a Population Balance Model (PBM) are coupled. The hydrodynamic equations are solved by means of a finite volume method, while the population balance equations are solved using the Direct Quadrature Method of Moments (DQMOM). The moments of the solids phase velocity are modeled using classical kinetic theory, while the moments of the PDD are described using quadrature weights and abscissas. To account for the catalyst PDD, three different approaches namely simple, surface-averaged and volume-averaged coupling have been attempted. The latter two approaches, assuming surface and volumetric reaction kinetics respectively, predict with a good precision the yields of the different product families obtained in an industrial FCC unit showing a slight improvement from a conventional heterogeneous reactor model with a monodispersed distribution.

The Kiliani reaction, i.e. the elongation of the carbon chain by means of cyanide addition to the carbonyl group of carbohydrate derivatives, is studied on lower C3-, C4- and C6-ketoses under continuous flow conditions. Depending on the process parameters, the corresponding cyanohydrins or alpha-hydroxycarboxylic acids are obtained. A simple on-line purification of the effluent is studied using cation exchange resins. Reactions provide high yields and selectivity within short residence times, emphasizing the assets of the continuous flow process versus the batch process.

A coupled and a decoupled solution method are applied to the steady-state simulation of one-dimensional, reactive gas flow. The accuracy of the numerical steady-state solution depends to a significant extent on the molar expansion of the gas. The convergence rate of the coupled solution method is almost independent of molar expansion. The convergence rate of the decoupled solution method is at least 50% lower for strong molar expansion than for nonexistent molar expansion. By adding a transport equation for molar mass, the convergence rate of the decoupled solution method becomes almost independent of molar expansion. The results for the decoupled solution method apply to other methods in which composition is determined on a fixed flow field. A tool is presented to quantify the perturbation of the flow field by the chemical reactions.

A hybrid Lagrangian-Eulerian methodology is developed for the numerical simulation of turbulent reactive gas-solid flow. The SO2-NOx Adsorption Process (SNAP) in a riser reactor with dilute gas-solid flow is taken as a test case. A threedimensional time-dependent simulation is performed. By using the transported composition PDF method [1], modeling of the mean chemical source term and mass transfer terms in the gas-solid flow model equations is no longer needed. A notional particle-based Monte-Carlo algorithm is used to solve the transported composition PDF equations. A Finite-Volume technique is used to calculate the hydrodynamic fields from the Reynolds Averaged Navier Stokes (RANS) equations combined with the k-e turbulence model for the gas phase and the Kinetic Theory of Granular Flow (KTGF) for the solid phase [2]. The newly developed hybrid solution technique is tested with the SNAP chemistry that has a total of 13 scalars (i.e., 5 gas phase components and 8 solid phase species) for which the composition fields of the reactive species are calculated. A good agreement between simulated and experimental gas-outlet composition of a demonstration unit is obtained.

s Hydrodynamics of a gas–solid rotating bed reactor (RBR) in static geometry are investigated. Tangential injection of a gas at mass flow rate of 0.4–1 kg/s in a cylindrical vessel with a diameter of 0.54 m generates a rotating gas phase flow field. Introduction of solid particles in this field results into an annular dense gas–solid rotating bed. A stable annular gas–solid rotating bed without solids particles loss is achieved over a wide range of operating conditions. Goal of the presented work is to investigate, by means of experiments, the window for a stable operation of the gas–solid RBR, as a function of the solid particle diameter and density, the geometry of the RBR and the gas flow rate. If the solid particle diameter is comparable to tangential gas injection slot width, the establishment of a stable flow is delayed due to an increased slugging tendency. The upper limit of the solids content is found to decrease with decreasing solid particle diameter. Obtained experimental cold flow results are the initial steps in assessing the potentials of a RBR as an efficient gas–solid processing reactor from a process intensification point of view.

