A new process analytical technology soft sensor based on electrical tomography for real-time monitoring of multiphase systems.

BACKGROUND: Electrical tomography is widely recognized for its high time resolution and low cost. However, the implementation of electrical tomographic solutions has been hindered by the high computational overhead associated, which causes delays in the analysis, and numerical instability, that results in unclear reconstructed images. Therefore, it has been mostly applied offline, for qualitative tasks and with some delay. Applications requiring fast response times and quantification have been hindered or ruled out. RESULTS: In this article, we propose a new process analytical technology soft sensor that maps directly electrical tomography signals to the relevant parameter to be monitored. The data acquisition and estimation steps occur almost instantaneously, and the final accuracy is very good (R2 = 0,994). SIGNIFICANCE AND NOVELTY: The proposed methodology opens up good prospects for real-time quantitative applications. It was successfully tested on a pilot piping installation where the target property is the interface height between two immiscible fluids.

Assessment of the Performance of Cationic Cellulose Derivatives as Calcium Carbonate Flocculant for Papermaking.

Cationic polyacrylamides (CPAMs) are usually used as filler retention agents in papermaking formulations. However, increasing environmental restrictions and their non-renewable origin have driven research into bio-based alternatives. In this context, cationic lignocellulosic derivatives have been attracting considerable research interest as a potential substitute. In this work, distinct cationic celluloses with degrees of substitution of between 0.02 and 1.06 and with distinct morphological properties were synthesized via the cationization of bleached eucalyptus kraft pulp, using a direct cationization with (3-chloro-2-hydroxypropyl) trimethylammonium chloride (CHPTAC) or a two-step cationization, where the cellulose was first oxidized to form dialdehyde cellulose and was then made to react with Girard's reagent T (GT). Fibrillated samples were produced by subjecting some samples to a high-pressure homogenization treatment. The obtained samples were evaluated regarding their potential to flocculate and retain precipitated calcium carbonate (PCC), and their performance was compared to that of a commercial CPAM. The cationic fibrillated celluloses, with a degree of substitution of ca. 0.13-0.16, exhibited the highest flocculation performance of all the cationic celluloses and were able to increase the filler retention from 43% (with no retention agent) to ca. 61-62% (with the addition of 20 mg/g of PCC). Although it was not possible to achieve the performance of CPAM (filler retention of 73% with an addition of 1 mg/g of PCC), the results demonstrated the potential of cationic cellulose derivatives for use as bio-based retention agents.

High-performance delignification of invasive tree species wood with ionic liquid and deep eutectic solvent for the production of cellulose-based polyelectrolytes.

An efficient and eco-friendly process for lignocellulosic biomass fractionation is essential for the production of high value-added bioproducts from biomass. The present work aimed to obtain cellulose-rich materials from the wood of an invasive tree species (Acacia dealbata) using an appropriate choice of ionic liquids (ILs) and deep eutectic solvents (DESs), and of the processing conditions, for the subsequent production of cationic wood-based polyelectrolytes. In the pretreatment step, the 1-butyl-3-methylimidazolium methyl sulfate (IL) + H2O and choline chloride + imidazole (DES) systems demonstrated a remarkable ability to remove lignin from acacia, reaching up to 92.4 and 90.2% of delignification, respectively. However, the DES pretreatment revealed to be more selective for lignin removal with lower cellulose losses (less than 15%) than the IL treatment (up to 30%) and less cellulose depolymerization. The hemicellulose was also removed but in a lesser extent with the DES treatment. Both systems could provide treated materials with a very high cellulose content (≥89%). Afterwards, cationic polyelectrolytes having a considerable content of quaternary ammonium groups (up to 3.6 mmol g-1) were obtained directly from the IL- and DES-pretreated woods. The treated woods, when used as raw materials for cationization reaction, allow to synthesize water-soluble polyelectrolytes with potential to be applied in wastewater treatment, pharmaceutical or cosmetic products.

Effect of cationization pretreatment on the properties of cationic Eucalyptus micro/nanofibrillated cellulose.

Micro/nanofibrillated celluloses (M/NFCs) have attracted considerable research interest over the past few decades, with various pretreatments being used to reduce energy consumption and/or increase fibrillation. To date, few studies have considered cationization as a pretreatment for their preparation. In this work, quaternary ammonium groups were attached to cellulose fibers by a direct reaction with 2,3-epoxypropyltrimethylammonium chloride or by a two-step method (periodate oxidation + Girard's reagent T). The cationic fibers with degrees of substitution (DS) between 0.02 and 0.36, were subjected to homogenization treatment. The morphological properties, chemical composition, and rheological behavior were evaluated to assess the effect of DS and the effect of the cationization method (for samples with similar DS). The two-step cationization resulted in significant degradation of the cellulose structure, leading to the formation of short fibrils and solubilization of the material, ranging from 6% to almost complete solubilization at a DS of 0.36. Direct cationization resulted in longer fibrils with an average diameter of 1 µm, and no significant cellulose degradation was observed, leading to a more cohesive gel-like material (at 1 wt%). These observations clearly show the strong influence of the cationization method on the final properties of the cationic cellulosic materials.

