Thermogravimetric characteristics of <Emphasis Type="Italic">α</Emphasis>-cellulose and decomposition kinetics in a micro-tubing reactor

The pyrolysis characteristics and kinetics of α-cellulose were investigated using thermogravimetric analyzer (TGA) and micro tubing reactor, respectively. Most of the α-cellulose decomposed between 250 and 400 °C at heating rate of 5–20 °C/min. The apparent activation energy was observed in the range of 263.02 kJ mol^?1 to 306.21 kJ mol^?1 at the conversion of 10-80%. The kinetic parameters were determined by nonlinear least-squares regression of the experimental data, assuming first-order kinetics. It was found from the kinetic rate constants that the predominant reaction pathway was A(α-cellulose) to B(bio-oil) rather than A(α-cellulose) to C(gas; C₁-C₄) and/or to B(bio-oil) to C(gas; C₁-C₄) at temperatures of 340-360 °C.     

A testing procedure for triaxial tests and a numerical method for the calculation of powder flow properties

A testing procedure for measuring flow properties of powders is developed which makes it possible to use results from triaxial tests in the Jenike bin theory. For the elaboration of the results a numerical method is used, based upon the Warren Spring equation (τ/C)^N = (σ + T)/T. In this equation σ and τ are the normal and shear stresses respectively, C and T the cohesion and tension, and N a curvature parameter. A constant K = C/T and a constant curvature parameter N are assumed for a material. The algorithm used is a least-squares method using Newton's zero finding technique. The solutions obtained by this procedure are not influenced by the initial estimates.     

Influence of the adjustable parameters of the DPD on the global and local dynamics of a polymer melt

We present DPD simulations of linear polyethylene melts with force fields derived from microscopic simulations using the concept of potential of mean force. We aim at simulating realistic short polymers from a qualitative and quantitative point of view. An interesting issue is then to know the influence of the adjustable parameters of the DPD: γ, the friction coefficient, and r_C, the cut-off radius, on the global and local dynamics of the polymer, i.e., the diffusion coefficient, D_CM, the end-to-end decorrelation time, τ_R and the Rouse times. By varying these two parameters, we investigate structural and dynamical properties for different polymeric systems at a given chain length. Although scaling laws typical of the Rouse model have been reproduced using this DPD method, we observe deviation from the Rouse theory for the local dynamics of certain systems. The dynamical properties of the polymer melt are defined simultaneously by γ and r_C. Therefore we combine these two parameters, introducing a new parameter, the effective friction coefficient, γ^eff.     

Thermal degradation of shale oils: 1. Kinetics of vapour phase oil degradation

As vertical modified in-situ retorts (VMIS) have been scaled up and tested, the overall oil yield has declined and is generally lower than that observed in an above-ground process. This reduced oil yield could adversely affect the economics of VMIS retorting. Diminished yields are attributed to a combination of factors associated with scale-up such as in complete rubblization, wide particle size distributions (large blocks of shale), and poor flow distributions. Additionally, oil losses can occur by comparatively long exposure of the oil vapours to high temperatures, by exposure to successive condensation and revaporization of the oil as it travels down the retort, and finally by long time thermal exposure of the condensed oil retained in the bottom portion of large VMIS retorts. To study such vapour phase degradation of shale oil using oil produced from Occidental Petroleum's No. 6 VMIS retort, a tubular continuous flow reactor, with an on-line gas chromatograph for gas composition monitoring was used to study thermal degradation of shale oil under retorting conditions. Oil and a combination of gases including steam were metered into the preheater and then the vapours passed into a quartz tubular reactor where the temperature and residence time of the gaseous mixture were controlled. Complete mass balances were performed giving the weight fraction of oil converted to noncondensable hydrocarbon gases and coke. This experimental design is novel because high temperature thermal degradation of shale oil was studied for the first time under steady state flow conditions with carefully controlled residence time and temperature. A range of temperatures (425–625 °C) and residence times (2–10 s) were used in a series of factorial-designed experiments (3²) to accurately determine the effects of these variables. Results of the study showed that the addition of steam to the carrier gas did not reduce oil degradation losses but did react with the coke thereby changing the product gas composition and quantity. A first-order oil degradation rate expression was used to model the rate of oil loss. The calculated activation energy was 17.3 kcal mol^?1. Chemical analyses of the product liquids and gases confirmed previously reported findings that the oil loss indices (alkene/alkane, ethylene/ethane, naphthalene/(C₁₁ + C₁₂), and gas/coke) increase with increasing oil degradation.     