The presence of liquid hydrocarbon droplets in the convection section of a steam cracker may cause serious fouling problems due to coke formation, especially in high temperature zones. In order to investigate these fouling problems, a model has been developed and implemented in a CFD code to accurately simulate the behavior of a hydrocarbon droplet impinging on a hot surface. The impact energy of the droplet and the hot surface temperature are found to determine the impact behavior. On the basis of the newly developed model, the positions where droplets preferentially collide with the convection section tube walls and liquid material is deposited are determined. Furthermore, a kinetic model describing coke formation out of liquid hydrocarbon droplets in the temperature range of 450−700 K has been developed to calculate the rate of coke formation in each zone of the convection section tube. The calculated coke layer thickness on the most vulnerable tube locations and the industrially available values corre...

A method is proposed to simulate reactive flow, fully taking into account the effect of the reactions on the flow. Operator splitting is used to separate the computation of convection and reaction. A fast solver for mildly stiff ordinary differential equations and parallelization of the reaction term evaluation have been implemented to reduce the CPU time. The proposed method is applied to the steady-state, two-phase gas–solid simulation of a Fluid Catalytic Cracking riser reactor. A relatively simple kinetic model with four lumped components is used to demonstrate the feasibility of the method. The results show that the method is able to handle reactive flow with significant feedback of the reactions on the flow.

Computational fluid dynamics (CFD) simulations of the hydrodynamic behavior of rotating fluidized beds in static geometry (RFB-SG) are carried out for gas–solid flows. The rotating motion of the reactor bed is induced by the tangential injection of the gas along the circumference of the fluidization chamber. Steep gradients in the gas velocity fields both in radial and tangential direction generate turbulence. The radial and tangential drag forces fluidize the particle bed in both radial and tangential direction. An Eulerian two-fluid model is used. Gas phase turbulence is accounted for by a k–e model adapted for rotational flows. The RFB-SG simulations provide guidelines for a design and operation with a high efficiency in gas–solid momentum transfer, excellent gas–solid separation and limited solids losses. Hydrodynamic variables like the centrifugal force, the injection pressure, the radial and tangential slip velocities, solids hold-up are calculated for both polymer particles (300 μm, 950 kg/m3, Geldart Group B) and glass beads (70 μm, 2500 kg/m3, Geldart Group A) to allow for a comparison among different fluidization chamber designs. Unstable bed behavior, like slugging and channeling, is also numerically predicted.

A coupled simulation of the flue gas and process gas side of the convection section of a steam cracker is performed, making use of the CFD software package Fluent. A detailed overview of the operating mode of the different heat exchangers suspended in the convection section is obtained. The asymmetric inlet flow field of the flue gas in the convection section, and the radiation from the convection section walls leads to large differences in outlet temperatures of the tubes located in the same row. The flow fields and temperature fields in the tubes of a single heat exchanger differ significantly with e.g., outlet temperatures of the hydrocarbon-steam mixture ranging from 820 K to 852 K. Moreover, the simulations reveal the presence of hot spots on the lowest tube row, possibly causing fouling. © 2009 American Institute of Chemical Engineers AIChE J, 2009

A hybrid Lagrangian-Eulerian methodology is developed for the numerical simulation of turbulent reactive gas-solid flow. The SO2-NOx Adsorption Process (SNAP) in a riser reactor with dilute gas-solid flow is taken as a test case. A three-dimensional time-dependent simulation is performed. By using the transported composition PDF method [1], modeling of the mean chemical source term and mass transfer terms in the gas-solid flow model equations is no longer needed. A notional particle-based Monte-Carlo algorithm is used to solve the transported composition PDF equations. A Finite-Volume technique is used to calculate the hydrodynamic fields from the Reynolds Averaged Navier Stokes (RANS) equations combined with the k-epsilon turbulence model for the gas phase and the Kinetic Theory of Granular Flow (KTGF) for the solid phase [2]. The newly developed hybrid solution technique is tested with the SNAP chemistry that has a total of 13 scalars (i.e., 5 gas phase components and 8 solid phase species) for which the composition fields of the reactive species are calculated. A good agreement between simulated and experimental gas-outlet composition of a demonstration unit is obtained.