Lignin Extraction from Waste Pine Sawdust Using a Biomass Derived Binary Solvent System.

Lignocellulosic biomass fractionation is typically performed using methods that are somehow harsh to the environment, such as in the case of kraft pulping. In recent years, the development of new sustainable and environmentally friendly alternatives has grown significantly. Among the developed systems, bio-based solvents emerge as promising alternatives for biomass processing. Therefore, in the present work, the bio-based and renewable chemicals, levulinic acid (LA) and formic acid (FA), were combined to fractionate lignocellulosic waste (i.e., maritime pine sawdust) and isolate lignin. Different parameters, such as LA:FA ratio, temperature, and extraction time, were optimized to boost the yield and purity of extracted lignin. The LA:FA ratio was found to be crucial regarding the superior lignin extraction from the waste biomass. Moreover, the increase in temperature and extraction time enhances the amount of extracted residue but compromises the lignin purity and reduces its molecular weight. The electron microscopy images revealed that biomass samples suffer significant structural and morphological changes, which further suggests the suitability of the newly developed bio-fractionation process. The same was concluded by the FTIR analysis, in which no remaining lignin was detected in the cellulose-rich fraction. Overall, the novel combination of bio-sourced FA and LA has shown to be a very promising system for lignin extraction with high purity from biomass waste, thus contributing to extend the opportunities of lignin manipulation and valorization into novel added-value biomaterials.

Revisiting the dissolution of cellulose in H3PO4(aq) through cryo-TEM, PTssNMR and DWS.

Cellulose can be dissolved in concentrated acidic aqueous solvents forming extremely viscous solutions, and, in some cases, liquid crystalline phases. In this work, the concentrated phosphoric acid aqueous solvent is revisited implementing a set of advanced techniques, such as cryo-transmission electronic microscopy (cryo-TEM), polarization transfer solid-state nuclear magnetic resonance (PTssNMR), and diffusing wave spectroscopy (DWS). Cryo-TEM images confirm that this solvent system is capable to efficiently dissolve cellulose. No cellulose particles, fibrils, or aggregates are visible. Conversely, PTssNMR revealed a dominant CP signal at 25 °C, characteristic of C-H bond reorientation with correlation time longer than 100 ns and/or order parameter above 0.5, which was ascribed to a transient gel-like network or an anisotropic liquid crystalline phase. Increasing the temperature leads to a gradual transition from CP to INEPT-dominant signal and a loss of birefringence in optical microscopy, suggesting an anisotropic-to-isotropic phase transition. Finally, an excellent agreement between optical microrheology and conventional mechanical rheometry was also obtained.

Evaluation of Anionic Eco-Friendly Flocculants Prepared from Eucalyptus Pulps with Diverse Lignin Contents for Application in Effluent Treatment.

Modification of cellulosic-rich materials for the production of cellulose-based polyelectrolytes (PELs) can bring several benefits, such as high biodegradability and low or no toxicity, for numerous applications, when compared with the use of traditional, synthetic PELs. Moreover, cellulose-based PELs originating from wood wastes, contribute to the valorisation of such wastes. In this work, Eucalyptus pulps with diverse lignin contents, extracted from Eucalyptus wood wastes, were anionized by a two-step reaction procedure (periodate oxidation followed by sulfonation). Applying different reaction times (24-144 h) in the sulfonation step allowed for producing a range of cellulose-based anionic polyelectrolytes with different characteristics. PELs obtained after 24 and 72 h of sulfonation were thoroughly characterized (Fourier transform infrared and 1H nuclear magnetic resonance spectroscopies, zeta potential and degree of substitution (elemental analysis) and hydrodynamic diameter (dynamic light scattering)) and subsequently evaluated as flocculants in decolouration processes of model effluents (Methylene Blue and Crystal Violet) and an industrial effluent from a textile industry. Furthermore, possible flocculation mechanisms induced by the use of the various PELs are discussed. Results are compared with those obtained with a commonly applied, synthetic flocculant (polyacrylamide). It is demonstrated that it was possible to obtain water-soluble lignocellulosic PELs starting from raw materials with different degrees of purity and that those PELs are promising eco-friendly alternative flocculation agents for the decolouration of effluents.

