Process optimization of lignin conversion into value added chemicals by
          thermochemical pretreatment and electrooxidation on a stainless steel
          anode

Sandeep Singh; Himadri Roy Ghatak

doi:10.1515/hf-2017-0108

Article

Process optimization of lignin conversion into value added chemicals by thermochemical pretreatment and electrooxidation on a stainless steel anode

Sandeep Singh and Himadri Roy Ghatak

Published/Copyright: November 2, 2017

Published by

Become an author with De Gruyter Brill

Submit Manuscript Author Information

From the journal Holzforschung Volume 72 Issue 3

Abstract

Wheat straw soda lignin was subjected to thermochemical (TC) pretreatment at low to moderate temperatures followed by electrooxidation (EO) on an SS-304 anode to produce some value-added organic chemicals. The influence of independent process variables on the product yield of major organic chemical groups, namely, aromatic carbonyl compounds (CO_arom), aromatic hydrocarbons (HC_arom), and aliphatic hydrocarbons (HC_aliph), was studied. Response surface methodology (RSM) was used to optimize the process conditions for maximizing the amount of chemical production according to the Box-Behnken experimental design (BBD). For CO_arom, the optimal conditions were 2 h TC pretreatment at 200°C followed by 12 h of EO at 2.24 mA cm⁻² current density to yield 24.7% of desired products. The optimized synthesis conditions for HC_arom are 2 h TC treatment at 200°C yielding 16.1% desired products. As individual compounds, vanillin, acetosyringone, syringaldehyde, acetovanillone, o-xylene and toluene were significantly produced in different product groups. A small amount of organosilicon compounds (ORG_Si) and HC_aliph was also produced.

Keywords: Box-Behnken experimental design (BBD); electrooxidation; response surface optimization; thermochemical pretreatment; value added chemicals; wheat straw soda lignin

Acknowledgment

This work was supported by Extramural Research grant no. 02(0135)/13/EMR-II, from the Council of Scientific and Industrial Research, Government of India.

Author contributions: All the authors have accepted responsibility for the entire content of this submitted manuscript and approved submission.
Research funding: None declared.
Employment or leadership: None declared.
Honorarium: None declared.

Appendix A: The optimized regression equation for different compounds synthesized in terms of coded factors

Aromatic carbonyl compounds:

(1)Amount (mg)=1769.78–38.92*A–5863.34*B+859.30*C +12.56*D –71.08*D2–67.73*A*B –2997.35*B*C

Vanillin:

(2)Amount (mg)=24.84+9.87*A+0.016*B+4.55*C+0.38*D–1.86*D2+2.15*A*B+5.69*A*C

Acetosyringone:

(3)Amount (mg)=14957.78–1.50*A–325.53*B+15256.57*C+0.47*D+2.12*B2+3890.75*C2–2.62*D2–2.68*A*B–166.28*B*C

Aromatic hydrocarbons:

(4)Amount (mg)=114463.6–1606.02*B+117110.7*C+475.15*D+10.91*B2+29955.59*C2–825.47*B*C+247.93*C*D

Aliphatic hydrocarbons:

(5)Amount (mg)=4249.62–112.59*B+4352.92*C–44.90*D+0.41*B2+114.66*C2–57.55*B*C–23.05*C*D

where A, furnace temperature (°C); B, time in furnace (h); C, current density (mA/cm²); and D, electrooxidation time (h).

Appendix B: GC/MS under optimized conditions

Appendix B:

GC/MS chromatograms under optimized conditions for (a) aromatic carbonyl compounds, (b) vanillin, (c) acetosyringone, (d) aromatic hydrocarbons and (e) aliphatic hydrocarbons.

