Master-eğriler kinetik yönteminin izotermal olmayan selüloz pirolizine uygulanması ve piroliz işleminin termodinamik analizi

Abstract

Biyorafineriler için piroliz gibi termokimyasal dönüşüm yöntemlerinin kinetik olarak modellenmesi en zorlu konulardan biridir. Temelde biyokütle pirolizini selüloz ile birlikte lignin ve hemiselüloz özelliklerinin etkilediği bilinmektedir. Ancak çok fazlı karmaşık piroliz tepkimelerine giren bu biyopolimerlerin termal davranışları hakkında halen literatürde sınırlı bilgi bulunmaktadır. Bu nedenle, bu çalışmada selülozun piroliz kinetiği ve termodinamiği incelenmiştir. Pirolize ait kinetik parametreler master eğriler ve Friedman yönteminin birleştirilmesi ile hesaplanmıştır. Selülozun aktif pirolizinin 263 ile 455 °C arasında gerçekleştiği saptanmıştır. Uygulanan Friedman yöntemi deneysel veriler ile çok iyi uyum sağlamış, termokimyasal dönüşüm işleminin aktivasyon enerjileri 150.8 ile 190.2 kJ/mol arasında bulunmuş ve ortalama aktivasyon enerjisinin 164.3 kJ/mol olduğu hesaplanmıştır. Katı hal bozunma süreçlerinde kullanılan kinetik yöntemlerin karşılaştırılması ile selüloz piroliz mekanizmasının düşük dönüşümlerde (0<α<0.5) difüzyon kontrollü bir bozunma işlemi (D3) ile sürdüğü ve daha yüksek dönüşümlerde tepkime derecesine bağlı olduğu saptanmıştır.

Keywords

• selüloz,kinetik

Application of master-plots kinetic method to non-isothermal cellulose pyrolysis and thermodynamic analysis of the pyrolysis process

Abstract

Kinetic modeling of thermochemical conversion methods such as pyrolysis is one of the most challenging issues for bio-refineries. It is known that cellulose together with hemicellulose and lignin mainly affect the characteristics of biomass pyrolysis. However, there is still limited knowledge about the thermal behaviors of biopolymers that go into complex multi-phase pyrolysis reactions in the literature. Therefore, cellulose pyrolysis kinetics and thermodynamics were investigated in this study. Kinetic parameters of the pyrolysis process were calculated by a combined method of master-plots and Friedman method. Active pyrolysis of cellulose is found to occur between 263 and 455 °C. Applied Friedman method was perfectly fitted with the experimental data and activation energy of the thermochemical conversion process was found between 150.8 and 190.2 kJ/mol while the mean activation energy was calculated as 164.3 kJ/mol. The comparison of kinetic models used of solid-state thermal decomposition processes indicated that the cellulose pyrolysis mechanism is a diffusion-controlled (D3) degradation process at lower conversions (0<α<0.5) and the process can be explained by reaction-based mechanisms at higher conversion degrees.

Keywords

• pyrolysis,kinetic,cellulose

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