Debottlenecking a Pulp Mill by Producing Biofuels from Black Liquor in Three Steps.

By extracting lignin, pulp production can be increased without heavy investments in a new recovery boiler, the typical bottleneck of a pulp mill. The extraction is performed by using 0.20 and 0.15 weight equivalents of CO2 and H2 SO4 respectively. Herein, we describe lignin esterification with fatty acids using benign reagents to generate a lignin ester mixable with gas oils. The esterification is accomplished by activating the fatty acid and lignin with acetic anhydride which can be regenerated from the acetic acid recycled in this reaction. The resulting mass balance ratio is fatty acid/lignin/acetic acid (2 : 1 : 0.1). This lignin ester can be hydroprocessed to generate hydrocarbons in gasoline, aviation, and diesel range. A 300-hour continuous production of fuel was accomplished. By recirculating reagents from both the esterification step and applying a water gas shift reaction on off-gases from the hydroprocessing, a favorable overall mass balance is realized.

Synthesis of stable phosphomide ligands and their use in Ru-catalyzed hydrogenations of bicarbonate and related substrates.

New benzoyl- and naphthoyl-substituted phosphines have been synthesized, which are stable to air and moisture. Testing these so-called phosphomide ligands in the presence of different ruthenium precursors, the hydrogenation of sodium bicarbonate (NaHCO(3)) to sodium formate (NaHCO(2)) proceeded with good catalyst turnover numbers in the range of 1300-1600 at 80°C and a total pressure of hydrogen of 60 bar in the absence of amines or other additives. Similarly, catalytic hydrogenations of carbon dioxide, cinnam-, and benzaldehyde were possible with these new ruthenium complexes. As an intermediate of the catalytic cycle the defined ruthenium complex [(η(6)-C(6)H(6))-RuCl(2)(Cy(2)P(1-naphthoyl)] (Cy=cyclohexyl) was prepared and characterized by X-ray crystallography.

Well-defined iron catalyst for improved hydrogenation of carbon dioxide and bicarbonate.

The most efficient, stable, and easy-to-synthesize non-noble metal catalyst system for the reduction of CO(2) and bicarbonates is presented. In the presence of the iron(II)-fluoro-tris(2-(diphenylphosphino)phenyl)phosphino]tetrafluoroborate complex 3, the hydrogenation of bicarbonates proceeds in good yields with high catalyst productivity and activity (TON > 7500, TOF > 750). High-pressure NMR studies of the hydrogenation of carbon dioxide demonstrate that the corresponding iron-hydridodihydrogen complex 4 is crucial in the catalytic cycle.