Investigation of acid hydrolysis for carbohydrate analysis in kraft black liquor

Black liquor (BL) from the kraft process is considered a promising feedstock for several biorefinery scenarios. Besides lignin and carboxylic acids, this liquor also contains hemicelluloses and their degradation products. A simple and reliable detection of those is of importance for further processing of the liquor. The present paper presents a thorough investigation of quantitative analysis of carbohydrates, by performing acid hydrolysis experiments with a concentrated BL sample of 44% total dry solids. The hydrolysates were then analysed for the four monosaccharides arabinose, xylose, galactose and glucose, by high performance ion chromatography (HPIC) with pulsed amperometric detection. The amount of sulphuric acid needed for complete hydrolysis of the carbohydrates was determined in the range of 3.5–5 mol kg−1 of BL. A lower acid concentration led to insufficient liberation of galactose and glucose, while higher acid concentrations led to degradation of arabinose and xylose. The carbohydrate degradation was also investigated over time for different dilutions and hydrolysis temperatures. These experiments confirmed that the hexoses require considerably harsher conditions for complete liberation compared to xylose and arabinose. The use of internal recovery standards (RSs) was tested; the highest recoveries were obtained by direct spiking of the samples with the RS prior to hydrolysis.

Spray atomization simulation of bamboo kraft black liquor with high solid content at splash-plate nozzle

Increasing the solids content of pulping black liquor burned in a furnace is a development trend of the alkali recovery system in the pulp and paper industry. However, the viscosity of kraft black liquor increases exponentially with an increase in solids content, especially in the case of non-wood pulping black liquor, such as bamboo. This brings great difficulties to the pulping system and atomization of black liquor at the splash-plate nozzle, which is a complete atomization unit constituted of a splash nozzle and a splash plate. To obtain instructive results for industry, a simulation of the atomization process was made using Fluent software for the bamboo kraft black liquor with solids contents of 70 wt% and 80 wt%, which flowed through splash nozzles with the diameter of 22 or 20 mm. The studies were conducted on the distribution of flow field in the nozzle and atomization region through changing the injection pressure and nozzle diameter. The variation of atomization characteristic parameters, such as liquid film thickness, and breakup length, were elucidated. The results reveal the relationship between spray atomization with injection pressure and nozzle diameter, which provides a theoretical basis for improving the concentration of black liquor entering alkali recovery in the future.

Valorization of Lignin Side-Streams into Polyols and Rigid Polyurethane Foams—A Contribution to the Pulp and Paper Industry Biorefinery

Valorization of industrial low-value side-streams are of great interest, contributing to boosts in the circular economy. In this context, lignin side-streams of the pulp and paper industry were oxypropylated to produce biobased polyols and tested in the synthesis of rigid polyurethane (RPU) foams. E. globulus lignins, namely a lignin isolated from an industrial Kraft black liquor and depolymerized lignins obtained as by-products of an oxidation process, were used. RPU foams, synthesized with 100% lignin-based polyols and using a 1.1 NCO/OH ratio, were characterized concerning apparent density, morphology, thermal conductivity, thermal stability, and heat release rate (HRR). Foams containing the lignin-based polyols presented densities varying from 44.7 to 112.2 kg/m3 and thermal conductivity in the range of 37.2–49.0 mW/mK. For the reference foam (sample produced with 100% wt. Daltofoam TP 32015 polyol), values of 70.9 kg/m3 and 41.1 mW/mK were obtained, respectively. The achieved results point out the viability of using the generated lignin-based polyols at 100% content in RPU foams, mainly when depolymerized lignins are used. Moreover, fire retardancy was favored when the lignin-based polyols were introduced. The proposed strategies can contribute to establishing the integrated pulp and paper biorefinery concept where material synthesis (polyols and RPU foams) can be combined with chemical production (vanillin and syringaldehyde).

Development of Ultralow Interfacial Tension Lignosulfonate from Kraft Black Liquor for Enhanced Oil Recovery

Indonesia aims to implement large-scale enhanced oil recovery (EOR) to increase the national oil production. Chemical EOR is a promising technology to boost the production of old reservoirs with the aid of surfactants and polymers. Thus, the production of low-cost EOR surfactants from local resources with acceptable performance is highly attractive. The objective of the present work was to demonstrate the development of low-cost lignosulfonate surfactant production from kraft black liquor (BL). First, lignin was isolated from black liquor using a novel CO2 bubbling technique, followed by addition of coagulants. Next, sodium lignosulfonate (SLS) was synthesized from the resulting lignin, followed by formulation of SLS with octanol and palm fatty acid distillate (PFAD) soap to obtain an ultralow interfacial tension (IFT) surfactant. The initial IFT value of the SLS solution was already high at 0.7 mN/m. After formulation, the composition SLS:PFAD soap:octanol = 70:22:8 (wt%) improved the IFT value to 3.1 10-3 mN/m. An ultralow IFT in the range of 10-3 mN/m as achieved here fulfills the required IFT value for EOR surfactant.