SEARCH · Search NASA
Results for “black liquor”
Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.
Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.
Field Validation of a Pilot-scale Black Liquor Membrane for Water Removal at Ahlstrom-Munksjö Paper Mill in Mosinee, WI
Project Background: The Industrial Technology Validation (ITV) program aims to identify and demonstrate the performance of new, emerging, and underutilized technologies in the industrial sector to help inform decisions towards accelerating commercialization and deployment. Pulp and paper is considered one of the most energy-intensive industries in the manufacturing sector. There are several methodologies for converting wood into pulp in the paper-making industry. The kraft process is a chemical method for producing wood pulp. The kraft process generates black liquor as a byproduct of pulp production. Traditionally, water is evaporated from the liquor by a set of multi-effect evaporators (MEEs), which concentrate weak black liquor (WBL) into strong black liquor (SBL) to support efficient combustion in a recovery boiler. Concentrating black liquor is an energy-intensive step in recovering pulping chemicals and generating high-pressure steam from dissolved wood solids. About 7% of pulp and paper energy usage, or nearly 164 trillion Btu, is used to remove water from black liquor in U.S. kraft pulp mills per year. The U.S. DOE’s IEDO is interested in the black liquor membrane technology evaluated in this report because it offers the potential for a more energy-efficient and less carbon-intensive kraft pulping process across 99 kraft pulp mills in 24 states (Agenda 2020 Technology Alliance 2016). This ITV project validates an innovative black liquor membrane technology for kraft pulp mills to understand its impact and benefits. Via Separations is a technology vendor that developed a graphene oxide membrane system to remove water from WBL before entering the evaporator set. High-pressure positive displacement (HPR) pumps move the black liquor through membranes that separate water and create a more concentrated black liquor. The vendor claims their pre-commercial technology reduces evaporator steam consumption by dewatering WBL before entering the evaporators. They also claim their technology has non-energy benefits such as enhanced soap collection and improved pulp throughput. This evaluation focuses on validating the energy and carbon dioxide (CO 2 e) emissions benefits associated with the membrane system.
Field Validation of a Pilot-Scale Black Liquor Membrane for Water Removal
Pulp and paper processing is considered one of the most energy-intensive industries in the manufacturing sector. Concentrating black liquor is a particularly energy-intensive process in this industry, used to recover pulping chemicals and generate high-pressure steam from dissolved wood solids. About 7% of pulp and paper energy usage, or nearly 164 trillion British thermal units (Btu) per year, is used to remove water from black liquor in U.S. kraft mills. The U.S. Department of Energy’s Industrial Efficiency and Decarbonization Office is interested in this black liquor membrane technology because it offers the potential for a more energy-efficient and less carbon-intensive kraft pulping process. The membrane is intended to pretreat black liquor to reduce natural gas usage in evaporators that remove water from black liquor. This technology has the potential to be replicated across 99 kraft pulp mills in 24 states. This membrane technology is considered precommercial, and the demonstration was a small-scale side-stream field validation. To make an assessment on performance with a higher level of certainty, additional studies at larger scales are recommended.
Pyrolysis of Large Black Liquor Droplets
This paper presents the results of experiments involving the pyrolysis of large black liquor droplets in the NASA KC-135 reduced gravity aircraft. The reduced gravity environment facilitated the study of droplets up to 9 mm in diameter extending the results of previous studies to droplet sizes that are similar to those encountered in recovery boilers. Single black liquor droplets were rapidly inserted into a 923 K oven. The primary independent variables were the initial droplet diameter (0.5 mm to 9 mm), the black liquor solids content (66.12% - 72.9% by mass), and the ambient oxygen mole fraction (0.0 - 0.21). Video records of the experiments provided size and shape of the droplets as a function of time. The results show that the particle diameter at the end of the drying stage (D(sub DRY) ) increases linearly with the initial particle diameter (D(sub O)). The results further show that the ratio of the maximum swollen diameter (D(sub MAX)) to D(sub O) decreases with increasing D(sub O) for droplets with D(sub O) less than 4 mm. This ratio was independent of D(sub O) for droplets with D(sub O) greater than 4 mm. The particle is most spherical at the end of drying, and least spherical at maximum swollen size, regardless of initial sphericity and droplet size.
