Synthesis of lignin-based resin and fabrication of sustainable transparent wood based on bio-recycling concept.

Transparent wood (TW) has attracted much attention in the field of energy saving building structural materials because of its high light transmittance, good thermal insulation performance and good toughness. However, the polymeric resins used in the present study to impregnate lignin-based wood templates are usually derived from petroleum-based chemical resources, which pose a fatal threat to human beings both in terms of consuming large amounts of resources and causing environmental pollution problems. It is therefore important to develop alternatives to petroleum-derived chemicals in renewable natural resources. Here, we report a green and sustainable TW production process based on the bio-recycling concept. Lignin-based sustainable resin (LSR) was prepared from waste lignin produced during delignification by polymerization of guaiacol. At the same time, according to FT-IR and NMR data analysis combined with previous studies, the synthesis mechanism of LSR was proposed, and this result provided a reference for bio-based resins made from biomass materials. The prepared lignin-based sustainable transparent wood (LSTW) has good light transmittance and good dimensional stability. In addition, the LSTW also shows good thermal insulation and indoor temperature regulation capabilities compared with the common glass.

Ball-milling as effective and economical process for biodiesel production under Kraft lignin activated carbon stabilized potassium carbonate.

Biodiesel is a typical renewable energy and the previous transesterification processes for biodiesel production mainly focus on thermocatalytic methods. In this paper, the ball-milling process was investigated into the biodiesel production under Kraft lignin activated carbon stabilized K2CO3. Biodiesel yield increased to 66 % after only 5 min and reached 100 % within 25 min under optimal ball-milling conditions (0.5 g of the catalyst; methanol/oil molar ratio 18:1; 195 g of ball-mill beads; 1400 rpm; 25 °C). The power demand between the thermocatalytic method and the ball-milling method was also compared. Based on the computation, the ball-milling method has lower power demand than the traditional method (38 vs 201 kWh·mol-1). Therefore, the ball-milling method is an effective and economical process for biodiesel production.

Insecticidal characteristics and mechanism of a promising natural insecticide against saw-toothed grain beetle.

The prevention of grain storage pests is a universal concern all over the world. It is in high demand to explore novel, safe and green insecticidal techniques to address such concerns. In this work, both raw and calcined diatomite were used as a natural insecticide to remove common grain storage pests with improved lethal effect on the saw-toothed grain beetle. Interestingly, the raw diatomite showed higher insecticidal efficiency than the calcined diatomite, and its associated insecticidal properties and preparation conditions were also optimized through orthogonal tests. The optimal conditions for processing the raw diatomite insecticide were identified as follows: the diatomite dust was 500 mesh (A 3), the temperature was 25 °C (B 1), the relative humidity was 65% (C 2), the diatomite dosage was 20 g m-2 (D 2), the influence factor order was C ≥ D > A > B. The observation of surface morphology indicated that the raw diatomite had a complete, multi hole surface morphology and good adsorption performance, whereas the structure of the calcined diatomite was uncomplete with collapsed pores, resulting in poor adsorption performance. The special pore structure and excellent adsorption capacity of diatomite make the stored grain pests lose water to lethal effect. Acute toxicity and long-term toxicity tests in mice showed that diatomite has no harmful effects on mammals. The findings from our work led to a green and effective approach in producing a highly efficient and safe storage grain insecticide.

Correlation between physicochemical characteristics of lignin deposited on autohydrolyzed wood chips and their cellulase enzymatic hydrolysis.

Enzymatic hydrolysis is a method to generate biofuel from biomass, and autohydrolysis is a popular method to pretreat biomass prior to enzymatic hydrolysis. The primary aim of the present study was to determine the role of lignin produced in the autohydrolysis process on the enzymatic hydrolysis of biomass. The HSQC and 31P NMR analyses confirmed that ß-O-4 of lignin was reduced, while ß-5, ß-ß, and S/G-ratio of lignin were increased with intensifying the hydrolysis intensity.The increase in the hydrolysis intensity significantly enhanced the condensed and non-condensed phenolic OH group of lignin. Interestingly, the cellulase enzyme adsorbed more on lignin that had more phenolic content, and its association with lignin reduced its activity for hydrolyzing cellulose microcrystals. Strong negative correlations were observed between the enzymatic hydrolysis yield and the condensed S-OH (r2 = 0.978) and G-OH (r2 = 0.961) of lignin generated in the autohydrolysis process.

