Solvolysis of Technical Lignin in Water and Alcohol Solutions of Sodium Hydroxide

Complete text of the article:

Download article (pdf, 0.6MB )

UDС

547.992.3

DOI:

10.17238/issn0536-1036.2015.3.123

Abstract

Hydrolysis lignin represents particular interest as a promising feedstock for the production of aromatic compounds for further organic synthesis. One of the lignin depolymerisation methods is its degradation with bases under appropriate conditions. This work is devoted to research the solvolysis of hydrolysis lignin in sodium hydroxide solution in different condi-tions. For research hydrolysis lignin was taken from Kirov Biochemical Plant. Air-dried lignin was sieved (~0.25 mm) and was grinded by a rotary-vortex mill (~5mkm). The influ-ence of solvolysis conditions of technical hydrolysis lignin on the degradation extent was defined: alkali concentration (2-10%), duration of treatments (0,5-2,5h), hydromodule (1:10?1:25), temperature (100-240°С) in aqueous and alcoholic solutions. To estimate the depth of lignin fragmentation degree in aqueous and alcohol environments lignin degrada-tion products were analyzed by size-exclusion chromatography. The results showed that with increasing of treatment temperature increases content of low molecular weight com-pounds (oligomers). For structural changing determination of lignin samples during solvoly-sis process lignin degradation products were analyzed by solid state 13С nuclear magnetic resonance. Quantitative ratio of «СAr-O», «СAr-C», «СAr-H» clusters in initial hydrolysis lignin and lignin degradation products were defined in treatments at 200°C and 220°C. Amount increasing of carbon-carbon bonds in lignin with the increasing treatments temperature was shown. The studies found that most degree of hydrolysis lignin destruction achieved by us ing the following conditions: 5% NaOH, with a 2h treatments time, hydromodule 1?20. Increasing of degradation degree was shown in the temperature range 180-240°C, the dissolution degree of lignin reached to 99%. In these conditions the degradation process of studied lignin samples was faster with an alcohol solution of sodium hydroxide comparatively with an aqueous solution.

Authors

E.V. Ipatova1, Postgraduate Student S.M. Krutov1, Candidate of Chemistry, Professor I.V. Gribkov2, Candidate of Chemistry, Director Iu.N. Sazanov3, Doctor of Chemistry, Professor

Affiliation

per., 5, Saint-Petersburg, 194021, Russia; e-mail: ftaorgchem@yandex.ru  2GCE Ecology, Bukharestskaya, 6, Saint-Petersburg, 192102, Russia;  e-mail: ivan.gribkov@gmail.com 3Institute of Macromolecular Compounds of Russian Academy of Sciences, Bol'shoy pr., 31, Saint-Petersburg, 199004, Russia; e-mail: sazanov@hq.macro.ru

