Investigation of Catalyst Activity in Iron Oxide-Based Catalytic Pyrolysis of High Density Polyethylene and Polypropylene Plastic Wastes: Kinetic and Thermodynamic Analysis

Öz

In the chemical recycling of plastic wastes, many catalysts based on transition metals (Fe, Co, Mo, Ni, etc.) with different physicochemical activities are used. Impregnating metal salts (such as nitrates) prepare these metal-containing catalysts with high water solubility onto acidic and mostly spherical (1-3 mm) supports such as SiO₂, Al₂O₃. These catalysts are used in the catalytic pyrolysis of many thermoplastic polymers such as polyethylene(s), polypropylene, polystyrene, polyvinyl chloride, polyethylene terephthalate in inert atmospheres. In this study, SiO₂-supported iron oxide-based catalysts with spherical structures of 1-3 mm in diameter were prepared by applying the impregnation method. The recycling of disposable waste plastic injectors produced from high density polyethylene (HDPE) and polypropylene (PP) plastics into chemical products by catalytic pyrolysis was investigated. Total product conversions (a) of both PP and HDPE plastic wastes increased at different rates depending on the temperature. In the catalytic pyrolysis of PP plastic wastes, the activation energy was calculated as 133.81 kJ/mol and in the catalytic pyrolysis of HDPE plastic wastes, it was calculated as 171.98 kJ/mol. This result shows that the pyrolysis conditions of HDPE plastic wastes are more endothermic than PP and therefore more energy is required. This situation showed similar results in thermodynamic variables and the enthalpy values ​​were positive at all temperatures in the plastic waste pyrolysis, which is an endothermic reaction. It was observed that there were significant decreases in the enthalpy values ​​for both waste plastics with the use of catalyst. The calculated entropy and free energy values ​​also showed that these reactions did not tend to spontaneously.

Anahtar Kelimeler

• Pyrolysis
• Catalyst
• plastic recycling
• Kinetic and thermodynamic analysis.

Yüksek Yoğunluklu Polietilen ve Polipropilen Plastik Atıkların Demir Oksit Esaslı Katalitik Pirolizinde Katalizör Etkinliğinin Araştırılması: Kinetik ve Termodinamik Analiz

Öz

Plastik atıkların kimyasal geri dönüşümünde, farklı fizikokimyasal etkinliğe sahip geçiş metalleri esaslı (Fe, Co, Mo, Ni, vs.) birçok katalizör kullanılmaktadır. Bu metal içerikli katalizörler, suda çözünürlüğü yüksek olan metal tuzlarının (nitratlar gibi) SiO₂, Al₂O₃, gibi asidik ve çoğunlukla küresel (1-3 mm) destek maddelerine emdirilmesi ile hazırlanırlar. Bu katalizörler, inert atmosferde polietilen(ler), polipropilen, polistiren, polivinil klorür, polietilen tereftalat gibi birçok termoplastik polimerin katalitik pirolizinde kullanılmaktadır. Bu çalışmada, emdirme yöntemi uygulanarak, 1-3 mm çapında küresel yapıda olan SiO₂ destekli Fe₂O₃ esaslı katalizörler hazırlanmıştır. Yüksek Yoğunluklu Polietilen (YYPE) ve Polipropilen (PP) plastiklerden üretilen, tek kullanımlık atık plastik enjektörlerin katalitik pirolizi ile kimyasal ürünlere dönüştürülebilirliği araştırılmıştır. Gerek PP gerekse YYPE plastik atıkların her ikisinin de toplam ürün dönüşümleri (a), sıcaklığa bağımlı olarak farklı oranlarda artış göstermiştir. PP plastik atıkların katalitik pirolizinde, aktivasyon enerjisi 133.81 kJ/mol, YYPE plastik atıkların katalitik pirolizinde ise 171.98 kJ/mol olarak hesaplanmıştır. Bu sonuç, YYPE plastik atıkların piroliz koşullarının PP’e göre daha fazla endotermik olduğunu ve dolayısıyla daha fazla enerji gereksinimi olduğunu göstermektedir. Bu durum termodinamik büyüklüklerde de benzer sonuçlar göstermiş ve endotermik tepkime olan plastik atık pirolizinde entalpi değerleri bütün sıcaklıklarda pozitif çıkmıştır. Katalizör kullanımı ile her iki atık plastik için de entalpi değerlerinde kayda değer düşüşlerin olduğu görülmüştür.  Hesaplanan entropi ve serbest enerji değerlerine göre bu tepkimelerin istemli olmadığı değerlendirilmiştir.

Anahtar Kelimeler

• Piroliz
• Katalizör
• Plastik geri dönüşüm
• kinetik ve termodinamik analiz.

Kaynakça

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