Lignin Precipitation Research Articles

Efficient Recovery of Lignin and Hemicelluloses from Kraft Black Liquor

Black liquor (BL) from kraft pulping industries contains a large fraction of lignin and hemicelluloses and their efficient separation can open up new possibilities for integrated biorefineries. In this work, lignin and hemicelluloses were separated from BL and concentrated BL (obtained by ultrafiltration), by precipitation using acidification and antisolvent precipitation method, respectively. For lignin precipitation, different organic acids, namely acetic, lactic and citric acid, were used and the yield and purity of the extracted lignin were compared with the lignin precipitated using inorganic acids, namely sulphuric and phosphoric acid. Among the organic acids, the highest yield of lignin (57.2%) was obtained by lactic acid, but the extract also contained the highest levels of inorganic impurities (9.2%). The extract obtained from acetic acid contained lower inorganic impurities and the lignin yield was 48.1%. The hemicellulose was extracted from BL liquor that was concentrated using the ZnObased PES mixed matrix ultrafiltration membrane, which was started by first separating lignin (at pH 3.5, 4 and 4.5) from it. The supernatants from the lignin precipitation process were used as a source of hemicellulose and this was precipitated by using acetone as an antisolvent. The highest hemicellulose yield (54.4%) was obtained from the supernatant with the lowest lignin content and highest acetone to supernatant ratio.
 Keywords: acidification, antisolvent precipitation, hemicelluloses, kraft black liquor, lignin

Laboratory- to Pilot-Scale Fractionation of Lignocellulosic Biomass Using an Acetone Organosolv Process

Acetone organosolv fractionation of beech and birch wood at the lab-scale results in high sugar yields from the (hemi)cellulose and the isolation of a high-purity lignin. In this study, the process is scaled up to validate the technology at the pilot scale using industrial-size beech and birch wood chips and low liquid-to-solid ratios as a next step toward commercialization. Translation of the fractionation process to the pilot-scale showed a similar performance as compared to the lab-scale processing with a good conversion of the wood polymeric pentoses to mostly monomeric sugars and a high delignification. Continuous lignin precipitation by solvent evaporation using the LigniSep process resulted in the formation of nonsticky lignin aggregates with a good filterability. The improved lignin yields and advanced process design as compared to the traditional dilutive lignin precipitation approaches are likely to translate to a better process economy. The pulp washing efficiency and the recovery of (nonprecipitable) lignin from the aqueous hemicellulose stream still need to be improved for an efficient process design. However, the fractionation performance and high product concentrations in the spent liquor provide an excellent start position for improved process design at the commercial scale.

Energy-efficient microbial electrochemical lignin and alkaline hydroxide recovery from DMR black liquor

Black liquor is a complex waste stream generated from the fast-expanding biorefinery industry, and the high management cost has been known as a major development barrier. In this work, we demonstrated a rationally designed 4-chamber microbial electrolysis process that was capable of recovering the value-added lignin, NaOH, and H2 products while removing waste organics from the Deacetylation and Mechanical Refining (DMR) black liquor, which could potentially reduce the disposal cost by up to 40%. The lab-scale MEC achieved 52% organic removal from a highly concentrated feedstock (28,960 ± 212 mg/L COD) and recovered 83.2 mM NaOH under a small voltage application (1.2 V). Lignin recovery was observed to be as high as 13.98 ± 0.28 g/L, and 0.35 L/L/day H2 was produced with a faradaic efficiency of 93.5%. This work provided a good example on how complex liquid waste stream can be valorized via multi-functional microbial electrochemical technology, and how the traditionally unfavored pH gradient in an electrochemical reactor can be manipulated for lignin precipitation and alkaline recovery at the same time. The versatility and good performance in concurrent contaminants removal, lignin precipitation, H2 production and NaOH recovery demonstrate a good potential for microbial electrolysis in black liquor treatment.