Pyrolysis of Large Black Liquor Droplets
This paper presents the results of experiments involving the pyrolysis of large black liquor droplets in the NASA KC-135 reduced gravity aircraft. The reduced gravity environment facilitated the study of droplets up to 9 mm in diameter extending the results of previous studies to droplet sizes that are similar to those encountered in recovery boilers. Single black liquor droplets were rapidly inserted into a 923 K oven. The primary independent variables were the initial droplet diameter (0.5 mm to 9 mm), the black liquor solids content (66.12% - 72.9% by mass), and the ambient oxygen mole fraction (0.0 - 0.21). Video records of the experiments provided size and shape of the droplets as a function of time. The results show that the particle diameter at the end of the drying stage (D(sub DRY)) increases linearly with the initial particle diameter (D(sub O)). The results further show that the ratio of the maximum swollen diameter (D(sub MAX)) to D(sub O) decreases with increasing D(sub O) for droplets with D(sub O) less than 4 mm. This ratio was independent of D(sub O) for droplets with D(sub O) greater than 4 mm. The particle is most spherical at the end of drying, and least spherical at maximum swollen size, regardless of initial sphericity and droplet size.
Cross-flow separation characteristics and piloting of graphene oxide nanofiltration membrane sheets and tubes for kraft black liquor concentration
Dewatering of weak black liquor (WBL) in the kraft cycle by evaporation is highly energy intensive. Membranes are an attractive alternative for energy-efficient dewatering, but existing commercial polymeric or ceramic membranes are either degraded in BL or have high capital costs. Our recent works have demonstrated the engineering of graphene oxide (GO) nanofiltration membranes, their stability and promising performance in BL conditions, and preliminary scale-up into sheets and tubes. Here, we describe in detail the separation characteristics of GO membrane sheets and tubes under real BL conditions and crossflow operation. Recycle-mode piloting of a GO tubular membrane showed average “production flux” of 16 L/m2/h (LMH) and high rejections of lignin (98.3%), total solids (66%), and total organic carbon (83%), with no signs of irreversible fouling identified. A corresponding GO sheet membrane produced an average flux of ~25 LMH and maintained high lignin rejection of ~97% during a slipstream pilot at a kraft mill site using WBL with ~16 wt% total solids (TS). Finally, we piloted a Dow/DuPont XUS1808 polyamide composite reverse osmosis (RO) membrane for last-mile processing of the GO nanofiltration membrane permeate. The RO membrane showed a steady state flux of 19 LMH at 65 bar and produced ~0.02 wt% TS water product, which is highly suitable for reuse in pulp washing operations in the kraft process. The results have strong positive implications for the industrial application of GO membranes in BL concentration and other related applications.
Cementless Concrete: Advancing Alkali-Activated Slag Composites with Black Liquor
This project explores the use of black liquor, a byproduct of sustainable aviation fuel production, as an alkaline activator for industrial byproducts such as steel slags to produce alkali-activated composites (AACs). The resulting cementless concrete cures at ambient temperature, demonstrates comparable performance to conventional cement, and offers a safer, lower-energy alternative for durable construction materials.
Gradient synthesis of carbon quantum dots and activated carbon from pulp black liquor for photocatalytic hydrogen evolution and supercapacitor
Black liquor (BL) is a by-product of the chemical pulping industry and is mainly used as a low-value fuel; however, its potential to produce high-value products has not been fully exploited. In this study, a green and simple strategy is reported for the gradient production of Na + -functionalized carbon quantum dots (Na + -CQDs) for the first time, N and S co-doped CQDs (N/S-CQDs), and N and S co-doped KOH-activated carbon (N/S-KAC) from BL by dialysis, hydrothermal carbonization and activation-carbonization, respectively. Due to the good electron trapping ability, photoluminescence and promising up-conversion luminescence of CQDs, the hydrogen evolution efficiency of Na + -CQDs/TiO 2 and N/S-CQDs/TiO 2 photocatalysts was improved by 2.45 and 1.46 times, respectively, compared with pure TiO 2 . N/S-KAC with a high specific surface area of 2294 m 2 g -1 provides an excellent specific capacitance of 253 F g -1 at 0.5 A g -1 and a promising energy density of 26.92 Wh kg -1 under a power density of 566 W kg -1 for the fabricated symmetrical supercapacitor. Moreover, the electrode material has good cycling stability with a capacitance retention of ~ 93.91% after 5000 cycles. In conclusion, this pathway provides a versatile and scalable approach for the construction and co-production of nanostructured materials, photocatalysts and energy storage devices.
