The aim of the study was to determine the quantitative and qualitative changes taking place in biomass components actively participating in methane fermentation, i.e., in carbohydrates, as a result of chemical pretreatment. Analyses were conducted on agricultural waste (corn stover, also called corn straw, and corncobs) as materials most commonly used in methane fermentation, as well as poplar wood, a material relatively rarely used in biogas production. Pretreatment with the aim of increasing efficiency of methane fermentation was carried out with the use of acid and alkaline solutions of different concentrations. The effect of pretreatment on carbohydrates was analyzed based on the quantitative and qualitative changes in this component. Due to the structural heterogeneity of carbohydrates, their varied reactivity and fermentability were determined in terms of holocellulose, cellulose, and pentosans. The chemical structure of cellulose was also analyzed. It is shown in this study that chemical pretreatment causes transformations of carbohydrate components, which differ quantitatively and qualitatively in the compared raw materials. It was found that the alkaline treatment caused smaller changes in the percentage shares of the carbohydrate biomass components as compared to the acid treatment. Moreover, it was observed that the compared materials differ in terms of quantitative changes in their chemical composition depending on the composition of the raw material prior to pretreatment. In the case of corn waste subjected to the action of 1 and 3% NaOH, the share of pentosans in the biomass increased. It was established that this is a change with a positive effect on fermentation efficiency. The action of acids and alkalis on the biomass led to similar structural changes in cellulose, which are adverse for the fermentation process.

The aim of the research is to identify the changes which occur in lignin from miscanthus and sorghum, one of the main biomass components, as a result of an anaerobic digestion (AD) process. The percentage content and structure of lignin before and after the fermentation process were analysed using biomass harvested in two growing periods—before and after vegetation. It was shown that plants at different developmental stages differ in lignin content. During plant growth, the lignin structure also changes—the syringyl-to-guaiacyl ratio (S/G) increases, whereas the aliphatic and aromatic structure ratio (Al/Ar) decreases. The AD process leads to an increase in percentage lignin content in cell walls, and the increase is higher for plants harvested during vegetation. It has been shown in studies that the methane fermentation of miscanthus and sorghum produces waste containing a large amount of lignin, the structure of which is altered relative to native lignin. The quantity and the new, simplified structure of lignin create new possibilities for using this aromatic polymer.

In the described study, the relationships between the percentage and structure of selected lignocellulosic components and the efficiency of their anaerobic digestion and the quality of the produced biogas were analyzed. This research included various lignocellulosic raw materials. The biogas efficiency and quality tests were carried out according to DIN standard 38 414-8 (1985) and VDI standard 4630 (2016). Multiple TAPPI standards and the Seifert method were used to determine the chemical composition of the lignocellulose materials. Lignin structure analysis was performed using Fourier transform infrared spectroscopy. Wide-angle X-Ray scattering analysis was used to determine the degree of crystallinity of cellulose. The biogas was positively correlated with C=O and the syringyl to guaiacyl ratio, and negatively correlated with the crystalline structure of cellulose, lignin, cellulose, and extractives. In addition, methane was positively correlated with holocellulose and extractives and negatively correlated with the crystalline structure of cellulose, cellulose, substances soluble in NaOH, and the OH groups. The found independent features accounted for 86.0% of the biogas variability and 68.0% of the methane variability.

Changes in chemical composition and structure of corncob lignocellulosic biomass were investigated relative to pretreatment and anaerobic digestion. The pretreatment involved 1% and 3% sodium hydroxide, 3% and 7% sulphuric acid, as well as medium and high temperature extrusion (in 110 °C and in the range from 140 °C to 160 °C). The chemical components content was studied using a gravimetric method, whereas structure and relations between the carbohydrate and lignin participation were investigated using Fourier transform infrared spectroscopy. It was determined that the chemical treatment, both acidic and alkaline, changed the chemical composition of corncob more significantly than the extrusion. Alkaline pretreatment contributed to significant delignification, while acidic pretreatment reduced the share of hemicelluloses and increased the proportion of lignin, the so-called “pseudolignin”. The composition of corncob (control and after pre-treatment) was changed after anaerobic digestion, i.e., a decreased carbohydrate substance content and a significantly increased lignin content. FTIR analysis showed changes in their structure. Although the control corncob differed from that processed by various pretreatment methods, the chemical composition of the digested pulp obtained from them was similar. The NaOH pretreatment was judged to be the preferred method for delignification of the raw material.