Model based on population balance for the simulation of bubble columns using methods of the least-square type

A novel model is presented which uses mass and momentum equations based on population balances to describe the dispersed phase of bubble columns. A set of integro-differential non-linear equations constitutes the model, which can be solved directly using the least-squares methods. The implementation for these is presented.The model presents a degree of flexibility, as different density functions (number, mass and volume) and different internal coordinates (bubble diameter, volume and mass) can be used.A simplified 1D model of a bubble column is solved using the least-squares spectral element method. The results obtained for two different gas volume fluxes at the inlet are compared with experiments by several authors. The simulations show good agreement with the measured data.     

Compressibility factor model of sweet,sour, and condensate gases using genetic programming

Gas compressibility factor (z-factor) is necessary in most petroleum engineering calculations. The most common sources of z-factor values are experimental measurements, equations of state (EOS) and empirical correlations. There are more than twenty correlations available with two variables for calculating the z-factor from fitting Standing–Katz chart values in an EOS or just through fitting techniques. However, these correlations are too complex, which require initial value and longer computations, and have significant error. This work presents a new model for estimating z-factors of sweet gases, sour gases and gas condensates using genetic programming (GP). The z-factor model was developed using pseudo-reduced pressure, and pseudo-reduced temperature. Moreover, two new models of pseudo-critical pressure and temperature were built as a function of the gas composition (mol percent of C₁–C₇₊, H₂S, CO₂, and N₂) and the specific gravity of the C₇₊. The developed new GP-based model yields a more accurate prediction of gas z-factor compared to the commonly used correlations and EOS's.     

Volatile trace element behaviour in the Sasol fixed-bed dry-bottom (FBDB)™ gasifier treating coals of different rank

Trace element simulation and validation of model predictions for the elements Hg, As, Se, Cd and Pb have recently been undertaken for the Sasol^® FBDB™ gasification process operating on lump coal. The validation was conducted by interpolating the residual trace elements content remaining behind in the solid coal/char/ash fractions after sequential mining of a quenched commercial-scale gasifier operating on low rank grade C bituminous Highveld coal used for gasification in South Africa. This paper extends the research understanding by comparing the volatile trace element behaviour of these same elements, using the same gasification technology, but operating on North Dakota lignite. The focus will be on the behaviour of the volatile Class III trace elements: Hg, As, Se, Cd and Pb within the Sasol^® FBDB™ gasifier as function of coal rank. This study excludes the downstream gas cleaning partitioning and speciation behaviour of these elements.Findings indicate that although the feed concentration and mode of occurrence of these elements differ quite substantially between the two coal types studied, that the volatilization profiles of the elements are indeed quite similar; being within 0.1%-15% lower in the case of the lignite when compared to the bituminous coal. In both cases, Hg was found to be the most volatile and As the least; with the volatility order varying slightly for the metals Se, Cd and Pb for the two coal types. The differences observed in the trace element volatilization rate are supported by the temperature profile which was inferred from the reflectance of vitrinite (RoV) measurements of the dissected fuel bed material. The highly reactive lignite, is successfully gasified at a lower temperature than is the case for bituminous coal using the Sasol^® FBDB™ gasification process. Speciation predictions have earlier shown that: H₂ Se, CdS, PbS/Pb/PbCl, and AsH₃ species possibly exist in the gas phase. In reality, organically-associated trace elements will also be volatilized into the gas phase, but due to a lack of thermodynamic data for the lignite organo-metallic species at this stage only inorganic associations could be modelled.     

hp-Adaptive spectral element solver for reactor modeling

The study, analysis and optimization of chemical reactors has shown a significant increase in complexity of the models used during the last decades. This complexity increased the computational cost of the models demanding the development of efficient solution techniques. This paper discusses the implementation of an hp-adaptive refinement technique applied to a least-squares spectral element formulation as a mathematical framework for reactor modeling. The refinement is based on an estimate of the local Sobolev regularity index of the underlying solution by monitoring the decay rate of its Legendre expansion coefficients. The performance of the method is demonstrated numerically by using an analytical test case.     

