The Role of Lignin Molecular Weight on Activated Carbon Pore Structure.

Over the past decade, the production of biofuels from lignocellulosic biomass has steadily increased to offset the use of fuels from petroleum. To make biofuels cost-competitive, however, it is necessary to add value to the "ligno-" components (up to 30% by mass) of the biomass. The properties of lignin, in terms of molecular weight (MW), chemical functionality, and mineral impurities often vary from biomass source and biorefinery process, resulting in a challenging precursor for product development. Activated carbon (AC) is a feasible target for the lignin-rich byproduct streams because it can be made from nearly any biomass, and it has a market capacity large enough to use much of the lignin generated from the biorefineries. However, it is not known how the variability in the lignin affects the key properties of AC, because, until now, they could not be well controlled. In this work, various fractions of ultraclean (<0.6% ash) lignin are created with refined MW distributions using Aqueous Lignin Purification using Hot Agents (ALPHA) and used as precursors for AC. AC is synthesized via zinc chloride activation and characterized for pore structure and adsorption capacity. We show that AC surface area and the adsorption capacity increase when using lignin with increasing MW, and, furthermore, that reducing the mineral content of lignin can significantly enhance the AC properties. The surface area of the AC from the highest MW lignin can reach ~1830 m2/g (absorption capacity). Furthermore, single step activation carbonization using zinc chloride allows for minimal carbon burn off (<30%), capturing most of the lignin carbon compared to traditional burn off methods in biorefineries for heat generation.

Carbon fibers derived from liquefied and fractionated poplar lignins: The effect of molecular weight.

Lignin recovered from poplar, a key woody biomass resource proposed for lignocellulosic refineries, was investigated for conversion into carbon fibers. Aqueous solutions of ethanol at selected temperatures and compositions, where the requisite solvent and liquefied-lignin phases form, were used to purify and fractionate hybrid poplar (HP) lignin using the Aqueous Lignin Purification with Hot Agents (ALPHA) process. Sugars (<0.1%) and ash (0.01 ± 0.01%) content of the highest molecular weight fraction (Mw = 52 kDa) approached the limits of detection. This 52 kDa fraction could be dry spun with excellent stability and was subsequently converted into carbon fibers having strength (1.1 ± 0.2 GPa) and modulus (78 ± 8 GPa) essentially double those previously achieved with neat poplar and other hardwood lignins. Of equal importance, stabilization times were decreased by a factor of five. Such stabilization and strength/modulus improvements are essential for reducing the overall manufacturing cost of carbon fibers being proposed for cost-sensitive applications.

Fractionating and Purifying Softwood Kraft Lignin with Aqueous Renewable Solvents: Liquid-Liquid Equilibrium for the Lignin-Ethanol-Water System.

Hot ethanol-water solutions can be used to simultaneously fractionate and purify softwood Kraft lignin through the Aqueous Lignin Purification with Hot Agents (ALPHA) process, using the regions of liquid-liquid equilibrium (LLE) that form at selected temperatures and solvent-to-lignin feed (S/F) ratios. Lignin, ethanol, and water compositions are measured for the solvent-rich (SR) and lignin-rich (LR) liquid phases in mutual equilibrium, as well as the lignin and metals mass distributions between the two phases. As depicted in quasi-ternary diagrams for clarity, both temperature and S/F ratio can be used to grow, merge, and even split the regions of LLE, giving significant control over both molecular weight (MW) and lignin purity. For example, a solvent comprising 45:55 EtOH/H2 O at 75 °C and an S/F ratio of 6:1 enables recovery of an ultrapure (95 % of Na removed), higher MW (Mn =8400 Da) lignin fraction in the LR phase. On the other hand, 95:5 EtOH/H2 O at 45 °C and S/F=3:1 enables recovery of an ultrapure, low MW (1500 Da) lignin in the SR phase.