Influence of Lignin Content on Morphology and Properties of Poly(Lactic Acid)/Lignin Composite Films

In this work, PLA/lignin composite films have been developed for packaging films. The composite films were prepared by a solution casting method. The lignin was prepared from black liquor from the paper industry, by extracting with acetic acids at 50°C. The lignin contents in PLA matrix were 0.5, 1, 3 and 5 phr. Fourier-transformed infrared spectroscopy (FTIR) analysis demonstrated similar structure of lignin precipitation when compared with the standard lignin. The addition of lignin reduced the tensile strength of PLA/lignin films, whereas the composite film at 1 phr of lignin was more elongation than neat PLA. Scanning electron microscopy (SEM) micrographs showed the roughness surface and voids in the composite films, except 1 phr and 5 phr of lignin with a better interface between PLA and lignin. UV-Vis analysis indicated reduced light transmission with increasing lignin contents in UV region.

Enhancing Lignin Dispersion and Bioconversion by Eliminating Thermal Sterilization

Thermal sterilization is widely applied in fermentation to ensure a pure culture. In this study, a facile and energy-efficient strategy by eliminating thermal sterilization (ETS) was unveiled for upgrading lignin bioconversion. Through alkaline solubilization and neutralization, lignin dispersion in aqueous fermentation media was significantly enhanced by ETS. Small-angle X-ray scattering and dynamic light scattering analyses indicated that the lignin colloid size was dramatically reduced. Compared to 20.5 wt % lignin precipitation during the conventional thermal sterilization, precipitated lignin was not observed within the ETS medium. 31P NMR characterization demonstrated an 11.7% increase of phenolic OH in ETS lignin. Ionization of phenolic OH presented more negatively charged groups, strengthening electrostatic repulsion, resulting in smaller colloidal particles. Interestingly, the pure culture of Rhodococcus opacus PD630 was achieved within the ETS medium due to the lack of lignin degradation ability with most natural microbes. R. opacus PD630 cell amount, lignin degradation, and lipid production by ETS increased by 330, 16.6, and 20.7%, respectively. Overall, an energy-efficient ETS strategy that promoted lignin dispersion and bioconversion significantly is reported in this study.

The Effect of the Kraft Pulping Process, Wood Species, and pH on Lignin Recovery from Black Liquor

Lignin has shown a great potential to produce fuels, value-added chemicals, and functional materials due to its high-energy density and intrinsic aromatic-based structure. Yet, the lignin precipitation of different biomasses needs investigation because most of the work has been performed on softwood and much less is known about hardwoods. In fact, the lignin from these two wooden biomasses vary in composition and pulping performance, which can reflect on lignin precipitation. Therefore, the present study investigated the precipitation and composition of 40 distinct kraft lignins obtained from pine, acacia, sweetgum, and eucalyptus black liquors. Two lignin fractions were precipitated at different pHs, according to known industrial lignin separation practices (pH = 9.5 and 2.5) from black liquors taken at different levels of pulping. Overall, lignin recovery increased with increasing lignin concentration in the black liquor, i.e., higher amounts of lignin were obtained at higher levels of delignification. In addition, pine lignins showed superior yields than the hardwoods and were around five times purer. Among the hardwoods, lignin recovery increased with the S–G ratio of the native lignin, and eucalyptus showed the best performance by achieving the highest yields and purities. Finally, the present work compared the lignin recovery yield and the purity of softwood and different hardwood lignins in a systematic way, which will increase awareness of this underutilized green material and could potentially increase the interest in establishing new lignin plants across the globe.

Influence of Temperature and Lignin Concentration on Formation of Colloidal Lignin Particles in Solvent-Shifting Precipitation

Colloidal lignin particles offer a promising route towards material applications of lignin. While many parameters influencing the formation of these particles in solvent-shifting precipitation have been studied, only a small amount of research on the influence of temperature has been conducted so far, despite it being a major influence parameter in the precipitation of colloidal lignin particles. Temperature influences various other relevant properties, such as viscosity, density, and lignin solubility. This makes investigation of both temperature and lignin concentration in combination interesting. The present work investigates the precipitation at different temperatures and initial lignin concentrations, revealing that an increased mixing temperature results in smaller particle sizes, while the yield is slightly lowered. This effect was strongest at the highest lignin concentration, lowering the hydrodynamic diameter of the particles from 205 to 168 nm. Decreasing the lignin concentration resulted in significantly smaller particles (from 205 to 121 nm at 20 °C mixing temperature) but almost no change in particle yield (between 81.2 and 84.6% at 20 °C mixing temperature). This opens up possibilities for the process control and optimization of lignin precipitation.