References

Aleboyeh, A., Daneshvar, N., Kasiri, M.B. (2008) Optimization of CI Acid Red 14 azo dye removal by electrocoagulation batch process with response surface methodology. Chem. Eng. Process. Process Intensif. 47:827–832.10.1016/j.cep.2007.01.033Search in Google Scholar

Anglès, M.N., Reguant, J., Garcia-Valls, R., Salvadó, J. (2003) Characteristics of lignin obtained from steam-exploded softwood with soda/anthraquinone pulping. Wood Sci. Technol. 37:309–320.10.1007/s00226-003-0183-7Search in Google Scholar

Araújo, J.D., Grande, C.A., Rodrigues, A.E. (2010) Vanillin production from lignin oxidation in a batch reactor. Chem. Eng. Res. Des. 88:1024–1032.10.1016/j.cherd.2010.01.021Search in Google Scholar

Baker, C.J., Mock, N.M., Whitaker, B.D., Roberts, D.P., Rice, C.P., Deahl, K.L., Averyanov, A.A. (2005) Involvement of acetosyringone in plant–pathogen recognition. Biochem. Biophy. Res. Commun. 328:130–136.10.1016/j.bbrc.2004.12.153Search in Google Scholar PubMed

Canetti, M., Bertini, F. (2007) Supermolecular structure and thermal properties of poly (ethylene terephthalate)/lignin composites. Composites Sci. Technol. 67:3151–3157.10.1016/j.compscitech.2007.04.013Search in Google Scholar

Costa, C.A.E., Pinto, P.C.R., Rodrigues, A.E. (2015) Radar tool for lignin classification on the perspective of its valorization. Ind. Eng. Chem. Res. 54:7580–7590.10.1021/acs.iecr.5b01859Search in Google Scholar

da Silva, E.B., Zabkova, M., Araújo, J.D., Cateto, C.A., Barreiro, M.F., Belgacem, M.N., Rodrigues, A.E. (2009) An integrated process to produce vanillin and lignin-based polyurethanes from Kraft lignin. Chem. Eng. Res. Design. 87:1276–1292.10.1016/j.cherd.2009.05.008Search in Google Scholar

Deng, H. (2013) Method for preparing syringaldehyde by oxidative degradation of lignin. CN Patent 102146025 B.Search in Google Scholar

Elfadly, A.M., Zeid, I.F., Yehia, F.Z., Abouelela, M.M., Rabie, A.M. (2017) Production of aromatic hydrocarbons from catalytic pyrolysis of lignin over acid-activated bentonite clay. Fuel Proc. Technol. 163:1–7.10.1016/j.fuproc.2017.03.033Search in Google Scholar

Fierro, V., Torné-Fernández, V., Celzard, A. (2006) Kraft lignin as a precursor for microporous activated carbons prepared by impregnation with ortho-phosphoric acid: synthesis and textural characterisation. Microporous Mesoporous Mater. 92:243–250.10.1016/j.micromeso.2006.01.013Search in Google Scholar

Ghatak, H.R. (2008) Spectroscopic comparison of lignin separated by electrolysis and acid precipitation of wheat straw soda black liquor. Ind. Crops Prod. 28:206–212.10.1016/j.indcrop.2008.02.011Search in Google Scholar

Ghatak, H.R. (2011) Biorefineries from the perspective of sustainability: feedstocks, products, and processes. Ren. Sust. En. Rev. 15:4042–4052.10.1016/j.rser.2011.07.034Search in Google Scholar

Güven, G., Perendeci, A., Tanyolac, A. (2009) Electrochemical treatment of simulated beet sugar factory wastewater. Chem. Eng. J. 151:149–159.10.1016/j.cej.2009.02.008Search in Google Scholar

Hayashi, J.I., Muroyama, K., Gomes, V.G., Watkinson, A.P. (2002) Fractal dimensions of activated carbons prepared from lignin by chemical activation. Carbon 40:630–632.10.1016/S0008-6223(02)00017-9Search in Google Scholar

Heald, S., Myers, S., Walford, T., Robbins, K., Hill, C. (2013) Preparation of vanillin from microbial transformation media by extraction by means of supercritical fluids or gases. U.S. Patent 8563292 B2.Search in Google Scholar

Hinkelmann, K., Kempthorne, O. Design and Analysis of Experiments, Volume 3, Special Designs and Applications. Wiley, New York, 2012.10.1002/9781118147634Search in Google Scholar

Huang, M., Luo, J., Fang, Z., Li, H. (2016) Biodiesel production catalyzed by highly acidic carbonaceous catalysts synthesized via carbonizing lignin in sub-and super-critical ethanol. Appl. Catal. B Environ. 190:103–114.10.1016/j.apcatb.2016.02.069Search in Google Scholar

