Producing Cellulose Microfibrils at a High Solid Content with and without Mechanical or Enzymatic Pretreatment.

This study conducted a detailed evaluation of the feasibility of producing cellulose microfibrils (CMF) from a kraft-bleached hardwood pulp at high solid contents with and without pretreatments. CMFs produced by planetary ball milling at solid contents 17 and 28% were compared with those from 1 to 5% under the same milling conditions. Fiber pretreatments using a commercial endoglucanase and mechanical refining using a laboratory PFI mill were also applied before ball milling at a solid content of 28%. Two mechanisms of fiber fibrillation were identified from the results obtained: (i) ball and fiber/fibril interactions─the primary mechanism and (ii) interfiber/fibril frictional and tensional interactions─the secondary mechanism. The secondary mechanism plays an important role only in early-stage fibrillation and became less important as fibrillation proceeded in the later stage toward nanofibrillation. Improving fiber dispersion at lower solid content facilitated fibrillation. Endoglucanase pretreatment substantially shortened fibers to result in a "pulverized-like" CMF with short fibrils at an extended milling time. Mechanical refining of fibers facilitated fibrillation to result in CMFs with a morphology similar to that from runs without any fiber pretreatment but for a much shorter milling time. Both CMF water retention value (WRV) measurements and CMF suspension sedimentation experiments showed results consistent with imaging observations. The insights gained through this study provide relevant information with commercial significance regarding CMF production at high solids, which is not currently available in the literature.

Relationship between the Change in E/T Ratio and the Cooking Performance of Eucalyptus and Acacia Woods during Kraft Pulping Process.

Lignin structure is an important factor affecting the cooking part of the pulping process. In this study, the effect of lignin side chain spatial configuration on cooking performance was analyzed, and the structural characteristics of eucalyptus and acacia during cooking were compared and studied by combining ozonation, GC-MS, NBO, and 2D NMR (1H-13C HSQC). In addition, the changes in the lignin content of four different raw materials during the cooking process were studied via ball milling and UV spectrum analysis. The results showed that the content of lignin in the raw material decreased continuously during the cooking process. Only in the late cooking stage, when the lignin removal reached its limit, did the lignin content tend to be stable due to the polycondensation reaction of lignin. At the same time, the E/T ratio and S/G ratio of the reaction residual lignin also followed a similar rule. At the beginning of cooking, the values of E/T and S/G decreased rapidly and then gradually rose when they reached a low point. The different initial E/T and S/G values of different raw materials lead to the disunity of cooking efficiency and the different transformation rules of different raw materials in the cooking process. Therefore, the pulping efficiency of different raw materials can be improved using different technological means.

Review on the oxidative catalysis methods of converting lignin into vanillin.

Vanillin plays an important role not only in food and flavouring, but also as a platform compound for the synthesis of other valuable products, mainly derived from the oxidative decarboxylation of petroleum-based guaiacol production. In order to alleviate the problem of collapsing oil resources, the preparation of vanillin from lignin has become a good option from the perspective of environmental sustainability, but it is still not optimistic in terms of vanillin production. Currently, catalytic oxidative depolymerization of lignin for the preparation of vanillin is the main development trend. This paper mainly reviews four ways of preparing vanillin from lignin base: alkaline (catalytic) oxidation, electrochemical (catalytic) oxidation, Fenton (catalytic) oxidation and photo (catalytic) oxidative degradation of lignin. In this work, the working principles, influencing factors, vanillin yields obtained, respective advantages and disadvantages and the development trends of the four methods are systematically summarized, and finally, several methods for the separation and purification of lignin-based vanillin are briefly reviewed.

Dual Network Hydrogel with High Mechanical Properties, Electrical Conductivity, Water Retention and Frost Resistance, Suitable for Wearable Strain Sensors.

With the progress of science and technology, intelligent wearable devices have become more and more popular in our daily life. Hydrogels are widely used in flexible sensors due to their good tensile and electrical conductivity. However, traditional water-based hydrogels are limited by shortcomings of water retention and frost resistance if they are used as the application materials of flexible sensors. In this study, the composite hydrogels formed by polyacrylamide (PAM) and TEMPO-Oxidized Cellulose Nanofibers (TOCNs) are immersed in LiCl/CaCl2/GI solvent to form double network (DN) hydrogel with better mechanical properties. The method of solvent replacement give the hydrogel good water retention and frost resistance, and the weight retention rate of the hydrogel was 80.5% after 15 days. The organic hydrogels still have good electrical and mechanical properties after 10 months, and can work normally at -20 °C, and has excellent transparency. The organic hydrogel show satisfactory sensitivity to tensile deformation, which has great potential in the field of strain sensors.