Influence of the lift force closures on the numerical simulation of bubble plumes in a rectangular bubble column

Numerical Eulerian-Eulerian simulations of the unsteady gas-liquid flow in a centrally aerated two-dimensional bubble column were carried out in order to understand the effect of different formulations of the lift force coefficient (C_L) on the computational results. Three different values of the superficial gas velocity (U_G=2.4, 12.0 and 21.3 mm s⁻¹) that ensure the existence of different flow regimes were experimentally and computationally studied. The validation of the simulated results was based on visual observations and measurements of the global gas hold-up (ε_G) and the plume oscillation period (POP). The results presented reveal that, at U_G=12.0 and 21.3 mm s⁻¹, using C_L<0 results in under- and over-estimation of the ε_G and POP, respectively. On the other hand, taking C_L>0 does not affect the POP while it leads to increasingly higher ε_G values, which are different from those experimentally reported. At U_G=2.4 mm s⁻¹, the effect of the lift force is not so evident, although it slightly improves the prediction of experimental values. Particularly interesting is the case of C_L>0.4 at U_G=21.3 mm s⁻¹, producing a non-symmetric bubble plume oscillation. Since using Tomiyama's lift coefficient correlation does not improve the results, including the lift force into the simulation of bubble plumes is not recommended.     

A mathematical relationship for the explanation of ion exchange for boron adsorption

The present study was undertaken to investigate a method for boron removal from wastewaters from boric acid and borax plants. The ion-exchange method is effective for the removal of boron from solution. The experimental results under different initial concentrations are first converted into dimensionless variables by taking ratios of volumes and concentrations and subsequently plotted on double logarithmic graph papers. The scatter diagram appeared as a straight line on double logarithmic paper, which implied an empirical relationship as C/C₀ = 0.05 (V₁/V₂^2.72 where C and C₀ are the effluent boron concentrations at any time and initial time, respectively. In short, there appears to be a power relationship between the dimensionless concentrations and volume variables.     

Gas absorption with first-order chemical reaction in laminar falling films—calculation of rates and enhancement factors

The differential equation describing the absorption of a gas by a liquid film failing down a vertical wall can be solved, in the simple cases of (a) physical absorption and (b) absorption with first-order chemical reaction, by the method of separation of variables and subsequent solution of the space equation with Kummer's function [7]. The resultant concentration profiles are used to evaluate absorption rates and enhancement factors (here defined as the ratio of the actual absorption rate to that in a very deep stagnant liquid with the same surface exposure time but no chemical reaction).It is found that the film thickness and velocity profile only have an influence when the dimensionless group ? = f²k/D is less than 5 (D being the diffusivity of the dissolved gas in the liquid, f the film thickness and k the reaction rate constant). When the Hatta number, √M′, is greater than 0.7, the enhancement factor is given, for all values of ?, by a simplified form of the solution with an error of less than 2%.     

Performance limits of isothermal packed bed and perforated monolithic bed reactors operated under laminar flow conditions. I. General optimization analysis

A global optimization analysis of a general class of perforated monolithic bed reactors is presented for the case of an isothermal first-order reaction and for laminar flow conditions. The resulting design rules indicate how a given amount of catalyst material should best be perforated or distributed in space as a function of the available inlet pressure. It is shown that the influence of the different process variables (k,ΔP,V_cata,C_in/C_out,D_mol, S_reac) on the reactor productivity and on the optimal bed design can be grouped into a single dimensionless number E. This number also allows to discuss the sensitive relation between the total and the volumetric productivity of single bed reactors in a very general, compact manner. Two different perforated monolithic bed designs, a slit pore bed (SPB) and a cylindrical pore bed (CPB) are considered. It is found that, when there is an excess inlet pressure (i.e., for E?1), the optimal catalyst layer thickness is given by φ=0.3-0.5 and that the optimal pore diameter is in both cases 1.4-1.45 times smaller than the catalyst layer, independently of the internal catalyst diffusivity (D_int) and the other process variables. When the available inlet pressure is limiting (E>10⁻⁴), and when the absolute reactor productivity is more important than the volumetric productivity, it is found that much more open structures, with much wider pores are needed, i.e., perforated beds show the same behavior as packed beds, where the occurrence of a pressure-drop limitation also induces a shift from the use of full particles to the use of hollow extrudates.     

