Valuable Monomers Research Articles

A Tandem Photovoltaic-Electrochemical Photothermal Process for CO2 Conversion to Butene

Decarbonizing the chemicals industry requires net carbon negative technologies capable of displacing current greenhouse gas emitting processes. In particular, the generation of valuable monomers, such as butene, are currently produced by significant greenhouse gas emitting processes, including ethylene oligomerization and crude oil refining, which require high temperatures and pressures. Integrated, tandem solar fuels devices for the conversion of CO2 to ethylene, using solar-driven CO2 reduction (CO2R), combined with a photothermal reactor for ethylene oligomerization, offers a potential path to producing clean butene from CO2, using solar energy as the only driving force. A key challenge for the successful operation of a tandem photo-driven electrochemical-photothermal system is the co-design of the two processes, which are typically optimized under different operating conditions. Specifically, photo-driven electrochemical CO2R (pCO2R) reactors operate under ambient temperature and pressure conditions while thermally-driven ethylene oligomerization reactors prefer elevated temperatures (80-140 °C) and pressures (30-150 atm) to promote high activity as well as pure ethylene in the inlet stream. Operation of the tandem process under solar-driven conditions imposes additional constraints on the maximum power output of the pCO2R reactor and the maximum temperature which can be obtained in the photothermal reactor. Herein, we present an unassisted solar-driven tandem system coupling pCO2R with photothermal ethylene oligomerization for the conversion of CO2 to butene in a single pass. This work presents a critical advancement in the development of solar fuels technologies for larger hydrocarbon generation and identifies the co-design principles which must be considered for implementation of tandem, solar-driven electrochemical-thermal processes.

Room temperature catalytic upgrading of unpurified lignin depolymerization oil into bisphenols and butene-2

Lignin is the largest source of renewable aromatics on earth. Despite numerous techniques for lignin depolymerization into mixtures of valuable monomers, methods for their upgrading into final products are scarce. The state of the art upgrading methods generally rely on catalytic funneling, requiring high temperatures, catalyst loadings and hydrogen pressure, and lead to the loss of functionality and bio-based carbon content. Here an alternative approach is presented, whereby the target monomers are selectively converted in unpurified mixtures into easily separable final products under mild conditions. We use reductive catalytic fractionation of wood to convert lignin into iso-eugenol and propenyl syringol enriched oil followed by an olefin metathesis to yield bisphenols and butene-2, thus, valorizing all bio-based carbons. To further demonstrate the synthetic utility of the obtained bisphenols we converted them into polyesters with a high glass transition temperature (Tg = 140.3 °C) and thermal stability (Td50% = 330 °C).

Oxidative Cleavage of α-O-4, β-O-4, and 4-O-5 Linkages in Lignin Model Compounds Over P, N Co-Doped Carbon Catalyst: A Metal-Free Approach.

Developing efficient metal-free catalysts for lignin valorization is essential but challenging. In this study, a cost-effective strategy is employed to synthesize a P, N co-doped carbon catalyst through hydrothermal and carbonization processes. This catalyst effectively cleaved α-O-4, β-O-4, and 4-O-5 lignin linkages, as demonstrated with model compounds. Various catalysts were prepared at different carbonization temperatures and thoroughly characterized using techniques such as XRD, RAMAN, FTIR, XPS, NH3-TPD, and HRTEM. Attributed to higher acidity, the P5NC-500 catalyst exhibited the best catalytic activity, employing H2O2 as the oxidant in water. Additionally, this metal-free technique efficiently converted simulated lignin bio-oil, containing all three linkages, into valuable monomers. Density Functional Theory calculations provided insight into the reaction mechanism, suggesting substrate and oxidant activation by P-O-H sites in the P5NC-500, and by N-C-O-H in the CN catalyst. Moreover, the catalyst's recyclability and water utilization enhance its environmental compatibility, offering a highly sustainable approach to lignin valorization with potential applications in various industries.

