Kraft black liquor concentration with graphene oxide membranes: Process simulations and technoeconomic analysis

Black liquor (BL) dewatering by multi-effect evaporation in the kraft paper-making process is highly energy-intensive. It was previously shown that graphene oxide (GO) nanofiltration membranes can remove lignin, other organics, and inorganic salts from BL while exhibiting stability in caustic BL conditions. Here, we design and simulate several candidate dewatering processes and evaluate their technoeconomic characteristics. All processes concentration BL from 15 to 30 wt % solutes while producing aqueous permeate. Two process options were analyzed - option A including "last-mile" permeate treatment to reduce solutes to 0.2 wt %, and option B excluding this treatment and producing a 3-4 wt % solutes stream. These processes were simulated in custom-built ASPEN Plus flowsheets interfaced with Microsoft Excel and MATLAB. All processes deliver large (>40%) energy savings. Detailed technoeconomic analysis showed that option A processes are profitable in mills equipped with condensing turbines, but unprofitable with only purchased fuel savings. Option B. processes are profitable in both situations, but require the caustic permeate to be utilized in other kraft process units. They are also profitable with electricity generation when operated at smaller scales matching the requirements of other process units. Mont-Carlo sensitivity analysis shows that Option A can yield median 20-year NPVs up to $10MM and Option B up to $25MM. Overall, GO membrane-based BL dewatering is economically promising, assuming successful slipstream piloting and scale-up campaigns. It would have immediate sustainability benefits from large energy savings, and broader implications for biorefinery processes due to the ability to fractionate biomass feedstock components under harsh conditions.