A model has been developed allowing to simulate the flow boiling process of a hydrocarbon feedstock. For the calculation of the different horizontal two-phase flow regimes that evolve during flow boiling, use is made of the Volume Of Fluid (VOF) model that uses a Piecewise Linear Interface Calculation (PLIC) method to reconstruct the interface between both phases in each computational cell. In-house developed codes calculate the mass and energy transfer phenomena occurring during this flow boiling process. As such, an existing CFD code is completed with a newly developed complete evaporation model. The developed model is used to simulate the flow boiling process of a hydrocarbon feedstock in the tubes of a convection section heat exchanger of a steam cracker. The simulation results show a succession of horizontal two-phase flow regimes in agreement with the literature.

The efficiency of the application of high-emissivity coatings on the furnace walls in steam cracking technology can only be evaluated on the basis of a description of radiative heat transfer distinguishing between the frequency bands. To this end, a non-grey gas radiation model based on the exponential wide band model (EWBM) has been developed and applied in the context of three-dimensional CFD simulations of an industrial naphtha cracking furnace with side-wall radiation burners. Applying a high-emissivity coating on the furnace wall decreases the net outgoing radiation from the furnace wall in the absorption bands and increases the net outgoing radiation from the furnace wall in the clear windows. Since radiation that is emitted by the furnace wall and travels through the flue gas in the clear windows can reach the reactor tubes without partially being absorbed by the flue gas, contrary to radiation that is emitted by the furnace wall and travels through the flue gas in the absorption bands, the thermal efficiency of the furnace increases. It was found that application of a high-emissivity coating on the furnace walls improves the thermal efficiency of the furnace (∼1%), the naphtha conversion (∼1%) and the ethylene yield (∼0.5%). These differences are small but, considering the industrial importance and scale of the steam cracking process, significant.

The endothermic thermal cracking process of hydrocarbons takes place in tubular reactor coils suspended in large gas-fired pyrolysis furnaces. Heat transfer to the reactor tubes is mostly due to radiation from the furnace refractory walls and the flue gas. A three-dimensional (3-D) simulation of the flow in an industrial scale steam cracking furnace is performed. The renormalization group (RNG) k − ɛ turbulence model is used. The combustion kinetics is modeled by a three-step reaction mechanism, while turbulence–chemistry interaction is taken into account through the Finite Rate/Eddy-Dissipation model. The Discrete Ordinates model (DOM), the P-1 and the Rosseland Radiation model are used for modeling of the radiative heat transfer. The results of using the different radiation models are compared mutually with adiabatic simulation results. The absorption coefficient of the gas mixture is calculated by means of a Weighted-Sum-of-Gray-Gas model (WSGGM). The effect is discussed of the use of different radiation models on the predicted wall, tube skin and flue gas temperature profiles and heat fluxes towards the reactor tubes, as well as on the predicted species concentration profiles and structure of the furnace flames under normal firing conditions.

To account for meso-scale phenomena in coarse grid simulations, correlation terms appearing in the filtered gas-solid flow equations have to be modeled. Possible approaches to describe filtered gas-solid momentum transfer are evaluated via a mixture speed of sound test. In contrast to the effective drag coefficient closure model for the filtered drag force, the generalized added mass closure model for the correlation between the solid volume fraction and the gas phase pressure gradient shows an acceptable behavior. Furthermore, the generalized added mass may become determining in describing filtered gas-solid momentum transfer when sufficiently coarse grids are used. 3D steady-state riser simulations demonstrate the impact of the generalized added mass based description of filtered gas-solid momentum transfer on the calculated gas-solid flow behavior, in particular on the gas-solid slip velocity profile. (c) 2007 Elsevier Ltd. All rights reserved.

