Lignin Extraction by Using Two-Step Fractionation: A Review.

Lignocellulosic biomass represents the most abundant renewable carbon source on earth and is already used for energy and biofuel production. The pivotal step in the conversion process involving lignocellulosic biomass is pretreatment, which aims to disrupt the lignocellulose matrix. For effective pretreatment, a comprehensive understanding of the intricate structure of lignocellulose and its compositional properties during component disintegration and subsequent conversion is essential. The presence of lignin-carbohydrate complexes and covalent interactions between them within the lignocellulosic matrix confers a distinctively labile nature to hemicellulose. Meanwhile, the recalcitrant characteristics of lignin pose challenges in the fractionation process, particularly during delignification. Delignification is a critical step that directly impacts the purity of lignin and facilitates the breakdown of bonds involving lignin and lignin-carbohydrate complexes surrounding cellulose. This article discusses a two-step fractionation approach for efficient lignin extraction, providing viable paths for lignin-based valorization described in the literature. This approach allows for the creation of individual process streams for each component, tailored to extract their corresponding compounds.

Enzymatic Conversion of Different Qualities of Refined Softwood Hemicellulose Recovered from Spent Sulfite Liquor.

Spent sulfite liquor (SSL) from softwood processing is rich in hemicellulose (acetyl galactoglucomannan, AcGGM), lignin, and lignin-derived compounds. We investigated the effect of sequential AcGGM purification on the enzymatic bioconversion of AcGGM. SSL was processed through three consecutive purification steps (membrane filtration, precipitation, and adsorption) to obtain AcGGM with increasing purity. Significant reduction (~99%) in lignin content and modest loss (~18%) of polysaccharides was observed during purification from the least pure preparation (UFR), obtained by membrane filtration, compared to the purest preparation (AD), obtained by adsorption. AcGGM (~14.5 kDa) was the major polysaccharide in the preparations; its enzymatic hydrolysis was assessed by reducing sugar and high-performance anion-exchange chromatography analysis. The hydrolysis of the UFR preparation with Viscozyme L or Trichoderma reesei ß-mannanase TrMan5A (1 mg/mL) resulted in less than ~50% bioconversion of AcGGM. The AcGGM in the AD preparation was hydrolyzed to a higher degree (~67% with TrMan5A and 80% with Viscozyme L) and showed the highest conversion rate. This indicates that SSL contains enzyme-inhibitory compounds (e.g., lignin and lignin-derived compounds such as lignosulfonates) which were successfully removed.

Hemicellulose Recovery from Spent-Sulfite-Liquor: Lignin Removal by Adsorption to Resins for Improvement of the Ultrafiltration Process.

In this work, three polymeric resins were examined as alternatives for the separation of hemicellulose and lignin. The aim was to remove the lignin from spent-sulfite-liquor (SSL) prior to ultrafiltration, producing a hemicellulose-rich retentate with high purity, and increase the capacity of the membrane filtration. The lignin in the SSL was sulfonated; thus, two of the resins were anion exchangers and 1 was hydrophobic. The data from the equilibrium studies and adsorption kinetics were fitted to established models, and the results were interpreted based on these observations. The strongly basic anion exchanger performed best with regard to lignin removal. The adsorption followed the Sips isotherm, indicating that the process was cooperative with chemisorption as the main reaction between the adsorbate and adsorbent based on the kinetics. Regeneration of the adsorbent was also possible, wherein 100 g/L NaCl was sufficient to recover 98% of the lignin. The lignin removal had a positive effect on the ultrafiltration process, in which the flux increased by 38% and the extent of separation between the hemicellulose and lignin rose from 17% to 59%.

Comprehensive Analysis of Foulants in an Ultrafiltration Membrane Used for the Treatment of Bleach Plant Effluent in a Sulfite Pulp Mill.

Fouling is a major obstacle in the introduction of membrane processes in new applications in the pulping industry. Due to the complex nature of the feed solutions, complementary analysis methods are usually needed to identify the substances involved. Four different methods were used for the comprehensive analysis of a membrane removed from an ultrafiltration plant treating alkaline bleach plant effluent in a sulfite pulp mill to identify the substances causing fouling. Magnesium was detected both on the membrane surface and in the nonwoven membrane backing and a small amount of polysaccharides was detected after acid hydrolysis of the fouled membrane. This study provides information on foulants, which can be used to improve processing conditions and cleaning protocols and thus the membrane performance in pulp mill separation processes. It also provides an overview of the usefulness of various analytical methods.

Bicontinuous cubic liquid crystalline phase nanoparticles stabilized by softwood hemicellulose.

The colloidal stability of lipid based cubosomes, aqueous dispersion of inverse bicontinuous cubic phase, can be significantly increased by a stabilizer. The most commonly used stabilizers are non-ionic tri-block copolymers, poloxamers, which adsorb at the lipid-water interface and hence sterically stabilize the dispersion. One of the challenges with these synthetic polymers is the effect on the internal structure of the cubosomes and the potential toxicity when these nanoparticles are applied as nanomedicine platforms. The natural polysaccharide, softwood hemicellulose, has been proved to be an excellent stabilizer for oil-in-water emulsions, partially due to the presence of hydrophobic lignin in the extract which to some extent is associated to hemicellulose. Herein, we reported for the first time cubosomes stabilized by two types of softwood hemicelluloses, where one is extracted through thermomechanical pulping (TMP, low lignin content) and the other obtained from sodium-based sulfite liquor (SSL, high lignin content). The effect of the two hemicellulose samples on the colloidal stability and structure of monoolein-based cubosomes have been investigated via DLS, SAXS, AFM and cryo-TEM. The data obtained suggest that both types of the hemicelluloses stabilize monoolein (GMO) based cubosomes in water without significantly affecting their size, morphology and inner structure. SSL-extracted hemicellulose yields the most stable cubosomes, likely due to the higher content of lignin in comparison to TMP-stabilized ones. In addition, the stability of these particles was tested under physiological conditions relevant to possible application as drug carriers.

