Cellulose Fiber Rejects as Raw Material for Integrated Production of Pleurotus spp. Mushrooms and Activated Biochar for Removal of Emerging Pollutants from Aqueous Media.

Cellulose fiber rejects from industrial-scale recycling of waste papers were dried and de-ashed using a combined cyclone-drying and sieving process. The upgraded fiber reject was used as a component of substrates for the cultivation of Pleurotus ostreatus and Pleurotus eryngii mushrooms. Acetic acid (AA) and acid whey (AW) were used to adjust the pH of fiber reject-based substrates. Spent substrate (SMS) was used for the production of activated biochar using H3PO4 and KOH as activating agents and pyrolysis temperatures of 500, 600, and 700 °C. The effectiveness of the biochars in removing pollutants from water was determined using acetaminophen and amoxicillin. By using a feeding rate of 250 kg/h and a drying air temperature of 70 °C, the moisture content of the raw fiber rejects (57.8 wt %) was reduced to 5.4 wt %, and the ash content (39.2 wt %) was reduced to 21.5 wt %. Substrates with 60 and 80 wt % de-ashed cellulose fiber were colonized faster than a birch wood-based control substrate. The adjustment of the pH of these two substrates to approximately 6.5 by using AA led to longer colonization times but biological efficiencies (BEs) that were higher or comparable to that of the control substrate. The contents of ash, crude fiber, crude fat, and crude protein of fruit bodies grown on fiber reject-based substrates were comparable to that of those grown on control substrates, and the contents of toxic heavy metals, that is, As, Pb, Cd, and Hg, were well below the up-limit values for food products set in EC regulations. Activated biochar produced from fiber reject-based SMS at a temperature of 700 °C resulted in a surface area (BET) of 396 m2/g (H3PO4-activated biochar) and 199 m2/g (KOH-activated biochar). For both activated biochars, the kinetics of adsorption of acetaminophen and amoxicillin were better described using the general order model. The isotherms of adsorption were better described by the Freundlich model (H3PO4-activated biochar) and the Langmuir model (KOH-activated biochar).

Metal free synthesis of ethylene and propylene carbonate from alkylene halohydrin and CO2 at room temperature.

Herein we describe a metal free and one-pot pathway for the synthesis of industrially important cyclic carbonates such as ethylene carbonate (EC) and propylene carbonates (PC) from molecular CO2 under mild reaction conditions. In the actual synthesis, the alkylene halohydrins such as alkylene chloro- or bromo or iodohydrin and organic superbase, 1,8-diazabicyclo-[5.4.0]-undec-7-ene (DBU) reacted equivalently with CO2 at room temperature. The syntheses of cyclic carbonates were performed in DMSO as a solvent. Both 1,2 and 1,3 halohydrin precursors were converted into cyclic carbonates except 2-bromo- and iodoethanol, which were reacted equivalently with DBU through n-alkylation and formed corresponding n-alkylated DBU salts instead of forming cyclic carbonates. NMR analysis was used to identify the reaction components in the reaction mixture whereas this technique was also helpful in terms of understanding the reaction mechanism of cyclic carbonate formation. The mechanistic study based on the NMR analysis studies confirmed that prior to the formation of cyclic carbonate, a switchable ionic liquid (SIL) formed in situ from alkylene chlorohydrin, DBU and CO2. As a representative study, the synthesis of cyclic carbonates from 1,2 chlorohydrins was demonstrated where the synthesis was carried out using chlorohydrin as a solvent as well as a reagent. In this case, alkylene chlorohydrin as a solvent not only replaced DMSO in the synthesis but also facilitated an efficient separation of the reaction components from the reaction mixture. The EC or PC, [DBUH][Cl] as well as an excess of the alkylene chlorhydrin were separated from each other following solvent extraction and distillation approaches. In this process, with the applied reaction conditions, >90% yields of EC and PC were achieved. Meanwhile, DBU was recovered from in situ formed [DBUH][Cl] by using NaCl saturated alkaline solution. Most importantly here, we developed a metal free, industrially feasible CO2 capture and utilization approach to obtain EC and PC under mild reaction conditions.

Hydrogen sulfide gas capture by organic superbase 1,8-diazabicyclo-[5.4.0]-undec-7-ene through salt formation: salt synthesis, characterization and application for CO2 capture.

Hydrogen sulfide (H2S) is a toxic and environment polluting gas like other acid gases and hence its capture and sequestration is equally important before release into the atmosphere. In this regard, solvent-based processes involving aqueous tertiary amine systems were extensively studied and used. Herein, in line with an analogous pathway, we report capture of H2S gas in the form of its salt with an organic superbase such as 1,8-diazabicyclo-[5.4.0]-undec-7-ene (DBU) and the obtained salt was thoroughly studied. Spectroscopic analyses such as NMR and FTIR analyses confirmed that the H2S molecule formed an ionic solid adduct with DBU through protonation of its sp2-hybridized N atom. The stability of formed [DBUH][SH] salt in aqueous solution as well as under thermal treatment was also studied and monitored by NMR and thermogravimetric analysis (TGA), respectively. In aqueous medium, compared to DBU, the [DBUH][SH] salt exhibited long term stability without decomposition whereas under thermal treatment both DBU and its salt with H2S turned out to be thermally unstable where salt showed a volatile nature like a sublimized solid. Dissolution feasibility of [DBUH][SH] salt was also compared with DBU in polar as well as non-polar solvents and even though the [DBUH][SH] salt had an ionic nature, like DBU, it was also found soluble in various polar and non-polar solvents. Considering the stability of [DBUH][SH] salt in aqueous medium, its aqueous solution was further explored as a solvent media for CO2 capture where the influence of process parameters such as the influence of concentration of water in the solvent and CO2 flow rate was studied. Most importantly, here we demonstrated the synthesis of [DBUH][SH] salt for easy capture of H2S gas following reaction with DBU under ambient reaction conditions.

Selective Hydrodeoxygenation of Alkyl Lactates to Alkyl Propionates with Fe-based Bimetallic Supported Catalysts.

Hydrodeoxygenation (HDO) of methyl lactate (ML) to methyl propionate (MP) was performed with various base-metal supported catalysts. A high yield of 77 % MP was obtained with bimetallic Fe-Ni/ZrO2 in methanol at 220 °C and 50 bar H2 . A synergistic effect of Ni increased the yield of MP significantly when using Fe-Ni/ZrO2 instead of Fe/ZrO2 alone. Moreover, the ZrO2 support contributed to improve the yield as a phase transition of ZrO2 from tetragonal to monoclinic occurred after metal doping giving rise to fine dispersion of the Fe and Ni on the ZrO2 , resulting in a higher catalytic activity of the material. Interestingly, it was observed that Fe-Ni/ZrO2 also effectively catalyzed methanol reforming to produce H2 in situ, followed by HDO of ML, yielding 60 % MP at 220 °C with 50 bar N2 instead of H2 . Fe-Ni/ZrO2 also catalyzed HDO of other short-chain alkyl lactates to the corresponding alkyl propionates in high yields around 70 %. No loss of activity of Fe-Ni/ZrO2 occurred in five consecutive reaction runs demonstrating the high durability of the catalyst system.