Hydrothermal Treatment of Cellulose in Hot-Pressurized Water for the Production of Levulinic Acid

Abstract

In this paper, hot-pressurized water, operating above boiling point and below critical point of water (374. 15 °C and 22.1 MPa), was used as a reaction medium for the decomposition of cellulose to high-value chemicals, such levulinic acid. Effects of reaction temperature, pressure, time, external oxidant type and concentration on the cellulose degradation and product distribution were evaluated. In order to compare the cellulose decomposition and yields of levulinic acid, experiments were performed with and without addition of oxidizing agents (H₂SO₄ and H₂O₂). Analysis of the liqueur was monitored by HPLC and GC-MS at different temperatures (150 - 280 °C), pressures (5-64 bars) and reaction times (30 - 120 mins). Levulinic acid, 5-HMF and formic acid were detected as main products. 73% cellulose conversion was achieved with 38% levulinic acid yield when 125 mM of sulfuric acid was added to the reaction medium at 200 °C for 60 min reaction time. 

Keywords

• Cellulose,levulinic acid,5-HMF,hot-pressurized water

LEVULİNİK ASİT ÜRETİMİ İÇİN SELÜLOZUN SICAK-BASINÇLI SUDA HİDROTERMAL MUAMELESİ

Abstract

Bu makalede selülozu değerli kimyasallara, özellikle levulinik asite, parçalamak amacı ile suyun kaynama noktası üzerinde ve kritik noktası altında (374. 15 °C ve 22.1 MPa) çalışılan sıcak-basınçlı su, reaksiyon ortamı olarak kullanılmıştır. Reaksiyon sıcaklığı, basıncı, süresi, oksitleme ajanı çeşidi ve miktarının selülozun parçalanmasına ve ürün dağılımına olan etkileri incelenmiştir. Selüloz bozunma yüzdesi ve levulinik asit oluşum verimini kıyaslamak amacı ile deneyler hem oksitleme ajanı (H₂SO₄ ve H₂O₂) kullanarak, hem de kullanmayarak gerçekleştirilmiştir. Farklı sıcaklık (150 - 280 °C), basınç  (5-64 bar) ve tepkime sürelerinde (30 - 120 dk.) oluşan likit ürünlerin analizleri HPLC ve GC-MS ile gerçekleştirilmiştir. Ana sıvı ürünler olarak levulinik asit, 5-HMF ve formik asit tespit edilmiştir. 125 mM sülfürik asit eklenerek 200 °C sıcaklıkta ve 60 dk boyunca gerçekleştirilen tepkime sonucunda, %73 selüloz bozunmuş ve %38 verimle levulinik asit elde edilmiştir.

Keywords

• Selüloz,levulinik asit,5-HMF,sıcak-basınçlı su

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