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Black liquor, primarily consisting of lignin, polysaccharides, and inorganic substances, is a potential precursor of porous carbon materials for high-performance supercapacitors. However, the laborious purification of black liquor lignin and the introduction of exogenous heteroatoms have hindered their practical applications. Herein, the full components of black liquor were utilized to synthesize hierarchical porous sulfur self-doped lignin carbons (S-LCs) through a self-activation process aimed at improving the performance of supercapacitors. Benefiting from the intensified reactivity and crosslinking degree of the polysaccharide component and the sulfur self-doping and self-activation effect of inorganic substances, the resulting S-LCs exhibit a high specific surface area (SSA), abundant porous structure, and enhanced defect activity, all contributing toward increasing the energy storage capacity of supercapacitors. The as-obtained S-LC-G250/700 features a high SSA of 892.94 m 2  g -1 and a sulfur content of 3.3 at.%. The S-LC-G250/700 demonstrates excellent specific capacitance (e.g., 405.06 F g -1 at 0.5 A g -1 ), remarkable stability (103 % capacity retention after 10,000 cycles), and high energy density of 30.4 Wh kg -1 . Density functional theory calculations verified the advantages of the high-content sulfur self-doping of black liquor, suggesting that self-doped sulfur contributes to charge adsorption on porous carbon surfaces and promotes electron transfer in the electrolyte., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier B.V.)

This study investigates the production of lignin/silica hybrid nanoparticles (LSNPs) from rice husks, an abundant agricultural waste, and their capacity to stabilize Pickering emulsions for biocatalysis. Lignin extracted from rice husks under alkaline conditions was co-precipitated with silica to produce LSNPs in the presence or absence of ethanol as a co-solvent. Characterization of LSNPs revealed that ethanol played a key role in forming uniform, spherical nanoparticles and minimizing aggregation. Lignin imparted amphiphilicity to the LSNPs, which significantly improved their capacity to form stable Pickering emulsions. LSNPs were able to form stable oil-in-water Pickering emulsions while droplet size and emulsion stability were influenced by LSNPs concentration, oil/water ratio, temperature and pH. LSNPs-stabilized Pickering emulsions were evaluated for lipase-mediated biosynthesis of phytosterol esters, which are plant bioactive compounds that can reduce dietary cholesterol uptake. LSNPs-stabilized emulsions provided 1.915 × 10 6 times larger interfacial areas compared to conventional biphasic systems which facilitated improved mass transfer and lipase activity. Under optimal conditions, LSNPs-stabilized Pickering emulsion systems delivered 90.6% phytosterol ester conversion in 4 h, compared to 10 h in biphasic systems. This research highlights the potential of sustainable, biomass-derived nanoparticles in Pickering emulsion applications and offers an environmentally friendly approach to produce bioactive compounds., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier B.V. All rights reserved.)

The paper industry faces two critical challenges: the scarcity of raw materials and the environmental impact of chemical waste pollution. Addressing the first challenge involves harnessing alternative, sustainable raw materials, while the second challenge can be mitigated through the adoption of bio-bleaching processes, which significantly reduce chemical consumption while enhancing paper brightness and quality. This study proposes a solution to both challenges by using non-woody Calotropis procera (Ankara) and a xylanase-producing microbial consortium for sustainable handmade paper production, a combination not extensively explored in prior research . To evaluate this approach, the process was divided into three stages. In stage I, Ankara fibre was pulped through open hot digestion. In stage II, the pulp was subjected to bio-bleaching in two experimental setups: Set I (without sucrose) and Set II (with sucrose) for 5 days. In stage III, chemical bleaching was used to improve the final brightness of the treated pulps. A novel comparison was made between the bio-bleaching efficiency of an individual isolate g5 (BI) and a bacterial consortium (BC). This research highlighted that bio-bleaching with the consortium effectively removed lignin (140±60 mg/l) and colour (1830±50 PCU), especially in the presence of sucrose, compared to using a single xylanase isolate. Pulp residue/filtrate collected at each stage was estimated based on parameters such as colour and lignin content. After stage III (chemical bleaching), the release of colour and lignin in pulp filtrate was higher in BI compared to BC, indicating the consortium's effectiveness during bio-bleaching, which leaves fewer degradable lignin structures for the chemical bleaching stage. Papers crafted from consortium-treated pulp also exhibited higher brightness than those treated with the isolate. This study reveals the synergistic effect of microbial consortia, leading to more efficient lignin degradation and enhanced bio-bleaching capabilities, supporting the development of greener industrial processes. Ultimately, this study demonstrates a unique and eco-friendly approach to papermaking, combining C. procera and enzymatic bio-bleaching to reduce dependency on hazardous chemicals and support sustainable industry practices., Competing Interests: The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (© 2024 The Author(s).)

The escalating industrialization trend underscores the imperative for sustainable waste management practices. The present investigation explores a sustainable methodology for managing the waste generated from the kraft process by directly converting it into activated carbon (BLAC) through a cost-effective hydrothermal-assisted activation method. The research involved a comparative analysis of BLAC with acid-washed black liquor lignin-derived activated carbon (ABLAC) and commercial lignin-derived activated carbon (SALAC). The analysis revealed that BLAC possesses a well-developed micro and mesoporous structure, yielding a significantly higher surface area of 2277.2 m 2 /g as compared to ABLAC (1260 m 2 /g) and SALAC (1558.4 m 2 /g). The presence of inherent alkali in the black liquor is the main factor influencing the surface area of the BLAC. Furthermore, it demonstrated impressive electrochemical performance, showing a specific capacitance value of 871.4 F/g at 1 A/g current density, positioning it as a formidable electrode material for supercapacitor applications. The proposed direct conversion strategy will eliminate the need for high-temperature pre‑carbonization and additional lignin extraction, reducing chemical usage and presenting a greener approach., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

In pulp mills, lags obscure the effect of upstream operations on downstream measurements. Here, we estimate lags in a Canadian pulp mill using autoregressive exogenous (ARX) models. First, we show that ARX models can approximate lags in a process simulation that resembles the liquor storage tanks in pulp mills, a major source of lag in the kraft recovery cycle. Then, we use ARX models to estimate the lagged effect of a change in species pulped on as-fired liquor heating value, viscosity, and boiling point rise. Additionally, we compare the predictions of the ARX models to autoregressive (AR) models and a persistence model. The estimated lags between a change in species and heating value (49 h) and boiling point rise (41 h) agree with a detailed simulation of the mill and are close to estimated hydraulic residence times, suggesting that the liquor tanks exhibit imperfect mixing. A lagged effect of species change on viscosity could not be identified. ARX and AR models produce similar predictions that are slightly better than those of a persistence model. Finally, we show that process measurements upstream of units characterized by large residence times will likely provide little benefit to prediction accuracy., Competing Interests: Competing interests: The authors state no conflict of interest., (© 2024 Walter de Gruyter GmbH, Berlin/Boston.)