Components Analysis of Recycled Alkali Black Liquor Combined with Corn Straw Under Ozone Pretreatment

Alkali combined with ozone pretreatment of corn straw could improve the enzymatic hydrolysis degree of cellulose to realize the biomass conversion of straw waste. In order to recycle the alkali black liquor derived from this process and realize the environment-friendly effect, the main components of alkali combined with ozone pretreatment of straw recycling black liquor were investigated in this paper. To this end, the alkali black liquor was sequentially withdrawn for 0–6 times under the optimal pretreatment conditions, and solid content, organic and inorganic matter, acid precipitation, alkali precipitation, and organic composition were analyzed to identify the main factors inhibiting cellulase hydrolysis in recycled alkali black liquor. The results showed that the cellulase hydrolysis rate presented a significant decrease at the fourth cycle, which was decreased by 11.39%, and the content of alkali precipitation was maximum (0.707 g). Meanwhile, the organic matter content in alkali precipitation also reached the maximum value of 0.491 g. Through the component analysis, the contents of lignin and acid precipitation increased throughout the cycles. Moreover, GC–MS results showed that phenols, benzene ring heterocyclic, and furans were main degradation products in cycles of black liquor. Accordingly, it was indicated that small molecular organics and lignin were inhibitors of cellulase hydrolysis, which accumulated during recycling, and reduced alkali utilization and delignification efficiency, resulting in lower enzymatic hydrolysis rate.

Process intensification of the ionoSolv pretreatment: effects of biomass loading, particle size and scale-up from 10\xa0mL to 1\xa0L

The ionoSolv process is one of the most promising technologies for biomass pretreatment in a biorefinery context. In order to evaluate the transition of the ionoSolv pretreatment of biomass from bench-scale experiments to commercial scale, there is a need to get better insight in process intensification. In this work, the effects of biomass loading, particle size, pulp washing protocols and 100-fold scale up for the pretreatment of the grassy biomass Miscanthus giganteus with the IL triethylammonium hydrogen sulfate, [TEA][HSO4], are presented as a necessary step in that direction. At the bench scale, increasing biomass loading from 10 to 50 wt% reduced glucose yields from 68 to 23% due to re-precipitation of lignin onto the pulp surface. Omitting the pulp air-drying step maintained saccharification yields at 66% at 50 wt% loading due to reduced fiber hornification. 100-fold scale-up (from 10 mL to 1 L) improved the efficacy of ionoSolv pretreatment and increasing loadings from 10 to 20 wt% reduced lignin reprecipitation and led to higher glucose yields due to the improved heat and mass transfer caused by efficient slurry mixing in the reactor. Pretreatment of particle sizes of 1–3 mm was more effective than fine powders (0.18–0.85 mm) giving higher glucose yields due to reduced surface area available for lignin re-precipitation while reducing grinding energy needs. Stirred ionoSolv pretreatment showed great potential for industrialization and further process intensification after optimization of the pretreatment conditions (temperature, residence time, stirring speed), particle size and biomass loading. Pulp washing protocols need further improvement to reduce the incidence of lignin precipitation and the water requirements of lignin washing.

Selective acid precipitation of Kraft lignin: a tool for tailored biobased additives for enhancing PVA films properties for packaging applications