A 3D RANS simulation of lean premixed turbulent combustion in an industrial scale steam cracking furnace is performed. Turbulence is represented by a renormalization group (RNG) k − e model, while combustion is modeled with a skeletal mechanism. The eddy dissipation concept (EDC) model is used to account for turbulence/combustion interaction. The turbulent combustion regime is identified as a “thin flame regime with pockets” or a “corrugated flamelet regime”. A weighted sum of gray gases model (WSGGM) is used to account for the gas radiative properties. The radiative transfer equation is solved using the P-1 and discrete ordinates method in the conservative finite volume formulation. NOx calculations are performed as a postprocessing step, with the flow field, temperature, and species concentrations fixed. The formation of NO through thermal, prompt, and N2O intermediate mechanisms is considered. The in situ adaptive tabulation technique is used to decrease the computational time required to treat the combustion chemistry. The effect of radiation models on the predicted furnace wall, tube skin, and flue gas temperature profiles and heat fluxes toward the reactor tubes, as well as on the predicted species and NO concentration profiles and structure of the furnace flames under normal firing conditions, is discussed. © 2007 American Institute of Chemical Engineers AIChE J, 2007

Inlet phenomena in a 0.1 m diameter cold-flow riser with a 35 ∘ inclined side inlet are studied experimentally using 3D-Laser Doppler Anemometry for solids fluxes of 0.5– 4.5 kg / m 2 / s and gas velocities of 5.3–7.4 m/s. In the vicinity of the solids inlet, radial gas-solids mixing is hindered and bypassing of the solids jet occurs, resulting in steep velocity gradients and off-centre maxima in the velocity field. The feeding conditions and the type of the solids affect the bottom operation and gas–solids mixing to a large extent: compared to FCC particles, silica particles extend the acceleration zone in the riser. Low gas flow rates and/or high solids feeding rates result in an increased penetration depth of the solids jet and in explicit bypass zones in the plane facing the inlet. High root mean square fluctuating particle velocities are observed at the solids jet boundaries. A non-aerated Y-inlet configuration causes vortex formation, inducing a small reflux into the upper dilute part of the standpipe. The influence of dilution of the inlet solids jet is also investigated using an “aerated” inlet configuration. Aerated inlets lead to better entrainment, improved radial mixing, less pronounced broader bypass zones and a firm reduction of the penetration depth. In the 0.1 m diameter riser, radial mixing quickly dissipates the non-uniformities introduced by the solids inlet. Reflection phenomena can, however, occur in the case of a non-aerated solids inlet.

A constant composition gray gas and a constant composition nongray gas radiation model are developed and applied in computational fluid dynamic simulations of an industrial scale steam cracking furnace. Both models are based on the exponential wide band model. The gray gas model simplification, commonly used for simulations of industrial applications, is found to have an effect on predicted variable fields like flue gas flow, temperature, and heat flux to the reactor tubes. When the nongray gas model is used, higher energy absorption by the flue gas in the furnace and lower energy transfer to the process gas in the reactor tubes is calculated because of the high absorption coefficients in the strongly absorbing bands of 2.7 and 4.3 mm. Thus, the calculated thermal efficiency increases from 37.5% when using the nongray gas model to 42.6% when using the gray gas model. A 5% difference in the thermal efficiency is large considering the scale and the importance of the process and should be taken into account by the furnace designer. It is also shown that although both models reproduce the basic characteristics of the flow pattern in the furnace, quantitative differences in the flue gas speed are predicted in some regions of the furnace domain. 2007 American Institute of Chemical Engineers AIChE J, 53: 1658–1669, 2007

Using a heterogeneous plug flow model for the reactor tubes and a general gas−solid reaction/diffusion model with intrinsic reaction kinetics for coke combustion and coke gasification, an in-depth study on the influence of seven operating parameters of the decoking procedure of an ethane cracking furnace is performed. On the basis of the results of this study, the air and steam flow to the reactor tubes during the decoking procedure are adapted to propose an optimized decoking procedure that allows reducing the required decoking time of an industrial ethane cracking furnace by a factor of 3. In the new decoking conditions for the ethane cracker, the air flow rate is raised by a factor of 3, while the steam dilution is lowered by a factor of 4.5.

A combined furnace and reactor calculation is performed for the simulation of the decoking of an ethane cracker with a steam/air mixture. Different gas–solid reaction/diffusion models with a corresponding texture model describing the solid phase changes during the decoking operation are combined with kinetics for the decoking by combustion and gasification, determined based on experimental data [Heynderickx, G.J., Schools, E.M., Marin, G.B., 2005. Coke combustion and gasification kinetics in ethane steam crackers. A.I.Ch.E. Journal 51 (5), 1414–1428]. By comparing the calculated coil outlet temperatures and the calculated partial pressures of carbon dioxide at the coil outlet with the measured values in an industrial unit, the need for a general gas–solid reaction/diffusion model and the corresponding decoking kinetics is confirmed. The decoking time for an industrial unit is simulated adequately.