This study aimed to investigate a novel method for the green synthesis of iron nanoparticles (FeNPs) using marigold extract (Calendula officinalis L), kraft pulping black liquor, and nanocellulose. Then, the efficacy of FeNPs as a direct nanofertilizer on the growth parameters of marigold was investigated. Characterization techniques including FESEM, EDX, VSM, and FTIR were used to confirm the successful synthesis of FeNPs. The characterization results confirmed the formation and presence of FeNPs in the 20-100 nm range. FeNPs synthesized with nanocellulose notably enhanced marigold growth parameters compared to other materials. However, all nanoparticle variants, including those from marigold extract and black liquor, improved germination, plant height, root length, and plant dry weight compared to the control. Moreover, treatments exhibited higher available iron and total plant iron levels than the control. Thus, employing 10 mg FeNPs (prepared with 5.0 % nanocellulose) appears optimal for enhancing marigold growth and yield., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

The current investigation concerns with preparation eco-friendly and cost-effective adsorbent (mesoporous silica nanoparticles (SBL)) based on black liquor (BL) containing lignin derived from sugarcane bagasse and combining it with sodium silicate derived from blast furnace slag (BFS) for thorium adsorption. Thorium ions were adsorbed from an aqueous solution using the synthesized bio-sorbent (SBL), which was then assessed by X-ray diffraction, BET surface area analysis, scanning electron microscopy with energy dispersive X-ray spectroscopy (EDX), and Fourier transforms infrared spectroscopy (FTIR). Th(IV) sorption properties, including the pH effect, uptake rate, and sorption isotherms across various temperatures were investigated. The maximum sorption capacity of Th(IV) on SBL is 158.88 mg/L at pH value of 4328 K, and 60 min contact time. We demonstrated that the adsorption processes comport well with pseudo-second-order and Langmuir adsorption models considering the kinetics and equilibrium data. According to thermodynamic inspections results, the Th(IV) adsorption process exhibited endothermic and random behavior suggested by positive ΔH° and ΔS° values, while the negative ΔG° values indicated a spontaneous sorption process. The maximum Th(IV) desorption from the loaded SBL (Th/SBL) was carried out at 0.25 M of NaHCO 3 and 60 min of contact. Sorption/desorption processes have five successive cycles. Finally, this study suggests that the recycling of BFS and BL can be exploited for the procurement of a promising Th(IV) adsorbents., (© 2023. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

A lab-scale gravity-driven bioreactor (GDB) was designed and constructed to evaluate the simultaneous treatment of black liquor and domestic wastewater. The GDB was operated with a mixture of black liquor and domestic wastewater at a ratio of 1:1 and maintained at an average organic loading rate of 1235 mg-COD/L-Day. The wastewater was fed to the primary sedimentation tank at a flow rate of approximately 12 mL/min and subsequently passed through serially connected anaerobic and aerobic chambers with the same flow rate. Each wastewater sample was allowed to undergo a hydraulic retention time of approximately 72 h, ensuring effective treatment. The GDB was actively operated for nine samples (W1-W9) at a weekly frequency. The entire process was conducted within the workstation's ambient temperature range of 30-35 °C to sustain microbial activity and treatment efficiency in an open environment. The performance of the GDB was evaluated in terms of various pollution indicators, including COD, BOD 5 , lignin removal, TDS, TSS, EC, PO 4 3- , SO 4 2- , microbial load (CFU/mL and MPN index), total nitrogen, and color reduction. The results showed that the GDB achieved promising treatment efficiencies: 84.5% for COD, 71.80% for BOD 5 , and 69.36% for TN. Additionally, about 80% reduction in lignin content and 57% color reduction were observed after the treatment. The GDB substantially reduced microbial load in CFU/mL (77.98%) and MPN (90%). This study marks the first to report on wastewater treatment from two different sources (black liquor and domestic wastewater) using a simple GDB design. Furthermore, it highlights the GDB's potential as a cost-effective, environmentally friendly, and efficient solution for wastewater treatment, with no need for supplementary chemical or physical agents and zero operational costs.4 3- , 81% for SO 4 2- , and 69.36% for TN. Additionally, about 80% reduction in lignin content and 57% color reduction were observed after the treatment. The GDB substantially reduced microbial load in CFU/mL (77.98%) and MPN (90%). This study marks the first to report on wastewater treatment from two different sources (black liquor and domestic wastewater) using a simple GDB design. Furthermore, it highlights the GDB's potential as a cost-effective, environmentally friendly, and efficient solution for wastewater treatment, with no need for supplementary chemical or physical agents and zero operational costs., (© 2023. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

The valorization of the black liquor produced during the chemical pulping of wheat straw is the key to the sustainable use of this abundant agricultural waste. However, the silica problem has hampered the recovery process. Herein, nanoprecipitation technology was used to produce lignin nanoparticles (LNPs) from wheat straw black liquor using γ-valerolactone (GVL) as a solvent and water as an anti-solvent. The results showed that a uniform, well-dispersed, and stable LNP was produced. The particle size and Zeta potential of 161 nm and -24 mV of the LNP suspension were obtained at a GVL concentration of 87%. The chemical structure and bonding of the lignin were adequately preserved after nanoprecipitation based on two-dimensional heteronuclear single quantum coherence nuclear magnetic resonance (2D-HSQC NMR) spectroscopy, Fourier transform infrared (FTIR) analysis, and thermal stability was improved based on thermogravimetric analysis. In addition, the abundant phenolic hydroxyl groups of LNP quantified by 31 P-NMR analysis are beneficial for chemical cross-linking and modification. This work not only achieved the valorization of wheat straw black liquor but also opened up a new avenue for advanced nanomaterials.

The present study demonstrates the potential of an integrated vertical flow-constructed wetland (IVFCW) for simultaneously treating black liquor and domestic wastewater. IVFCW was operated and monitored for 12 samples with the frequency of one sample per week with the following specifications viz,4 L of wastewater, a blend of 1:1 of pulp and paper industry effluent (black liquor BL), and domestic wastewater, was fed daily in a continuous mode with organic loading rate (OLR) of 1230 mg COD/L-Day, at a temperature range of 40-45℃ (natural temperature of the workstation). Valves controlled each chamber's hydraulic retention time (HRT) of 3 days and flow rate of 10 mL/minute. The IVFCW showed remarkable efficiency in removing various pollutants, including total suspended solids (TSS) and total dissolved solids (TDS), by 100 % and 83 %, respectively, and organic contaminants such as chemical oxygen demand (COD) and biological oxygen demand (BOD) by 80 % and 81 %, respectively. Moreover, the IVFCW efficiently reduced nutrients such as sulfates (SO₄ -2 ), phosphates (PO₄ -3 ), and total nitrogen by about 81 %, 63 %, and 61 %, respectively. The treatment also led to the reduction of lignin content by 83 %. Microbiological analysis revealed a significant reduction in fecal coliforms, and microbial profiling of Typha latifolia roots confirmed the presence of bacteria involved in lignin degradation. Seed germination and seedling survival were found to be negativelyaffected by untreated wastewater in a phytotoxicity study, suggesting that the wastewater's toxic chemicals could be harmful to plant life.This study highlights the effectiveness of IVFCW as a sustainable, economically viable, and resilient wastewater treatment system for mitigating environmental concerns related to the release of untreated wastewater., Competing Interests: The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (© 2023 The Authors.)