Improvement of Filter Tow Quality through Statistical Analysis

Filter tow production is controlled by individual supervision of the main variables based on the determination of the C_pk, which indicates instability when individual values are below 1. This paper describes a process improvement methodology, which uses statistical tools to correlate the production variables, and thus control the variability of the dependent variables. The analysis was performed over several sets of data, identifying dependent variables – yield (g) and tensile strength (daN) – and establishing relationships of cause and effect with the production variables, indicating the possibility of achieving a new form of control through adjusted multiple regression models, resulting in the C_pk of the dependent variables being greater than 1. These results were improved through an industrial test, using DOE 2^k, which led to the conclusion that the process can be supervised by means of the fitted models, ensuring better control and greater stability.     

Optimal operation of a membrane reactor network

In this contribution, the operation of a membrane reactor network (MRN) for the oxidative coupling of methane is optimized. Therefore, three reactors, a fixed bed reactor (FBR) and two packed bed‐membrane reactors, are modeled. For the (CPBMR), a two‐dimensional (2‐D) model is presented. This model incorporates radial diffusion and thermal conduction. In addition, two 10 cm long cooling segments for the CPBMR are implemented based on the idea of a fixed cooling temperature positioned outside the reactor shell. The model is discretized using a newly developed 2‐D orthogonal collocation on finite elements with a combination of Hermite for the radial and Lagrangian polynomials for the axial coordinate. Membrane thickness, feed compositions, temperatures at the inlet and for the cooling, diameters, and the amount of inert packing in the reactors are considered as decision variables. The optimization results in C₂ yields of up to 40% with a selectivity in C₂ products of more than 60%. The MRN consisting of an additional packed‐bed membrane reactor with an alternative feeding policy and a FBR shows a lower yield than the individual CPBMR. © 2013 American Institute of Chemical Engineers AIChE J, 60: 170–180, 2014     

Kinetics of ethylene oxidation on plane Pt/SiO2 catalysts in the viscous pressure regime: evidence of support activity

C₂H₄ oxidation on plane Pt/SiO₂ model catalysts with various Pt loadings was studied atT = 373–473 K and in the pressure ranges 10^–6–10² Torr C₂H₄ and 0.3–1500 Torr 02 (1 Torr = 133.3 Pa). Mass spectrometry combined with spatially resolved gas sampling enabled kinetic data to be collected far into the viscous pressure regime. Reaction orders and activation energies were similar to those of a macroscopic Pt surface. However, under fuel-lean conditions the global reaction rate decreases faster than the decrease in metal area. On the other hand, the global rate wasindependent of Pt loading and metal surface area in fuel-rich gas mixtures. This is interpreted in terms of a spillover effect.     

Simultaneous determination of quality parameters of biodiesel/diesel blends using HATR-FTIR spectra and PLS, iPLS or siPLS regressions

Partial least-squares (PLS), interval partial least squares (iPLS) and synergy partial least squares (siPLS) regressions were used to simultaneous determination of quality parameters of biodiesel/diesel blends. Biodiesel amount, specific gravity, sulfur content and flash point were evaluated using spectroscopic data in the mid-infrared region obtained with a horizontal attenuated total reflectance (HATR) accessory. Eighty-five binary blends were prepared using biodiesel and two types of diesel, in concentrations from 0.2 to 30% (v/v). Fifty-seven samples were used as a calibration set, whereas 28 samples were used as an external validation set. All samples were characterized using the appropriated standard methods. The specific gravity values at 20 °C were in the range of 848.2-866.2 kg/m³. Flash point values lay between 47.0 and 79.5 °C. Sulfur content values varied from 312 to 1351 mg/kg. Raw spectra of the samples were corrected by multiplicative scatter correction (MSC) and were pre-processed using a mean-centered procedure. Algorithms iPLS and siPLS were able to select the most adequate spectral region for each property studied. For all the properties studied, the siPLS algorithm produced better models than the full-spectrum PLS, selecting the most important bands. The quantification of biodiesel was performed using two spectral regions between 650-1909 cm⁻¹ and 2746-3165 cm⁻¹, and an excellent correlation coefficient of R² = 0.9996 was obtained. The specific gravity was determined from the spectral region from 650 to 1070 cm⁻¹, which yielded a very good correlation coefficient of R² = 0.9987. The sulfur content was evaluated from the spectral regions of 1070-1491 cm⁻¹ and 2746-3165 cm⁻¹. A very good correlation coefficient of R² = 0.9995 was obtained, regardless of whether the samples were formulated with metropolitan or countryside diesel. Finally, the flash point was determined from the spectral region between 756 and 968 cm⁻¹ and a very good correlation coefficient of R² = 0.9982 was obtained.     

