Parameters controlling pyrolysis

Pyrolysis is a complex process, and its outcome can be evaluated based on the values of the kinetic parameters controlling the concurring chemical reactions. On the other hand, the kinetic parameters depend on thermodynamic stability of different participating molecules in the thermal degradation. This explains the necessity to use thermochemical kinetics concepts [1] for the study of pyrolytic processes. Considering for example a simple reaction of the form ... 

PARAMETERS CONTROLLING THE ANALYTICAL PYROLYSIS PROCESS - General aspects... 

The results of open-system pyrolysis (Rock-Eval II) have been used to specify the kinetic parameters controlling maturation. Hydrocarbon yield rates as determined by these experiments are shown in Fig. 6.9a. Both nonlinear optimization technique (Levenberg-Marquardt method Press et al. 1986 Issler and Snowdon 1990) and linear methods are used to determine the values of the reaction parameters Aj, Ej, andX, . This technique minimizes an error function by comparing the hydrocaibon release rates, Sj, calculated by Eq. 6.9 and those rates measured in open-system pyrolysis. An example of the spectrum of activation energies obtained from this analysis is shown in Fig. 6.9b. 

The application of a selective pyrolysis process to the recovery of chemicals from waste PU foam is described. The reaction conditions are controlled so that target products can be collected directly from the waste stream in high yields. Molecular beam mass spectrometry is used in small-scale experiments to analyse the reaction products in real time, enabling the effects of process parameters such as temperature, catalysts and co-reagents to be quickly screened. Fixed bed and fluidised bed reactors are used to provide products for conventional chemical analysis to determine material balances and to test the concept under larger scale conditions. Results are presented for the recycling of PU foams from vehicle seats and refrigerators. 12 refs. 

Chemical vapor deposition (CVD) of carbon from propane is the main reaction in the fabrication of the C/C composites [1,2] and the C-SiC functionally graded material [3,4,5]. The carbon deposition rate from propane is high compared with those from other aliphatic hydrocarbons [4]. Propane is rapidly decomposed in the gas phase and various hydrocarbons are formed independently of the film growth in the CVD reactor. The propane concentration distribution is determined by the gas-phase kinetics. The gas-phase reaction model, in addition to the film growth reaction model, is required for the numerical simulation of the CVD reactor for designing and controlling purposes. Therefore, a compact gas-phase reaction model is preferred. The authors proposed the procedure to reduce an elementary reaction model consisting of hundreds of reactions to a compact model objectively [6]. In this study, the procedure is applied to propane pyrolysis for carbon CVD and a compact gas-phase reaction model is built by the proposed procedure and the kinetic parameters are determined from the experimental results. 

The TGA system was a Perkin-Elmer TGS-2 thermobalance with System 4 controller. Sample mass was 2 to 4 mgs with a N2 flow of 30 cc/min. Samples were initially held at 110°C for 10 minutes to remove moisture and residual air, then heated at a rate of 150°C/min to the desired temperature set by the controller. TGA data from the initial four minutes once the target pyrolysis temperature was reached was not used to calculate rate constants in order to avoid temperature lag complications. Reaction temperature remained steady and was within 2°C of the desired temperature. The actual observed pyrolysis temperature was used to calculate activation parameters. The dimensionless "weight/mass" Me was calculated using Equation 1. Instead of calculating Mr by extrapolation of the isothermal plot to infinity, Mr was determined by heating each sample/additive to 550°C under N2. This method was used because cellulose TGA rates have been shown to follow Arrhenius plots (4,8,10-12,15,16,19,23,26,31). Thus, Mr at infinity should be the same regardless of the isothermal pyrolysis temperature. A few duplicate runs were made to insure that the results were reproducible and not affected by sample size and/or mass. The Me values were calculated at 4-minute intervals to give 14 data points per run. These values were then used to... 

Cellulose pyrolysis kinetics, as measured by isothermal TGA mass loss, were statistically best fit using 1st- or 2nd-order for the untreated (control) samples and 2nd-order for the cellulose samples treated with three additives. Activation parameters obtained from the TGA data of the untreated samples suggest that the reaction mechanism proceeded through an ordered transition state. Sample crystallinity affected the rate constants, activation parameters, and char yields of the untreated cellulose samples. Various additives had different effects on the mass loss. For example, phosphoric acid and aluminum chloride probably increased the rate of dehydration, while boric acid may have inhibited levoglucosan... 

An advanced control system has been implemented for efficient operation of the pyrolysis reactor. However, it faced problems due mainly to the difficulty of measuring the high coil and coil skin temperature reliably and consistently, because of regular drifting of the high-temperature sensors. Thus, there is a need for a data reconciliation package (DRP) to increase the level of confidence in key measured variables, to indicate the status of sensors, and to estimate the value of some unmeasured variables and parameters (Weiss et al., 1996). 

The analysis of co-current flame spread is very similar to that of opposed flame spread. However, it is further complicated because the flame covers the fuel thus, the flame length is a further parameter that needs to be analyzed. The flame length can be represented empirically as being proportional to the pyrolysis length or can be calculated using boundary layer theory and the assumption of infinitely fast gas-phase chemistry [22], Despite the added complexity, co-current flame spread is controlled by the same physical parameters as ignition or opposed flame spread. 

Figure 1 shows a computational framework, representing many years of Braun s research and development efforts in pyrolysis technology. Input to the system is a data base including pilot, commercial and literature sources. The data form the basis of a pyrolysis reactor model consistent with both theoretical and practical considerations. Modern computational techniques are used in the identification of model parameters. The model is then incorporated into a computer system capable of handling a wide range of industrial problems. Some of the applications are reactor design, economic and flexibility studies and process optimization and control. 

The kinetics of these pyrolysis reactions were followed by several complementary methods under conditions as close to the product studies as possible. The most frequently-used ampule technique14 17) with gc analysis of 5 and the scavenger technique, with chloranil or Koelsch radical as scavenger 18), for very labile compounds 5 were complemented by the DSC method, in which the heat flow under conditions of linear temperature increase is analysed. It proved to be a particularly convenient and reliable technique 18- 21). Rates were followed over a temperature span of at least 40 °C with temperature control of 0.1-0.2 °C. All rate data and activation parameters were subjected to a thorough statistical analysis including statistical weights of errors. The maximum statistical errors in k were 3%, in AH 1 kcal mol-1 in AS 513 e.u. and in AG (at the temperature of measurement) g0.5 kcal mol-1. 

Heated-filament pyrolyzers are often used to analyze lignins (Kratzl et al. 1965, Lindberg et al. 1982, Obst 1983, Gardner et al. 1985, Faix et al. 1987, 1991, Funazukuri et al. 1987, Salo et al. 1989). In this type of analyzer, electric current is passed through a resistance ribbon or coiled wire, both made of platinum. The dissipation of power increases the temperature of the conductor. Heat-up and pyrolysis times are selected from an instrument control. Characteristic parameters of this type of pyrolyzer have been described by Wells et al. (1980) and Wampler and Levy (1987). 

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