Chaotic Behavior of Industrial Fluidized‐Bed Reactors for Polyethylene Production

Recent theories of bifurcation and chaos are used to analyze the dynamic behavior of the UNIPOL process for the production of polyethylene in the gas phase using the Ziegler‐Natta catalyst. Dynamic behavior covers wide regions of the design and operating parameters domain of this industrially important unit. A conventional proportional‐integral (PI) controller was implemented to stabilize the desired operating point on the unstable steady‐state branch. The presence of the PI controller stabilized the desired unstable steady‐state regions to a certain range of catalyst injection rate, by contrast, it is found out that the controlled process can go through a period doubling sequence leading to chaotic strange attractors. The practical implications of this analysis can be very serious, since chaos is shown to exist right near the desired operating point where high polyethylene production rates can be achieved     

A Novel Fluidized‐Bed Membrane Dual‐Type Reactor Concept for Methanol Synthesis

A novel fluidized‐bed membrane dual‐type methanol reactor (FBMDMR) concept is proposed in this paper. In this proposed reactor, the cold feed synthesis gas is fed to the tubes of the gas‐cooled reactor and flows in counter‐current mode with a reacting gas mixture in the shell side of the reactor, which is a novel membrane‐assisted fluidized bed. In this way, the synthesis gas is heated by heat of reaction which is produced in the reaction side. Hydrogen can penetrate from the feed synthesis gas side into the reaction side as a result of a hydrogen partial pressure difference between both sides. The outlet synthesis gas from this reactor is fed to tubes of the water‐cooled packed bed reactor and the chemical reaction is initiated by the catalyst. The partially converted gas leaving this reactor is directed into the shell of the gas‐cooled reactor and the reactions are completed in this fluidized‐bed side. This reactor configuration solves some drawbacks observed from the new conventional dual‐type methanol reactor, such as pressure drop, internal mass transfer limitations, radial gradient of concentration, and temperature in the gas‐cooled reactor. The two‐phase theory of fluidization is used to model and simulate the proposed reactor. An industrial dual‐type methanol reactor (IDMR) and a fluidized‐bed dual‐type methanol reactor (FBDMR) are used as a basis for comparison. This comparison shows enhancement in the yield of methanol production in the fluidized‐bed membrane dual‐type methanol reactor (FBMDMR).     

Manufacture of Granular Polysilicon from Trichlorosilane in a Fluidized‐Bed Reactor

Manufacturing of polysilicon by chemical vapor deposition from SiHCl₃ in a fluidized‐bed reactor was studied. The effects of reaction temperature, H₂/SiHCl₃ ratio, gas velocity, and seed particle loading were evaluated. The outlet gas composition was analyzed by gas chromatography. The physical features of the product particles were determined by scanning electron microscopy and laser particle size analyzer. Well‐grown product particles were obtained. The temperature and H₂/SiHCl₃ ratio significantly affected conversion, yield, and selectivity, which were less affected by gas velocity and seed particle loading at higher temperatures. The surface reaction kinetics determined the product yield only at lower temperatures, and thermodynamic equilibrium was approached at temperatures above 900 °C.     

Catalytic Oxidation of Methanol to Formaldehyde in a Continuous Fluidized‐Bed Reactor

Partial oxidation of methanol to formaldehyde by using a mixture of ferric and molybdenum oxides as the reaction catalyst at 280–330 °C has been studied in a continuous fluidized bed reactor. The reactor was a cylindrical tube of 20 mm in i.d. and 36 mm in o.d. placed vertically and connected to a truncated coneshaped cyclone separator. The catalyst was prepared by the precipitation method using aqueous solutions of ammonium heptamolybdate and ferric nitrate. The effect of certain parameters, such as temperature, superficial gas velocity and feed flow rates, on the extent of oxidation reaction has been investigated. The maximum size of the catalyst particles was 990 μm, therefore, neither external nor internal diffusion was expected to be effective in the process. The experimental data were correlated with three classes of hydrodynamic models presented for fluidized systems. The best correlation was obtained with compartment type models.     

