Upgraded bio-oil production with catalytic co-pyrolysis of spruce sawdust

Abstract

This paper aimed to upgrade the bio-oils with the catalytic co-pyrolysis of spruce sawdust. A bubble-fluidized bed pyrolysis reactor was used in the experiments. The effects of the different mixing ratios of spruce sawdust with glycerol (10, 20, and 30 wt%), the usage of different catalysts (HZSM-5 and dolomite), and pyrolysis temperatures (400 °C, 450 °C, 500 °C, 550 °C and 600 °C) on the yields and quality of obtained bio-oils were examined. The experimental results revealed that the bio-oil yield improved with an additive of glycerol at all mixing ratios. The highest bio-oil yield (46.4 wt%) was received at a 20 wt% mixing ratio of glycerol and a pyrolysis temperature of 550 °C with a dolomite catalyst. The results of GC-MS indicated that the pyrolysis oil included a high proportion of ketones, phenols, and alcohols, which supported the potential of the catalytic co-pyrolysis of spruce sawdust with glycerol for bio-oil upgrading. The pyrolysis oil from spruce sawdust pyrolysis consisted of a ratio of 4.81% (GC-MS peak area) of unoxygenated hydrocarbons. Furthermore, the unoxygenated components were found to be 8.02% in the bio-oil produced by co-pyrolysis with glycerol. The number of unoxygenated hydrocarbons increased significantly during ex-situ catalytic co-pyrolysis. The unoxygenated hydrocarbons in the bio-oils produced by catalytic co-pyrolysis with HZSM-5 and dolomite were found to be 19.10% and 22.24%, respectively. The co-pyrolysis and catalytic co-pyrolysis results also revealed that the average carbon number of the compounds in the bio-oils depends on the chosen methods and catalysts. Using the catalyst in the reactor resulted in the formation of low-carbon number hydrocarbons. However, when used outside the reactor, the catalysts were observed to be more effective for deoxygenation.

Keywords

• Catalytic co-pyrolysis
• Biomass
• Glycerol
• HZSM-5
• Dolomite

Ladin talaşının katalitik kopiroliziyle geliştirilmiş biyo-yağ üretimi

Abstract

Bu makale, ladin talaşının katalitik ko-pirolizi ile biyo-yağların yükseltilmesini amaçlamaktadır. Deneylerde kabarcıklı akışkan yataklı piroliz reaktörü kullanılmıştır. Ladin talaşının gliserol ile farklı karıştırma oranlarının (%10, 20 ve 30 ağırlık), farklı katalizörlerin (HZSM-5 ve dolomit) kullanımının ve piroliz sıcaklıklarının (400 °C, 450 °C, 500 °C, 550 °C ve 600 °C) elde edilen biyo-yağların verimi ve kalitesi üzerindeki etkileri incelenmiştir. Deneysel sonuçlar, biyo-yağ veriminin tüm karıştırma oranlarında gliserol katkı maddesiyle arttığını ortaya koymuştur. En yüksek biyo-yağ verimi (%46.4 ağırlıkça), %20 gliserol karıştırma oranında ve dolomit katalizörüyle 550 oC'lik bir piroliz sıcaklığında elde edilmiştir. GC-MS sonuçları, piroliz yağının yüksek oranda keton, fenol ve alkol içerdiğini göstermiştir; bu da biyo-yağ iyileştirmesi için gliserol ile ladin talaşının katalitik eş-pirolizinin potansiyelini desteklemektedir. Ladin talaşı pirolizinden elde edilen piroliz yağı, %4.81 oranında (GC-MS pik alanı) oksijensiz hidrokarbonlardan oluşmuştur. Ayrıca, gliserol ile eş-pirolizle üretilen biyo-yağda oksijensiz bileşenlerin %8.02 olduğu bulunmuştur. Ex-situ katalitik eş-piroliz sırasında oksijensiz hidrokarbonların sayısı önemli ölçüde arttı. HZSM-5 ve dolomit ile katalitik eş-pirolizle üretilen biyo-yağlardaki oksijensiz hidrokarbonların sırasıyla %19.10 ve %22.24 olduğu bulundu. Eş-piroliz ve katalitik eş-piroliz sonuçları ayrıca biyo-yağlardaki bileşiklerin ortalama karbon sayısının seçilen yöntem ve katalizörlere bağlı olduğunu ortaya koydu. Reaktörde katalizörün kullanılması düşük karbon sayılı hidrokarbonların oluşumuyla sonuçlandı. Ancak katalizörlerin reaktör dışında kullanıldığında oksijensizleştirme için daha etkili olduğu görülmüştür.

Keywords

• Katalitik kopiroliz
• Biyokütle
• Gliserol
• HZSM-5
• Dolomit

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