Lignin solubilisation and gentle fractionation in liquid ammonia

We present a simple method for solubilising lignin using liquid ammonia. Unlike water, which requires harsh conditions, ammonia can solubilise technical lignins, in particular kraft lignin. A commercial pine wood Kraft lignin (Indulin AT) was solubilized instantaneously at room temperature and 7–11 bars autogeneous pressure, while a commercial mixed wheat straw/Sarkanda grass soda lignin (Protobind™ 1000) was solubilized within 3 h at ambient temperature, and 30 min at. 85 °C. Hydroxide salts were not required. Wheat straw, poplar and spruce organosolv lignins, as well as elephant grass native lignin (MWL) were also solubilized, albeit at lower values. Different sequences of solubilisation and extraction were tested on the Protobind™ 1000 lignin. The remaining lignin residues were characterized by FTIR, size exclusion chromatography (SEC), elemental analysis (ICP), 2D-NMR and 31P NMR. Liquid ammonia is not an innocent solvent, as some nitrogen was incorporated in the residual lignin which then rearranged to higher molecular weight fractions. Nevertheless, the mild solubilisation conditions make liquid ammonia an attractive candidate as a solvent for lignin in future biorefinery processes

Ab Initio Screening Approach for the Discovery of Lignin Polymer Breaking Pathways

The directed depolymerization of lignin biopolymers is of utmost relevance for the valorization or commercialization of biomass fuels. We present a computational and theoretical screening approach to identify potential cleavage pathways and resulting fragments that are formed during depolymerization of lignin oligomers containing two to six monomers. We have developed a chemical discovery technique to identify the chemically relevant putative fragments in eight known polymeric linkage types of lignin. Obtaining these structures is a crucial precursor to the development of any further kinetic modeling. We have developed this approach by adapting steered molecular dynamics calculations under constant force and varying the points of applied force in the molecule to diversify the screening approach. Key observations include relationships between abundance and breaking frequency, the relative diversity of potential pathways for a given linkage, and the observation that readily cleaved bonds can destabilize adjacent bonds, causing subsequent automatic cleavage.Massachusetts Institute of Technology (Research Support Corporation, Reed Grant)United States. Dept. of Energy. Computational Science Graduate Fellowship Program (DOE-CSGF)Burroughs Wellcome Fund (Career Award at the Scientific Interface

Preparative Aspects of Supported Ni2P Catalysts for Reductive Upgrading of Technical Lignin to Aromatics

Supported Ni2P was evaluated as a hydrodeoxygenation (HDO) catalyst in the reductive upgrading of a soda lignin in supercritical ethanol by a hydrotalcite-derived mixed Cu-Mg-Al oxide (CuMgAlOx) catalyst. Various Ni2P catalysts were prepared by different approaches on silica, γ-alumina and a siliceous amorphous silica-alumina (ASA) supports. Calcined NiO/SiO2 precursors were impregnated with phosphate, phosphite and hypophosphite followed by reduction. With γ-alumina, the desired Ni2P could not be obtained, presumably due to the reaction of the P-source with alumina. NiO on ASA could be converted to Ni2P by addition of phosphite, preferably at a P/Ni ratio of 1. Low P/Ni ratio avoids blockage of the pores by P-oxide species remaining after reduction. By further comparison to a sol–gel prepared NiO/SiO2 and co-impregnated silica, it was established that the most active Ni2P catalyst was obtained by impregnation of NiO/SiO2 with phosphate at P/Ni = 1 and reduction at 620 °C. In combination with CuMgAlOx, more than half of soda lignin can be converted to aromatics monomers with a relatively high degree of deoxygenation and limited degree of ring hydrogenation. The co-catalyst system is more active than the separate catalysts

The pros and cons of lignin valorisation in an integrated biorefinery

This short critical review outlines possible scenarios for using lignin as a feedstock in a biorefinery environment. We first explain the position of biomass with respect to fossil carbon sources and the possibilities of substituting these in tomorrow's transportation fuels, energy, and chemicals sectors. Of these, the conversion of biomass to chemicals is, in our opinion, the most worthy. Focusing on lignin, we describe the four main processes for its industrial separation (the Sulfite, Soda, Kraft, and Organosolv processes). Then, we detail several short-and long-term perspectives for its valorisation to aromatics, polymers and materials, as well as new products and in-the-pipeline processes. Finally, we examine the limitations in current lignin valorisation and suggest possible ways forward. Combining the chemical aspects with up-to-date data from economic analyses gives a pragmatic and realistic overview of the commercial applications and possibilities for lignin in the coming decades, where biomass will join shale gas and crude oil as a valid and economical carbon source

Sequence of Stages in the Microstructure Evolution in Copper under Mild Reciprocating Tribological Loading

Tailoring the surface properties of a material for low friction and little wear has long been a goal of tribological research. Since the microstructure of the material under the contact strongly influences tribological performance, the ability to control this microstructure is thereby of key importance. However, there is a significant lack of knowledge about the elementary mechanisms of microstructure evolution under tribological load. To cover different stages of this microstructure evolution, high-purity copper was investigated after increasing numbers of sliding cycles of a sapphire sphere in reciprocating motion. Scanning electron and focused ion beam (FIB) microscopy were applied to monitor the microstructure changes. A thin tribologically deformed layer which grew from tens of nanometers to several micrometers with increasing number of cycles was observed in cross-sections. By analyzing dislocation structures and local orientation changes in the cross-sectional areas, dislocation activity, th