Synthesis of 5‐Hydroxymethylfurfural from Waste Biomass Feedstocks Using Carbon Solid Acid Catalyst

Öz

In this study biomass derived carbon solid acid catalyst (BH250S) was obtained by hydrothermal carbonization method from wheat straw, 5-HMF synthesis activity of the catalyst from waste biomass sources in optimum conditions was determined and compared with commercial catalyst (Amberlyst-15). Characterization of the catalyst was completed by elemental analysis, BET, SEM and XRD analysis. Corn straw, fluff and linter were used as waste biomass, microcrystalline cellulose was used as a model compound and conversion efficiency to 5-HMF was found to be higher than that of commercial catalyst for BH250S for corn straw, fluff and microcrystalline cellulose. The highest amount of 5-HMF per gram biomass was obtained from the conversion of model compound microcrystalline cellulose with BH250S catalyst was 14.2 mg while the value obtained from economically non-useful waste fluff was 12.5 mg. As a result of this study, waste lignocellulosic/cellulosic biomass materials with low economic value were evaluated and 5-HMF was obtained by a eco-friendly, sustainable and cheap catalytic method.

Anahtar Kelimeler

• Biomass,Carbon solid acid catalyst,5-Hydroxymethylfurfural

Karbon Katı Asit Katalizör ile Atık Biyokütle Kaynaklarından 5-Hidroksimetilfurfural Eldesi

Öz

Bu çalışmada, buğday samanı biyokütlesinden hidrotermal karbonizasyon yöntemi ile biyokütle türevli karbon katı asit katalizör (BH250S) elde edilmiş, katalizörün atık biyokütle kaynaklarından 5-Hidroksimetilfurfural (5-HMF) sentezi aktivitesi belirlenen optiumum koşullarda sulu reaksiyon ortamında ticari katalizör (Amberlyst-15) ile kıyaslanmıştır. Katalizörün karakterizasyon çalışması elemental analiz, BET, SEM ve XRD analizleri yapılarak tamamlanmıştır. Atık biyokütle olarak mısır samanı, hav, linter, model bileşik olarak ise mikrokristalin selüloz kullanılmış, 5-HMF’ye dönüşüm verimleri kıyaslandığında mısır samanı, hav ve mikrokristalin selüloz için BH250S katalizörünün aktivitesinin ticari katalizörden daha yüksek olduğu gözlenmiştir. Gram biyokütle başına en yüksek 5-HMF miktarı 14,2 mg olarak BH250S katalizörü ile model bileşik mikrokristalin selülozun dönüşümünden elde edilirken, ekonomik değeri olmayan atık biyokütle havdan elde edilen değer 12,5 mg’ dır. Çalışma sonucunda ekonomik değeri düşük atık lignoselülozik/selülozik biyokütle materyalleri değerlendirilmiş, çevreye dost, sürdürülebilir ve ucuz katalitik yolla 5-HMF eldesi sağlanmıştır.

Anahtar Kelimeler

• Biyokütle,Karbon katı asit katalizör,5-Hidroksimetilfurfural

Kaynakça

1. [1] Mukherjee, A., Dumont, M-J., Raghavan, V. 2015. Review: Sustainable production of hydroxymethylfurfural and levulinic acid: Challenges and opportunities. Biomass and Bioenergy, 72, 143-183.
2. [2] Dutta, S., De, S., Alam, M., Abu-Omar, M. M., Saha, B., 2012. Direct conversion of cellulose and lignocellulosic biomass into chemicalsand biofuel with metal chloride catalysts. Journal of Catalysis, 288, 8-15.
3. [3] Rathod, P. V. and Jadhav V. H., 2018. Efficient Method for Synthesis of 2,5-Furandicarboxylic Acid from 5-Hydroxymethylfurfural and Fructose Using Pd/CC Catalyst under Aqueous Conditions. ACS Sustainable Chemistry and Engineering, 6, 5766−5771.
4. [4] Chang, C., Xu, G., Jiang, X., 2012. Production of ethyl levulinate by direct conversion of wheat straw in ethanol media. Bioresource Technology, 121, 93-99.
5. [5] Dutta, S., Yu, I. K. M., Tsang, D. C. W., Ng, Y. H., Ok, Y. S., Sherwood, J., Clark, J. H., 2019. Green synthesis of gamma-valerolactone (GVL) through hydrogenation of biomass-derived levulinic acid using non-noble metal catalysts: A critical review. Chemical Engineering Journal, 372, 992-1006.
6. [6] Fukuhara, K., Nakajima, K., Kitano, M., Kato, H., Hayashi, S., Hara, M. 2011. Structure and catalysis of cellulose-derived amorphous carbon bearing SO3H groups. Chemsuschem, 4:778–784.
7. [7] Hara, M. 2010. Biomass conversion by a solid acid catalyst. Energy & Environmental Science, 3:601–607.
8. [8] Uskan, B. 2009. Odun Talaşının Hidrotermal Dönüşümünden Elde Edilen Kimyasalların Karakterizasyonu. Ankara Üniversitesi, Fen Bilimleri Enstitüsü, Yüksek Lisans Tezi, 109s, Ankara.

9. [9] ASTM, 2009. Standard Test Method for Determination of Acid-Insoluble Residue in Biomass, Pennsylvania United States: ASTM
10. [10] Foyle, T., Jennıngs, L., Mulcahy, P. 2007. Compositional analysis of lignocellulosic materials: Evaluation of methods used for sugar analysis of waste paper and straw. Bioresource Technology, 98, 3026-3036.
11. [11] Sun, R. C., Tomkınson, J. 2002. Characterizations of hemicelluloses obtained by classical and ultrasonically assisted extractions from wheat straw. Carbohydrate Polymers, 50, 263-271.
12. [12] Gan, L., Zhu, J., Lv, L. 2017. Cellulose hydrolysis catalyzed by highly acidic ligninderived carbonaceous catalyst synthesized via hydrothermal carbonization. Cellulose, 24, 5327-5339.
13. [13] Suganuma, S., Nakajima, K., Kitano, M., Yamaguchi, D., Kato, H., Hayashi, S., Hara, M. 2008. Hydrolysis of Cellulose by Amorphous Carbon Bearing SO3H, COOH, and OH Groups. Journal of American Chemical Society, 130, 12787-12793.
14. [14] Wu, Y., Fu, Z.,Yin, D., Xu, Q., Liu, F., Lu, C., Mao, L. 2010. Microwave-assisted hydrolysis of crystalline cellulose catalyzed by biomass Char sulfonic acids. Green Chemistry,12, 696–700.
15. [15] Irmak, S., Meryemoglu, B., Sandip, A., Subbiah, J., Mitchell, R. B., Sarath, G. 2018. Microwave pretreatment effects on switchgrass and miscanthussolubilization in subcritical water and hydrolysate utilization for hydrogen production. Biomass and Bioenergy, 108, 48-54.
16. [16] Huang Y-B. ve Fu Y. 2013. Hydrolysis of cellulose to glucose by solid acid catalysts. Green Chemistry, 15, 1095-1111.
17. [17] Yan, L., Liu, N., Wang, Y., Machida, H., & Qi, X. 2014. Production of 5-hydroxymethylfurfural from corn stalk catalyzed by corn stalk-derived carbonaceous solid acid catalyst. Bioresource Technology, 173, 462-466.