Project description:With the aim to investigate new strategies for upcycling of plastic waste, we performed aminolysis of poly(lactic acid) (PLA), using N,N-dimethylethylenediamine (DMEDA), N,N-dimethylpropylenediamine (DMPDA), and 3-aminopropylimidazole (API) as nucleophiles. The N-substituted lactamides obtained were alkylated by using alkyl halides differing in alkyl chain length, obtaining organic salts that in most cases behaved as ionic liquids (ILs). Both aminolysis of PLA and alkylation of amides were carried out taking into consideration the basic principles of the holistic approach to green chemistry, applied at a laboratory scale, and carefully selecting the nature of the reaction solvent, temperature range, and amount of reagents. Organic salts obtained from the alkylation of N-substituted lactamides were investigated to determine their glass or solid-liquid transitions and their thermal stability. Furthermore, cytotoxicity toward normal lung fibroblasts was also assessed. Data collected show that the proposed strategy represents a valuable protocol to upcycle plastic waste, using it as starting material to obtain alternative solvents of potential industrial relevance.
Project description:Chemical upcycling of waste plastics can play an important role in developing greater circularity in the material flows associated with the plastics industries. In this study, a fundamental understanding of upcycling poly(ethylene terephthalate) (PET) using ammonolysis is established. First, rate constants are determined for model studies of the ammonolysis of dimethyl terephthalate (DMT) in methanol. Ammonolysis proceeds sequentially, and a first ester group of DMT reacts with ammonia to produce methanol and the monoamide methyl 4-carbamoylbenzoate (MCB). Next, MCB reacts with ammonia to yield methanol and terephthalamide (TPD). At 100 °C, the pseudo first order rate constants are k 1 ' = 0.25 ± 0.02 h-1 and k 2 ' = 0.11 ± 0.02 h-1. Experiments conducted at 50, 75, 100, and 125 °C yield activation energies for the first and second reactions of E a1 = 27.9 ± 2.2 kJ/mol and E a2 = 37.3 ± 3.3 kJ/mol. Ammonolysis is demonstrated to be catalyzed by ethylene glycol (EG) with a first order concentration dependence. At 100 °C with EG present in a 3:1 excess, the pseudo first order rate constants are k 3 ' = 6.3 ± 0.7 h-1 and k 4 ' = 1.7 ± 0.3 h-1, representing a 22-fold increase. Demonstration experiments with reclaimed mixed postconsumer thermoform containers reveal that the ammonolysis of PET is self-catalyzed by the generated EG; the upcycling reaction on polymer substrates is autocatalytic. This new detailed understanding of the self-catalyzed chemical kinetics of ammonolysis suggests EG as the natural choice for the solvent, a topic pursued in part II of this work.
Project description:The upcycling of poly(ethylene terephthalate) (PET) waste can simultaneously produce value-added chemicals and reduce the growing environmental impact of plastic waste. In this study, we designed a chemobiological system to convert terephthalic acid (TPA), an aromatic monomer of PET, to β-ketoadipic acid (βKA), a C6 keto-diacid that functions as a building block for nylon-6,6 analogs. Using microwave-assisted hydrolysis in a neutral aqueous system, PET was converted to TPA with Amberlyst-15, a conventional catalyst with high conversion efficiency and reusability. The bioconversion process of TPA into βKA used a recombinant Escherichia coli βKA expressing two conversion modules for TPA degradation (tphAabc and tphB) and βKA synthesis (aroY, catABC, and pcaD). To improve bioconversion, the formation of acetic acid, a deleterious factor for TPA conversion in flask cultivation, was efficiently regulated by deleting the poxB gene along with operating the bioreactor to supply oxygen. By applying two-stage fermentation consisting of the growth phase in pH 7 followed by the production phase in pH 5.5, a total of 13.61 mM βKA was successfully produced with 96% conversion efficiency. This efficient chemobiological PET upcycling system provides a promising approach for the circular economy to acquire various chemicals from PET waste.
Project description:Herein, the data acquired regarding the preliminary and exploratory experiments conducted with potato peel as a biomass source for the direct thermochemical liquefaction is disclosed. The procedure was carried out in a 2-ethylhexanol/DEG solvent mixture at 160 °C in the presence of p-Toluenesulfonic acid. The adopted procedure afforded a bio-oil in high yield (up to 93%) after only 30 min. For longer reaction times, higher amounts of solid residues were obtained leading, consequently, to lower yields.
