Please take a look of this paper: Chapter Compositional Variability of Lignin in Biomass
2.3.4. Analytical pyrolysis
Pyrolysis transforms a nonvolatile compound into a volatile degradation mixture by heat in the absence of oxygen and by the breaking of chemical bonds using thermal energy [54, 55]. The ground biomass sample (particle sizes from mm to μm) is heated at temperatures from 400 to 1000°C, in the absence of oxygen, for 300 s to less than 0.5 s, producing charcoal (solid), bio-oil (liquid) and fuel gas products [56, 57]. Analytical pyrolysis was perfected for the pyrolysis of small samples for analytical purposes: a mixture of volatile compounds derived from the three macromolecular constituents of biomass (cellulose, hemicelluloses and lignin) is obtained and separated through a capillary column, identified by mass spectrometry (MS) and quantified by a flame ionization detector (FID). The MS identification of pyrolysis products was mostly made by Faix et al. [58, 59, 60, 61] and by Ralph and Hatfield [62]. Nowadays, quantification is also made by Py-GC/MS [63]. Pyrolysis is particularly interesting to characterize the lignin monomeric composition into the phenolic S, G and H precursor monomers. The ratio of monomers is given in the form of H:G:S or, more frequently, as the S/G ratio.
Pyrolysis GC-MS, Potassium permanganate oxidation + GC, 13C NMR, old method is nitrobenzene oxidation + GC, may be for you would be enough just methoxyl group analysis
You can try dissolving a small sample (~25 mg) in 1 mL of reiterated solvent (DMSO, CDCl3, Acetone, water etc.). Then, you can do 1H-13C-2D-HSQC NMR analysis of this sample. There is literature available on correlating the signals from your results with the corresponding signals from S/G/H units of lignin. The area under the curve for these signals can give you the relative amount of S/G/H units. This method is more accurate.
Alternatively, you can perform a fast pyrolysis of this sample (in a reactor or in an instrument called 'Pyroprobe'). Then you can analyze and quantify the products using GC-MS. The ratio of products that have S/G/H type structures will give you an approximate idea of the S/G/H ratio in the original lignin. This method is less accurate.