The use of renewable materials with unique properties has brought new perspectives regarding their use as potential substitutes to the petroleum-based products. The aim of this work was to evaluate the effects caused by the addition of Kraft lignins, selectively precipitated in acid and alkaline medium, on the thermal, thermo-oxidative, UV-blocking, antioxidant, antimicrobial and mechanical properties of polyvinyl alcohol (PVA) films. Kraft lignins (KL) were selectively precipitated in alkaline (KL A) and acid (KL B) media. KL A and KL B were characterized by FTIR, 1H-13C HSQC, 31P NMR and GPC. PVA films were produced through casting method and characterized by TGA, DSC, OOT, UV–Vis, mechanical, antioxidant and antimicrobial properties. The selective precipitation process yielded lignins with different concentration of phenolic and total hydroxyls for KL A and KL B. The addition of KL A and KL B at 1.0% wt. in PVA films produced materials with enhanced thermal, thermo-oxidative, UV-blocking, mechanical, antioxidant and antimicrobial properties. It can be concluded that the selective precipitation of lignin represents an alternative for obtaining fractions with peculiar structural features that can improve their compatibility with thermoplastics, yielding potential bio-based products with suitable features to be used as packaging materials.

A low capital method for silicon interference in bamboo kraft pulping alkaline recovery system

The problem posed by the silicon interference in bamboo pulp black liquor has been troubling bamboo pulp mills as well as hindering the development of non-wood pulp mills. Silica is separated from bamboo pulp black liquor by acid precipitation, accompanied by the sediment of lignin, which is disadvantageous to alkali recovery system. The amount of carboxylate increases through the oxidation of lignin, and the solubility of lignin increases. So the lignin precipitation and the removal of silica can be quantified by the combination of acidification and light oxidation. For solving the problem, we separate the silicon in the black liquor through oxygen oxidation and carbon dioxide acidification without affecting the stability of the alkali recovery system. TG, combustion calorific value and visible light absorption are tested after oxidation and acidification. Finally, by comparing with the mature pulp black liquid alkali recovery system, it is concluded that when taking economic capital into consideration, oxidizing to pH 12.45(at 80 °C) and acidifying to pH 10 (at 50 °C) are suitable for our goal. In this case, the silicon removal rate reaches 76.41 wt%; the amount of separated lignin is 17.58 wt% and the calorific value loss of black liquor reaches 26.47%.

SYNTHESIS, STRUCTURE AND PROPERTIES OF ORGANIC GELS BASED ON LARCH BARK TANNINS AND HY-DROLYSIS LIGNIN

For the first time, tannin-lignin-formaldehyde and tannin-lignin-furfuryl organic gels were obtained on the basis of larch bark tannins and hydrolysis lignin by sol-gel condensation with formaldehyde and furfuryl alcohol. Their physico-chemical properties were studied by varying the content of lignin (from 5 to 30 wt%) and a fixed mass ratio of polyphenolic substances to the crosslinking reagent (1 : 1.5). With an increase in the lignin content the density of tannin-lignin formaldehyde gels decreases from 0.83 to 0.53 g/ cm3, and that of tannin-lignin-furfuryl gels is from 0.32 to 0.14 g / cm3. According to the FTIR data, the structures of tannin-lignin-formaldehyde and tannin-lignin-furfuryl gels are formed by aromatic fragments cross-linked with methylene and methylene-ether bridges. Scanning electron microscopy shows that the addition of appropriate amounts of lignin to tannins (up to 10 wt% when using formaldehyde and up to 20 wt% when using furfuryl alcohol) promotes the formation of gels with a more developed porous structure. In the case of tannin-lignin-formaldehyde gel, the specific surface area and sorption of methylene blue are 12 m2 / g and 43 mg / g and for tannin-lignin-furfuryl gel – 72 m2 / g and 114.5 mg/g, respectively. It was found that an increase in the lignin content in the gel composition over 20 wt.% is accompanied by the phase localization of lignin (precipitation), which reduces the strength of the resulting gel and reduces its specific surface area.