Hydrothermal liquefaction of Kraft black liquor is a promising method for the production of valuable organic chemicals. However, the separation of the biochar and biocrude leaves a residual aqueous phase in large volumes, which needs to be properly managed to make the process profitable. In this work, the persulphate-based advanced oxidation was assessed, for the first time ever, as a pretreatment of this aqueous phase to reduce its content of phenolic compounds and alcohols, which hinder further valorisation strategies. Results revealed that the phenolic compounds and the alcohols were oxidised in presence of low persulphate anion concentrations (<50 mM), mainly to quinone-like compounds and organic acids. At higher oxidant concentrations, these intermediates were subsequently oxidised to valuable acetic acid. When Fe (II) was added as the catalyst, low concentrations (<9 mM) enhanced the degradation of both phenolic compounds and alcohols due to the increase of the sulphate radicals, consequently reducing persulphate requirements for their removal. Nevertheless, higher Fe (II) doses produced the sequestration of sulphate radicals, thus decreasing the oxidation performance and generating undesired parallel reactions., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Authors. Published by Elsevier Ltd.. All rights reserved.)

The effluents generated in the paper industry, such as black liquor, have a high content of lignin and other toxic components; however, they represent a source of lignin-degrading bacteria with biotechnological potential. Therefore, the present study aimed to isolate and identify lignin-degrading bacteria species in paper mill sludge. A primary isolation was carried out from samples of sludge present in environments around a paper company located in the province of Ascope (Peru). Bacteria selection was made by the degradation of Lignin Kraft as the only carbon source in a solid medium. Finally, the laccase activity (Um-L -1 ) of each selected bacteria was determined by oxidation of 2,2'-azinobis-(3-etilbencenotiazolina-6-sulfonate) (ABTS). Bacterial species with laccase activity were identified by molecular biology techniques. Seven species of bacteria with laccase activity and the ability to degrade lignin were identified. The bacteria Agrobacterium tumefasciens (2), Klebsiella grimontii (1), and Beijeinckia fluminensis (1) were reported for first time. K. grimowntii and B. fluminensis presented the highest laccase activity, with values of 0.319 ± 0.005 UmL -1 and 0.329 ± 0.004 UmL -1 , respectively. In conclusion, paper mill sludge may represent a source of lignin-degrading bacteria with laccase activity, and they could have potential biotechnological applications.

Herein, we present a synthesis route for high-efficiency nitrogen-doped carbon materials using kraft pulping residue, black liquor, and wood charcoal as carbon sources. The synthesized nitrogen-doped carbon materials, based on black liquor and its mixture with wood charcoal, exhibited high specific surface areas (SSAs) of 2481 and 2690 m 2 g -1 , respectively, as well as a high volume of mesopores with an average size of 2.9-4.6 nm. The nitrogen content was approximately 3-4 at% in the synthesized nitrogen-doped carbon materials. A specific capacitance of approximately 81-142 F g -1 was achieved in a 1 M Na 2 SO 4 aqueous solution at a current density of 0.2 A g -1 . In addition, the specific capacitance retention was 99% after 1000 cycles, indicating good electrochemical stability.

Lignin is a natural biopolymer with a complex three-dimensional network and it is rich in phenol, making it a good candidate for the production of bio-based polyphenol material. This study attempts to characterize the properties of green phenol-formaldehyde (PF) resins produced through phenol substitution by the phenolated lignin (PL) and bio-oil (BO), extracted from oil palm empty fruit bunch black liquor. Mixtures of PF with varied substitution rates of PL and BO were prepared by heating a mixture of phenol-phenol substitute with 30 wt.% NaOH and 80% formaldehyde solution at 94 °C for 15 min. After that, the temperature was reduced to 80 °C before the remaining 20% formaldehyde solution was added. The reaction was carried out by heating the mixture to 94 °C once more, holding it for 25 min, and then rapidly lowering the temperature to 60 °C, to produce the PL-PF or BO-PF resins. The modified resins were then tested for pH, viscosity, solid content, FTIR, and TGA. Results revealed that the substitution of 5% PL into PF resins is enough to improve its physical properties. The PL-PF resin production process was also deemed environmentally beneficial, as it met 7 of the 8 Green Chemistry Principle evaluation criteria.

In this study, selective extraction towards ionic liquid trihexyltetradecylphosphonium chloride ([P 66614 ]Cl) of lignin residues, polysaccharides and organic acids present in black liquor (BL), the main principal wastewater of pulping industry was studied. With the objective of finding optimized conditions allowing to extract lignin residues while polysaccharides and organic acids remain in aqueous solution, a design of experiments approach based on a response surface methodology was used. Three continuous factors, namely initial pH varying from 9 to 13.5, dilution of BL varying from 5 to 20 and volumetric ratio of black liquor vs. ionic liquid R V ., varying from 1 to 19, were investigated. Concentration of lignin residues, polysaccharides and organic acids were measured using Folin-Ciocalteu method, the anthrone method and HPLC, respectively. Results showed that a multi-response optimization led to the extraction of 84.8 % of lignin residues, 66.0 % of polysaccharides, and no extraction of OA under optimised conditions., (© 2023 The Authors. ChemPlusChem published by Wiley-VCH GmbH.)

In this paper, the relationship between black liquor and microbial growth, enzymatic secretion and humus formation in composting was studied. The results showed that black liquor inoculation is an effective way to promote fermentation process. After black liquor inoculation, the abundance of Corynebacterium , Aequorivita , and Pedobacter , which have the catalase and oxidase activity, has been significantly increased. The enzymatic activity of alkaline phosphatase, catalase, peroxidase and invertase was 40 mg/(g·24h), 6.5 mg/(g·20 min), 13 100 mg/(g·24h), and 6100 mg/(g·24h) respectively at day 18. Humic acid and fulvic acid concentration was 12 g/kg and 11 g/kg which is higher than that of the treatments of no black liquor inoculation. The results suggested that black liquor inoculation was beneficial to indigenous microorganisms reproduce efficiently, then the secretion of enzymes related to cellulose, hemicellulose, and lipid hydrolysis, and the formation of humic substances., (© 2023 The Authors.)

In kraft pulping, large quantities of biomass degradation products dissolved in the black liquor are incinerated for power generation and chemical recovery. The black liquor is, however, a promising feedstock for carboxylic acids and lignin. Efficient fractionation of black liquor can be used to isolate these compounds and recycle the pulping chemicals. The present work discusses the fractionation of industrial black liquor by a sequence of nanofiltration and bipolar membrane electrodialysis units. Nanofiltration led to retention of the majority of lignin in the retentate and to a significant concentration increase in low-molecular-weight carboxylic acids, such as formic, acetic, glycolic and lactic acids, in the permeate. Subsequent treatment with bipolar membrane electrodialysis showed the potential for simultaneous recovery of acids in the acid compartment and the pulping chemical NaOH in the base compartment. The residual lignin was completely retained by the used membranes. Diffusion of acids to the base compartment and the low current density, however, limited the yield of acids and the current efficiency. In experiments with a black liquor model solution under optimized conditions, NaOH and acid recoveries of 68-72% were achieved., Competing Interests: The funders had no role in the design of the study; in the collection, analyses, or interpretation of data; in the writing of the manuscript; or in the decision to publish the results.

