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Exploring large pore size alumina and silica-alumina based catalysts for decomposition of lignin

1 Chemical Engineering Department, University of North Dakota, Grand Forks, ND, USA
2 Department of Chemistry, University of North Dakota, Grand Forks, ND, USA

Special Issue: Sustainable bioenergy and biomaterials from agri-food waste/lignocellulosic biomass

Evaluation of copper doped silica-alumina and γ-alumina catalysts for lignin decomposition was conducted using a suite of chemical analysis protocols that enabled a comprehensive characterization of the reaction product. X-ray diffraction analysis was used to verify the concentration of doped copper on catalyst supports. Then, batch experiments were performed to study the significance of catalyst support type, catalyst dopant concentration, lignin concentration, catalyst-to-lignin ratio, reactor stirring rate and reaction time. Aqueous products were extracted with dichloromethane and analyzed using a detailed gas chromatography-mass spectrophotometry analytical protocol, allowing for quantification of over 20 compounds. Solid residues were analyzed by thermogravimetric analysis and scanning electron microscopy. The highest yield of monomeric products from these screening experiments occurred with 5 wt% Cu on silica-alumina with a 1:1 w/w ratio of catalyst to lignin. A second set of experiments were conducted at these conditions to evaluate the effect of varying the reaction temperature between 300 and 350 ºC. Lower reaction temperatures (300 ºC) resulted in more unreacted lignin while higher temperatures (>350 ºC) led to an increased formation of liquid phase products, but also increased char formation. While the total amount of liquid phase products increased, the combined yield of monomer phenolic products was only 5–7 wt% of the liquid extracted product and statistically independent of temperature and other operational parameters, although the yields of different chemicals varied with temperature. Unlike most pyrolytic processes, the concentration of gas phase products gradually decreased with increasing reaction temperature and became negligible at 400 ºC, while the formation of coke increased with temperature. This seemingly contradictory result is likely due to increased product polymerization occurring at higher temperatures.
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References

1. Constant S, Wienk HLJ, Frissen AE, et al. (2016) New insights into the structure and composition of technical lignins: A comparative characterisation study. Green Chem 18: 2651–2665.    

2. Crestini C, Lange H, Sette M, et al. (2017) On the structure of softwood kraft lignin. Green Chem 19: 4104–4121.    

3. Deuss PJ, Lancefield CS, Narani A, et al. (2017) Phenolic acetals from lignins of varying compositions via iron(III) triflate catalyzed depolymerization. Green Chem 19: 2774–2782.    

4. Lancefield CS, Wienk HLJ, Boelens R, et al. (2018) Identification of a diagnostic structural motif reveals a new reaction intermediate and condensation pathway in kraft lignin formation. Chem Sci 9: 6348–6360.    

5. Hita I, Heeres HJ, Deuss PJ (2018) Insight into structure-reactivity relationships for the iron-catalyzed hydrotreatment of technical lignins. Bioresour Technol 267: 93–101.    

6. Xu C, Arancon R, Labidi J, et al. (2014) Lignin depolymerisation strategies: Towards valuable chemicals and fuels. Chem Soc Rev 43: 7485–7500.    

7. Asina F, Brzonova I, Kozliak E, et al. (2017) Microbial treatment of industrial lignin: Successes, problems and challenges. Renew Sust Energ Rev 77: 1179–1205.    

8. Kozliak E, Kubatova A, Artemyeva A, et al. (2016) Thermal liquefaction of lignin to aromatics: Efficiency, selectivity, and product analysis. ACS Sust Chem Eng 4: 5106–5122.    

9. Chang H, Allan G (1971) Oxidation, Lignins: Occurrence, formation and reactions. Wiley, 433–485.

10. Brebu M, Vasile C (2010) Thermal degradation of lignin-a review. Cellul Chem Technol 44: 353.

11. Jae J, Tompsett G, Foster A, et al. (2011) Investigation into the shape selectivity of zeolite catalysts for biomass conversion. J Catal 279: 257–268.    

12. Xie Z, Liu Z, Wang Y, et al. (2010) An overview of recent development in composite catalysts from porous materials for various reactions and processes. Int J Mol Sci 11: 2152–2187.    