Minimizing water consumption for sugar and lignin recovery via the integration of acid and alkali pretreated biomass and their mixed filtrate without post-washing

Excessive post-washing of pretreated biomass leads to huge water consumption and chemical loss. To address this issue, parallel HOAc and NaOH pretreatments of biomass followed by integration of their biomass and filtrate were investigated. Pretreatment effectiveness including morphology, crystallinity, and component recovery, were elucidated. Results showed that HOAc and NaOH in the mixed filtrate were neutralized to achieve a pH of around 4.80 prompting the alkali lignin precipitation. Lignin (46.01 and 48.38 g/kg-biomass for hemp and poplar, respectively) exhibiting comparable FTIR characteristics with the commercial alkali lignin was recovered. Compared to sodium acetate buffer as a control, integrating HOAc and NaOH pretreated biomass and their mixed filtrate for enzymatic hydrolysis boosted total sugar concentration (hemp: 42.90 vs. 38.27 g/L; poplar: 43.18 vs. 38.76 g/L) without compromising glucose yield (hemp: 70.86 vs. 70.69%; poplar: 66.48 vs. 69.48%) but improving xylose yield (hemp: 60.10 vs. 35.92%; poplar: 56.90 vs. 29.39%).

Highly Efficient Semi-Continuous Extraction and In-Line Purification of High β-O-4 Butanosolv Lignin.

Innovative biomass fractionation is of major importance for economically competitive biorefineries. Lignin is currently severely underutilized due to the use of high severity fractionation methodologies that yield complex condensed lignin that limits high-value applicability. Mild lignin fractionation conditions can lead to lignin with a more regular C-O bonded structure that has increased potential for higher value applications. Nevertheless, such extraction methodologies typically suffer from inadequate lignin extraction efficiencies and yield. (Semi)-continuous flow extractions are a promising method to achieve improved extraction efficiency of such C-O linked lignin. Here we show that optimized organosolv extraction in a flow-through setup resulted in 93–96% delignification of 40 g walnut shells (40 wt% lignin content) by applying mild organosolv extraction conditions with a 2 g/min flowrate of a 9:1 n-butanol/water mixture with 0.18 M H2SO4 at 120°C in 2.5 h. 85 wt% of the lignin (corrected for alcohol incorporation, moisture content and carbohydrate impurities) was isolated as a powder with a high retention of the β-aryl ether (β-O-4) content of 63 linking motifs per 100 C9 units. Close examination of the isolated lignin showed that the main carbohydrate contamination in the recovered lignin was butyl-xyloside and other butoxylate carbohydrates. The work-up and purification procedure were investigated and improved by the implementation of a caustic soda treatment step and phase separation with a continuous integrated mixer/separator (CINC). This led to a combined 75 wt% yield of the lignin in 3 separate fractions with 3% carbohydrate impurities and a very high β-O-4 content of 67 linking motifs per 100 C9 units. Analysis of all the mass flows showed that 98% of the carbohydrate content was removed with the inline purification step, which is a significant improvement to the 88% carbohydrate removal for the traditional lignin precipitation work-up procedure. Overall we show a convenient method for inline extraction and purification to obtain high β-O-4 butanosolv lignin in excellent yields.

QUICK NON-DESTRUCTIVE ANALYSIS OF CONDENSED LIGNIN BY FTIR. PART 2. PULP SAMPLES FROM ACID SULFITE COOKING

"In our previous work, we demonstrated how lignin condensation and precipitation taking place in kraft pulping can be detected and even quantified by Fourier Transform Infrared (FTIR) spectroscopy. Because lignin reactions in acid sulfite pulping are very different from those occurring during kraft cooking, a new analysis method is proposed to rapidly analyze the condensed lignin in acid sulfite pulp. This kind of analysis is useful for sulfite pulp mills to detect the elevated risk of black cook. This paper presents and discusses the novel method using FTIR spectroscopy to rapidly analyze lignin condensation in softwood pulp samples from acid sulfite processes. Several softwood pulp samples from acid sulfite pulping at varying levels of condensation were included in this research. According to the results, FTIR spectroscopy allows indirect quantification of lignin condensation in a difficult matrix of wood constituents, such as in incompletely delignified acid sulfite pulp."