In present research, a potent fungal strain was isolated from paper mill effluent (black liquor) in order to investigate its potential for the biodegradation of lignin. Two step strategy was used to screen most efficient fungal strain having ability to growin MSM-black liquor medium and to degrade alkali lignin.The results of initial screening indicated that the strain M-2 produced comparatively higher ligninolytic zone on MSN agar plates supplemented with black liquor (BL) and alkali ligninase compared to the other isolates.The results of 18S rRNA gene sequencing revealed that strain M-2 showed ≥ 99% sequence homology with Dipodasceus australiansis.The process for the biodegradation of lignin was optimized using Taguchi Orthogonal Array design. Under optimized conditions of pH 9, 40 °C and 4% inoculum, a maximum of 89% lignin was degraded with 41% color reduction after 8 days of incubation period by Dipodasceus australiansis M-2. The pH and temperature were found to be significant terms with the p-values of 0.002 and 0.001 respectively. The laccase activity of the Dipodascus australiensis was found to be maximum of 1.511 U/mL. The HPLC analysis of lignin biodegradation indicated sharp transformation of peaks as compared to the control. Our results suggested that the strain Dipodascus australiensis M-2 possess excellent lignin degradation and color reduction capability and can be applied in waste treatment systems for pulp and paper mill effluent. In present work we are reporting first hand information regarding biodegradation of lignin by a potent strain of Dipodascus australiensis and statistical optimization of the bioprocess., Competing Interests: Conflict of interest The authors declare that they have no competing interests., (Copyright © 2022 Elsevier GmbH. All rights reserved.)

The black liquor of bamboo pulp contains a large amount of silicon, which makes it difficult to separate industrial lignin, thus hindering its high-value utilization. Herein, this paper dedicates to exploring the high-value use of silica-containing lignin. Tetraethyl silicate (TEOS) was added to the above silicon-containing lignin for crosslinking with the lignin to prevent disintegration during carbonization and provide an additional source of silica. The carbonization is carried out at 600 °C (LT-6), 900 °C (LT-9) and 1200 °C (LT-12), and the structural evolution of SiO x C y is innovatively analyzed. The results show that LT-9 is dominated by the SiO 3 C structure and has a specific surface area of 269 m 2  g -1 . The specific capacitance of LT-9 and LT-12 as supercapacitors electrodes is 78.6 F g -1 and 74.8 F g -1 at a current density of 1 A g -1 , and remains 95 % and 91.7 % after 10,000 cycles. Moreover, LT-9 has a high yield of 54 %. In this work, silicon-containing lignin is exploratively prepared as a silicon-carbide-derived material. Furthermore, the potential relationship between different SiO x C y molecular structures and electrochemical performance is evaluated, which is instructive for the high-value utilization of black liquor in bamboo pulp., (Copyright © 2022 Elsevier B.V. All rights reserved.)

This study reports an alternative method for black liquor treatment with potential for energy and process savings in the paper and pulp industry. Gasification of black liquor was carried out under sub- and supercritical conditions, varying the black liquor feed composition (0.10, 2.55 and 5.00 wb%) and temperature (350, 425 and 500 °C). Liquid products were identified by high resolution mass spectrometry (FT-Orbitrap MS) and compounds belonging to classes O 3 and O 4 were found to be the most representative in the products of reactions performed at 500 °C. The mass spectra results also revealed the overall selectivity of reactions, where decarboxylation and demethoxylation reactions were favored under subcritical and supercritical conditions, respectively. Among the gaseous products, hydrogen and methane were produced with maximum of 69.04 and 28.75 mol%, respectively, at 2.55 wb% and 425 °C. The proposed thermodynamic modelling of the reaction system satisfactorily predicted the gas phase behavior of the system. In the economic analysis, the simulated conditions indicated that the main energy requirements for a scaled-up black liquor gasification process are related to the necessary heat exchangers and pressurizing of the black liquor solution. Furthermore, the cost of the black liquor gasification is around 0.06 US$ per kg of feed stream. Liquid and gaseous products from gasification could be obtained at a cost of 56.64 US$ and 3.35 US$ per tonne of stream, respectively. Therefore, black liquor gasification is an interesting route for obtaining combustible gases and value-added bioproducts., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

The pulp and paper industry consumes a huge amount of water and releases more polluted and colored wastewater every year. Many conventional techniques are used in the treatment of paper industry wastewater. However, for color removal from paper mill effluent, there is no proven method so far, on an industrial scale. Due to high energy input and high cost, there is an urgent need to find out a new technique that must be sustainable, economical, and environment friendly. Various methods have been investigated on bench scale and pilot scale also but no proven method for color removal on an industrial scale. The paper provides an overview of the color removal techniques from different sources of pulp and paper mill wastewater discharged by various industries. The review described various components involved in various processes for color removal from paper mill waste water. The present works focus on processes like chemical, chemical/physical, biological, physicochemical, and electrochemical applied in color removal from paper mill wastewater. The present review gives key information on the effectiveness, use, betterment, and limitations of numerous methods of treatment targeted at color removal from paper mill wastewater using various techniques still under evolution., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Lignin is a major byproduct of pulp and paper industries, which is resistant to depolymerization due to its heterogeneous structure. The enzymes peroxidases can be utilized as potent bio-catalysts to degrade lignin. In the current study, an Efeb gene of 1251bp encoding DyP-type peroxidase from Bacillus sp. strain BL5 (DyPBL5) was amplified, cloned into a pET-28a (+) vector and expressed in Escherichia coli BL21 (DE3) cells. A 46 kDa protein of DyPBL5 was purified through ion-exchange chromatography. Purified DyPBL5 was active at wide temperature (25-50 °C) and pH (3.0-8.0) range with optimum activity at 35 °C and pH 5.0. Effects of different chemicals on DyPBL5 were determined. The enzyme activity was strongly inhibited by SDS, DDT and β-mercaptoethanol, whereas stimulated in the presence of organic solvents such as methanol and ethanol. The kinetic parameters were determined and K m , V max and K ca t values were 1.06 mM, 519.75 μmol/min/mg and 395 S̶ 1 , respectively. Docking of DyPBL5 with ABTS revealed that, Asn 244, Arg 339, Asp 383 and Thr 389 are putative amino acids, taking part in the oxidation of ABTS. The recombinant DyPBL5 resulted in the reduction of lignin contents up to 26.04 %. The SEM and FT-IR analysis of test samples gave some indications about degradation of lignin by DyPBL5. Various low molecular weight lignin degradation products were detected by analyzing the samples through gas chromatography mass spectrometry. High catalytic efficiency and lignin degradation rate make DyPBL5 an ideal bio-catalyst for remediation of lignin-contaminated sites., (Copyright © 2021 Elsevier Inc. All rights reserved.)