Advanced nuclear reactor integration opportunities for the pulp and paper industry in the U.S. context: Technical perspectives, gap analysis, and preliminary technoeconomic assessment
Pulp and paper (P&P) manufacturing requires a large amount of low-pressure (LP) steam to digest, wash wood fibers and dry pulp into paper. Most of the LP steam is extracted from backpressure turbines that produce power from high-pressure (HP) steam. This HP steam is generated from burning wood waste material; bark is burned in hog boilers, and lignin is boiled in a black liquor recovery boiler. In a typical integrated P&P mill, 50–100% of the steam is produced from these sources, while additional steam is produced in natural gas (NG), fuel oil, or coal boilers. The other energy-intensive process in the plant is the chemical-recovery section (e.g., lime kiln), which requires high-temperature processing from NG combustion to retrieve and recirculate spent chemicals. This paper assesses the energy and heat demand and material balances of a typical generic kraft pulp mill, along with the nuclear heat, steam, and power integration opportunities to replace conventional combustion systems. The paper also addresses steam and electricity generation through a comprehensive technical and engineering gap analysis of five different nuclear-integration opportunities and their process economics, thus enabling the lignin and bark to be further processed into biobased chemicals or fuels, as well as the potential to reduce overall emissions from kraft pulping. Preliminary findings have shown that the P&P industry could achieve technological benefits by integrating their current manufacturing process with small modular nuclear reactors (SMNRs) on a national level. This research aims to set the path forward for a cleaner and more resilient P&P industry.
Technoeconomic Analysis of Kraft Pulp Mill Integration with an Advanced Nuclear Reactor
This study focuses on post-combustion capture and oxy-fuel combustion for the boilers at the mill, as well as steam integration with the nuclear power plant. The primary goal of the research outlined in this report is to design, analyze, and document the integration of industrial-scale HTGR with a reference Kraft Pulp Mill. The purpose is to deliver reliable, cost-effective, and sustainable clean energy alternatives while reducing CO2 emissions. Specifically, this study focuses on 6 different scenarios that include carbon capture equipment and some of them use nuclear power to meet the heat and electricity needs of the reference plant. Also, 2 of these scenarios are created while also producing clean hydrogen through integrated High-Temperature Steam Electrolysis (HTSE). This report offers a detailed techno-economic assessment of different scenarios for a Kraft Pulp Mill, including an analysis of tax credits (section 45V, 45Q, and 48E) provided by the Inflation Reduction Act (IRA) of 2022. The evaluation explores the potential economic benefits and challenges of incorporating different configurations, including nuclear energy, into Kraft Pulp Mill operations, with particular attention to energy efficiency, economic implications, and environmental impact. By assessing both the technical feasibility and economic viability, this analysis aims to identify existing gaps and propose solutions for the successful implementation of nuclear integration. The findings are intended to provide valuable insights for stakeholders considering the adoption of advanced nuclear reactors in the pulp and paper industries.