Recovery of lignin and phenolics via one-pot pretreatment of oil palm empty fruit bunch fiber and palm oil mill effluent

This is a pioneer research carried out to investigate the novel use of palm oil mill effluent (POME) as an extraction solvent of lignin and phenolics from oil palm empty fruit bunch fiber (OPEFBF). In the present study, lignin and phenolics were removed from OPEFBF using different solvents, namely POME, sodium hydroxide (NaOH), aqueous ammonia (NH3), POME containing 5% w/w NaOH (NaOH-POME), and POME containing 5% w/w NH3 (NH3-POME) at different temperatures and times. Results obtained suggest that NaOH-POME was the best solvent to produce the highest yield of lignin (24.2±0.36%) and phenolics (2.4±0.1 g L−1). Chemical oxygen demand (COD) of solvent was increased drastically after treatment but reduced substantially after lignin precipitation. The delignified liquor was a rich source of aromatic aldehydes and acids such as hydroxybenzoic acid, syringaldehyde, syringic acid, vanillin, p-coumaric acid, ferulic acid, and trace amounts of hydroxybenzaldehyde and vanillic acid. Utilization of POME as a solvent to extract lignin and phenolics from OPEFBF is recommended as a win-win approach to simultaneously prepare OPEFBF and POME as a feedstock for downstream processes.

Renewable Biopolyols from Residual Aqueous Phase Resulting after Lignin Precipitation

The aim of this work was to obtain two biopolyols from the liquid residue resulting from the precipitation of lignin contained in two different black liquors, Eucalyptus globulus organosolv black l...

Ternary Phase Diagram of Water/Bio-Oil/Organic Solvent for Bio-Oil Fractionation

Separating bio-oil by fractionation with different chemical compositions is a critical step to refine these oils and obtain high-value products. Cold water precipitation of pyrolytic lignin from bi...

Lignin Precipitation and Fractionation from OrganoCat Pulping to Obtain Lignin with Different Sizes and Chemical Composition.

Fractionation of lignocellulose into its three main components, lignin, hemicelluloses, and cellulose, is a common approach in modern biorefinery concepts. Whereas the valorization of hemicelluloses and cellulose sugars has been widely discussed in literature, lignin utilization is still challenging. Due to its high heterogeneity and complexity, as well as impurities from pulping, it is a challenging feedstock. However, being the most abundant source of renewable aromatics, it remains a promising resource. This work describes a fractionation procedure that aims at stepwise precipitating beech wood (Fagus sp.) lignin obtained with OrganoCat technology from a 2-methyltetrahydrofuran solution, using n-hexane and n-pentane as antisolvents. By consecutive antisolvent precipitation and filtration, lignin is fractionated and then characterized to elucidate the structure of the different fractions. This way, more defined and purified lignin fractions can be obtained. Narrowing down the complexity of lignin and separately valorizing the fractions might further increase the economic viability of biorefineries.

Effects of Ethanol Concentration on Organosolv Lignin Precipitation and Aggregation from Miscanthus x giganteus

This work assesses the behavior of organosolv lignin aggregates derived from Miscanthus x giganteus using different ethanol concentrations (10%, 25%, 50%, and 75% by volume). The percentage of lignin recovery was found to decrease from 75.8% to 71.4% and 25.1%, as the ethanol concentration was increased from 10% to 25% and 50%, respectively. Increasing the ethanol concentration further to 75% led to zero recovery. The purity of the precipitated lignin was consistently found to be ≥90%. Lignin derived from the dried supernatant obtained at 50% ethanol concentration resulted in high lignin purity (51.6%) in comparison with the other ethanol concentrations used. Fourier transform infrared spectroscopy analysis showed that the precipitated lignin and dried supernatant at 50% ethanol concentration possessed the highest peak intensity apportioned to wavenumber of lignin as compared to that of at 25% and 10% ethanol concentrations, and the results linked with the percentage of lignin purity. The results of particle size analysis for precipitated lignin demonstrated particle sizes of 306, 392, and 2050 nm for 10%, 25%, and 50% ethanol concentrations, respectively, and the remaining supernatant with average particle sizes of 1598, 1197, and 875 nm, respectively. These results were verified with the morphology of lignin macromolecules in scanning electron microscopy images. Results of the particle size distribution of lignin revealed that the overall size of lignin aggregates decreased with decreasing ethanol concentration. In summary, these findings suggest that ethanol concentration affected the behavior of lignin aggregates in water–ethanol solution.