Lignin recovery from black liquor is an important task for producing valuable chemical products. Acidification processes are currently applied by pulp and paper industries for black liquor treatment, in which two main streams are produced: the precipitated lignin fraction and a lignin-lean black liquor. Membrane filtration is a suitable alternative for lignin recovery from black liquor, but studies on lignin-lean black liquor filtration are scarce. Here, we evaluated the ultrafiltration process for lignin recovery from the both fractions of black liquor acidification. The lignin-lean black liquor presented 22 wt% of total solids with 4.6 wt% of lignin. Lignin retention from the lignin-lean black liquor by the 5 kDa ultrafiltration membrane was equal to 85%, with reduction in total solid concentration from 219.8 to 68.1 g L -1 . Due to the relatively high solid concentration in the lignin-lean black liquor, cake formation was the main fouling mechanism during ultrafiltrations. The precipitated lignin solution presented 4.8 wt% of total solids with equivalent lignin concentration (4.7 wt%). The used membrane was able to retain almost 100% of solids and lignin from the solution prepared from the precipitated lignin. All fouling mechanisms were responsible for flux decay in ultrafiltration of the precipitated lignin solution. Steady state fluxes for lignin-lean black liquor and precipitated lignin solution were 0.9 and 15.9 L h -1 m -2 , respectively. According to TGA analyses up to 800 °C, precipitated lignin and lignin-lean black liquor presented total mass losses of 63.5% and 44.3%, respectively. Also, the permeate samples presented lower mass losses than their respective feed samples. The ultrafiltration process reduced the average weight molar mass (M w ) of the precipitated lignin solution and lignin-lean black liquor from 1817 to 486 g mol -1 and from 2876 to 1095 g mol -1 , respectively. Thus, the 5 kDa ultrafiltration membrane was efficient for lignin recovery from the lignin-lean black liquor, while membranes with lower cut-off should be proposed for lignin purification from the precipitated fraction., (© 2021. The Author(s), under exclusive licence to Springer Science+Business Media, LLC, part of Springer Nature.)

The aim of the study was to use black liquor produced during the soda pulping process in a pulp and paper mill to increase methane production during pulp and paper industry sludge treatment and decrease the treatment cost. The effects of black liquor on sludge solubilization and methane production were assessed and the economic feasibility of the process was evaluated. Black liquor and NaOH were found to be equivalent in the thermochemical pretreatment process to solubilize sludge and disintegrate flocs. However, adding black liquor increased the background chemical oxygen demand and volatile fatty acid concentration and increased the amount of methane produced by approximately 7-30%. A start-up delay was emphasized by first-order kinetics model due to black liquor addition while methane production remained stable. Economic assessments of five scenarios were performed. It was found to be economically feasible to use black liquor to replace NaOH for the thermal pretreatment process. The surplus methane generated suggested that co-digestion of sludge and black liquor allows surplus bioenergy to be produced during the thermochemical pretreatment anaerobic digestion process., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Water hyacinth (WH) is considered as the worst aquatic weed in the world because of its rapid growth and fast spread into new areas of fresh water bodies. We investigated the potentiality of using WH as a raw material for production of handmade paper and compost in Bangladesh. Potash pulping was done using potassium hydroxide (KOH) at different alkali concentrations (8-12%) with a liquor to solid ratio of 7:1 at 145 °C for 2 h. The pulp was bleached using hydrogen peroxide (H 2 O 2 ), and pulp properties (brightness, tear index and tensile index) of bleached and unbleached pulps were analyzed following the respective TAPPI standards. The produced black liquor was mixed with WH along with kitchen bio-wastes to produce compost. The properties of the compost were tested following the published protocols, i.e., wet digestion, Kjeldahl, vanadomolybdophosphoric acid, and Flame Spectrophotometry methods. Brightness, tensile index and tear index of bleached hand sheets were found to be 37.2%, 49.2 N m/g and 6.79 m.Nm 2 /g, respectively suggesting significant contribution of bleaching on WH paper quality. Addition of black liquor significantly increased the nitrogen and potassium content of bio-waste compost. Thus, WH can be used as a raw material for making handmade paper while the process by-product can be supplemented to improve the nutritional quality of compost. Such cottage-industry fabrication of WH green products could be developed to control the infestation of WH in water bodies, and this technology may provide for new possible sustainable livelihood option., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Recycling wastes back into a manufacturing process, or into a separate product, is an important challenge. The primary aim of this work was to combine wastes from the steel industry, the galvanizing industry and the pulp and paper industry to form two new useful products. The steel industry generates the wastes red dust, mill scale, blast oxygen furnace slag and iron ore fines. Galvanizing industrial facilities dispose of sulfuric acid contaminated with iron. The pulp and paper industry produces the byproduct black liquor, which is high in lignin. Inserting these wastes as resources into the steel industry, or as stand-alone products, could reduce the need for virgin materials. The main methodology of the work was three-fold. First, spent sulfuric acid was used to precipitate the lignin from black liquor. Second, this lignin was combined with steel industry wastes and geopolymeric materials to make briquettes, a sustainable reducing material for steelmaking furnaces. Briquettes contained red dust, mill scale, blast oxygen furnace slag, iron ore fines and lignin precipitated from black liquor with spent sulfuric acid. Key research findings of compressive strength and weight loss testing showed the briquettes to be feasible for steel-making furnace use. Third, these steel industry wastes were investigated as a partial fly ash replacement in geopolymers. Main research findings were that compared to the control geopolymer, these geopolymer samples improved compressive strength and gave similar workability. Thus, the investigated wastes have the potential to both increase recycling in the steel industry and to improve geopolymeric products., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Here, firstly lignin sulfonate was produced from sulfite liquor provided by Mazandaran wood & paper industries (Chookam). Then, the role of effective parameters including reaction temperature, duration time, and amounts of pyridine and acetic anhydride respectively as the catalyst and the esterification agent on the acetylation rate of lignin sulfonate were studied and the process parameters were optimized through multiple experiments. In this investigation, using 1 g lignin sulfonate, the effect of various levels of temperature (ranged from room temperature to 140 °C), reaction time (12-72 h), pyridine volume (0-30 mL), and acetic anhydride volume (5-30 mL) were evaluated. Based on the results of several esterification processes, the optimal values of temperature and reaction time were obtained to be 100 °C and 48 h, respectively, and the optimal volumes of acetic anhydride and pyridine were 20 mL (with equal amounts). Besides, the characterization tests of lignin sulfonate and acetylated lignin sulfonate were performed using FT-IR and NMR techniques. Also in this paper, the morphology and crystallinity/amorphicity of lignin sulfonate and acetylated lignin sulfonate were examined using SEM images and XRD patterns., Competing Interests: Declaration of competing interest The authors declare that they have no conflicts of interest with the contents of this article., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Papermaking raw materials are usually digested by NaOH and Na 2 S solution. The fate of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) during the kraft pulping process is still poorly known. In this study, a comprehensive investigation was conducted on the variation in PCDD/Fs in the kraft pulping section of 3 modern non-wood pulp mills adopting elemental chlorine-free (ECF) bleaching technology. Similar dioxin homologue profiles, dominated by Cl 1-3 DF and Cl 2 DD homologues, were observed in the raw materials, black liquors and brown pulps; and the partitioning behaviors of dioxin congeners between black liquor and brown pulp were found to be partly dependent on their octanol-water partitioning coefficients. Dioxin mass flow analysis indicated that the raw materials contributed more than 95 % to the dioxins entering the pulping section. Approximately 7 - 30 % of the input dioxins were exported by black liquor, and the brown pulp carried 44 - 51 % of the input dioxins into the subsequent bleaching section. The kraft pulping process caused a 40 - 48 % reduction in input dioxins. Alkaline hydrolysis and coupling reaction between dioxins and the aromatic fragments of lignin were proposed as two most possible mechanisms for dioxin elimination. In general, modern pulp mills have actually become industrial plants that eliminate environmental dioxins., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Black liquor (BL) is an agro-industrial residue with high number of lignocellulosic components which could be recognized as a biomass feedstock. In this work, BL coupled with red mud (RM), were applied to prepare cost-effective zero-valent iron (ZVI) embedded in biochar. The oligomers in BL acted as reductants for RM to generate ZVI, while the organic components could be converted into biochar during pyrolysis. The RM/BL demonstrated excellent performance in the removal of Cr(VI) (349.5 mg/g), as the mechanisms were reduction and adsorption. The fixed-bed column study was conducted and 1.7 L simulated wastewater could be treated by 1.0 g RM/BL. After reaction, 95.5% ± 0.8% and 82.5%±3.2% Cr-loaded adsorbents could be recovered by an external magnet for batch and fixed-bed experiments, respectively. All these results shed light on valorizing these two widespread agro-industrial byproducts, and bridged the knowledge gap between magnetic bio-adsorbent preparation and its industrial practicality on wastewater purification., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