Green solvents-based molecular weight controllable fractionation process for industrial alkali lignin at room temperature.

The molecular weight is one of the most important factors influencing the utilization of industrial lignin obtained from chemical pulping process. In this paper, a facile operative green solvent system was successfully developed for molecular weight-controllable fractionation of industrial alkali lignin (IAL) at room temperature. The results showed that through adjusting the ratio of water, ethanol and γ-Valerolactone (GVL), the industrial lignin was fractionated into six levels with molecular weight stepwise controllable from low to high. The fractionation is a physical process according to FTIR and 2D-HSQC NMR analysis, and the chemical structure of lignin has not changed. Additionally, the polydispersity of fractionated lignin with higher molecular weight tends to be narrower. The content of hydroxyl and carboxyl group is higher for the fractionated lignin with lower molecular weight, which would be beneficial for the chemical reactivity in the down-stream application.

Research on Resin Used for Impregnating Polyimide Fiber Paper-Based Composite Materials.

In this paper, a resin with high adhesion, easy curing, good flexibility, and high temperature resistance was prepared from polyimide fiber paper. First, in order to improve the toughness and curability of impregnating resin, epoxy resin was modified by addition of vinyl silicone resin. Subsequently, ternary resin with high temperature stability was obtained by polyimide resin addition. Among the investigated conditions, the optimal additive amount of vinyl silicone resin and polyimide resin was 30% and 5%, respectively. The prepared ternary resin has better toughness, crosslinking degree, high temperature stability (5% mass loss at 339.2 °C) and no obvious glass transition at high temperature. Finally, the polyimide fiber paper-based composite material was impregnated with modified epoxy resin and ternary resin, respectively. The results shows that the paper-based composite material impregnated with modified epoxy resin has a better fiber bonding degree, a smooth surface, and contact angle could reach up to 148.71°. Meanwhile, the paper-based composite material impregnated with ternary resin has good high temperature resistance, and the tensile index of the paper-based composite material could reach up to 35.1 N·m/g at 200 °C.

Adsorption and Release Kinetics, Equilibrium, and Thermodynamic Studies of Hymexazol onto Diatomite.

Pesticide sustained-release agents have advantages of low toxicity, high efficiency, and long duration. However, the sustained-release effects were not ideal, such as short release time and low release rate. The physical and chemical properties of diatomite are high stability, high porosity, and good sustained-release and controlled-release abilities. A series of diatomite-based pesticide sustained-release agents were prepared by adsorbing hymexazol onto diatomite. Kinetics, equilibrium, and thermodynamic studies for adsorption were carried out as well. It was found that the modified diatomite has a better adsorption effect for hymexazol, and the adsorption rate reached 16.64%. The equilibrium data followed with the Langmuir isotherm model, and the adsorption process was an endothermic process. Release results showed that the diatomite-based pesticide has a significant sustained-release effect. The sustained-release time reached more than 25 days, and the maximum release rate was above 70%. The experimental data was fitted into the Ritger-Peppas equation, and it was found that the release was controlled by the Fick diffusion mechanism. This confirmed the applicability of the modified diatomite as an efficient adsorption carrier for pesticide release.

Surface sediments formation during auto-hydrolysis and its effects on the benzene-alcohol extractive, absorbability and chemical pulping properties of hydrolyzed acacia wood chips.

The aim of this work was to study the sedimentary substances formed on the surface of auto-hydrolyzed wood chips. And its potential effect on the subsequent chemical pulping was then investigated by the analysis of surface morphology, benzene-alcohol extractive, absorbability and kraft pulping of wood chips hydrolyzed. The results showed that sediments on the surface of auto-hydrolyzed wood chips were microspheric and the amount of them increased with intensifying the severity of treatment. The benzene-alcohol extractives and lignin content in the extractives increased from 1.36% and 16.42% in the control sample to 9.42% and 47.68% in the hydrolyzed wood chips at the P-factor of 808. The absorbability of hydrolyzed wood chips firstly improved in the early stage (P-factor < 306) and after then decreased. Negative effect of the sediments on the surface of hydrolyzed wood chips was found on the subsequent kraft chemical pulping and the properties of final pulp.

Preparation and characterization of thermo-sensitive gel with phenolated alkali lignin.