Scalable aqueous-phase fabrication of reduced graphene oxide nanofiltration membranes by an integrated roll-to-roll (R2R) process
Economic fractionation of multicomponent biomass-derived streams is a key challenge in biobased fuels and chemicals production. Kraft black liquor (BL) is generated at ~1 billion tons/yr globally from biomass pulping and contains ~15wt% total solids including lignin, hemicellulose fragments, and inorganics. Membrane-based BL concentration is attractive but challenged by low solute rejections and poor stability in BL, which combines alkaline pH (~13), high dissolved solids content (15+ wt%) and high temperature (70–85°C). Here we discuss the scaled fabrication and characterization of reduced graphene oxide (rGO) nanofiltration membranes by slot die coating on a roll-to-roll (R2R) with integrated vacuum filtration. Here, we obtain high-quality 90×30 cm rGO membranes (referred to as “R2R-rGO membranes” in this work) with ~100 nm average thickness supported on porous poly(ethersulfone) (PES) sheets, and an effective area of 2700cm 2 . We present characterizations of their microstructure and uniformity as mapped over large areas by scanning electron microscopy (SEM), ellipsometry, adhesion test and X-ray photoelectron spectroscopy (XPS). The constructed ellipsometry model for the rGO membrane/PES substrate composite was successfully applied to 48 different locations of the R2R-rGO membranes. The R2R-rGO membranes showed >98% lignin rejection with a steady state flux of ~12 LMH at 50bar in a 15.7wt% total solids (TS) kraft BL stream at 72°C and 2–3 gal/min crossflow rates. Slot die coating on a R2R platform with integrated vacuum filtration can enable rapid fabrication of high-quality GO membranes at scale without organic solvents or volatile organic compounds.
Sustainability perspectives of integrated pulp and paper biorefineries – A systematic critical review
As the pulp and paper industry is impacted by changing product demand trends, an opportunity arises to utilize existing pulp and paper mills (PPMs) and byproduct biomass to produce a wide range of value-added products, i.e., by converting existing PPMs into integrated pulp and paper biorefineries (IPPBs), a form of industrial symbiosis. In addition to the conventional products that a pulp and paper mill produces, IPPBs produce bio-based products that can help generate a new income stream. This paper provides a systematic critical review of IPPBs with a focus on the types of IPPBs and sustainability perspectives. Specifically, this review's objective is to identify and discuss current and emerging types of IPPBs, provide insights into the types of value-added products produced, and the opportunities and barriers they have according to published literature. We reviewed 97 articles and proposed a robust definition for IPPBs. The results show that there is a dominance of studying bioethanol as the main value-added product and black liquor as one of the main feedstocks. Additionally, we found that there are different types of market challenges for bioproducts depending on the conventional product being replaced and that location and policies play a crucial role. This review identified the limited sustainability focus on this topic and the crucial need to invest in new research to more thoroughly cover the environmental, economic, and social impacts of IPPBs.
Metabolic Modification of Sphingobium lignivorans SYK-6 for Lignin Valorization Through the Discovery of an Unusual Transcriptional Repressor of Lignin-Derived Dimer Catabolism
Sphingobium lignivorans SYK-6 catabolizes guaiacylglycerol-..beta..-guaiacyl ether (GGE, a ..beta..-O-4-type dimer) and 1,2-diguaiacylpropane-1,3-diol (DGPD, a ..beta..-1-type dimer) derived from lignin. Recently, SLG_35860 containing TetR- and MarR-type transcriptional regulator motifs was suggested to be involved in the regulation of GGE and DGPD catabolism. Here we investigated the role of SLG_35860 in the transcriptional regulation of GGE and DGPD catabolism genes. SLG_35860 designated ligS repressed 11 genes involved in GGE and DGPD catabolism. LigS binds directly to specific sequences in the promoter region of each gene. The MarR domain was shown to be involved in these bindings; however, GGE, DGPD, and their metabolites did not function as effectors of LigS. We discovered unidentified compound(s) in the black liquor of oxygen-soda anthraquinone pulping of Japanese cedar that SYK-6 cannot metabolize and that acted as effector(s). Therefore, LigS constantly represses the transcription of the GGE and DGPD catabolism genes to low levels. Based on these findings, we examined the productivity of a polymer building block, 2-pyrone-4,6-dicarboxylic acid (PDC), from GGE, DGPD, and a GGE metabolite using an engineered ligS mutant. The rates of PDC production from each compound by this strain were 1.5-6.0 times higher than those of a PDC-producing strain carrying ligS.