Optical-quality diamond growth from CO2-containing gas chemistries

From interpretation of the Bachmann diagram, it is conceivable that there may be some advantage to be gained by moving up the H–CO tie line for optical-quality diamond deposition. A convenient system for achieving this are gas chemistries containing CO₂, which, when combined with gases such as CH₄ and C₂H₄ (ethylene), enables the diamond deposition region to be traversed and, with the addition of hydrogen, to move along the H–CO tie line. The fabrication of free-standing diamond wafers using combinations of these feed-stock gases with a high-pressure, 2.45-GHz microwave source reactor (HPMS) able to operate at up to 140 Torr and 6 kW has been investigated. The FWHM line width of the 1332 cm⁻¹ Raman peak is found to be predominately a function of the gas composition. The growth rate is also dependent on the input power and the deposition pressure. The deposition plasmas are bright green in colour, and optical emission spectroscopy (OES) of the plasma reveals distinctive C₂ and Hα peaks. In some cases, it is possible to correlate characteristics of the deposited diamond layer to features in the OES spectra.     

Formal potential estimation for a quasi-reversible charge transfer followed by a first-order irreversible chemical reaction

A method is presented for estimating the formal potential of a quasi-reversible charge-transfer with a coupled following chemical reaction. The method is based on the dc polarographic half-wave potential variation with drop-time. Results of data analysis of digitally simulated polarograms using following first-order rate constants of 10⁵ and 10⁷ s^?1 indicate that formal potential estimates are generally accurate to within 3–4 mV. Effects of error in the required estimates of the first-order chemical rate constant and the charge-transfer coefficient are described. The charge-transfer standard rate constant can also be estimated.     

Analysis and Modeling of the Hydroisomerization Process for <Emphasis Type="Italic">n</Emphasis>-Hexane

A stage six-path mechanism for the reaction of n-hexane hydroisomerization on a BEA Pt-zeolite catalyst has been proposed. The mass flow rate of n-hexane in the feed stream varies in the range of 0.7?2.8 h^?1; the mole ratio of hydrogen to the n-hexane range of 2.7–14.6; the reactor temperature falls in the range from 453 to 573 K; and the gas flow pressure varies in the range of 1.0–10.0 atm. Thirty experiments have been carried out. In the product stream, the concentrations of n-hexane, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane, propane, C₁-alkanes, and C₂-alkanes are analyzed by gas chromatography. A kinetic model has been constructed for the six-path mechanism of the reaction of n-hexane hydroisomerization, which contains 15 kinetic constants. Based on the results of laboratory experiments, the kinetic constants of the model have been estimated by the method of nonlinear least squares. The model has been shown to correspond with the experiment in the selected field of experimentation.     

A transient method to study the pressure drop characteristics of the cyclone in a CFB system

A transient method was developed and applied to study the variation of pressure drop characteristics of the cyclone ^ΔP_c used in a circulating fluidized bed (CFB) system with the solid concentration at the inlet C_s,in. Experiments were conducted in a CFB apparatus, with a square riser of 0.1 m × 0.1 m in cross-section and 3.2 m in height, and with a smooth riser exit. When the system was in a steady state with a large C_s,in, the supply of solid material to the riser was suddenly cut-off while the gas velocity was maintained at a constant. C_s,in was derived by the pressure drop measured across the smooth riser exit. ^ΔP_c and C_s,in were measured on-line during the transient process. Experimental results showed that ^ΔP_c and C_s,in obtained by the transient method were in good agreement with those obtained by the steady state experiments. Furthermore, ^ΔP_c decreased at first with increasing C_s,in and then reached at a minimum at the critical C_s,in, thereafter it increased with C_s,in. The transient method offers an acceptable accurate, cost-effective and productive means to study the ^ΔP_c over a wide range of C_s,in.