Chemical and engineering bases for green H2O2 production and related oxidation and ammoximation of olefins and analogues.

Plastics, fibers and rubber are three mainstream synthetic materials that are essential to our daily lives and contribute significantly to the quality of our lives. The production of the monomers of these synthetic polymers usually involves oxidation or ammoximation reactions of olefins and analogues. However, the utilization of C, O and N atoms in current industrial processes is <80%, which represents the most environmentally polluting processes for the production of basic chemicals. Through innovation and integration of catalytic materials, new reaction pathways, and reaction engineering, the Research Institute of Petroleum Processing, Sinopec Co., Ltd. (RIPP) and its collaborators have developed unique H2O2-centered oxidation/ammoximation technologies for olefins and analogues, which has resulted in a ¥500 billion emerging industry and driven trillions of ¥s' worth of downstream industries. The chemical and engineering bases of the production technologies mainly involve the integration of slurry-bed reactors and microsphere catalysts to enhance H2O2 production, H2O2 propylene/chloropropylene epoxidation for the production of propylene oxide/epichlorohydrin, and integration of H2O2 cyclohexanone ammoximation and membrane separation to innovate the caprolactam production process. This review briefly summarizes the whole process from the acquisition of scientific knowledge to the formation of an industrial production technology by RIPP. Moreover, the scientific frontiers of H2O2 production and related oxidation/ammoximation processes of olefins and analogues are reviewed, and new technological growth points are envisaged, with the aim of maintaining China's standing as a leader in the development of the science and technologies of H2O2 production and utilization.

Preparation of chitin twisted fiber and its functional applications.

Chitin has garnered significant attention due to its renewable, biocompatibility and biodegradability, while its practical application seriously hindered as the functionality of chitin itself can no longer meet people's increasing requirements for materials. Here, an effective method is successfully built for high-performance chitin fibers fabrication through a multi-step strategy that involved chemical pre-crosslinking, followed by wet-twisting and wet-stretching techniques, combined with physical cross-linking. The as-prepared chitin fiber exhibited a smooth surface, adjustable diameter, and mechanical strong properties (144.6 MPa). More importantly, functional chitin fiber with magnetic or conductive abilities can be easily obtained by spraying Fe3O4 particles or Ag nanowire on the chemical pre-crosslinking chitin gel film before stretching and twisting. The doped functional inorganic particles exist in a continuous ribbon structure in the fiber reduced the decrease in material strength caused by uneven particles dispersion, resulting 88.4 % of stress and 91.6 % of strain retention. This work not only bestow invaluable insights into the fabrication of functional chitin fibers but also provide a novel approach to solve the problem of poor compatibility between organic and inorganic composite materials.

Augmenting the Efficacy of a Polyvinyl Alcohol Selective Layer Coated on Polyvinylidene Fluoride Support Membranes with Kaolinite Introduction for Improved Pervaporation Dehydration of Epichlorohydrin/Isopropanol/Water Ternary Systems.

Composite membranes with a polyvinyl alcohol (PVA) selective layer composed of well-dispersed hydrophilic kaolinite particles coated on a polyvinylidene fluoride (PVDF) support were developed. They were applied to the pervaporation dehydration of the industrially important epichlorohydrin (ECH)/isopropanol (IPA)/water ternary mixture. In comparison with raw kaolinite (RK), hydrophilic kaolinite (HK) enhanced the mechanical properties, hydrophilicity, and thermal stability of the PVA selective layer, as confirmed by universal testing, the contact angle, and TGA analyses, respectively. The pervaporation results revealed that the addition of HK particles significantly enhanced the separation factor (3-fold). Only a marginal reduction in flux was observed with ECH/IPA/water, 50/30/20 (w/w %) at 40 °C. An HK particle concentration of 4 wt.% with respect to PVA delivered the highest flux performance of 0.86 kg/m2h and achieved a separation factor of 116. The PVA-kaolinite composite membrane exhibited pronounced resistance to the ECH-containing feed, demonstrating a sustained flux and separation factor throughout an extended pervaporation stability test lasting 250 h.

Aminated Rapeseed Husks (Brassica napus) as an Effective Sorbent for Removing Anionic Dyes from Aqueous Solutions.

The study investigated the effect of modifying rapeseed husks with ammonia and epichlorohydrin on their sorption capacity against anionic reactive dyes: Reactive Black 5 (RB5) and Reactive Yellow 84 (RY84). Its scope included sorbents characterization (FTIR, pHPZC), determination of pH influence on the sorption effectiveness of dyes, the adsorption kinetics of dyes, as well as the maximum sorption capacity. The study proved that the reaction of rapeseed husk biomass with ammonia can lead to its amination, namely to the introduction of amine functional groups into the material's structure. The sorption effectiveness of RB5 and RY84 on the tested sorbents was the highest in the pH range of 2-3. The dye sorption kinetics was well described by the pseudo-second-order model. The sorption equilibrium time ranged from 90 to 180 min, and depended on the initial concentration of dyes and the number of amino groups on the sorbent's surface. The most efficient of the sorbents tested were rapeseed husks pre-activated with epichlorohydrin and then aminated with ammonia. Their sorption capacity determined for RB5 and RY84 was 135.83 mg/g and 114.23 mg/g, respectively, which was 794% and 737% higher than that of the non-modified husks.