In the present study, black liquor generated during mild alkali pre-treatment was evaluated as a moistening agent to produce cost effective hydrolytic enzymes using novel cellulo-xylano fungal strain Aspergillus tubingensis M7. The fungus competently produced 21.90 and 22.46 filter paper, 1004 and 1369 endoglucanase, 117 and 142 β-glucosidase and 8188 and 7981 U/g xylanase activity by using modified Mandel & weber's and black liquor medium, respectively. The crude hydrolytic enzymes from black liquor were evaluated for saccharification of pre-treated biomass. Reducing sugar yields (mg/g substrate) and the corresponding saccharification efficiency (%) from rice straw, corncob, sugarcane bagasse and banana stem were 745.50 (86.02; 18 h); 596 (74.50; 24 h); 358.15 (42.98; 24 h) and 245.70 (33.00; 24 h), respectively. Residual biomass compositional analysis revealed that reduced onset temperature, increased activation energy and pre-exponential factor in saccharified biomass as compared to pre-treated and untreated biomass, suggesting their utilization for pyrolysis to obtain value added products., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

In this work, black liquor as a waste from paper industry was used to pretreat corn stover before anaerobic digestion. The batch mode anaerobic digestion achieved a methane production up to 260.5 mL/g VS when the corn stover was pretreated the black liquor of 12 g NaOH/L alkalinity for 24 h, which was 59.1% higher than the control. In the semi-continuous mode anaerobic digestion, black liquor pretreatment increased the buffering capacity of the digestate to maintain suitable pH and total VFA/alkalinity ratio with no adverse effect resulted from the presence of ions. The structural and chemical changes of corn stover after the pretreatment were investigated to rationalize the enhanced performance of anaerobic digestion., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Black liquor has caused a tremendous degree of pollution and waste. Exploring the utilization of lignin, which is the major component of black liquor, has become a key factor in dealing with the problem. In this study, lignin derived from black liquor was used as a raw material to prepare carbon materials through different activation methods including KOH, H 3 PO 4 , and steam activation. The structure and properties of obtained samples were characterized as well as electrochemical performance when applied on a lithium-oxygen battery. Results of N 2 adsorption/desorption showed that all obtained samples possessed high surface area of over 1000 m 2 /g. XRD, Raman, and XPS also indicated that obtained samples possessed a large defect area and many functional groups. Electrochemical measurements illustrated that all obtained samples exhibited a high discharge capacity over 2.8 mAh/cm 2 at 0.02 mA/cm 2 , while LKAC exhibited the highest discharge capacity of 7.2 mAh/cm 2 . Cycling tests of all obtained samples indicated a long cycle life of at least 300 cycles. LSAC maintained a 100% retention rate of capacity and stable terminal voltage even after 800th cycle, and its cycling performance was investigated further by XRD and EIS. This study demonstrated excellent performance for lignin-based carbon materials, and provided alternative materials for positive electrode of lithium-oxygen battery.

Lignin nano-/microstructures are widely employed for agricultural drug delivery and heavy metal removal from wastewater, and facile low-cost methods of their large-scale production are therefore highly sought after. Herein, uniform-morphology polydisperse lignin microspheres were directly extracted from black liquor by lowering its pH to <4 followed by hydrothermal treatment and featured several lignin-typical characteristics, e.g., functional groups, thermal stability, amorphousness, and monolignol units. It was assumed that lignin rearranged and assembled into microspheres of various size, shape, and uniformity depending on pH, temperature, and hydrothermal treatment time. Lignin microsphere extraction efficiency was estimated as 15.87-21.62 g L -1 , and the average size of microspheres obtained under different conditions was calculated as ∼1 µm, while the C, H, O, and N contents equaled 48-62, 5-6, 30-36, and 0.2-1.5%, respectively. Thus, our method was deemed suitable for direct large-scale extraction of lignin microspheres from black liquor., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

With the increase in lignin availability, materials derived from micro- and nano-scale lignin developed rapidly. However, the tedious processes of raw-lignin pretreatment and poor stability seriously restrict the large-scale applications of lignin nanoparticles. To overcome these problems, in this work, a novel green and simple approach was developed to produce super long-term stable lignin nanoparticles (LTSL NPs). The LTSL NPs were prepared directly from black liquor via an acid precipitation method. The obtained LTSL NPs exhibited well uniformity, excellent dispersibility, controllable size, and super long-term stability in aqueous media (no apparent size increase or any particle precipitation for 90 days in neutral water medium). Analyses of nuclear magnetic resonance and ion chromatography revealed that LTSL NPs exhibited higher S/G ratio and higher content of hemicellulose comparing with the lignin nanoparticles which obtained from traditional solvent exchange (ethanol/H 2 O) method. In addition, the size of the LTSL NPs can be well controlled by tuning the degree of acid precipitation (the final pH value). This work not only can promote the development of lignin-based nanomaterials, but also provides a promising utilization pathway for black liquor that simultaneously achieves the fabrication of lignin materials and hemicellulose application., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Black liquor-derived calcium-activated biochars (Ca-biochar) were synthesized by treating rice straw with Ca(OH) 2 to create an adsorbent that was effective for removing phosphate from aqueous waste streams. The Ca(OH) 2 acts to separate lignin from the biomass, create pores in the biochar solids and form active adsorption sites. The Ca-biochar adsorbent was efficient for the removal of phosphate from aqueous solutions (pH 1.0 to pH 13.0) with a highest phosphate adsorption capacity of 197 mg/g. Phosphate adsorption was correlated with pseudo-second-order kinetics and the Langmuir model with primary mechanisms being attributed to chemical precipitation and ligand exchange. Application of the Ca-biochar (0.2 g/L) to actual wastewater from a cattle farm (phosphorus content 3.78 mg/L) reduced the phosphorus content to 0.021 mg/L. This work utilizes waste black liquor to prepare functionalized biochar materials, providing a promising approach for black liquor reuse and phosphate removal and recovery from phosphorus-rich waste streams., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