Evaluation of Anionic and Cationic Pulp-Based Flocculants With Diverse Lignin Contents for Application in Effluent Treatment From the Textile Industry: Flocculation Monitoring.

In wastewater treatment, flocculation is a widely used solid/liquid separation technique, which typically employs a charged polymer, a polyelectrolyte (PEL). Polyelectrolytes features, such as charge type, charge density and molecular weight, are essential parameters affecting the mechanism of flocculation and subsequent floc sedimentation. The effectiveness of the process is also influenced by the characteristics of the system (e.g., type, size, and available surface area of suspended particles, pH of the medium, charge of suspended particles). Thus, a good understanding of the flocculation kinetics, involved mechanisms and flocs structure is essential in identifying the most adequate treatment conditions, having also into consideration possible subsequent treatments. In this study, Eucalyptus bleached pulp and a cellulosic pulp with high lignin content (~4.5 wt%) obtained from Eucalyptus wood waste were used for bio-PELs production. Firstly, a pre-treatment with sodium periodate increased the pulps reactivity. To produce cationic cellulose the oxidation step was followed by the introduction of cationic groups in the cellulose chains, through reaction with Girard's reagent T. Applying different molar ratios (0.975 and 3.9) of Girard's reagent T to aldehyde groups led to cationic PELs with diverse charge density. On the other hand, to obtain anionic cellulose a sulfonation reaction with sodium metabisulfite was applied to the intermediate dialdehyde cellulose-based products, during 24 or 72 h, and anionic-PELs with diverse features were obtained. The developed water soluble, anionic and cationic bio-PELs were characterized and tested as flocculation agents for a textile industry effluent treatment. Initially, jar-tests were used to tune the most effective flocculation procedure (pH, flocculant dosage, etc.). Flocculation using these conditions was then monitored continuously, over time, using laser diffraction spectroscopy (LDS). Due to the small size of the dyes molecules, a dual system with an inorganic complexation agent (bentonite) was essential for effective decolouration of the effluent. Performance in the treatment was monitored first by turbidity removal evaluation (75-88% with cationic-PELs, 75-81% with anionic-PELs) and COD reduction evaluation (79-81% with cationic-PELs, 63-77% with anionic-PELs) in the jar tests. Additionally, the evolution of flocs characteristics (structure and size) during their growth and the flocculation kinetics, were studied using the LDS technique, applying the different PELs produced and for a range of PEL concentration. The results obtained through this monitoring procedure allowed to discuss the possible flocculation mechanisms involved in the process. The results obtained with the bio-PELs were compared with those obtained using synthetic PELs, commonly applied in effluents treatment, polyacrylamides. The developed bio-PELs can be competitive, eco-friendly flocculation agents for effluents treatment from several industries, when compared to traditional synthetic flocculants with a significant environmental footprint. Moreover, LDS proved to be a feasible technique to monitor flocculation processes, even when a real industrial effluent is being tested.

Stabilization of Palygorskite Aqueous Suspensions Using Bio-Based and Synthetic Polyelectrolytes.

Palygorskite is a natural fibrous clay mineral that can be used in several applications, for which colloidal stability in aqueous suspensions is a key point to improve its performance. In this study, methods of magnetic stirring, high-speed shearing, and ultrasonication, as well as different chemical dispersants, combined with these methods, namely carboxymethylcellulose, alginate, polyphosphate, and polyacrylate, were used to improve the dispersibility and the formation of stable suspensions of palygorskite in different conditions of pH. The stability and particle size of suspensions with a low concentration of palygorskite were evaluated by visual inspection, optical and electron microscopy, dynamic light scattering, and zeta potential measurements. Moreover, the palygorskite used in this work was initially characterized for its mineralogical, chemical, physical, and morphological properties. It was found that more stable suspensions were produced with ultrasonication compared to the other two physical treatments, with magnetic stirring being inefficient in all tested cases, and for higher pH values (pH of 12 and pH of 8, the natural pH of the clay) when compared to lower pH values (pH of 3). Remarkably, combined with ultrasonication, carboxymethylcellulose or in a lesser extent polyphosphate at near neutral pH allowed for the disaggregation of crystal bundles of palygorskite into individualized crystals. These results may be helpful to optimize the performance of palygorskite in several domains where it is applied.

Up-scaling of tannin-based coagulants for wastewater treatment: performance in a water treatment plant.

