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. 2024 Sep 17;124(19):10701–10876. doi: 10.1021/acs.chemrev.4c00087

Table 25. Overview of Solvolytic Methodologies for the Depolymerization of Lignin with Yields of Phenolic Monomers.

Entry Feedstock Medium Conditions Oil yield Composition Notes Ref
1 Softwood Kraft lignin (Indulin AT) 10 wt% solution in 5 wt% NaOH (aq) 270–315 °C, continuous-flow reactor with LHSV 1.4–4.0 h–1 Up to 19.1 wt% of a monomer-rich fraction obtained after acidification and extraction Up to 8.4 wt% identified monomers Main products: guaiacol and pyrocateechol; also other lignins were studied (430,431)
2 Olive tree prunings ethanosolv lignin 5 wt% solution in 4 wt% NaOH (aq) 300 °C, 90 MPa, batch reactor, 40 min 20 wt% oil yield after acidification, extraction, and evaporation Oil contained 10 wt% catechol and 5 wt% methyl catechol Also neutral water, KOH, LiOH, K2CO3, and Ca(OH)2 were tested, as were other organosolv lignins (432,433)
3 Kraft lignin 100 mg lignin, 25 mL aqueous 10 mM NaOH 200 °C, batch reactor, 8 h Not provided 13 wt% monomers >80% selectivity to guaiacol (434)
4 Beech wood organosolv lignin 2.5 wt% NaOH (aq) 250–340 °C, 5–20 kg/h plug-flow reactor, 450–900 s residence time Oil yield up to 80–85 wt% at 250 °C to <60 wt% above 300 °C Guaiacol, catechol, and syringol up to about 40 wt% in the oil Catechol component increases at higher T (435)
5 Spruce wood Kraft lignin 2.5–7.5 wt% lignin and NaOH (aq) 250–300 °C, 5–20 kg/h plug-flow reactor, 450–750 s residence time Oil yield up to 80–85 wt% at 250 °C to around 60 wt% at 300 °C Guaiacol and catechol up to about 30 wt% in the oil Catechol component increases at higher T (435)
6 Alkali lignin Lignin:NaX (solid base cat):EtOH:H2O 1:1:40:60 250 °C, batch reactor, 1000 rpm stirring 51 wt% oil yield after acidification, extraction, and solvent evaporation About 16 wt% of the main identified monomers derived from lignin Methyl guaiacol, vanillin, and vannilone as main products; also other supported metal catalysts and lignins were tested (436,437)
7 Wheat straw alkali lignin 1 g lignin, 20 g ethylene glycol, and 10 wt% H2SO4 120 °C, batch microwave reactor, 40 min 97% liquified Up to 14 wt% identified monophenolics, mainly methyl guaiacol Showing benefit of microwave irradiation and effect of reaction conditions (438)
8 Wheat straw soda lignin (Protobind 1000) Different ratios of lignin, HCOOH, and EtOH 360–400 °C, batch reactor and CSTR, 15–1180 min Approx. 60–70% liquid yield Up to around 40 mg/g lignin combined yield of phenol, guaiacol, catechol, and alkylated phenolics Kinetic model for the formation of main components was demonstrated (439,440)
9 Norway spruce ethanosolv lignin Different ratios of lignin, formic acid, and water 320–360 °C batch reactor, 2 h 78–94 wt% based on lignin input Up to 9.5 wt% identified monomeric products Main components are guaiacol and methyl/ethyl/propyl guaiacol (441)
10 Pine wood lignin extracted from black liquor from acid hydrolysis 3 g lignin in 90 mL 1:1:0.4 H2O:EtOH:HCOOH 330 °C, batch reactor, 2 h 64.2 wt% 23.0 wt% monomers based on lignin intake Mainly 4-n-proply guaiacol (5.5 wt%), methylguaiacol (3.4 wt%), catechol (3.0 wt%), ethylguaiacol (2.7 wt%), and phenol (2.1 wt%) (442)
11 Softwood Kraft lignin (Indulin AT) 0.5 g lignin, 10 mL EtOH, 10 mL 1,4-dioxane, and 2 mL HCOOH 300 °C, batch reactor, 2 h About 50 wt% 22.4 wt% phenolic monomers Mainly 4-n-propyl guaiacol (443)
12 Norway spruce weak acid–enzymatic hydrolysis lignin 2 g lignin, 3 g HCOOH, 5 g H2O, and 0.2 g cat (Rh, Ru, or Pd supported on alumina) 340–380 °C, batch reactor, 2–6 h 80–91 wt% oil yield (highest for Ru on alumina) Up to 18.5 wt% identified monomers in the oil Main product is cresol (444)
13 Corn stover acetosolv lignin 1 g lignin, 100 mL acetic acid, and 0.1 g Zr-KIT-5 (Lewis acid cat) 250 °C, batch reactor, 1000 rpm stirring, 6 h 43 wt% oil yield based on lignin intake 28 wt% cumulative yield of identified phenolic monomers Catalysts could be reused in multiple runs; GVL and MeOH/H2O were tested as medium with other lignins (445447)
14 Bagasse organosolv lignin 1.75 w/v lignin in MIBK and 1 wt% heterogeneous carbonaceaus solid acid catalyst 350 °C, batch reactor, 3 h Over 90% lignin conversion 32% identified phenolic monomers, mainly ethyl guaiacol Also other acidic catalysts and solvents were evaluated (448)