Thermo-sensitive gel exhibits great potential industrial application. It has been widely used in tissue repair, drug release and water purification for its property of phase transition in response to external stimuli, reusability and biocompatibility. In this study, a novel lignin-based thermo-sensitive gel was synthesized with alkali lignin by two steps. Firstly, phenolated lignin (PPAL) was synthesized with purified alkali lignin (PAL) catalyzed by sulfuric acid. Subsequently, thermo-sensitive gel was achieved by thermal polymerization of phenolated alkali lignin and N-isopropylacrylamide (NIPAAm). Furthermore, the prepared hydrogels were characterized in terms of thermal behavior, interior morphology and their swelling behavior. Compared with PAL-based gel, the obtained PPAL-based gel exhibits a higher crosslinking density and lower critical solution temperature (LCST) due to the increase of reaction site and smaller space volume of the hydrophobic side groups grafted on NIPAAm. TGA data revealed that thermal stability of gel was enhanced (50% weight loss at ~380 °C) by using lignin as precursor. SEM images showed that a more regular interior morphology, better compressive strength was also found (PPAL0.05, 11.15 KPa). Furthermore, the swelling ratio of PPAL-based gel was lower than that of PAL-based gel due to its more complex structure.

Synthesis of Renewable Triketones, Diketones, and Jet-Fuel Range Cycloalkanes with 5-Hydroxymethylfurfural and Ketones.

A series of renewable C9 -C12 triketones with repeating [COCH2 CH2 ] units were synthesized in high carbon yields (ca. 90 %) by the aqueous-phase hydrogenation of the aldol-condensation products of 5-hydroxylmethylfurfural (HMF) and ketones over an Au/TiO2 catalyst. Compared with the reported routes, this new route has many advantages such as being environmentally friendly, having fewer steps, using a cheaper and reusable catalyst, etc. The triketones as obtained can be used as feedstocks in the production of conducting or semi-conducting polymers. Through a solvent-free intramolecular aldol condensation over solid-base catalysts, the triketones were selectively converted to diketones, which can be used as intermediates in the synthesis of useful chemicals or polymers. As another application, the tri- and diketones can also be utilized as precursors for the synthesis of jet-fuel range branched cycloalkanes with low freezing points (224-248 K) and high densities (ca. 0.81 g mL-1 ).

Direct Synthesis of Renewable Dodecanol and Dodecane with Methyl Isobutyl Ketone over Dual-Bed Catalyst Systems.

For the first time, we demonstrated two integrated processes for the direct synthesis of dodecanol or 2,4,8-trimethylnonane (a jet fuel range C12 -branched alkane) using methyl isobutyl ketone (MIBK) that can be derived from lignocellulose. The reactions were carried out in dual-bed continuous flow reactors. In the first bed, MIBK was selectively converted to a mixture of C12 alcohol and ketone. Over the Pd-modified magnesium- aluminium hydrotalcite (Pd-MgAl-HT) catalyst, a high total carbon yield (73.0 %) of C12 oxygenates can be achieved under mild conditions. In the second bed, the C12 oxygenates generated in the first bed were hydrogenated to dodecanol over a Ru/C catalyst or hydrodeoxygenated to 2,4,8-trimethylnonane over a Cu/SiO2 catalyst. The as-obtained dodecanol can be used as feedstock in the production of sodium dodecylsulfate (SDS) and sodium dodecyl benzene sulfonate (SDBS), which are widely used as surfactants or detergents. The asobtained 2,4,8-trimethylnonane can be blended into conventional jet fuel without hydroisomerization.

Synthesis of high density aviation fuel with cyclopentanol derived from lignocellulose.

For the first time, renewable high density aviation fuels were synthesized at high overall yield (95.6%) by the Guerbet reaction of cyclopentanol which can be derived from lignocellulose, followed by the hydrodeoxygenation (HDO). The solvent-free Guerbet reaction of cyclopentanol was carried out under the co-catalysis of solid bases and Raney metals. Among the investigated catalyst systems, the combinations of magnesium-aluminium hydrotalcite (MgAl-HT) and Raney Ni (or Raney Co) exhibited the best performances. Over them, high carbon yield (96.7%) of C10 and C15 oxygenates was achieved. The Guerbet reaction products were further hydrodeoxygenated to bi(cyclopentane) and tri(cyclopentane) over a series of Ni catalysts. These alkanes have high densities (0.86 g mL(-1) and 0.91 g mL(-1)) and can be used as high density aviation fuels or additives to bio-jet fuel. Among the investigated HDO catalysts, the 35 wt.% Ni-SiO2-DP prepared by deposition-precipitation method exhibited the highest activity.