A three-dimensional mathematical model has been developed for the simulation of flow, temperature and concentration fields in the radiation section of industrial scale steam cracking units. The model takes into account turbulence–chemistry interactions through the Eddy Dissipation Concept (EDC) model and makes use of Detailed Reaction Kinetics (DRK), which allows the detailed investigation of the flame structure. Furthermore, simulation results obtained with the EDC-DRK model are compared with simulation results obtained with a simplified model combining the Eddy Break Up (EBU)/finite rate formulation with Simplified Reaction Kinetics (SRK). When the EBU-SRK model is used, much faster fuel oxidation and products formation is predicted. The location of the peak temperature is shifted towards the burner, resulting in a smaller flame and the confinement of the combustion process into a smaller area. This is most likely because of the inherent deficiency of the simplified model to correctly predict the overall (effective) burning rate when the turbulent mixing rate and the reaction rate are comparable. It is shown that when neither the “fast-chemistry” nor the “slow-chemistry” approximation is satisfied, the overall burning rate is overpredicted. The smaller flame volumes obtained with the EBU-SRK model have important effects on the predicted temperature distribution in the furnace as well as on other significant design parameters like the refractory wall and tube skin temperatures. It is suggested that more sophisticated turbulence–chemistry interaction models like the EDC model and more Detailed Reaction Kinetics should be used for combustion modeling in steam cracking furnaces under normal firing conditions.

A systematic reduction of the detailed combustion chemistry based on the application of quasi steady state (QSS) approximation for some species leads to several reduced mechanisms (7- to 12-step) for a hydrocarbon-hydrogen fuel with a composition representative for industrial steam cracking furnaces. The basis for the construction of all reduced mechanisms is a skeletal mechanism obtained from the detailed GRI-Mech 3.0 and consisting of 223 elementary reaction steps. The performance of reduced chemistry was assessed under different flame regimes and over a wide range of operating conditions. An eight-step mechanism provides satisfactory temperature and major and minor species concentration predictions including NO. Therefore, it is put forward for combustion simulations in steam cracking furnaces.

The pre-exponential factor and the activation energy of the intrinsic rate coefficients for propagation, chain transfer to monomer, chain initiation by a Cl radical and termination in the suspension polymerization of vinyl chloride are estimated by regression of experimental data for the monomer conversion, ranging from 3 to 85%, and for the moments of the molecular mass distribution as a function of batch time over the temperature range of 308–338 K and for initiator ( tert -butyl peroxyneodecanoate) concentrations from 0.026 to 3.0 wt%, based on the monomer. Termination by combination is the dominant termination mechanism. Cl radicals, formed in the chain transfer to monomer, contribute to the termination by recombination with macroradicals and, hence, attenuate the gel effect. Physically meaningful and statistically significant estimates for the pre-exponential factors and activation energies, 24.9 kJ mol −1 for propagation and 54.3 kJ mol −1 for chain transfer, allow to describe the experimental data over the full range of investigated conditions.

A simulation model for the development of the optimal decoking procedure of a steam cracker is constructed. It is based on experimental data for the process gas side coke combustion with oxygen and the process gas side coke gasification with steam, using coke samples taken from an industrial steam cracker. The texture changes of the coke during the combustion and gasification are accounted for. Different kinetic models are combined with a coke porosity model and different gas–solid reaction/diffusion models. The model parameters are estimated from the experimental data and model discrimination is performed. For the coke combustion the kinetic model is based on the dissociative chemisorption of oxygen on the active coke sites, whereas a general gas–solid reaction/diffusion model is required. The growth of the pores and the overlap of the pores during the coke combustion are found to compensate each other. For the coke gasification, the kinetic mechanism is based on the dissociative chemisorption of steam, whereas a uniform gas–solid reaction/diffusion model is used. © 2005 American Institute of Chemical Engineers AIChE J, 2005