Analysis of membrane fouling by Brunauer-Emmet-Teller nitrogen adsorption/desorption technique.

Membrane fouling is the major factor limiting the wider applicability of the membrane-based technologies in water treatment and in separation and purification processes of biorefineries, pulp and paper industry, food industry and other sectors. Endeavors to prevent and minimize fouling requires a deep understanding on the fouling mechanisms and their relative effects. In this study, Brunauer-Emmett-Teller (BET) nitrogen adsorption/desorption technique was applied to get an insight into pore-level membrane fouling phenomena occurring in ultrafiltration of wood-based streams. The fouling of commercial polysulfone and polyethersulfone membranes by black liquor, thermomechanical pulping process water and pressurized hot-water extract was investigated with BET analysis, infrared spectroscopy, contact angle analysis and pure water permeability measurements. Particular emphasis was paid to the applicability of BET for membrane fouling characterization. The formation of a fouling layer was detected as an increase in cumulative pore volumes and pore areas in the meso-pores region. Pore blocking was seen as disappearance of meso-pores and micro-pores. The results indicate that the presented approach of using BET analysis combined with IR spectroscopy can provide complementary information revealing both the structure of fouling layer and the chemical nature of foulants.

Galactoglucomannan Recovery with Hydrophilic and Hydrophobic Membranes: Process Performance and Cost Estimations.

In this study, we compared the GR51PP (hydrophobic/polysulfone) membrane with a series of hydrophilic (regenerated cellulose) membranes with the aim of increasing the retention of products and decreasing membrane fouling. The raw material used was a sodium-based spent sulfite liquor from the sulfite pulping process of spruce and pine. The results show that the hydrophilic membranes were superior to the hydrophobic membranes in terms of higher fluxes (up to twice the magnitude), higher product retentions and less fouling (up to five times lower fouling). The fouling was probably caused by pore blocking as observed in earlier studies. However, the hydrophilic membranes had a lower affinity for lignin, which was indicated by the lower retention and fouling. This also resulted in a separation degree, which was higher compared with the hydrophobic membrane, thus yielding a higher galactoglucomannan (GGM) purity. 2D HSQC NMR results show that no major structural differences were present in the hydrophilic and hydrophobic retentates. A techno-economical evaluation resulted in the RC70PP being chosen as the most cost-efficient membrane in terms of flux and product recovery.

Membrane Separation of the Base-Catalyzed Depolymerization of Black Liquor Retentate for Low-Molecular-Mass Compound Production.

One way of valorizing the lignin waste stream from the pulp and paper industries is depolymerizing it into low-molecular-mass compounds (LMMC). However, a common problem in the depolymerization of Kraft lignin is the low yields of small aromatic molecules obtained. In the present work, the combination of the repeated depolymerization of lignin and the separation of LMMC from depolymerized lignin to upgrade them into value-added chemicals was studied. In so doing, we investigated the possibility of depolymerizing black liquor retentate (BLR). The base-catalyzed depolymerization of BLR was performed using a continuous flow reactor at 170-210 °C, with a 2 min residence time. The results obtained indicate that BLR can be depolymerized effectively under the experimental conditions. Depolymerized lignin LMMC can be successfully separated by a GR95PP membrane, and thus be protected from repolymerization. Through combining membrane filtration with base-catalyzed depolymerization, more than half of the lignin could be depolymerized into LMMC. Around 46 mg/g of lignin monomers (guaiacol, vanillin, acetovanillone, and acetosyringone), which can potentially be upgraded to high-valued chemicals, were produced. On the basis of our results, we suggest use of a recycling Kraft lignin depolymerization and filtration process for maximizing the production of LMMC under mild alkaline conditions.

Impact of Lignin Content on the Properties of Hemicellulose Hydrogels.

Hemicellulose is a promising renewable raw material for the production of hydrogels. This polysaccharide exists in large amounts in various waste streams, in which they are usually impure and heavily diluted. Several downstream processing methods can be combined to concentrate and purify the hemicellulose. However, such an approach can be costly; hence, the effect of impurities on the formation and properties of hydrogels must be determined. Lignin usually exists in these waste streams as a major impurity that is also difficult to separate. This compound can darken hydrogels and decrease their swellability and reactivity, as shown in many studies. Other properties and effects of lignin impurities are equally important for the end application of hydrogels and the overall process economy. In this work, we examined the feasibility of producing hydrogels from hemicelluloses that originated from sodium-based spent sulfite liquor. A combination of membrane filtration and anti-solvent precipitation was used to extract and purify various components. The influence of the purity of hemicellulose and the addition of lignosulfonates (emulated impurities in the downstream processing) to the crosslinking reaction mixture on the mechanical, thermal, and chemical properties of hydrogels was determined.