Ibrahim, M.N.M., Balakrishnan, R.S., Shamsudeen, S., Bahwani, S.A., Adam, F. (2012) A concise review of the natural existence, synthesis, properties, and applications of syringaldehyde. BioResources 7:4377–4399.Search in Google Scholar

International Energy Agency (2013) Biorefineries: adding value to the sustainable utilisation of biomass. http://www.ieabioenergy.com/wp-content/uploads/2013/10/Task-42-Booklet.pdf. last accessed on 15 May, 2017.Search in Google Scholar

Joffres, B., Lorentz, C., Vidalie, M., Laurenti, D., Quoineaud, A.A., Charon, N., Daudin, A., Quignard, A., Geantet, C. (2014) Catalytic hydroconversion of a wheat straw soda lignin: characterization of the products and the lignin residue. Appl. Catal. B Environ. 145:167–176.10.1016/j.apcatb.2013.01.039Search in Google Scholar

Joffres, B., Nguyen, M.T., Laurenti, D., Lorentz, C., Souchon, V., Charon, N., Daudin, A., Quignard, A., Geantet, C. (2016) Lignin hydroconversion on MoS 2-based supported catalyst: comprehensive analysis of products and reaction scheme. Appl. Catal. B Environ. 184:153–162.10.1016/j.apcatb.2015.11.005Search in Google Scholar

Kadla, J.F., Kubo, S., Venditti, R.A., Gilbert, R.D., Compere, A.L., Griffith, W. (2002) Lignin-based carbon fibers for composite fiber applications. Carbon 40:2913–2920.10.1016/S0008-6223(02)00248-8Search in Google Scholar

Kagawa, S. (1970) Studies on the utilization of alkali lignin (part 2). Japan Tappi J. 24:424–428.10.2524/jtappij.24.8_424Search in Google Scholar

Kagawa, S., Rokugawa, M. (1971) Studies on the utilization of alkali lignin (part 3). Japan Tappi J. 25:506–511.10.2524/jtappij.25.10_506Search in Google Scholar

Kobya, M., Demirbas, E., Gebologlu, U., Oncel, M.S., Yildirim, Y. (2013) Optimization of arsenic removal from drinking water by electrocoagulation batch process using response surface methodology. Desalin. Water Treat. 51:6676–6687.10.1080/19443994.2013.769700Search in Google Scholar

Körbahti, B.K. (2007) Response surface optimization of electrochemical treatment of textile dye wastewater. J. Hazard. Mater. 145:277–286.10.1016/j.jhazmat.2006.11.031Search in Google Scholar

Liu, Y., Liu, C., Wu, Y., Li, Y., Chen, C., Zheng, X., Wei, G. (2010) Carbon dioxide supercritical extraction method for vanillic aldehyde or ethyl vanillin raw product. CN Patent 101386570A.Search in Google Scholar

Mathias, A.L., Rodrigues, A.E. (1995) Production of vanillin by oxidation of pine kraft lignins with oxygen. Holzforschung 49:273–278.10.1515/hfsg.1995.49.3.273Search in Google Scholar

Mota, M.I.F., Pinto, P.C.R, Loureiro, J.M., Rodrigues, A.E. (2016a) Recovery of vanillin and syringaldehyde from lignin oxidation: a review of separation and purification processes. Sep. Purif. Rev. 45:227–259.10.1080/15422119.2015.1070178Search in Google Scholar

Mota, M.I.F., Pinto, P.C.R., Loureiro, J.M., Rodrigues, A.E. (2016b) Successful recovery and concentration of vanillin and syringaldehyde onto a polymeric adsorbent with ethanol/water solution. Chem. Eng. J. 294:73–82.10.1016/j.cej.2016.02.101Search in Google Scholar

Movil-Cabrera, O., Rodriguez-Silva, A., Arroyo-Torres, C., Staser, J.A. (2016) Electrochemical conversion of lignin to useful chemicals. Biomass Bioen. 88:89–96.10.1016/j.biombioe.2016.03.014Search in Google Scholar