Experimental Study on Flow Behavior in a Gas‐Solid Fluidized Bed for the Methanol‐to‐Olefins Process

A cold model experimental system is established to investigate the flow behavior in a gas‐solid fluidized bed for the methanol‐to‐olefins process catalyzed by SAPO‐34. The system comprises a gas distributor in a F 300 × 5000 mm acrylic column, double fiber optic probe system and a series of cyclones. The experiments are carried out under conditions of atmospheric pressure and room temperature with different superficial velocities (0.3930–0.7860 m s^–1) and different initial bed heights (600–1200 mm). The effects of radial distance, axial distance, superficial gas velocity, and initial bed height on the solid concentration and particle velocity in the bed are discussed. The time‐averaged solid concentration and rising particle velocity profiles under different conditions are obtained. The results show that an increase in the value of r/R or initial bed height results in an increase in the solid concentration but a decrease in the rising particle velocity in the dense phase area, while improvement of the superficial gas velocity has a negative influence on the solid concentration but results in an increase in the rising particle velocity.     

Synthesis of High‐Quality,Double‐Walled Carbon Nanotubes in a Fluidized Bed Reactor

Double‐walled carbon nanotubes (DWCNTs) were synthesized in a packed bed reactor (PBR) and a fluidized bed reactor (FBR) by cracking CH₄ on a Fe/MgO catalyst. It is observed that the dominant carbon product changes drastically from DWCNTs to multi‐walled CNTs along the axial direction of PBR. The studies indicated that the high concentration of H₂ from the high conversion of CH₄ causes the quick reduction and sintering of the iron catalyst and inhibits the nucleation of DWCNTs. Based on these results, the batch or continuous feeding mode of small amounts of catalyst was adopted in a FBR to maintain a high space velocity of CH₄ and to inhibit the negative effect of excess H₂. Finally, a DWCNT product with a specific surface area of 950 m²/g and a purity of 98 %, was obtained.     

Production of Electricity during Wastewater Treatment Using Fluidized‐Bed Microbial Fuel Cells

A membrane‐free fluidized‐bed microbial fuel cell (FB‐MFC) was applied to investigate the effects of fluidization parameters on its electrogenesis capacity. Active carbon particles were found to significantly decrease the start‐up time and increase the output voltage of the FB‐MFC. The fluidization behavior of the active carbon particles in the FB‐MFC reactor is one of the key parameters that influence the generation of electricity. With the FB‐MFC operating under optimal conditions, maximum power density with minimal internal resistance of the MFC could be obtained. The FB‐MFC could be operated in large‐scale wastewater treatment processes with high chemical oxygen demand removal efficiencies.     

Volumetric Heat Transfer Coefficient in Fluidized‐Bed Dryers

In literature, there are several Nu=f(Re) equations to specify the heat transfer coefficient between solids and the drying gas, but these equations differ significantly because of the inaccuracy of determining the contact surface between the two phases. A pilot‐plant fluidized‐bed dryer is developed to study the heat and mass transfer phenomena during the drying process. A volumetric heat transfer coefficient is applied for modeling fluidized‐bed dryers. A modified Nusselt number is defined to compare the experimental results and those of the literature. The modified Nu'=f(Re) equation exhibits a proper correlation between the results of the experiments in the literature and those of our experiments.     

One‐Dimensional Pseudo‐Homogeneous Packed‐Bed Reactor Modeling: I. Chemical Species Equation and Effective Diffusivity

Packed‐bed reactor experimentation is a key tool used in order to formulate chemical kinetics. The chemical species equation and overall methodology are described for a one‐dimensional pseudo‐homogeneous packed‐bed reactor model useful for experimental calibration of chemical kinetics. Over the history of simulation development for this equation there exist numerous different effective diffusivity correlations. The included historical review and parametric study of these correlations help to determine the correct choice based on numerical simplicity and model outcomes. A subsequent review paper describes the energy equation and effective thermal conductivity correlations while coming to a generalized conclusion regarding modeling efforts.     

