Acid-treated waste red mud as an efficient catalyst for catalytic fast copyrolysis of lignin and polyproylene and ozone-catalytic conversion of toluene.

In this study, red mud (RM), a highly alkaline waste generated from alumina production industries, was used as a catalytic material for both fast copyrolysis of organosolv lignin (OL) and polypropylene (PP) and toluene removal under ozone at room temperature. The RM was pretreated with HCl to investigate the effect of alkalinity. In the catalytic fast copyrolysis of the OL and PP, the acid-treated RM (HRM) produced more aromatics, phenolics, and light olefins (C3 to C5) but less oxygenates and heavy olefins (C6 to C46) than the RM. The difference in pyrolytic performance between the RM and HRM was likely attributed to the concentrated Fe2O3 species in the HRM catalyst. In addition, more efficient toluene removal was observed over MnOx/HRM than over MnOx/RM owing to the large Brunauer-Emmett-Teller surface area, high amounts of Al and Fe, and optimal Mn3+/Mn4+ ratio. This study demonstrates that the RM, an industrial waste, can be reused as an effective catalytic material for not only biofuel production but also pollutant removal.

Highly Dispersed Pt Nanoparticles for the Production of Aromatic Hydrocarbons by the Catalytic Degrading of Alkali Lignin.

Aromatic hydrocarbons were produced from lignin, a complex natural amorphous polymer commonly regarded as by-product of the pulping process and from biofuel production. The catalytic decomposition of lignin using supported Pt catalysts was performed to produce small molecule hydrocarbons. Aromatic small-molecule hydrocarbon products were identified and quantified using GC/MS and GC-FID, which demonstrated that 27.6% of aromatic hydrocarbons were obtained from the activated carbon-supported Pt (Pt/AC) catalyst which had the highest Pt surface area.

Catalytic Depolymerization of Alkali Lignin Using Supported Pt Nanoparticle Catalysts.

Alkali lignin, a byproduct of the pulping process, was depolymerized using Pt nanoparticle catalysts. A depolymerized lignin with a lower molecular weight was obtained and characterized with GPC and NMR. 31P-NMR using OH-sensitive probing molecules showed the formation of guaiacyl OHs during the reaction, indicating the cleavage of guaiacyl ether bonds.

Enhancing polyethylene terephthalate conversion through efficient microwave-assisted deep eutectic solvent-catalyzed glycolysis.

Chemical recycling of plastics is a promising approach for effectively depolymerizing plastic waste into its constituent monomers, thereby contributing to the realization of a sustainable circular economy. Glycolysis, which converts polyethylene terephthalate (PET) into the monomer bis(2-hydroxyethyl) terephthalate (BHET), has emerged as a cost-effective and commercially viable chemical recycling process. However, glycolysis requires long reaction times and high energy consumption, limiting its industrialization. In this study, we develop an energy-efficient microwave-assisted deep eutectic solvent-catalyzed glycolysis method to degrade PET effectively and rapidly, resulting in a high BHET yield. This combined approach enables the quantitative degradation of PET within 9 min, achieving a high BHET yield of approximately 99% under optimal reaction conditions. Furthermore, the proposed approach has a low specific energy consumption (45 kJ/g) and minimizes waste generation. The thermal behavior of PET and its degradation mechanism are systematically investigated using scanning electron microscopy and density functional theory-based calculations. The results obtained suggest that the proposed straightforward, swift, and energy-efficient strategy has the potential to offer a sustainable solution to plastic waste management challenges and expedite the industrialization of chemical recycling.

Chemical upcycling of PVC-containing plastic wastes by thermal degradation and catalysis in a chlorine-rich environment.