Pinto, P.C.R., Costa, C.E., Rodrigues, A.E. (2013) Oxidation of lignin from eucalyptus globulus pulping liquors to produce syringaldehyde and vanillin. Ind. Eng. Chem. Res. 52:4421–4428.10.1021/ie303349jSearch in Google Scholar

Pouteau, C., Dole, P., Cathala, B., Averous, L., Boquillon, N. (2003) Antioxidant properties of lignin in polypropylene. Polymer Deg. Stab. 81:9–18.10.1016/S0141-3910(03)00057-0Search in Google Scholar

Pucciariello, R., Villani, V., Bonini, C., D’Auria, M., Vetere, T. (2004) Physical properties of straw lignin-based polymer blends. Polymer 45:4159–4169.10.1016/j.polymer.2004.03.098Search in Google Scholar

Rajkumar, K., Muthukumar, M. (2012) Optimization of electro-oxidation process for the treatment of Reactive Orange 107 using response surface methodology. Environ. Sci. Poll. Res. 19:148–160.10.1007/s11356-011-0532-2Search in Google Scholar PubMed

Sales, F.G., Abreu, C.A.M., Pereira, J.A.F.R. (2004) Catalytic wet-air oxidation of lignin in a three-phase reactor with aromatic aldehyde production. Brazilian J. Chem. Eng. 21:211–218.10.1590/S0104-66322004000200010Search in Google Scholar

Sannami, Y., Kamitakahara, H., Takano, T. (2017) TEMPO-mediated electro-oxidation reactions of non-phenolic β-O-4-type lignin model compounds. Holzforschung 71:109–117.10.1515/hf-2016-0117Search in Google Scholar

Schmitt, D., Regenbrecht, C., Hartmer, M., Stecker, F., Waldvogel, S.R. (2015) Highly selective generation of vanillin by anodic degradation of lignin: a combined approach of electrochemistry and product isolation by adsorption. Beilstein J. Org. Chem. 11:473–480.10.3762/bjoc.11.53Search in Google Scholar PubMed PubMed Central

Schmitt, D., Regenbrecht, C., Schubert, M., Schollmeyer, D., Waldvogel, S.R. (2017) Treatment of black liquors (BL) by adsorption on AE resins and a subsequent electrochemical degradation of BL to obtain vanillin. Holzforschung 71:35–41.10.1515/hf-2015-0210Search in Google Scholar

Shiraishi, T., Takano, T., Kamitakahara, H., Nakatsubo, F. (2012a) Studies on electrooxidation of lignin and lignin model compounds. Part 1: direct electrooxidation of non-phenolic lignin model compounds. Holzforschung 66:303–309.10.1515/hf.2011.069Search in Google Scholar

Shiraishi, T., Takano, T., Kamitakahara, H., Nakatsubo, F. (2012b) Studies on electro-oxidation of lignin and lignin model compounds. Part 2: N-hydroxyphthalimide (NHPI)-mediated indirect electro-oxidation of non-phenolic lignin model compounds. Holzforschung 66:311–315.10.1515/hf.2011.140Search in Google Scholar

Sikarwar, V.S., Zhao, M., Clough, P., Yao, J., Zhong, X., Memon, M.Z., Shah, N., Anthony, E.J., Fennell, P.S. (2016) An overview of advances in biomass gasification. Energy Environ. Sci. 9:2939–2977.10.1039/C6EE00935BSearch in Google Scholar

Singh, S., Ghatak, H.R. (2017) Vanillin formation by electrooxidation of lignin on stainless steel anode: kinetics and by-products. J. Wood Chem. Technol. 37:407–422.10.1080/02773813.2017.1310899Search in Google Scholar

Staser, J.A., Movil-Cabrera, O. (2017) Electrochemical conversion of lignin to industrial chemicals. International Patent No. WO/2017/024220 A1.Search in Google Scholar

Stecker, F., Malkowsky, I.M., Fischer, A., Waldvogel, S.R., Regenbrecht, C. (2014a) Method for producing vanillin by electrochemical oxidation of aqueous lignin solutions or suspensions. US Patent No. 8,808,781 B2.Search in Google Scholar