13. Numan-Al-Mobin A, Voeller A, Bilek H, et al. (2016) Selective synthesis of phenolic compounds from alkali lignin in a mixture of sub-and supercritical fluids: Catalysis by CO2. Energ Fuel 30: 2137–2143.    

14. Yoshikawa T, Yagi T, Shinohara S, et al. (2013) Production of phenols from lignin via depolymerization and catalytic cracking. Fuel Process Technol 108: 69–75.    

15. Yu Y, Li X, Su L, et al. (2012) The role of shape selectivity in catalytic fast pyrolysis of lignin with zeolite catalysts. Appl Catal A 447–448: 115–123.

16. Zheng Y, Chen D, Zhu X (2013) Aromatic hydrocarbon production by the online catalytic cracking of lignin fast pyrolysis vapors using Mo2N/γ-Al2O3. J Anal Appl Pyrol 104: 514–520.    

17. Li X, Su L, Wang Y, et al. (2012) Catalytic fast pyrolysis of Kraft lignin with HZSM-5 zeolite for producing aromatic hydrocarbons. Front Environ Sci Eng 6: 295–303.    

18. Liguori L, Barth T (2011) Palladium-Nafion SAC-13 catalysed depolymerisation of lignin to phenols in formic acid and water. J Anal Appl Pyrol 92: 477–484.    

19. Nguyen T, Maschietti M, Belkheiri T, et al. (2014) Catalytic depolymerisation and conversion of Kraft lignin into liquid products using near-critical water. J Supercrit Fluid 86: 67–75.    

20. Joffres B, Lorentz C, Vidalie M, et al. (2014) Catalytic hydroconversion of a wheat straw soda lignin: Characterization of the products and the lignin residue. Appl Catal B 145: 167–176.    

21. Oasmaa A, Johansson A (1993) Catalytic hydrotreating of lignin with water-soluble molybdenum catalyst. Energ Fuel 7: 426–429.    

22. Yu Z, Li S, Wang Q, et al. (2011) Brønsted/lewis acid synergy in H–ZSM-5 and H–MOR zeolites studied by 1H and 27Al DQ-MAS solid-state NMR spectroscopy. J Phys Chem C 115: 22320–22327.    

23. Ennaert T, Van Aelst J, Dijkmans J, et al. (2016) Potential and challenges of zeolite chemistry in the catalytic conversion of biomass. Chem Soc Rev 45: 584–611.    

24. Wua Q, Maa L, Longb J, et al. (2016) Depolymerization of organosolv lignin over silica-alumina catalysts. Chin J Chem Phys 29: 474–480.    

25. Scherzer J, Gruia A (1996) Hydrocracking science and technology. CRC Press.

26. Hensen E, Poduval D, Degirmenci V, et al. (2012) Acidity characterization of amorphous silica-alumina. J Phys Chem C 116: 21416–21429.    

27. Van Borm R, Aerts A, Reyniers M, et al. (2010) Catalytic cracking of 2, 2, 4-trimethylpentane on FAU, MFI, and bimodal porous materials: Influence of acid properties and pore topology. Ind Eng Chem Res 49: 6815–6823.    

28. Yu Y, Li X, Su L, et al. (2012) The role of shape selectivity in catalytic fast pyrolysis of lignin with zeolite catalysts. Appl Catal A 447–448: 115–123.

29. Voeller K, Bilek H, Kreft J, et al. (2017) Thermal carbon analysis enabling comprehensive characterization of lignin and its degradation products. ACS Sust Chem Eng 5: 10334–10341.    

30. Pourjafar S (2017) An Investigation of the Thermal Degradation of Lignin. Doctoral dissertation, University of North Dakota, USA.

31. Wua Q, Maa L, Longb J, et al. (2016) Depolymerization of organosolv lignin over silica-alumina catalysts. Chin J Chem Phys 29: 474–480.    

© 2018 the Author(s), licensee AIMS Press. This is an open access article distributed under the terms of the Creative Commons Attribution Licese (http://creativecommons.org/licenses/by/4.0)

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