A low-temperature sodium hydroxide (NaOH) pretreatment for sugarcane bagasse (SCB) was obtained via the surface response design in this study. However, a large quantity of water consumption and wastewater generation which have been the common problems for alkaline pretreatment of lignocellulose still exists in this pretreatment. In order to reduce water consumption and wastewater generation, this study attempted to perform enzymatic hydrolysis and fermentation of NaOH-treated SCB without washing process. It showed that after pretreatment and solid-liquid separation, NaOH-treated SCB could be directly hydrolysed by cellulase via pH and solid-liquid adjustment without washing steps, and the maximum enzymatic hydrolysis efficiency could reach to 70.2%. A domesticated Saccharomyces cerevisiae Y2034 which can endure 6-times diluted BL was obtained, and realized 67.5% ethanol yield from the enzymatic hydrolysate of unwashed NaOH-treated SCB. It provided a clue for converting NaOH-treated lignocellulose to ethanol at low water consumption and wastewater generation., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Black liquor, an industrial waste product of papermaking, is primarily used as a low-grade combustible energy source. Despite its high lignin content, the potential utility of black liquor as a feedstock in products manufacturing, remains to be exploited. Demonstrated here in is the use of black liquor as a primary feed-stock for synthesizing graphene quantum dots that exhibit both up-conversion and photoluminescence when excited using visible/near-infrared radiation, thereby enabling the photosensitization of ultraviolet-absorbing TiO 2 nanosheets. In addition, these graphene quantum dots can trap photo-generated electrons to realize the effective separation of electron-hole pairs. Together, these two processes facilitate the solar-powered generation of H 2 from H 2 O, and CO from H 2 O-CO 2 , using broadband solar radiation., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Water-soluble kraft lignin-based polyoxyethylene ether (KL-PEG), synthesized from the black liquor of kraft pulping and PEG, was used to improve the enzymatic hydrolysis efficiency of dilute acid pretreated (DA-pretreated) Eucalyptus hardwood and cellulase stability. The physicochemical properties of KL-PEG polymer such as solubility, surface tension, charge and aggregation behavior in the solution were first studied. KL-PEG could enhance the enzymatic hydrolysis of Avicel and DA-pretreated Eucalyptus from 63.6% and 58.3% to 78.5% and 93.8%, respectively. The enzymatic activity of cellulase after the enzymatic hydrolysis of Avicel and DA-pretreated Eucalyptus for 72 h remained approximately 84% and 44% in the presence of KL-PEG polymer. KL-PEG could improve the stability and longevity of the cellulase, facilitate the recovery and save the amount of cellulase. The efficient utilization of the pulping black liquor lignin was of great significance to alleviate the pressure brought by the shortage of petrochemical resources, and build an energy-saving and low-carbon society., (Copyright © 2019 Elsevier B.V. All rights reserved.)

The present study assesses, for the first time, the use of the non-lignin residue from Kraft black liquor as a renewable source of carboxylic acids. For this purpose, the liquid fraction obtained after separating the lignin from the black liquor by acid precipitation was subjected to different hydrothermal treatments. It was found that the formation of carboxylic acids can be maximized at 190 °C, 70 bar and under an inert atmosphere, with concentrations after 2 h of 29.0 g/l of oxalic acid, 1.8 g/L of malic acid, 10.0 g/L of lactic acid, 4.1 g/L of formic acid, 11.8 g/L of acetic acid and 3.4 g/L of propionic acid. The presence of an oxidizing atmosphere generated a less concentrated, but more purified, stream of acids than that obtained by thermal hydrolysis, simplifying the subsequent downstream processing., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

The present research work aimed at hydrolytic treatment of kraft black liquor (KBL) at 200⁻300 °C for the production of low-molecular-weight depolymerized kraft lignin (DKL). Various process conditions such as reaction temperature, reaction time, initial kraft lignin (KL) substrate concentration, presence of a catalyst (NaOH), capping agent (phenol) or co-solvent (methanol) were evaluated. The research demonstrated effective depolymerization of KL in KBL at 250⁻300 °C with NaOH as a catalyst at a NaOH/lignin ratio of about 0.3 ( w / w ) using diluted KBL (with 9 wt. % KL). Treatment of the diluted KBL at 250 °C for 2 h with 5% addition of methanol co-solvent produced DKL with a weight-average molecular weight (M w ) of 2340 Da, at approx. 45 wt. % yield, and a solid residue at a yield of ≤1 wt. %. A longer reaction time favored the process by reducing the M w of the DKL products. Adding a capping agent (phenol) helped reduce repolymerization/condensation reactions thereby reducing the M w of the DKL products, enhancing DKL yield and increasing the hydroxyl group content of the lignin. For the treatment of diluted KBL (with 9 wt. % KL) at 250 °C for 2 h, with 5% addition of methanol co-solvent in the presence of NaOH/lignin ≈ 0.3 ( w / w ), followed by acidification to recover the DKL, the overall mass balances for C, Na and S were measured to be approx. 74%, 90% and 77%, respectively. These results represent an important step towards developing a cost-effective approach for valorization of KBL for chemicals.

In this work, an eco-friendly solution for the remediation of wastewater generated in the lignin recovery process from eco-industrial paper mill has been proposed in their way towards a more circular economy strategy. Thus, the application of the electro-Fenton process for the degradation of the non-recovered lignin and other organic compounds form a scarcely studied acid black liquor waste (ABLW) was successfully performed. This treatment was able to operate in a range of COD loads (0.5-19.5mgO 2 ·L -1 ) showing high degradation values of the ABLW determined by the abatement of color, total phenolic content and COD. Then, the optimization of the working conditions for the design of a sustainable treatment system with optimum efficiency was carried out using a response surface methodology. The experiment carried out in the calculated optimal conditions for the electro-Fenton degradation process (current intensity 132.5mA, catalyst dosage of 0.10mM, and temperature 40°C) showed a COD removal of 74.82% and current efficiency 77.79%, close to the theoretical value predicted by the model 73.12% and 77.06%, respectively. In addition, the identification of the final products permitted to confirm the mineralization efficiency., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Lignin in chemical pulping waste, or black liquor (BL), can be converted into various products via supercritical water gasification (SCWG). However, the inherited alkaline contents from the pulping chemicals may affect the product yields and properties. In this research, the influence of the residual alkali on the product distribution via SCWG of soda BL and kraft BL was evaluated. The SCWG was performed in a batch quartz reactor for 10 min at various temperatures (673, 773 and 873 K) and pressures (250, 300 and 400 bar). The highest hydrogen (H 2 ) production occurred at 873 K for the soda BL. The water-gas shift reaction with sodium ions played an important part in the H 2 production, while only small amounts of methane and carbon monoxide were detected. Hydrocarbons, carboxylic acids and esters were the dominant substrates in the liquid products, which denoted the potential of this method for bond cleaving of the lignin macromolecule. As a result, BL, which typically contains alkali salt, was an appropriate feedstock for the SCWG reaction to produce renewable fuel. This method not only has a positive influence on the generation of value added products from highly corrosive waste but also helps avoid some technical problems commonly encountered with direct firing in a recovery boiler.