Critical Bed Height for Solid Circulation in a Compartmented Gas‐Fluidized Bed

The influence of design and operating parameters on minimum upstream bed height required for steady solid circulation across a compartmented gas‐fluidized bed has been studied. The partition plate in the compartmented bed is fitted with two pairs of V‐valve and riser with orifices in them. Silica sand of three different sizes, viz., 490 μm, 325 μm and 250 μm, has been used and the range of the aeration rate tested covers 1–3U_mf through the bed, 5–60U_mf through the V‐valve and 0–60U_mf through the riser. A model incorporating pressure balance across the circulation loop has been developed to analyze the experimental findings. Studies show the existence of a unique critical bed height for a given set of fluidization velocities through the bed, V‐valve, riser and the size of the solids.     

Bubbling and Bed Expansion Behavior Under Vibration in a Gas‐Solid Fluidized Bed

The effect of vibration on the flow patterns and fluidization characteristics including the minimum fluidization velocity (u_mf), the void fraction (ϵ_mf) at u_mf and the bed expansion ratio were examined. The powders used were spherical glass beads and their diameters were 6, 20, 30, 60 and 100μm. For group A powders, the manner in which the vibration affects the bubble formation was examined from the bed expansion ratio and the index of n/4.65. The area of the homogeneous fluidization region was also observed. The homogeneous fluidization region was broadened at a certain vibration strength, where the value of n/4.65 was a minimum. The bubble formation was observed even for 20μm powder (group C), at large vibration strengths and at high gas velocities. Under such conditions, the bed expansion ratio increased suddenly due to bubble formation. The bubbles broke the irregular bed structure, including various properties of agglomerates. Although the channel breakage was dominant flow pattern for group C powders, the bubbles also played an important role in the improvement of the fluidization.     

Optimization of Reaction Conditions in a Fluidized‐Bed for Silane Pyrolysis

The fluidized‐bed chemical vapor deposition (CVD) process for polycrystalline silicon production is considered to be the most attractive alternative to the conventional bell‐jar process. In order to obtain stable operation, high space‐time‐yields and high purity of the product several obstacles have to be eliminated. Reaction conditions must be optimized to avoid the homogeneous decomposition of silane and minimize silicon dust formation. The effect of temperature, silane partial pressure, gas velocity and the size of bed particles has to be identified. These dependencies and the interaction between hydrodynamics and kinetics of homogeneous and heterogeneous CVD‐reactions were studied in a laboratory‐scale fluidized‐bed reactor.     

Reduction of the Volatile Matter Evolution Rate from a Plastic Pellet during Bubbling Fluidized Bed Pyrolysis by Using Porous Bed Material

Rapid volatile matter evolution from high‐volatile fuels such as wastes and biomass is one of problems associated with fluidized bed incinerators and gasifiers. When volatile matter evolves rapidly in the vicinity of the fuel feed point, the mixing of volatile matter with reactant gas is poor, and therefore, unreacted volatile matter is expected to be released from the reactor. In the present work, reduction of the volatile matter evolution rate was attempted by employing porous solids as bed materials instead of nonporous sand. The effect of bed material on the onset of devolatilization was measured by use of a bench‐scale bubbling fluidized bed reactor. Volatile matter capture by the porous solids (capacitance effect) and the heat transfer rate within the bed, both of which affect volatile matter evolution rate, were also measured. Four types of porous solids, both with and without capacitance effect, were employed as the bed material. By employing porous solids without capacitance effect, the contributions of reduced heat transfer rate and capacitance effect to the delay of volatile matter evolution can be evaluated separately. For porous bed materials with a moderate capacitance effect (volatile matter capture of up to 20 %), the delay of the onset of devolatilization, which was measured by detecting the flame combustion of the volatile matter, was explained by the lower heat transfer between the fuel and bed. However, for a porous particle with high capacitance effect (volatile matter capture of 30 %), the capacitance effect also affected the delay of the onset of the flame combustion.     