Tannin extracts from the bark of Acacia mearnsii and wood of Schinopsis balansae, commonly known as Quebracho, were employed. These were modified at laboratory sale via the Mannich aminomethylation with formaldehyde and dimethylamine hydrochloride. Some reaction conditions were varied, namely the formaldehyde dosage and reaction time, while keeping the Mannich solution activation time constant, and their influence on the shear viscosity of the created bio-coagulants was evaluated. The effect of the final pH of the products on their shear viscosity was also analyzed. Up-scaling of the Mannich reaction for tannin from South Africa was performed and the procedure developed at 1-L scale was reproducible in upscaled conditions. One example of a modified South Africa tannin and the modified Quebracho tannin was subsequently selected for the treatment of an industrial wastewater and tested for color and turbidity reduction in jar tests. The effluent treatment was carried out in a single and dual system with cationic synthetic flocculation agents of different charge degree. Good turbidity and decoloration results (93 and 89% reduction, respectively) were obtained with the simultaneous introduction of a cationic, 40% charged polyacrylamide, with minimal dosage (5 ppm) of the latter additive. The tannin-based coagulant from Acacia mearnsii was successfully applied in dual system with cationic polyacrylamide flocculant for industrial wastewater treatment at pilot plant scale. It was shown to satisfactorily treat the water and generate less sludge.

Cationization of Eucalyptus wood waste pulps with diverse lignin contents for potential application in colored wastewater treatment.

Modification of cellulosic-rich materials such as Eucalyptus wood waste and production of cellulose-based polyelectrolytes (PELs) presents several advantages for a variety of applications, when compared to the utilization of synthetic PELs, due to the nature, availability, high biodegradability and low or no toxicity of cellulosic materials. Moreover, valorization of the cellulosic waste itself to provide end products with higher added value is also an important aspect. In the present work, the objective was to evaluate the possibility of cationizing more complex and heterogeneous chemical pulps, obtained from Eucalyptus wood waste, with different cellulose purity and a relatively high lignin content (up to 4.5%). A two-step reaction (with sodium periodate and Girard's reagent T) was employed and a range of cellulose-based cationic polyelectrolytes were produced with different degrees of substitution. The final products were characterized by several analytical techniques and the bio-PELs with the highest and the lowest substitution degree by cationic groups were evaluated in a new application, as flocculants in the decoloration of model effluents, bentonite having been used as an inorganic aid. Also, possible mechanisms of flocculation were discussed and the results compared with those of a synthetic flocculant, often used in these treatments, cationic polyacrylamide. Lignocellulosic-PELs proved to be very favorable eco-friendly flocculation agents for the decoloration of dye-containing waters with potential application in several industries.

Environmentally friendly cellulose-based polyelectrolytes in wastewater treatment.

Natural-based polyelectrolytes (PELs), with all the advantages coming from being produced from renewable and biodegradable sources, are a potential solution for the removal of dyes from wastewater. In this work, surplus Eucalyptus bleached cellulose fibres from a paper mill were modified to increase the charge and solubility of cellulose. First, reactive aldehyde groups were introduced in the cellulose backbone by periodate oxidation of cellulose. Further modification with alkylammonium produced positively charged cellulose-based PELs. The final products were characterized by several analytical techniques. The PEL with the highest substitution degree of cationic groups was evaluated for its performance in decolouration processes, bentonite being used as aid. This was found to be effective for colour removal of either anionic or cationic dyes. Bio-PELs can thus be considered as very favourable eco-friendly flocculation agents for decolouration of harsh effluents from several industries, considering their biodegradable nature and thus the ability to produce less sludge.

Evaluation of the Performance of Dual Polyelectrolyte Systems on the Re-Flocculation Ability of Calcium Carbonate Aggregates in Turbulent Environment.

Flocculation can be used in turbulent environments resulting in floc breakage due to shearing. The degree of re-flocculation relates directly to product quality and process efficiency. This study aimed at looking for alternatives to improve the re-flocculation ability of aggregates when polyelectrolytes (PEL) are used as flocculation agents. Moreover, because branched PEL have proved previously to lead to high flocculation efficiencies, the work presented focus on the improvement of the re-flocculation ability of branched PEL. Thus, a selection of branched polymers were used primarily as flocculation aid and after flocs break up a linear polymer was added to the system in order to improve re-flocculation. Different mixtures were tested with the objective to try to induce, during re-flocculation, complementary flocculation mechanisms, favoring the patching mechanism. Re-flocculation improved significantly with this strategy. Laser Diffraction Spectroscopy was used to monitor the flocculation and re-flocculation processes supplying information about the floc size and structure. Since inorganic materials, namely bentonite, have been widely used to improve the re-flocculation capacity of polyelectrolytes, the results of using dual polyelectrolyte systems were compared with the effect of adding bentonite to the system.