Chlorine (Cl)-containing chemicals, including hydrogen chloride, generated during thermal degradation of polyvinyl chloride (PVC) and corresponding mixture impede the chemical recycling of PVC-containing plastic wastes. While upgrading plastic-derived vapors, the presence of Cl-containing chemicals may deactivate the catalysts. Accordingly, herein, catalytic upgrading of pyrolysis vapor prepared from a mixture of PVC and polyolefins is performed using a fixed-bed reactor comprising zeolites. Among the H-forms of zeolites (namely, ZSM-5, Y, ß, and chabazite) used in this study, a higher yield of gas products composed of hydrocarbons with lower carbon numbers is obtained using H-ZSM-5, thus indicating further decomposition of the pyrolysis vapor to C1-C4 hydrocarbons on it. Although the formation of aromatic compounds is better on H-ZSM-5, product distributions can be adjusted by further modifying the acidic properties via the alteration of the Si/Al molar ratio, and maximum yields of C1-C4 compounds (60.8%) and olefins (64.7%) are achieved using a Si/Al molar ratio of 50. Additionally, metal ion exchange on H-ZSM-5 is conducted, and upgrading of PVC-containing waste-derived vapor to aromatic chemicals and small hydrocarbon molecules was successfully performed using Co-substituted H-ZSM-5. It reveals that the highest yield of gas products on 1.74 wt% cobalt (Co)-substituted H-ZSM-5 is acquired via the selection of an appropriate metal and metal ion concentration adjustment. Nevertheless, introduction of excess Co into the H-ZSM-5 surface decreases the cracking activity, thereby implying that highly distributed Co is required to achieve excellent cracking activity. The addition of Co also adjusted the acid types of H-ZSM-5, and more Lewis acid sites compared to Brønsted acid sites selectively produced olefins and naphthenes over paraffins and aromatics. The proposed approach can be a feasible process to produce valuable petroleum-replacing chemicals from Cl-containing mixed plastic wastes, contributing to the closed loops for upcycling plastic wastes.

Decarboxylation of Hydroxybenzoic Acids to Phenol Via Deep Eutectic Solvents.

The development of greener and more sustainable synthesis processes for manufacturing commodity chemicals is of great importance. The majority of current phenol production methods involve harsh reaction conditions with high energy consumption, causing severe environmental pollution. In this study, we present a novel approach for the decarboxylation of hydroxybenzoic acids (HBAs) to phenol using a choline chloride-urea (ChCl-urea) deep eutectic solvent (DES). Our study reveals the remarkable dual performance of ChCl-urea both as a catalyst and solvent for the decarboxylation of HBA, resulting in a high phenol yield (94 mol %) under mild reaction conditions. The proposed reaction pathway, established through a combination of experiments and computational simulations, enhances our understanding of this process. The recyclability of the DES system during decarboxylation was also assessed. Our findings demonstrate that the integration of DES into conventional chemical processes can pave the way for sustainable manufacturing, exemplifying a novel approach for producing phenol from abundant natural resources using designer solvents.

Integrating experimental and computational approaches for deep eutectic solvent-catalyzed glycolysis of post-consumer polyethylene terephthalate.

To achieve a sustainable and circular economy, developing effective plastic recycling methods is essential. Despite advances in the chemical recycling of plastic waste, modern industries require highly efficient and sustainable solutions to address environmental problems. In this study, we propose an efficient glycolysis strategy for post-consumer polyethylene terephthalate (PET) using deep eutectic solvents (DESs) to produce bis(2-hydroxyethyl) terephthalate (BHET) with high selectivity. Choline chloride (ChCl)- and urea-based DESs were synthesized using various metal salts and were tested for the glycolysis of PET waste; ChCl-Zn(OAc)2 exhibited the best performance. The DES-containing solvent system afforded a complete PET conversion, producing BHET at a high yield (91.6%) under optimal reaction conditions. The degradation mechanism of PET and its interaction with DESs were systematically investigated using density functional theory-based calculations. Furthermore, an intuitive machine learning model was developed to predict the PET conversion and BHET selectivity for different DES compositions. Our findings demonstrate that the DES-catalyzed glycolysis of post-consumer PET could enable the development of a sustainable chemical recycling process, providing insights to identify the new design of DESs for plastic decomposition.

Manipulating crystal growth and polymorphism by confinement in nanoscale crystallization chambers.

The phase behaviors of crystalline solids embedded within nanoporous matrices have been studied for decades. Classic nucleation theory conjectures that phase stability is determined by the balance between an unfavorable surface free energy and a stabilizing volume free energy. The size constraint imposed by nanometer-scale pores during crystallization results in large ratios of surface area to volume, which are reflected in crystal properties. For example, melting points and enthalpies of fusion of nanoscale crystals can differ drastically from their bulk scale counterparts. Moreover, confinement within nanoscale pores can dramatically influence crystallization pathways and crystal polymorphism, particularly when the pore dimensions are comparable to the critical size of an emerging nucleus. At this tipping point, the surface and volume free energies are in delicate balance and polymorph stability rankings may differ from bulk. Recent investigations have demonstrated that confined crystallization can be used to screen for and control polymorphism. In the food, pharmaceutical, explosive, and dye technological sectors, this understanding and control over polymorphism is critical both for function and for regulatory compliance. This Account reviews recent studies of the polymorphic and thermotropic properties of crystalline materials embedded in the nanometer-scale pores of porous glass powders and porous block-polymer-derived plastic monoliths. The embedded nanocrystals exhibit an array of phase behaviors, including the selective formation of metastable amorphous and crystalline phases, thermodynamic stabilization of normally metastable phases, size-dependent polymorphism, formation of new polymorphs, and shifts of thermotropic relationships between polymorphs. Size confinement also permits the measurement of thermotropic properties that cannot be measured in bulk materials using conventional methods. Well-aligned cylindrical pores of the polymer monoliths also allow determination and manipulation of nanocrystal orientation. In these systems, the constraints imposed by the pore walls result in a competition between crystal nuclei that favors those with the fastest growth direction aligned with the pore axis. Collectively, the examples described in this Account provide substantial insight into crystallization at a size scale that is difficult to realize by other means. Moreover, the behaviors resulting from nanoscopic confinement are remarkably consistent for a wide range of compounds, suggesting a reliable approach to studying the phase behaviors of compounds at the nanoscale. Newly emerging classes of porous materials promise expanded explorations of crystal growth under confinement and new routes to controlling crystallization outcomes.

