Kinetic compensation effect in logistic distributed activation energy model for lignocellulosic biomass pyrolysis

Abstract

The kinetic compensation effect in the logistic distributed activation energy model (DAEM) for lignocellulosic biomass pyrolysis was investigated. The sum of square error (SSE) surface tool was used to analyze two theoretically simulated logistic DAEM processes for cellulose and xylan pyrolysis. The logistic DAEM coupled with the pattern search method for parameter estimation was used to analyze the experimental data of cellulose pyrolysis. The results showed that many parameter sets of the logistic DAEM could fit the data at different heating rates very well for both simulated and experimental processes, and a perfect linear relationship between the logarithm of the frequency factor and the mean value of the activation energy distribution was found. The parameters of the logistic DAEM can be estimated by coupling the optimization method and isoconversional kinetic methods. The results would be helpful for chemical kinetic analysis using DAEM.

Universal Kinetic Description for Thermal Decomposition of Copper(II) Hydroxide over Different Water Vapor Pressures

“…The variation in the E a value from 242.4±13.0 kJ mol −1 to 171.2±11.5 kJ mol −1 , as the physico-geometric reaction step proceeds from IP to PBR(1) via SR with 164.6±5.1 kJ mol −1 , is characteristic of the overall reaction, although we must account for the compensatory variation of the ln A value in line with the KCE when interpreting the variation in the E a value. [67][68][69][70][71][72][73][74] The universal kinetic characterization over different temperatures and partial pressures of the gaseous product in the reaction atmosphere provides further insights into the kinetic and mechanistic understanding of the thermal decomposition of inorganic solids and the reactions in a solid − gas system. Comparisons of the results of the universal kinetic characterization among various thermal decomposition of solids may allow pattern classification for the relationships between the conventional kinetic triplet (E a , A, f(α)) and exponents (a,b) in the AF, as well as variation trends in the kinetic parameters, including the exponents (a,b), as the reaction advances.…”

“…However, the actual effect of atmospheric water vapor should be interpreted by considering the accompanying increase in A values in line with the KCE. [67][68][69][70][71][72][73][74] The kinetic parameters, including the exponents (a, b) for the IP, SR, and PBR(1) steps determined using eq 12 with the AF in eq 3, characterize the kinetic behavior of the thermal decomposition from different viewpoints, i.e., the dependence of the apparent reaction rate on conversion, temperature, and p(H 2 O) in each physico-geometrical reaction step. The variations in each kinetic parameter as the consecutive reaction advances are also the kinetic characteristics of the reaction.…”

Revealing the effect of water vapor pressure on the kinetics of thermal decomposition of magnesium hydroxide

“…Superficially, the mutually dependent changes in the Ea and A values as the reaction steps evolve are interpreted considering the kinetic compensation effect (KCE). [99][100][101][102][103][104][105][106] Thus, the relationships of the actual reaction rates should be interpreted by considering the KCE.…”

Thermal Dehydration of Lithium Sulfate Monohydrate Revisited with Universal Kinetic Description over Different Temperatures and Atmospheric Water Vapor Pressures

“…to 272 kJ mol −1 depending on the experimental and calculational variabilities, that was accompanied by a compensative change in the A value, yielding a linear correlation between ln A and Ea values, known as the kinetic compensation effect, [27][28][29][30][31][32][33][34] as shown in Figure S1. Although the results exposed many problems related to the reliable kinetic analysis of solid-state reactions, various kinetic features of the reaction were identified, making the reaction in Eq.…”