Lignin-containing black liquor from pretreatment of rice straw by KOH aqueous solution was applied to prepare a carbonaceous solid acid catalyst, in which KOH played dual roles of extracting lignin from rice straw and developing porosity of the carbon material as an activation agent. The synthesized black liquor-derived carbon material was applied in catalytic hydrolysis of the residue solid from the pretreatment of rice straw, which was mainly composed of cellulose and hemicellulose, and showed excellent activity for the production of total reducing sugars (TRS) in ionic liquid, 1-butyl-3-methyl imidazolium chloride. The highest TRS yield of 63.4% was achieved at 140°C for 120min, which was much higher than that obtained from crude rice straw under the same reaction conditions (36.6% TRS yield). Overall, this study provides a renewable strategy for the utilization of all components of lignocellulosic biomass., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

A microbial fuel cell (MFC) is an emerging environment-friendly technology to recover the useful energy available in waste by using microorganisms as catalyst. In this study, double chamber mediator-less MFCs separated by proton exchange membrane (PEM; Nafion) were constructed to determine the efficiency of mixed culture in using complex substrates (molasses and black liquor). It was found that activated sludge can serve as efficient source of electricigens for biofilm development on an anode. Power density of 2.425 W/m² was generated from molasses with chemical oxygen demand (COD) removal efficiency of 67% as compared to power density of 3.55 W/m² produced from black liquor along with COD removal efficiency of 78%. Moreover, it was demonstrated that surface area of PEM has a significant effect on power generation. An almost 5- to 8-fold increase in voltage was observed as the size of PEM was increased from 6.5 to 25 cm².

The generation of a great quantity of black liquor (BL) and waste wash water (WWW) has been key problems of the alkaline pretreatment. This work tried to build a sustainable way to recycle the BL for pretreating sugarcane bagasse (SCB) and the WWW for washing the residual solid (RS) of alkali-treated SCB which would be subsequently hydrolysed and fermented. The enzymatic hydrolysis efficiency of the washed RS decreased with the recycling times of BL and WWW increasing. Tween80 at the loading of 0.25% (V/V) could notably improve the enzymatic hydrolysis and had no negative impact on the downstream fermentation. Compared with the non-recycling and BL recycling ways based on alkaline pretreatment, the BL-WWW recycling way could not only maintain high conversion of carbohydrate into monosaccharides and save alkali amount of 45.5%, but also save more than 80% water and generate less than 15% waste water., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

To reduce greenhouse gas emissions, more sustainable sources of energy, fuel and chemicals are needed. Biomass side streams such as black liquor, which is a by-product of pulp production, has the potential to be used for this purpose. The aim of the study was the production of carboxylic acids, such as lactic acid, formic acid and acetic acid, from kraft and non-wood black liquor. The processes studied were partial wet oxidation (PWO) and catalytic partial wet oxidation (CPWO). The results show that the yield of carboxylic acid is higher when treated by PWO than the results from CPWO at temperatures of 170 °C and 230 °C. The results shows that the PWO process can increase the yield of carboxylic acids and hydroxy acids in black liquor, reduce lignin content and decrease pH, which makes further separation of the acids more favourable. The hydroxy acids are valuable raw materials for biopolymers, and acetic acid and formic acid are commonly used chemicals conventionally produced from fossil feedstock., (© The Author(s) 2015.)

The production of biofuels as alternative energy source over fossil fuels has gained immense interest over the years as it can contribute significantly to reduce the greenhouse gas (GHG) emissions from energy production and utilization. Also with rapidly increasing fuel price and fall in oil wells, the present scenario forces us to look for an alternative source of energy that will help us in the operation of industrial as well as the transportation sector. The pulp mills in India are one of the many options. The pulp mills in India can help us to produce bio-fuels by thermo-chemical/biochemical conversion of black liquor and wood residues. These technologies include extraction of hemi-cellulose from wooden chips and black liquor, lignin from black liquor, methanol from evaporator condensates, biogas production from waste sludge, syngas production from biomass using gasification and bio-oil production from biomass using pyrolysis. The objective of this paper is to overview these emerging bio-refinery technologies that can be implemented in Indian Forest Industry to get bio-fuels, bio-chemicals and bio-energy to reduce GHG emissions., (Copyright © 2015 Elsevier Inc. All rights reserved.)

A new method to convert the potential of an ion-selective electrode to concentration or activity in potentiometric titration is proposed. The advantage of this method is that the electrode standard potential and the slope of the calibration curve do not have to be known. Instead two activities on the titration curve have to be estimated e.g. the starting activity before the titration begins and the activity at the end of the titration in the presence of large excess of titrant. This new method is beneficial when the analyte is in a complexed matrix or in a harsh environment which affects the properties of the electrode and the traditional calibration procedure with standard solutions cannot be used. The new method was implemented both in a method of linearization based on the Grans's plot and in determination of the stability constant of a complex and the concentration of the complexing ligand in the sample. The new method gave accurate results when using titrations data from experiments with samples of known composition and with real industrial harsh black liquor sample. A complexometric titration model was also developed., (Copyright © 2015 Elsevier B.V. All rights reserved.)

Kraft pulp mills use activated sludge systems to remove organic matter from effluents. Process streams may appear as toxic spills in treatment plant effluents, such as black liquor, which is toxic to microorganisms of the activated sludge. The present study evaluates the effects of black liquor shocks in activated sludge systems. Four black liquor shocks from 883 to 3,225 mg chemical oxygen demand-COD L(-1) were applied during 24 hours in a continuously operating lab-scale activated sludge system. Removal efficiencies of COD, color and specific compounds were determined. Moreover, specific oxygen uptake rate (SOUR), sludge volumetric index (SVI) and indicator microorganisms were evaluated. Results show that the addition of black liquor caused an increase in COD removal (76-67%) immediately post shock; followed two days later by a decrease (-19-50%). On the other hand, SOUR ranged between 0.152 and 0.336 mgO2 g(-1) volatile suspended solids-VSS• min(-1) during shocks, but the initial value was reestablished at hour 24. When the COD concentration of the shock was higher than 1,014 mg/L, the abundance of stalked ciliates and rotifers dropped. Finally, no changes in SVI were observed, with values remaining in the range 65.8-40.2 mL g(-1) total suspended solids-TSS during the entire operating process. Based on the results, the principal conclusion is that the activated sludge system with the biomass adapted to the kraft pulp effluent could resist a black liquor shock with 3,225 mgCOD L(-1) of concentration during 24 h, under this study's conditions.

This work demonstrates a novel method for rapid determination of total solid content in viscous liquid (polymer-enriched) samples. The method is based multiple headspace extraction gas chromatography (MHE-GC) on a headspace vial at a temperature above boiling point of water. Thus, the trend of water loss from the tested liquid due to evaporation can be followed. With the limited MHE-GC testing (e.g., 5 extractions) and a one-point calibration procedure (i.e., recording the weight difference before and after analysis), the total amount of water in the sample can be determined, from which the total solid contents in the liquid can be calculated. A number of black liquors were analyzed by the new method which yielded results that closely matched those of the reference method; i.e., the results of these two methods differed by no more than 2.3%. Compared with the reference method, the MHE-GC method is much simpler and more practical. Therefore, it is suitable for the rapid determination of the solid content in many polymer-containing liquid samples., (Copyright © 2014 Elsevier B.V. All rights reserved.)