Bis[(2,2-dimethyl-propano-yloxy)meth-yl] {[2-(6-amino-9H-purin-9-yl)eth-oxy]meth-yl}phospho-nate-succinic acid (2/1).

The title compound, C(20)H(32)N(5)O(8)P·0.5C(4)H(6)O(4), is composed of two 9-{2-[bis-(pivaloyloxymeth-oxy)phosphinylmeth-oxy]eth-yl}adenine, commonly known as adefovir dipivoxil (AD), mol-ecules linked to the carb-oxy-lic acid groups of succinic acid (SA). The asymmetric unit contains one mol-ecule of AD and half a mol-ecule of SA, which sits on an inversion center. Both adenine units in the two AD mol-ecules make AD-SA N-H⋯O and SA-AD O-H⋯N hydrogen bonds to SA. In addition, the inter-molecular AD-AD N-H⋯O-P hydrogen bond serves to stabilize the cocrystal. There is also a π-π stacking inter-action [inter-planar spacing 3.34 (19) Å] between adjacent inversion-related adenine groups.

Upgrading bio-oil model compound over bifunctional Ru/HZSM-5 catalysts in biphasic system: Complete hydrodeoxygenation of vanillin.

A complete hydrodeoxygenation(HDO) of vanillin to yield cycloalkanes was performed using bifunctional Ru loaded HZSM-5 catalysts with different metal loadings (0.1, 0.5, 1, 3, and 5 wt%) and Si/Al2 ratios (Si/Al2 = 23,300) in n-octane/water biphasic system. Both the reaction pathway and product distribution were influenced by the metal/acid balance of the catalysts. Higher metal/acid ratio promoted Caryl-C cleavage reaction, resulting in the increased yield of cyclohexane. Synergetic effect of metal and acid sites was observed in the bifunctional catalyst, attaining as high as 40-fold increase of metal efficiency in the ring hydrogenation reaction, compared to lone metal site catalyst. The effect of solvent composition was evaluated, revealing that the presence of water promoted the overall HDO reaction. By balancing metal/acid and introducing appropriate solvent system, efficient catalytic system that minimized carbon loss and improved metal efficiency for vanillin HDO was obtained.

Catalytic conversion of waste corrugated cardboard into lactic acid using lanthanide triflates.

The efficient strategy for waste conversion and resource recovery is of great interest in the sustainable bioeconomy context. This work reports on the catalytic upcycling of waste corrugated cardboard (WCC) into lactic acid using lanthanide triflates catalysts. WCC, a primary contributor to municipal solid wastes, has been viewed as a feedstock for producing a wide range of renewable products. Hydrothermal conversion of WCC was carried out in the presence of several lanthanide triflates. The reaction with erbium(III) triflate (Er(OTf)3) and ytterbium(III) triflate (Yb(OTf)3) resulted in high lactic acid yields, 65.5 and 64.3 mol%, respectively. In addition, various monomeric phenols were readily obtained as a co-product stream, opening up opportunities in waste management and resource recovery. Finally, technoeconomic analysis was conducted based on the experimental results, which suggests a significant economic benefit of chemocatalytic upcycling of WCC into lactic acid.

Delamination of layered zeolite precursors under mild conditions: synthesis of UCB-1 via fluoride/chloride anion-promoted exfoliation.