Effect of epichlorohydrin treatment on the coating process and performance of high-barrier paper packaging.

The fabrication of coated papers using hydrophilic and biodegradable polymers is important for developing sustainable packaging materials with high barrier and superior mechanical properties. However, water, which is used as the solvent in the paper coating process using hydrophilic polymers, deforms the shape of the paper and deteriorates performance. Therefore, we propose a new coating process that treats Kraft paper (KP) with epichlorohydrin (ECH) as a binder before the coating process. Crosslinked polyvinyl alcohol is coated on the ECH-treated KP using a solution casting method. ECH maintains the shape of the paper and improves coating uniformity; significantly enhances interfacial interactions, which increases barrier properties and sealing strength; and extends the shelf life of biscuits by reducing oxygen and moisture permeability. An ecotoxicity test using Lolium multiflorum demonstrates an insignificant phytotoxicity level for the as-prepared coated papers. Thus, ECH-treated KP is a potential candidate for high-barrier food packaging.

Water resistant, biodegradable and flexible corn starch/carboxymethyl cellulose composite film for slow-release fertilizer coating materials.

The inherent limitations of Cornstarch (CS) and Carboxymethyl Cellulose (CMC) membranes, such as brittleness, fragility, and water solubility, limit their use in controlled-release fertilizers. This study reports on the synthesis of crosslinked CMC/CS-20-E composite membranes using the casting technique, with epichlorohydrin (ECH) as the crosslinking agent in an acidic environment to crosslink CS and CMC. The synthesized composite film demonstrates remarkable water resistance, as evidenced by the insignificant alteration in its morphology and structure post 72 h of water immersion. Its flexibility is reflected in its capacity to endure knotting and bending, with an elongation at break reaching 78.1 %. Moreover, the degradation rate surpasses 90 % within a span of seven days. The CMC/CS-20-E-x-urea controlled-release fertilizer was subsequently produced using a layer-by-layer self-assembly technique, where urea particles were incorporated into the crosslinked composite solution. This CMC/CS-20-E-x-urea controlled-release fertilizer displayed superior controlled-release performance over a duration of seven days when juxtaposed with pure urea. In particular, the CMC/CS-20-E-3 %-urea controlled-release fertilizer showed a cumulative release rate of 84 % by the seventh day. The controlled-release fertilizers developed in this study offer a promising strategy for creating eco-friendly options that are crucial for fertilizing crops with short growth cycles.

Adjustable strength and toughness of dual cross-linked nanocellulose films via spherical cellulose as soft-phase.

Nanocellulose films possess numerous merits ascribing to their inherent biocompatibility, non-toxic and biodegradability properties. The potential for practical applications would be improved if their mechanical strength and toughness requirements could be met simultaneously. Herein, dual cross-linked nanocellulose (DC) film was fabricated by the treatments of chemical and physical cross-linking, which was mechanically superior to pure nanocellulose (CNF) films. To further increase the toughness of DC films, spherical cellulose (Sph) was incorporated into DC film (DC-Sph film), and analyzed under different humidity conditions (RH) (from 10 % to 90 %). The changes of functional groups of CNF, DC and DC-Sph films were detected by FTIR and XPS spectrum. The epichlorohydrin and Sph content were optimized, followed by the investigation of RH on the toughness of films. The highest tensile strength (146.6 ± 4.6 MPa) was obtained in DC film at 50 % RH, while the DC-Sph film showed the largest toughness (40.3 ± 3.7 kJ/m2) at 70 % RH. Furthermore, the possible toughening mechanism of DC-Sph film was also discussed.

A comparison of the exposure system of glycidol-related chemicals on the formation of glycidol-hemoglobin adducts.

Glycidol fatty acid esters that are present in foods are degraded in vivo to the animal carcinogen glycidol, which binds to the N-terminal valine of hemoglobin (Hb) to form N-(2,3-dihydroxypropyl)valine (diHOPrVal) adducts. The existence of other chemicals that are converted to glycidol is unknown. To determine the effect of different exposure conditions on the formation of diHOPrVal adducts, several glycidol-related chemicals (3-monochloropropane-1,2-diol; 3-MCPD, epichlorohydrin, glyceraldehyde, acrylic acid, and 1,2-propanediol) were evaluated using in vitro and in vivo (single/repeated dose) methods. In vitro, the reaction of 3-MCPD or epichlorohydrin with human Hb produced 17% and 0.7% of diHOPrVal, as compared to equimolar glycidol, respectively. Following a single administration of glycidol-related compounds to ICR mice, diHOPrVal formation was observed only in the epichlorohydrin-treated group after day 5 of exposure. After 14 days of repeated dosing, the amounts of diHOPrVal produced by epichlorohydrin and 3-MCPD in vivo were <1% of diHOPrVal produced by an equal molar concentration of glycidol. Furthermore, glyceraldehyde group produced 0.2% of diHOPrVal at the same molar concentration of glycidol equivalents, in which diHOPrVal formation could not be confirmed by the in vitro assay. The results indicate the usefulness of diHOPrVal as an exposure marker for glycidol; however, the contribution of its formation in vivo by exposure to various chemicals will be necessary to validate and interpret the results.