The possibility of precipitating high molecular weight (MW) softwood hemicelluloses has been investigated. Solids were precipitated from a sodium-based spent sulfite liquor with the anti-solvents acetone, ethanol and methanol and the effects of solute concentration, pH and temperature on the precipitation were studied. The product yield, degree of separation, MW and structure of the different fractions were determined using gravimetric analysis, high performance liquid chromatography (HPLC), ultraviolet–visible (UV-Vis) spectroscopy, size exclusion chromatography (SEC), and two-dimensional nuclear magnetic resonance (2D NMR). A direct correlation was found between the dielectric constant (also called relative permittivity) of the bulk solution and the yield of precipitants, based on which the separation of the solutes was predictable. The highest yield and degree of separation observed was an intercept around 76% with 47.5% acetone, which was the most efficient anti-solvent.
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.
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.
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.
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