Natural Calcium‐Based Residues for Carbon Dioxide Capture in a Bubbling Fluidized‐Bed Reactor

Used clamshells (Paphia undulata), as a precursor of calcium oxide (CaO) sorbents, were employed for carbon dioxide (CO₂) adsorption in a bubbling fluidized‐bed reactor. To find the optimal calcination conditions, a 2^k experimental design was used to vary the ground clamshell particle size, heating rate, and calcination time at 950 °C under a nitrogen atmosphere. The heating rate was the most significant factor affecting the CO₂ adsorption capacity of the obtained CaO sorbent. The maximum CO₂ adsorption capacity of the CaO obtained under these study conditions was higher than that of commercial CaO.     

Biological Nutrient Removal Using a Novel Laboratory‐Scale Twin Fluidized‐Bed Bioreactor

The capability of biological nutrient removal from wastewater of a novel laboratory‐scale twin fluidized‐bed bioreactor (TFBBR) was studied. The work showed approximately 96 % organic matter, 84 % nitrogen, and 12 % phosphorus removal efficiencies in the first three phases of the study at influent synthetic municipal wastewater (SMW) flow rates of 150, 190, and 240 L/d, with corresponding organic loading rates of 1.3, 1.7, and 2.3 kg COD m^–3 d^–1 and nitrogen loading rates of 0.14, 0.18 and 0.25 kg N m^–3 d^–1. The TFBBR effluent was characterized by <1.0 mg NH₄‐N/L, <4.3 mg NO₃‐N/L, <6 mg TN/L, <6 mg SBOD/L, and 6–10 mg VSS/L. For the three phases, biomass yields of 0.06, 0.066, and 0.071 g VSS/g COD were observed, respectively, which was a significant further reduction in yield compared to the liquid‐solid circulating fluidized‐bed bioreactor technology developed and patented by this research group, of 0.12–0.16 g VSS/g COD. The very low yield was due to a longer solid retention time of 72–108 d.     

Expansion Behavior of a Binary‐Solid Liquid Fluidized Bed with Large Particle Size Difference

The overall expansion of two dissimilar solid particle species with over a tenfold difference in their size and substantial density difference is investigated here for different compositions of the fluidized bed. Contrary to the widely held notion that the total bed height would be the sum of the heights of the two segregated mono‐component beds, the actual bed heights were, in fact, found to be lower. This volume contraction is found to strongly depend upon the mixing behavior prevailing in the binary‐solid fluidized bed. At the complete mixing of the two solid species, the bed‐contraction versus liquid velocity profile shows a global maximum. As a result, the overall bulk density profiles are similarly affected. Moreover, it is found here that correlations meant for predicting the porosity of the packing of binary particle mixtures can be satisfactorily extended to binary‐solid fluidized beds where solid species differ significantly in size.     

Characteristics of a Pressurized Gas‐Solid Magnetically Fluidized Bed

The hydrodynamic, heat and mass transfer characteristics of a pressurized co‐current gas‐solid magnetically fluidized bed (MFB) were systematically investigated considering major influence factors, such as magnetic field strength, superficial gas velocity, and operating pressure. It was shown that this pressurized gas‐solid MFB has the advantages of a wider operation range of the superficial gas velocity under bubble‐free particulate fluidization, a larger bed voidage with smaller pressure drop across the bed, and larger heat transfer efficiency, compared with a conventional fluidized bed. Moreover, the minimum bubbling velocity, gas‐solid mass, and heat transfer coefficients were correlated at high accuracy within the investigated range of operating conditions.