Keywords

hydrolysis lignin, lignin degradation

References

1. Andreev A.I., Selyanina S.B., Bogdanovich N.I. Sorbtsionnye svoystva listven-nykh i khvoynykh sul'fatnykh ligninov [Sorption Properties of Hardwood and Softwood Sulfate Lignins]. Khimiya rastitel'nogo syr'ya, 2012, no. 2, pp. 33–39. 2. Gribkov I.V., Krutov S.M., Zarubin M.Ya. Izuchenie stroeniya i svoystv promysh-lennykh gidroliznykh ligninov [The Structure and Properties of Industrial Hydrolysis Lig-nin]. Izvestiya SPbGLTA, 2007, no. 179, pp. 201–210. 3. Grushnikov O.P., Elkin V.V. Dostizheniya i problemy khimii lignina [Achieve-ments and Problems in Lignin Chemistry]. Moscow, 1973. 296 p. 4. Domburg G.E. Perspektivy pirogeneticheskoy pererabotki gidroliznogo lignina [Perspectives of Hydrolysis Lignin Pyrogenetic Processing]. Perspektivy ispol'zovaniya drevesiny v kachestve organicheskogo syr'ya [Perspectives of Wood Using as Organic Feed-stock]. Riga, 1982, pp. 134–151. 5. Evstigneev E.I. Okislenie gidroliznogo lignina peroksidom vodoroda v kisloy srede [Hydrolysis Lignin Oxidation with Hydrogen Peroxide in an Acidic Environment]. Zhurnal prikladnoy khimii, 2013, vol. 86, no. 2, pp. 278–285. 6. Zarubin M.Ya., Krutov S.M. Issledovanie tekhnicheskogo gidroliznogo lignina i produktov ego shchelochnoy destruktsii [Research of Technical Hydrolysis Lignin and Its Alkaline Destruction Products]. Izvestiia SPbGLTA, 2003, no. 179, pp. 222–228. 7. Kiryushina M.F., Fedulina T.G., Zarubin M.Ya. Kinetika shchelochnoy destruktsii preparatov lignina i lignin-uglevodnogo kompleksa v vodnykh rastvorakh vysokoosnovnykh organicheskikh rastvoriteley [The Kinetics of Alkaline Degradation Products of Lignin and Lignin-Carbohydrate Complex in Aqueous Solutions of Highly Basic Organic Solvents]. Khimiya rastitel'nogo syr'ya, 2009, no. 1, pp. 145–146. 8. Kovaleva V.V. Okislitel'naya destruktsiya lignina i lignotsellyuloznykh materialov pod deystviem ozona: diss. kand. khim. nauk [Oxidative Degradation of Lignin and Ligno-cellulose Materials in the Ozone Medium: Cand.Chem.Sci.Diss.]. Moscow, 2000. 150 p. 9. Krutov S.M., Zarubin M.Ia., Sazanov Iu.N. Ligniny [Lignins]. Saint-Petersburg, 2011. 381 p. 10. Kulikov K.V., Litvinov V.V., Piyalkin, V.N., Zabelkin S.A., Bashkirov V.N. Poluchenie i issledovanie zhidkikh biotopliv iz biomassy dereva metodom piroliza [Prepara-tion and Investigation of Liquid Biofuels from Biomass by Pyrolysis of Wood]. Vestnik Ka-zanskogo tekhnologicheskogo universiteta, 2012, no. 13, pp. 197–201. 11. Lakhmanov D.E., Habarov Yu.G., Popov V.A. Izuchenie depolimerizatsii gidroliznogo lignina azotnoy kislotoy v vodno-spirtovoy srede [The Study of Hydrolysis Lignin Depolymerization of Nitric Acid in an Aqueous-Alcoholic sphere]. Materialy V mezhdunarodnoy konferentsii «Fizikokhimiya rastitel'nykh polimerov [Physics and Chemis-try of Bioorganic Polymers: Proc.V’th Int.Conf.]. 2013, pp. 145–146. 12. Sazanov Yu.N. Potentsial'naya aktivnost' gidroliznogo lignina v reaktsiyakh sopolimerizatsii [Potential Activity of Hydrolysis Lignin in Copolymerization Reactions]. Zhurnal prikladnoy khimii, 2009, vol. 82, no. 9, pp. 1493–1499. 13. Sumerskiy I.V., Krutov S.M., Pranovich A.V., Zarubin M.Ia. Issledovanie gidroliznykh ligninov metodom DFRC [Investigation of Hydrolyzed Lignin by Method of DFRC ]. Lesnoy zhurnal, 2010, no. 2, pp. 141–146. 14. Chudakov M.I. Promyshlennoe ispol'zovanie lignina [Industrial Use of Lignin]. Moscow,1983. 127 p. 15. Hatakeyama H, Tsujimoto Y., Zarubin M.Ja., Krutov S.M. Thermal decomposi-tion and glass transition of industrial hydrolysis lignin. J. Therm. Anal. Calorim., 2010, 101, pp. 289–295. 16. Ipatova E.V., Evtuguin D.V., Krutov S.M., Santos S.A.O., Sazanov Yu.N. Modi-fication of hydrolysis lignin for valuable applications. Proceedings of 13 EWLP, 2014, pp. 431–434. 17. Matsumoto Y., Ishizu A., Nakano J. Studies on chemical structure of lignin by ozonation. Holzforschung, 1986, vol. 40, pp. 81–85. 18. Mu W., Ben H., Ragauskas A., Deng Y. Lignin Pyrolysis Components and Up-grading–Technology Review. BioEnergy Research. Springer US, 2013, vol. 6, iss. 4, pp. 1183–1204. 19. Navarro D., Couturier M. gaSilva G.G.D., Berrin J.G., Rouan X., Asther M., Bignon C. Automated assay for screening the enzymatic release of reducing sugars from micronized biomass. Microbial Cell Factories, 2010, no. 9, pp. 58–60. 20. Nenkova S., Vasileva T., Stanulov K. Production of phenol compounds by alka-line treatment of technical hydrolysis lignin and wood biomass. Chemistry of Natural Com-pounds, 2008, vol. 44, iss. 2. 182 p. 21. Ponomarev A.V., Kholodkova E.M., Metreveli A.K. Phase distribution of prod-ucts of radiation and post-radiation distillation of biopolymers: Cellulose, lignin and chitin. Radiation Physics and Chemistry, 2011, no. 80(11), pp. 1186–1194. 22. Toledano A., Serrano L., Labidi J. Organosolv lignin depolymerization with dif-ferent base catalysts. Journal of Chemical Technology and Biotechnology, 2012, vol. 87, pp. 1593–1599. 23. Yuan Z., Cheng S., Leitch M., Xu C. Hydrolytic degradation of alkaline lignin in hot-compressed water and ethanol. Bioresour.Technol, 2010, 101(23), pp. 9308–9313.