High-value utilization of bamboo pulp black liquor lignin: Preparation of silicon-carbide derived materials and its application.

The black liquor of bamboo pulp contains a large amount of silicon, which makes it difficult to separate industrial lignin, thus hindering its high-value utilization. Herein, this paper dedicates to exploring the high-value use of silica-containing lignin. Tetraethyl silicate (TEOS) was added to the above silicon-containing lignin for crosslinking with the lignin to prevent disintegration during carbonization and provide an additional source of silica. The carbonization is carried out at 600 °C (LT-6), 900 °C (LT-9) and 1200 °C (LT-12), and the structural evolution of SiOxCy is innovatively analyzed. The results show that LT-9 is dominated by the SiO3C structure and has a specific surface area of 269 m2 g-1. The specific capacitance of LT-9 and LT-12 as supercapacitors electrodes is 78.6 F g-1 and 74.8 F g-1 at a current density of 1 A g-1, and remains 95 % and 91.7 % after 10,000 cycles. Moreover, LT-9 has a high yield of 54 %. In this work, silicon-containing lignin is exploratively prepared as a silicon-carbide-derived material. Furthermore, the potential relationship between different SiOxCy molecular structures and electrochemical performance is evaluated, which is instructive for the high-value utilization of black liquor in bamboo pulp.

Synthesis and Properties of Novel Reactive Dyes Comprising Acyl Fluoride Group on Cotton Fabrics.

Novel reactive dyes with mono- and bi-acyl fluoride reactive groups have been designed and synthesized, which are obtained by using 2-amino-8-naphthol-6-sulfonic acid or 1-amino-8-naphthol-3,6-disulfonicacid as the coupling component and 4-aminobenzoyl fluoride (PABF) as the diazo component. Their structures have been defined by nuclear magnetic resonance spectroscopy and ultraviolet-visible spectra (UV-Vis). The novel reactive dyes were evaluated on cotton by using the exhaust dyeing method. The properties were examined in detail, and the results showed that the dye concentration of 4% (o.w.f), pH = 9, and salt-free was the most effective condition. The fixation of the novel reactive dyes on cotton was 60.27% and 64.13%, respectively. The micro-fluorine-containing reactive dyes have favorable dyeing properties owing to the covalent bond formed between the reactive group of dyes and the functional group of cotton fibers, which can achieve salt-free dyeing of cotton.

Processing nanocellulose foam into high-performance membranes for harvesting energy from nature.

Nanocellulose membranes exhibit good stability and high strength. However, the conventional synthetic routes rely on solvent volatilization of a nanocellulose suspension or solution. The complete hydrogen bonding that occurs in this process leads to a dense structure and poor strength in water. Hereby, lignosulfonate and polycation were mixed to form a complex and then attached to cellulose. The freeze-dried nanocellulose foam was hot-pressed to membrane, resulting in simultaneous co-crosslinking and membrane formation. The membrane had a porous structure with a high mechanical performance, excellent stability and a fast shape recovery. This also represents a method for processing functional nanocellulose membranes, as further demonstrated by the hybrid membrane with exceptional solar-driven seawater desalination and water-flow electricity generation properties. This work established facile methods for tackling the structural weakness of the conventional nanocellulose membrane, and opens the door to the application of nanocellulose membrane with a combination of mechanical stability and functionality.

Cellulose Nanofibril Based-Aerogel Microreactors: A High Efficiency and Easy Recoverable W/O/W Membrane Separation System.

Hereby we report a novel cellulose nanofirbril aerogel-based W/O/W microreactor system that can be used for fast and high efficient molecule or ions extraction and separation. The ultra-light cellulose nanofibril based aerogel microspheres with high porous structure and water storage capacity were prepared. The aerogel microspheres that were saturated with stripping solution were dispersed in an oil phase to form a stable water-in-oil (W/O) suspension. This suspension was then dispersed in large amount of external waste water to form W/O/W microreactor system. Similar to a conventional emulsion liquid membrane (ELM), the molecules or ions in external water can quickly transport to the internal water phase. However, the microreactor is also significantly different from traditional ELM: the water saturated nanocellulose cellulose aerogel microspheres can be easily removed by filtration or centrifugation after extraction reaction. The condensed materials in the filtrated aerogel particles can be squeezed and washed out and aerogel microspheres can be reused. This novel process overcomes the key barrier step of demulsification in traditional ELM process. Our experimental indicates the novel microreactor was able to extract 93% phenol and 82% Cu2+ from external water phase in a few minutes, suggesting its great potential for industrial applications.