New material UCB-1 is synthesized via the delamination of zeolite precursor MCM-22 (P) at pH 9 using an aqueous solution of cetyltrimethylammonium bromide, tetrabutylammonium fluoride, and tetrabutylammonium chloride at 353 K. Characterization by powder X-ray diffraction, transmission electron microscopy, and nitrogen physisorption at 77 K indicates the same degree of delamination in UCB-1 as previously reported for delaminated zeolite precursors, which require a pH of greater than 13.5 and sonication in order to achieve exfoliation. UCB-1 consists of a high degree of structural integrity via (29)Si MAS NMR and Fourier transform infrared spectroscopies, and no detectable formation of amorphous silica phase via transmission electron microscopy. Porosimetry measurements demonstrate a lack of hysteresis in the N(2) adsorption/desorption isotherms and macroporosity in UCB-1. The new method is generalizable to a variety of Si:Al ratios and leads to delaminated zeolite precursor materials lacking amorphization.

High-temperature hydrodechlorination of ozone-depleting chlorodifluoromethane (HCFC-22) on supported Pd and Ni catalysts.

The hydrodechlorination of chlorodifluoromethane (HCFC-22) was performed by a catalytic reaction and noncatalytic thermal decomposition at high temperatures of 400-800 °C. After 47 h of time-on-stream on a supported palladium (Pd) catalyst, the gas phase composition of difluoromethane (HFC-32) is 41.0%, with 4.9% of the HCFC-22 remaining, indicating the conversion of up to 95.1% of HCFC-22. The supported nickel catalyst's deactivation is significant as it exhibits the low conversion of HCFC-22 under the same reaction conditions. The deactivation of the catalyst is caused by the polymerization of adsorbed methyl radicals, which competes with the formation of HFC-32. With concentrated reactants at high reaction temperatures, there was an increase in the catalytic activity; however, unwanted tar, methane, and trifluoromethane (HFC-23) by-products are also produced. The use of catalyst suppresses the formation of these by-products. Considering the compositions of the products of the catalytic and noncatalytic reactions, we demonstrate that the use of the supported-metal catalysts and hydrogen flow suppresses tar formation and lowers the required reaction temperature.

Improved catalytic depolymerization of lignin waste using carbohydrate derivatives.

CARBOHYDRATE-: or sugar-derived compounds were used as environmentally friendly additives for the depolymerization of Kraft lignin waste and organosolv lignin prepared from Miscanthus giganteus. The yields of the aromatic monomers obtained from Kraft lignin increased from 5.1 to 49.2% with the addition of mannitol, while those obtained from organosolv lignin increased from 44.4 to 83.0% with the addition of sucrose. This improved lignin depolymerization was also confirmed by gel permeation chromatography and nuclear magnetic resonance spectroscopy. The above results clearly indicate the beneficial effects of carbohydrate derivatives on the lignin depolymersization process, more specifically, suggesting that the presence of carbohydrates improve the lignin depolymerization of lignocellulose, as observed for the raw lignocellulose feed.

The production of lactic acid from chemi-thermomechanical pulps using a chemo-catalytic approach.

Previous work has shown that sulfonation and oxidation of chemi-thermomechanical pulps (CTMPs) significantly enhanced enzyme accessibility to cellulose while recovering the majority of carbohydrates in the water-insoluble component. In the work reported here, modified (sulfonated and oxidized) CTMPs derived from hard-and-softwoods were used to produce a DL-mix of lactic acid via a chemo-catalytic approach using lanthanide triflate (Ln (OTf)3) catalysts (Ln = La, Nd, Er, and Yb). It was apparent that sulfonation and oxidation of chemi-thermomechanical pulps (CTMPs) also enhanced Ln(OTf)3 catalyst accessibility to the carbohydrate components of the pulps, with the Er(OTf)3 catalysts resulting in significant lactic acid production. Under optimum conditions (250 °C, 60 min, 0.5 mmol catalyst g-1 biomass), 72% and 67% of the respective total carbohydrate present in the hard-and-softwood CTMPs could be converted to lactic acid compared to the respective 59% and 51% yields obtained after energy-intensive ball milling.

Fast hydropyrolysis of biomass Conversion: A comparative review.

Recent studies show that fast hydropyrolysis (i.e., pyrolysis under hydrogen atmosphere operating at a rapid heating rate) is a promising technology for the conversion of biomass into liquid fuels (e.g., bio-oil and C4+ hydrocarbons). This pyrolysis approach is reported to be more effective than conventional fast pyrolysis in producing aromatic hydrocarbons and also lowering the oxygen content of the bio-oil obtained compared to hydrodeoxygenation (a common bio-oil upgrading method). Based on current literature, various non-catalytic and catalytic fast hydropyrolysis processes are reviewed and discussed. Efforts to combine fast hydropyrolysis and hydrotreatment process are also highlighted. Points to be considered for future research into fast hydropyrolysis and pending challenges are also discussed.