Waste to worth: a circular solution through lignin engineering
The inefficient management of industrial waste threatens environmental sustainability, requiring scalable resource recovery solutions. To address these challenges, we propose a novel and sustainable in-situ one-step strategy for the simultaneous recovery and functionalization of lignin from industrial black liquor, using a sustainable organic acid system assisted by choline chloride. The functionalized lignin adsorbent material (FLAM) exhibited superior adsorption performance, effectively treating animal feedlot wastewater to recover ammonia. The ammonia enriched FLAM was subsequently repurposed as a slow-release fertilizer, enhancing plant growth and demonstrating a closed-loop pathway for waste valorization and nutrient recycling. Methylene blue was used as a model cationic compound to simulate the adsorption behavior and interactions. FLAM achieved a high adsorption capacity of 725.98 mg/g across a broad pH range, significantly outperforming commercial kraft lignin. This sustainable approach advances circular economy principles by integrating remediation and resource recovery, offering a scalable, eco-friendly solution for environmental applications.
Feedstock/pretreatment screening for bioconversion of sugar and lignin streams via deacetylated disc-refining
Recent publications have shown the benefits of deacetylation disc-refining (DDR) as a pretreatment process to deconstruct biomass into sugars and lignin residues. Major advantages of DDR pretreatment over steam and dilute acid pretreatment are the removal of acetyl and lignin during deacetylation. DDR does not generate hydroxymethylfurfural (HMF) and furfural which are commonly produced from steam and dilute acid pretreatments. Acetate, lignin, HMF, and furfural are known inhibitors during enzymatic hydrolysis and fermentation. Another advantage of deacetylation is the production of lignin-rich black liquor, which can be upgraded to other bioproducts. Furthermore, due to the lack of sugar degradation during deacetylation, DDR has significantly less sugar loss than other pretreatment methods. Previous studies for DDR have primarily focused on corn stover, but lacked the investigative studies of other feedstocks. This study was designed to screen various DDR process conditions at pilot scale using three different feedstocks, including corn stover, poplar, and switchgrass. The impact of the pretreatment conditions was evaluated by testing hydrolysates for bioconversion to 2,3-butanediol. Pretreatment of biomass by DDR showed high-conversion-yields and 2,3-BDO fermentation production yields. Techno-economic analysis (TEA) of the pretreatment for biomass to sugar was also developed based on NREL’s Aspen Model. This study shows that the cellulose and hemicellulose in poplar was more recalcitrant than herbaceous feedstocks which ultimately drove up the sugar cost. Switchgrass was also more recalcitrant than corn stover but less than poplar.
Method for the determination of lignin content of a sample by flash pyrolysis in an atmosphere of hydrogen or helium and method therefor
The lignin content of wood, paper pulp or other material containing lignin (such as filter paper soaked in black liquor) is more readily determined by flash pyrolysis of the sample at approximately 550.degree. C. in a reducing atmosphere of hydrogen or in an inert atmosphere of helium followed by a rapid analysis of the product gas by a mass spectrometer. The heated pyrolysis unit as fabricated comprises a small platinum cup welded to an electrically-heated stainless steel ribbon with control means for programmed short duration (1.5 sec, approximately) heating and means for continuous flow of hydrogen or helium. The pyrolysis products enter an electron-ionization mode mass spectrometer for spectral evaluation. Lignin content is obtained from certain ratios of integrated ion currents of many mass spectral lines, the ratios being linearly related to the Kappa number of Klason lignin.
Techno-economic Analysis of CO2 Capture From Pulp/Paper Plants
This poster presentation evaluates the cost of capturing CO2 from a 400,000 air dried tonne (adt)/year pulp production plant, using Shell’s CANSOLV post-combustion capture process. There are five steps in a pulp/paper process: wood preparation, pulping, chemical recovery, bleaching and papermaking. There are three sources of CO2: combustion of waste wood in the wood-preparation step; combustion of black liquor, a product of pulping; and combustion of natural gas coupled with CO2 generated from calcination of limestone in the lime kiln used in chemical recovery. Standalone (pulp only) and integrated (pulp + paper) mills are modeled. The base case results and sensitivity analyses are displayed.
Case Study: NuScale Integrated Pulp and Paper Mill
This presentation covers the analysis methods and results of a nuclear integrated pulp and paper mill case study.