Stecker, F., Fischer, A., Kirste, A., Voitl, A., Wong, C.H., Waldvogel, S., Regenbrecht, C., Schmitt, D., Hartmer, M.F. (2014b) Method for obtaining vanillin from aqueous basic compositions containing vanillin. WO Patent 2014006108 A1.Search in Google Scholar

Stefanidis, S.D., Karakoulia, S.A., Kalogiannis, K.G., Iliopoulou, E.F., Delimitis, A., Yiannoulakis, H., Zampetakis, T., Lappas, A.A., Triantafyllidis, K.S. (2016) Natural magnesium oxide (MgO) catalysts: A cost-effective sustainable alternative to acid zeolites for the in situ upgrading of biomass fast pyrolysis oil. Appl. Catal. B Environ. 196:155–173.10.1016/j.apcatb.2016.05.031Search in Google Scholar

Suparno, O., Covington, A.D., Phillips, P.S., Evans, C.S. (2005) An innovative new application for waste phenolic compounds: Use of Kraft lignin and naphthols in leather tanning. Resour. Conserv. Recyc. 45:114–127.10.1016/j.resconrec.2005.02.005Search in Google Scholar

Tagwireyi, D., Majinda, R.R. (2017) Isolation and identification of acetovanillone from an extract of Boophone disticha (Lf) herb (Amaryllidaceae). South African J. Botany 108:100–101.10.1016/j.sajb.2016.10.012Search in Google Scholar

Tejado, A., Pena, C., Labidi, J., Echeverria, J.M., Mondragon, I. (2007) Physico-chemical characterization of lignins from different sources for use in phenol-formaldehyde resin synthesis. Bioresource Technol. 98:1655–1663.10.1016/j.biortech.2006.05.042Search in Google Scholar

Tir, M., Moulai-Mostefa, N. (2008) Optimization of oil removal from oily wastewater by electrocoagulation using response surface method. J. Hazard. Mater. 158:107–115.10.1016/j.jhazmat.2008.01.051Search in Google Scholar

Vibert, M., Cochennec, C., Etchebarne, A. (2013) Method for purifying vanillin by liquid-liquid extraction. WO Patent 2013087795 A1.Search in Google Scholar

Villar, J.C., Caperos, A., García-Ochoa, F. (1997) Oxidation of hardwood kraft-lignin to phenolic derivatives. Nitrobenzene and copper oxide as oxidants. J. Wood Chem. Technol. 17:259–285.10.1080/02773819708003131Search in Google Scholar

Villar, J.C., Caperos, A., Garcia-Ochoa, F. (2001) Oxidation of hardwood kraft-lignin to phenolic derivatives with oxygen as oxidant. Wood Sci. Technol. 35:245–255.10.1007/s002260100089Search in Google Scholar

Walton, N.J., Mayer, M.J., Narbad, A. (2003) Vanillin. Phytochemistry 63:505–515.10.1016/S0031-9422(03)00149-3Search in Google Scholar

Xiao, C., Bolton, R., Pan, W.L. (2007) Lignin from rice straw kraft pulping: effects on soil aggregation and chemical properties. Bioresource Technol. 98:1482–1488.10.1016/j.biortech.2005.11.014Search in Google Scholar PubMed

Zhang, Y.M., Peng, Y., Yin, X.L., Liu, Z.H., Li, G. (2014) Degradation of lignin to BHT by electrochemical catalysis on Pb/PbO₂ anode in alkaline solution. J. Chem. Technol. Biotechnol. 89:1954–1960.10.1002/jctb.4282Search in Google Scholar

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. Pyrolysis 104:514–520.10.1016/j.jaap.2013.05.018Search in Google Scholar

Received: 2017-07-06

Accepted: 2017-10-05

Published Online: 2017-11-02

Published in Print: 2018-02-23

You are currently not able to access this content.

Articles in the same Issue

https://doi.org/10.1515/hf-2017-0108

Keywords for this article

Box-Behnken experimental design (BBD); electrooxidation; response surface optimization; thermochemical pretreatment; value added chemicals; wheat straw soda lignin