Agricultural residues are promising and abundant feedstocks for the production of monomeric carbohydrates, which can be gained after pretreatment and enzymatic hydrolysis. These monomeric carbohydrates can be fermented to platform chemicals, like ethanol or succinic acid. Due to its high availability, corn stover is a feedstock of special interest in such considerations. The natural recalcitrance of lignocellulosic material against degradation necessitates a pretreatment before the enzymatic hydrolysis. In the present study, a novel combination of steam refining and alkaline lignin extraction was tested as a pretreatment process for corn stover. This combination combines the enhancement of the enzymatic hydrolysis and steam refining lignin can be gained for further utilization. Afterward, the obtained yields after enzymatic hydrolysis were compared with those after steam refining without alkaline extraction. After steam refining at temperatures between 160 °C and 210 °C and subsequent enzymatic hydrolysis with Cellic® CTec2, it was possible to enhance the digestibility of corn stover and to achieve 65.4% of the available carbohydrates at the lowest up to 89% at the highest conditions as monomers after enzymatic hydrolysis. Furthermore, the enzymatic degradation could be optimized with a subsequent alkaline lignin extraction, especially at low severities under three. After this combined pretreatment, it was possible to enhance the enzymatic digestibility and to achieve up to 106.4% of the available carbohydrates at the lowest conditions and up to 102.2% at the highest temperature as monomers after following enzymatic hydrolysis, compared to analytical acid hydrolysis. Regarding the utilization of the arising lignin after extraction, the lignin was characterized with regard to the molar mass and carbohydrate impurities. In this context, it was found that higher amounts and higher purities of lignin can be attained after pretreatment at severities higher than four.

Maize, also called corn, is one of the most available feedstocks worldwide for lignocellulosic biorefineries. However, a permanent biomass supply over the year is essential for industrial biorefinery application. In that context, ensiling is a well-known agricultural application to produce durable animal feed for the whole year. In this study, ensiled maize was used for steam refining experiments with subsequent enzymatic hydrolysis using the Cellic® CTec2 to test the application possibilities of an ensiled material for the biorefinery purpose of fermentable carbohydrate production. Steam refining was conducted from mild (log R0 = 1.59) to severe conditions (log R0 = 4.12). The yields were determined, and the resulting fractions were characterized. Hereafter, enzymatic hydrolysis of the solid fiber fraction was conducted, and the carbohydrate recovery was calculated. A conversion to monomers of around 50% was found for the mildest pretreatment (log R0 = 1.59). After pretreatment at the highest severity of 4.12, it was possible to achieve a conversion of 100% of the theoretical available carbohydrates. From these results, it is clear that a sufficient pretreatment is necessary to achieve sufficient recovery rates. Thus, it can be concluded that ensiled maize pretreated by steam refining is a suitable and highly available feedstock for lignocellulosic biorefineries. Ultimately, it can be assumed that ensiling is a promising storage method to pave the way for a full-year biomass supply for lignocellulosic biorefinery concepts.

The utilization of agricultural products and residues for the production of value-added and biobased products is a highly relevant topic in present research. Due to the natural recalcitrance of lignocellulosic biomass against enzymatic degradation, pretreatments are important requirement for further processes. For the raw material in this study, corn stover (CS) as highly available agricultural residue and maize silage (MS) as model substrate for an ensiled agricultural product were pretreated by steam refining. However, after processing a liquid fraction and fibers are present. Subsequent to steaming the fiber fraction is well characterized. Nonetheless, in depth characterizations of the filtrates are also important for their subsequent utilization. Decreasing molar masses from 7,900 g/mol to 1,100 g/mol for CS filtrates and 100.000–12.900 g/mol for MS filtrates were determined with increasing severity. Due to their proven inhibitory effect on microorganisms weak acids, furans and phenolic compounds within the liquid phased were analyzed. Especially formic acid increases with increasing severity from 0.27 to 1.20% based on raw material for CS and from 0.07 to 0.23% based on raw material for MS. Further GC/MS measurements indicate, that up to 8.25% (CS filtrate) and 5.23% (MS filtrates) of the total peak area is related to inhibitory phenols. Considering the data, detoxification strategies are of non-negligible importance for filtrates after steam refining and should be considered for further research and process or parameter optimizations. An alternative may be the application of milder process conditions in order to prevent the formation of inhibitory degradation products or the dilution of the gained filtrates.