THE ROLE OF Zn-Fe CATALYSTS IN THE REACTION OF ETHANOL CONVERSION TO ACETONE

Recently, processes for obtaining various organic compounds from ethanol, which is derived from the processing of plant raw materials, have become highly relevant. Acetone is a valuable monomer that can be obtained from ethanol. It has been previously demonstrated that catalysts based on zinc oxides exhibit high activity in the conversion of ethanol to acetone. A review of the literature has shown that catalysts based on iron oxides also demonstrate high activity in this reaction. Therefore, the aim of this work was to study the vapor-phase conversion of ethanol to acetone on various binary zinc-iron oxide catalysts. This article describes a process for studying the paraphase conversion of ethanol to acetone on zinc-iron oxide catalysts Zinc-iron oxide catalysts of various compositions have been synthesized. The activity of the obtained catalysts was studied in the reaction of ethanol conversion. It was shown that samples rich in zinc oxide exhibit the greatest activity in the studied reaction. It has been established that the yield of acetone on the best catalysts reaches its maximum yield. The zinc-iron oxide catalyst of composition 9:1 showed the highest activity. catalyst, the maximum yield of acetone reaches up to 80%. Keywords: catalyst, ethanol, acetone, zinc, iron, vapor-phase conversion, iron oxides, temperature, reaction rate.

Corrosion Engineering of Part-Per-Million Single Atom Pt1/Ni(OH)2 Electrocatalyst for PET Upcycling at Ampere-Level Current Density.

The plastic waste issue has posed a series of formidable challenges for the ecological environment and human health. While conventional recycling strategies often lead to plastic down-cycling, the electrochemical strategy of recovering valuable monomers enables an ideal, circular plastic economy. Here a corrosion synthesized single atom Pt1/Ni(OH)2 electrocatalyst with part-per-million noble Pt loading for highly efficient and selective upcycling of polyethylene terephthalate (PET) into valuable chemicals (potassium diformate and terephthalic acid) and green hydrogen is reported. Electro-oxidation of PET hydrolysate, ethylene glycol (EG), to formate is processed with high Faraday efficiency (FE) and selectivity (>90%) at the current density close to 1000mAcm-2 (1.444V vs RHE). The in situ spectroscopy and density functional theory calculations provide insights into the mechanism and the understanding of the high efficiency. Remarkably, the electro-oxidation of EG at the ampere-level current density is also successfully illustrated by using a membrane-electrode assembly with high FEs to formate integrated with hydrogen production for 500h of continuous operation. This process allows valuable chemical production at high space-time yield and is highly profitable (588-700$ton-1 PET), showing an industrial perspective on single-atom catalysis of electrochemical plastic upcycling.

Hydrogenation of waste PET degraded bis(2-hydroxyethyl)cyclohexane- 1,4-dicarboxylate to 1,4-cyclohexanedimethanol over Cu-based catalysts

Upcycling of waste polyethylene terephthalate derived bis(2-hydroxyethyl) cyclohexane-1,4-dicarboxylate (BHCD) to valuable monomer (1,4-cyclohexanedimethanol, CHDM) can decrease the emission of CO2 and microplastics. In this work, a stable Cu-based catalyst (Cu/MgAl2O4) with strong metal-support interaction was synthesized via calcination and reduction of CuMgAl-LDH precursor. The properties of precursor and final catalyst were characterized using XRD, TG-DTA, N2-adsorption, SEM/TEM, H2-TPR, CO2/NH3-TPD and XPS techniques. It was found that Cu/MgAl2O4 has high surface area, strong metal-support interaction and plenty basic sites. Cu/MgAl2O45 exhibited prominent performance for the hydrogenation of PET-derived BHCD to CHDM among the tested Cu/MgAl2O4, Cu/MnAl2O4 and Cu/ZnAl2O4 catalyst. The yield of CHDM over Cu/MgAl2O4 reached 98 % with a complete conversion of BHCD at 240 °C, 4 MPa and 0.525 g.gcat-1.h−1. Besides, it remains its activity for at least 80 h on stream under optimized condition. The structure-performance of these catalysts for the hydrogenation of BHCD to CHDM was discussed.

