A distributed activation energy model for the pyrolysis of lignocellulosic biomass

Cai, Junmeng; Wu, Weixuan; Liu, Ronghou; Huber, George W.

doi:10.1039/c3gc36958g

Cited by 223 publications

(135 citation statements)

References 67 publications

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“…Comparing with values found in literature for corn pyrolysis [28,30,31], the values are similar but some differences should be remarked: in the present study broader distribution of activation energies are found in general (i.e., higher values of σ i ); slight differences could be explained by variances in the materials used.…”

Section: Accepted Manuscriptsupporting

confidence: 63%

“…Table 2 shows all results. Table 2 also shows the values of the same parameters obtained by Cai et al [30] for corn stover pyrolysis and Trinic et al [31] for a similar material (corncob) for comparison. The first conclusion is that both processes can be satisfactorily fitted using DAEM with three pseudocomponents, even the uncommon behavior of combustion curves when decreasing temperature.…”

Section: Accepted Manuscriptmentioning

confidence: 86%

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Corn stover thermal decomposition in pyrolytic and oxidant atmosphere

Conesa¹,

Urueña²,

Dı́ez³

2014

Journal of Analytical and Applied Pyrolysis

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The pyrolysis and combustion of corn stover were studied by dynamic thermogravimetry and derivate thermogravimetry (TG-DTG) at heating rates of 5, 10, 20 and 50 K min -1 at atmospheric pressure. For the simulation of pyrolysis and combustion processes a kinetic model based on the distribution of activation energies was used, with three pools of reactants (three pseudocomponents) because of the complexity of the biomass samples of agricultural origin. The experimental thermogravimetric data of pyrolysis and combustion processes were simultaneously fitted to determine a single set of kinetic parameters able to describe both processes at the different heating rates. The model proposed achieves a good correlation between the experimental and calculated curves, with an error of less than 4 % for fitting four heating rates simultaneously. The experimental results and kinetic parameters may provide useful data for the design of thermo decomposition processing system using corn stover as feedstock. On the other hand, analysis of the main compounds in the evolved gas is given by means of a microcromatograph.

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Section: Accepted Manuscriptsupporting

confidence: 63%

Section: Accepted Manuscriptmentioning

confidence: 86%

Corn stover thermal decomposition in pyrolytic and oxidant atmosphere

Conesa¹,

Urueña²,

Dı́ez³

2014

Journal of Analytical and Applied Pyrolysis

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“…The two stages of pine pyrolysis are clearly distinguishable: (i) for α=0.06-0.8 fragmentation of hemicelluloses, cellulose and lignin occurs [83,84], whose respective energy barriers of 55-187, 195-236 and 35-267 kJ/mol had been determined [28]; and (ii) between α=0.81-0.91, whose high energy barrier is due to the formation of a complex polycyclic aromatic structure (char formation) [28,84]. It should be noted that thermal decomposition of lignin occurs during the entire process, especially at high temperatures, which demonstrates the wide variety of bonds in its structure [28,83]. Similar to the results reported here, Yao et al [85] obtained, using Friedman's method, a mean activation energy of 161.5±3…”

Section: Pyrolysis Kinetics and Thermodynamicsmentioning

confidence: 99%

Structure-reactivity relationship in pyrolysis of plastics: A comparison with natural polymers

Larraín

Carrier

Radović

2017

Journal of Analytical and Applied Pyrolysis

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Highlights• Global activation energy depends on conversion in pyrolysis of all polymers.• Activation energy variability is proportional to chemical complexity of polymers.• An Evans-Polanyi relationship for initiation reactions of polymer pyrolysis is proposed. AbstractRecent advances in plastics recycling confirm the high potential of pyrolysis technologies to enhance recovery and selectivity rates. Modelling the kinetics of this complex process to stimulate scaling-up opportunities remains a major challenge.This study is an attempt to develop practical quantitative reactivity indices for the pyrolysis of natural and synthetic polymers. Representative samples from both categories (coal and pine vs. PET, PE and PMMA) were selected. Their weight loss during pyrolysis was determined experimentally and analyzed using judicious lumping procedures for its initiation, propagation and termination steps. The combined experimental and theoretical approach allowed us to determine apparent activation energies using the isoconversional Friedman method; and the use of Benson's group contribution method generated reaction enthalpies for the initiation reactions. Increasing activation energies with conversion in each case indicated that bond scission proceeds in order of increasing bond strength. The greater chemical complexity of natural polymers was reflected in the higher coefficients of variability for activation energy and wider ranges of reaction enthalpies. A structure-reactivity relationship based on the Evans-Polanyi theory was used to test the hypothesis that primary pyrolysis kinetics is controlled by cleavage of weakest chemical bonds. While the results show that this approach is promising, especially if confirmed by extension to a larger data set, they also suggest the need to compare the relative kinetic importance of initiation and propagation steps in the sequence of polymer pyrolysis reactions.

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“…In particular, there is a shoulder in the conversion rate curve of raw material at low heating rates. The similar trend was also found in the experimental conversion rate curves of the slow pyrolysis of lignocellulosic biomasses by using thermogravimetric analysis [24,25]. Moreover, to obtain the pyrolysis time, the final concentration of decomposable components (the sum of cellulose, hemicellulose, and lignin) was assumed to be equal to 0.02(f H ?…”

Section: Resultsmentioning

confidence: 92%

Prediction of concentration profiles and theoretical yields in lignocellulosic biomass pyrolysis

Huang

Ding

Cai

2015

J Therm Anal Calorim

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This work involved the prediction of the concentration profiles and theoretical yields in lignocellulosic biomass pyrolysis under real pyrolysis conditions. The competing reaction model was used and verified by the experimental data of the pyrolysis of oilseed rape straw and sesame stalk. The pyrolysis kinetic behaviors of the pyrolysis of peach branch, cotton stalk, and corn stalk under various conditions were simulated based on the model and their chemical compositions. The influences of the heating rate and final temperature on the theoretical yields of pyrolysis products and the pyrolysis time were obtained. Under the same conditions, the pyrolysis of peach branch gave the highest yield of volatile products, while the pyrolysis of cotton stalk gave the highest yield of char. The method presented in this work enables us to predict the concentration profiles and theoretical yields of different lignocellulosic materials under various pyrolysis conditions.

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A distributed activation energy model for the pyrolysis of lignocellulosic biomass

Cited by 223 publications

References 67 publications

Corn stover thermal decomposition in pyrolytic and oxidant atmosphere

Corn stover thermal decomposition in pyrolytic and oxidant atmosphere

Structure-reactivity relationship in pyrolysis of plastics: A comparison with natural polymers

Prediction of concentration profiles and theoretical yields in lignocellulosic biomass pyrolysis

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