The efficiency of the application of high-emissivity coatings on reactor tubes and furnace walls in steam-cracking technology can be evaluated only on the basis of a description of radiative heat transfer in frequency bands. For the flue gases in the furnace, a radiation model is introduced in which the gas emits and absorbs radiation in discrete bands only; for the surfaces a nongray surface approach is applied. First, the influence of the model changes on the calculated radiative energy exchange is evaluated theoretically. Next, different furnace simulations are performed to do a numerical evaluation of the introduction of banded radiation models. The changes in the furnace thermal efficiency, attributed to the application of high-emissivity coatings on furnace walls and tube skins in steam-cracking furnaces, are calculated. © 2005 American Institute of Chemical Engineers AIChE J, 2005

The efficiency of the application of high-emissivity coatings on reactor tubes and furnace walls in steam cracking technology can only be evaluated based on a correct description of the radiative heat transfer in the furnace. For the flue gases, a banded gas radiation model is introduced; for the surfaces a non-grey surface approach is applied. For the same total heat input, a thermal efficiency rise of over 5% is calculated for a naphtha cracking furnace under normal operating conditions.

The vinyl chloride suspension polymerization is kinetically modeled with a general approach for the independent calculation of diffusion effects on polymerization reactions. For the initiator decomposition, propagation and termination an apparent rate coefficient is determined, built up from two contributions: the intrinsic rate coefficient and a diffusional contribution. The diffusional contribution is calculated with the Smoluchowski model, the diffusion coefficients being determined from the free volume theory. When applying the free volume theory no adjustable parameters are used. The intrinsic rate coefficients are taken from the literature. Hence, a model without any adjustable parameters is obtained. Calculations show that the glass effect appears only at (very) high conversions. Due to the cage effect the initiator efficiency decreases strongly as soon as the monomer phase has disappeared. The gel effect always occurs in the polymer-rich phase and results in a decrease of the termination rate coefficient at the start of the third stage in the polymerization process. There is a good agreement with experimental results.

Radial temperature profiles during steam cracking result in radial nonuniformities in the product yields due to radial variations in the concentration of the radicals. The effect of using a 1-D or a 2-D reactor model on the calculated product yields is evaluated for the cracking of ethane. With a 2-D reactor model the simulated ethylene yield decreases. Ethylene formed at the high-temperature zone near the hot wall diffuses to the center where secondary reactions are favored, generating C3 and C4 olefins. This effect is confirmed by the calculation of a reactor of a Kellogg Millisecond Furnace. In this small-diameter reactor the 1-D behavior is more pronounced, resulting in higher ethylene yields at comparable conversions. The effect of the radial gradients on the coking rate calculated with a fundamental kinetic coking model based on elementary reaction steps is even more pronounced. Only when the coke model is coupled to a 2-D reactor model, a good agreement with the reference data is observed. In order to obtain accurate simulation results the more detailed 2-D reactor model is required, even if this increases the computational effort. © 2004 American Institute of Chemical Engineers AIChE J, 50: 173–183, 2004

Simultaneous adsorption of SO 2 –NO x in a riser configuration is a novel route for flue gas cleaning. The riser operates at a low flux (2 kg m −2 s −1 ) of small diameter (d p =60 μm ) Na- γ -Al 2 O 3 sorbent particles. The reaction scheme is adopted from previous work (Ind. Eng. Chem. Res. 40 (2001) 119), without adjusting any of the kinetic parameters. The significant concentration gradient between the gas and solid phase mainly arises from the low solid fraction (typically 5×10 −4 ) in the riser. Enhancing the fluctuating kinetic motion of gas and solid phase increases the SO 2 adsorption, whereas the NO adsorption is decreased marginally. The solid recirculation in the top section of the riser, induced by the abrupt T outlets, significantly decreases the NO and NO 2 removal, while the SO 2 removal remains mostly unaffected. Therefore, it is desirable to avoid recirculation for a maximum NO x removal. A comparison of the 3D and a 1D model shows that higher SO 2 and NO removal efficiencies are predicted by the 3D model in the major part of the riser. However, these positive effects are largely neutralized by the negative effects of the outlet-induced recirculation, resulting in similar overall removal efficiencies calculated by the two models. Unlike the 1D model, the 3D simulation shows a considerable axial variation in the solid fraction and slip velocity. The 3D simulation also allows to calculate the effects of outlet geometry on the flow and reaction fields. The reactor efficiency can be improved by modifying the outlet configuration to minimize the recirculation.