Project description:The asymmetric unit of the title co-crystal, 2CH(4)N(2)O·C(6)H(10)O(4), contains two urea mol-ecules and two half-mol-ecules of adipic acid; the latter are completed by crystallographic inversion symmetry. The crystal packing is stabilized by O-H⋯O and N-H⋯O hydrogen bonds, generating a chain along [110]. Additional weak inter-chain O-H⋯O and N-H⋯O inter-molecular inter-actions lead to the formation of a three-dimensional network.
Project description:Biological synthesis of high added-value compounds like adipic acid (AA), levulinic acid (LA), or polyhydroxybutyrate (PHB) using pure culture has been separately reported. However, pure culture requires sterile conditions and the use of specific carbon sources resulting in high operating costs. Different alternatives based on the use of mixed microbial cultures (MMC) have been explored to resolve this problem. MMC have been widely reported for the production of PHB, but scarcely reported for LA production and never for AA synthesis. This work presents a novel strategy for the co-production of AA LA, and PHB using MMC. The strategy consists in selecting an MMC producer of AA, LA and PHB from an inoculum obtained from a wastewater treatment plant, which is then subjected to the feast and famine culture strategy in a sequential batch reactor, coupled with a batch reactor step to enhance the accumulation of AA and LA. The results showed that the MMC could produce a 16 ± 2, 23 ± 1 and 5 ± %1 (g compound/g volatile solids) of AA, LA and PHB, respectively, using a non-fermented residual biomass rich in pentose, namely synthetic hemicellulose hydrolysate (SHH) as the carbon source. These results contribute to generating future research to better understand and optimise the biosynthesis of these compounds by MMC.
Project description:Over the past years, disposable masks have been produced in unprecedented amounts due to the COVID-19 pandemic. Their increased use imposes significant strain on current waste management practices including landfilling and incineration. This results in large volumes of discarded masks entering the environment as pollutants, and alternative methods of waste management are required to mitigate the negative effects of mask pollution. While current recycling methods can supplement conventional waste management, the necessary processes result in a product with downgraded material properties and a loss of value. This work introduces a simple method to upcycle mask waste into multifunctional carbon fibers through simple steps of thermal stabilization and pyrolysis. The pre-existed fibrous structure of polypropylene masks can be directly converted into carbonaceous structures with high degrees of carbon yield, that are inherently sulfur-doped, and porous in nature. The mask-derived carbon product demonstrates potential use in multiple applications such as for Joule heating, oil adsorption, and the removal of organic pollutants from aqueous environments. We believe that this process can provide a useful alternative to conventional waste management by converting mask waste generated during the COVID-19 pandemic into a product with enhanced value.
Project description:Herein, the pyrolysis of two types of single-use disposable waste (single-use food containers and corrugated fiberboard) was investigated as an approach to cleanly dispose of municipal solid waste, including plastic waste. For the pyrolysis of single-use food containers or corrugated fiberboard, an increase in temperature tended to increase the yield of pyrolytic gas (i.e., non-condensable gases) and decrease the yield of pyrolytic liquid (i.e., a mixture of condensable compounds) and solid residue. The single-use food container-derived pyrolytic product was largely composed of hydrocarbons with a wide range of carbon numbers from C1 to C32, while the corrugated fiberboard-derived pyrolytic product was composed of a variety of chemical groups such as phenolic compounds, polycyclic aromatic compounds, and oxygenates involving alcohols, acids, aldehydes, ketones, acetates, and esters. Changes in the pyrolysis temperature from 500 °C to 900 °C had no significant effect on the selectivity toward each chemical group found in the pyrolytic liquid derived from either the single-use food containers or corrugated fiberboard. The co-pyrolysis of the single-use food containers and corrugated fiberboard led to 6 times higher hydrogen (H2) selectivity than the pyrolysis of the single-use food containers only. Furthermore, the co-pyrolysis did not form phenolic compounds or polycyclic aromatic compounds that are hazardous environmental pollutants (0% selectivity), indicating that the co-pyrolysis process is an eco-friendly method to treat single-use disposable waste.