New transportation fuels are badly needed to reduce our heavy dependence on imported oil and to reduce the release of greenhouse gases that cause global climate change; cellulosic biomass is the only inexpensive resource that can be used for sustainable production of the large volumes of liquid fuels that our transportation sector has historically favored. Furthermore, biological conversion of cellulosic biomass can take advantage of the power of biotechnology to take huge strides toward making biofuels cost competitive. Ethanol production is particularly well suited to marrying this combination of need, resource, and technology. In fact, major advances have already been realized to competitively position cellulosic ethanol with corn ethanol. However, although biotechno logy presents important opportunities to achieve very low costs, pretreatment of naturally resistant cellulosic mate rials is essential if we are to achieve high yields from biological operations; this operation is projected to be the single, most expensive processing step, representing about 20% of the total cost. In addition, pretreatment has pervasive impacts on all other major operations in the overall conversion scheme from choice of feedstock through to size reduction, hydrolysis, and fermentation, and on to product recovery, residue processing, and co-product potential. A number of different pretreatments involving biological, chemical, physical, and thermal approaches have been investigated over the years, but only those that employ chemicals currently offer the high yields and low costs vital to economic success. Among the most promising are pretreatments using dilute acid, sulfur dioxide, near-neutral pH control, ammonia expansion, aqueous ammonia, and lime, with signifi cant differences among the sugar-release patterns. Although projected costs for these options are similar when applied to corn stover, a key need now is to dramatically improve our knowledge of these systems with the goal of advancing pretreatment to substantially reduce costs and to accelerate commercial applications.

Compared with batch systems, flowthrough and countercurrent reactors have important potential advantages for pretreating cellulosic biomass, including higher hemicellulose sugar yields, enhanced cellulose digestibility, and reduced chemical additions. Unfortunately, they suffer from high water and energy use. To better understand these trade-offs, comparative data are reported on xylan and lignin removal and enzymatic digestibility of cellulose for corn stover pretreated in batch and flowthrough reactors over a range of flow rates between 160 degrees and 220 degrees C, with water only and also with 0.1 wt% sulfuric acid. Increasing flow with just water enhanced the xylan dissolution rate, more than doubled total lignin removal, and increased cellulose digestibility. Furthermore, adding dilute sulfuric acid increased the rate of xylan removal for both batch and flowthrough systems. Interestingly, adding acid also increased the lignin removal rate with flow, but less lignin was left in solution when acid was added in batch. Although the enzymatic hydrolysis of pretreated cellulose was related to xylan removal, as others have shown, the digestibility was much better for flowthrough compared with batch systems, for the same degree of xylan removal. Cellulose digestibility for flowthrough reactors was related to lignin removal as well. These results suggest that altering lignin also affects the enzymatic digestibility of corn stover.

The exploration of effective approaches for the valorization of lignin to valuable products attracts broad interests of a growing scientific community. By fully unlocking the potential of the world's most abundant resource of bio-aromatics, it could improve the profitability and carbon efficiency of the entire biorefinery process, thus accelerate the replacement of fossil resources with bioresources in our society. The successful realization of this goal depends on the development of technologies to overcome the following challenges, including: 1) efficient biomass pretreatment and lignin separation technologies that overcomes its diverse structure and complex chemistry challenges to obtain high purity lignin; 2) advanced chemical analysis for precise quantitative characterization of the lignin in chemical transformation processes; 3) novel approaches for conversion of biomass-derived lignin to valuable products. This review summarizes the latest cutting-edge innovations of lignin chemical valorization with the focus on the aforementioned three key aspects.