The deposition of stoichiometric TiO 2 films for V 2 O 5 /TiO 2 anatase catalysts was investigated. DC magnetron sputtering from ceramic oxide targets in an argon/oxygen atmosphere was chosen as deposition technique. The target behaviour upon sputtering was followed by means of the target voltage. The layers were prepared with different oxygen concentrations in the plasma and the influence upon electronic and optical properties of the deposited layers was investigated. Surface XPS measurements showed that stoichiometry is obtained for low oxygen mole fractions, while for higher oxygen contributions, Ti 3+ species are increasingly present. This departure from stoichiometry is ascribed to active resputtering of the deposited layer by O − ions. Due to the higher sputter yield of oxygen as compared to titanium, this resputtering resulted in the observed reduction. From optical transmission measurements, the refractive index was found to decrease with increasing oxygen mole fraction, while the band gap increased considerably. The variation of the optical absorption with the oxygen concentration in the plasma was found to confirm the XPS analysis regarding the stoichiometry of the layers. Polycrystalline anatase layers were obtained at elevated substrate temperatures.

Simultaneous adsorption of SO2–NOx is a new, promising process in treating industrial flue gases in a short-contact-time dilute phase riser with Na/γ-Al2O3 sorbent particles of 50–100 μm diameter at 370–430 K. A major part of the sorbent is recycled for maximum utilization of the sorbent capacity before regeneration. A steady-state model for the riser adsorber is developed by combining independently determined rate equations with a 1-D, two-phase hydrodynamic model of the riser. The simulation was validated with the operating data from a pilot-scale installation of 4.2 Nm3/s flue-gas capacity and solid fluxes between 1 and 3 kg·m−2·s−1. The riser operates in an extremely dilute phase with a solid volume fraction below 7.0 × 10−4 and a slip velocity that is constant for almost the entire riser length, indicating fully developed flow. The experimental observation that an increase in the SO2–NO ratio in the feed gas leads to a higher NO removal efficiency is explained as resulting from an increased concentration of the adsorbed SO2. The SO2 removal efficiency, however, may drop if free adsorption sites are not sufficiently available. Recycling of the sorbent has only a marginal effect on the NO removal, but helps to maximize the SO2 adsorption. For the first time, the simultaneous removal of SO2 above 95% and of NOx above 80% is reported using a dry, regenerable sorbent in a riser reactor.

Three-dimensional flue gas flow fields and temperature profiles are calculated in a 4/2/1 split coil naphtha-cracking furnace with long flame burners and an asymmetric flue gas outlet. The heat streams in the furnace connected to the asymmetric flue gas flow fields are found to be compensated for by a net radiative heat transfer in the opposite direction. As a result, the temperature distribution in the furnace remains nearly symmetrical. A furnace simulation under conditions of nonuniform heating confirms the compensating nature of radiative heat streams in the furnace. Furthermore, nonuniform heating was found to improve the thermal efficiency of the furnace and the cracking results. Optimization of heating conditions remains a point of interest.

A 3-D computational fluid-dynamics model containing equations for mass, heat and momentum transfer and using a k- ∈ closure model, was used to calculate the 3-D flue-gas flow pattern and the corresponding 3-D temperature field for a pyrolysis furnace. The computational fluid dynamics model is combined with a reactor model for the cracking tubes and a radiation model for the radiative heat transfer in the furnace box. Detailed reaction kinetics for the naphtha cracking reactions in the tubes and a five-step reaction mechanism for the combustion of methane in the flames were used. This complete model reveals asymmetric flow patterns in a naphtha-cracking furnace with 4/2/1 split-coil reactors and fired with long-flame burners.