Stabilization of acid-rich bio-oil by catalytic mild hydrotreating.

Although liquid products derived from the pyrolysis of biomass are promising for the production of petroleum-like hydrocarbon fuels, the catalytic burden of hydrodeoxygenation must be reduced to achieve feasible upgrading processes. Herein, mild hydrotreating of an acid-rich biomass pyrolysis oil (bio-oil) with an unusually high total acid number (588 mg KOH/g bio-oil) was performed to stabilize the low-quality bio-oil. Ru-added TiO2-supported transition metal catalysts stabilized the bio-oil by reducing its acidity more compared to what could be achieved by Ru-free catalysts; this process also leads to lower loss of organic compounds compared to when using a Ru/TiO2 catalyst. Based on the performance of transition metal catalysts, including Ni, Co, and Cu, supported on TiO2, tungstate-zirconia, or SiO2, supported bimetallic catalysts were prepared by adding Ru to the TiO2-supported metal catalysts. The bimetallic catalysts Ru/Ni/TiO2 and Ru/Co/TiO2 exhibited good decarboxylation activity for the removal of carboxylic acids and a higher yield of organic compounds compared to that provided by Ru, which can be deemed appropriate for feedstocks when hydrodeoxygenation needs to suppress the loss of organic reactants. Using these catalysts, the carboxylic acid concentration was reduced to 319-323 mg KOH/g bio-oil with organic yields of 62-63 wt% at reaction temperatures 150-170 °C lower than the temperature required for direct conversion of carboxylic acids to alcohols or deoxygenates. The improved catalytic hydrotreating activity of Ru-added transition metals can be attributed to the high acid site densities of these catalysts along with their improved hydrogenation activities.

SiO2@MnO x @Na2WO4@SiO2 core-shell-derived catalyst for oxidative coupling of methane.

SiO2@MnO x @Na2WO4@SiO2 core-shell catalysts were prepared and their fabrication was confirmed using transmission electron microscopy. The formation of Mn-based nanosheets on the silica spheres is important for the deposition of nanoscopic Na2WO4. The SiO2@MnO x @Na2WO4@SiO2 core-shell catalysts were used for the oxidative coupling of methane at a temperature of 700-800 °C at which the nanostructures were completely destroyed. Although the core-shell structures did not survive the high-temperature oxidative coupling of methane, the selective production of olefins and paraffins can be attributed to highly dispersed Na2WO4 derived from confined core-shell structures.

Study on the unsteady state oxidative coupling of methane: effects of oxygen species from O2, surface lattice oxygen, and CO2 on the C2+ selectivity.

This study examined the effects of oxygen species on the unsteady-state oxidative coupling of methane (OCM) using a lengthy catalyst bed of Na2WO4/Mn/SiO2. The reaction conditions, including the methane-to-oxygen ratio, ratio of feed gas dilution by N2, quantity of catalyst, and feed flow rate were adjusted for the continuous flow fixed bed reaction system. While the O2 gas initiated methyl radical formation from methane, the surface lattice oxygen atoms improved the dehydrogenation of paraffins to olefins without significant activation of methane. The addition of CO2 as a mild oxidizing agent was also tested and slightly improved OCM selectivity with slightly lower methane conversion were observed.

Enantiotropic phase transition and twinning in 2,2,3,3,4,4-hexafluoropentane-1,5-diol.

Four crystal structure determinations of 2,2,3,3,4,4-hexafluoropentane-1,5-diol (HFPD), C5H6F6O2, were conducted on a single specimen by varying the temperature. Two polymorphs of HFPD were found to be enantiotropically related as phases (I) and (II), both in the space group P1. These structures contain closely related R(4)(4)(20) sheets. A structure determination was completed on form (Ia) at 283 K. Form (Ia) was then supercooled below the phase transition temperature at 279 to 173 K to give form (Ib) for a second structure determination. Metastable form (Ib) was transformed by momentary warming and recooling to give form (II) for a third structure determination at 173 K. Form (II) transformed to form (Ic) upon warming to 283 K. Enantiotropic phase transitions between phases (I) and (II) were confirmed with X-ray powder diffraction and differential scanning calorimetry. Form (Ia) was found as a twin by nonmerohedry by a reflection in (011). This twinning persists in all phases described. Additional twinning was found after the phase (I) to phase (II) transformation. These two additional twin components are related to the first pair by a 180 degrees rotation about the (012) plane. This latter pair of twins persisted as the specimen was warmed back to form (Ic) at 283 K.