Efficient glycolysis of used PET bottles into a high-quality valuable monomer using a shape-engineered MnOx nanocatalyst

The nanorod morphology of the MnOx material with the application of optimal calcination temperature exhibited good catalytic efficiency in the chemical recycling of PET bottles into a valuable monomer.

Catalytic recycling of PET waste bottles into a value-added amide monomer using a heterogeneous niobium pentoxide nanocatalyst

Using a diverse heterogeneous nanocatalyst, aminolysis presents a promising approach for the chemical recycling of discarded PET waste bottles into a valuable monomer bis(2-hydroxyethyl) terephthalamide (BHETA). This study reports the...

Envisioning a BHET Economy: Adding Value to PET Waste

Poly(ethylene terephthalate), the fifth most produced polymer, generates significant waste annually. This increased waste production has spurred interest in chemical and mechanical pathways for recycling. The shift from laboratory settings to larger-scale implementation creates opportunities to explore the value and recovery of recycling products. Derived from the glycolysis of PET, bis(2-hydroxyethyl) terephthalate (BHET) exhibits versatility as a depolymerization product and valuable monomer. BHET exhibits versatility and finds application across diverse industries such as resins, coatings, foams, and tissue scaffolds. Incorporating BHET, which is a chemical recycling product, supports higher recycling rates and contributes to a more sustainable approach to generating materials. This review illuminates the opportunities for BHET as a valuable feedstock for a more circular polymer materials economy.

Paving the Way towards Sustainability of Polyurethanes: Synthesis and Properties of Terpene-Based Diisocyanate.

Due to growing concerns about environmental issues and the decline of petroleum-based resources, the synthesis of new biobased compounds for the polymer industry has become a prominent and timely topic. P-menthane-1,8-diamine (PMDA) is a readily available compound synthesized from turpentine, a cheap mixture of natural compounds isolated from pine trees. PMDA has been extensively used for its biological activities, but it can also serve as a source of valuable monomers for the polymer industry. In this work, commercial PMDA (ca. 85% pure) was purified by salinization, crystallization, and alkali treatment and then converted into p-menthane-1,8-diisocyanate (PMDI) through a phosgene-free synthesis at room temperature. A thorough analytical study using NMR techniques (1H, 13C, 13C-1H HSQC, 13C-1H HMBC, and 1H-1H NOESY) enables the characterization of the cis-trans isomeric mixtures of both PMDA and PMDI. These structural studies allowed for a better understanding of the spatial configuration of both isomers. Then, the reactivity of PMDI with a primary alcohol (benzyl alcohol) was studied in the presence of nine different catalysts exhibiting different activation modes. Finally, the use of PMDI in the synthesis of polyurethanes was explored to demonstrate that PMDI can be employed as a new biobased alternative to petrochemical-based isocyanates such as isophorone diisocyanate (IPDI).

Spiroborate-Linked Ionic Covalent Adaptable Networks with Rapid Reprocessability and Closed-Loop Recyclability

Covalent adaptable networks (CANs) represent a novel class of polymeric materials crosslinked by dynamic covalent bonds. Since their first discovery, CANs have attracted great attention due to their high mechanical strength and stability like conventional thermosets under service conditions and easy reprocessability like thermoplastics under certain external stimuli. Here, we report the first example of ionic covalent adaptable networks (ICANs), a type of crosslinked ionomers, consisting of negatively charged backbone structures. More specifically, two ICANs with different backbone compositions were prepared through spiroborate chemistry. Given the dynamic nature of the spiroborate linkages, the resulting ionomer thermosets display rapid reprocessability and closed-loop recyclability under mild conditions. The materials mechanically broken into smaller pieces can be reprocessed into coherent solids at 120 °C within only 1 min with nearly 100% recovery of the mechanical properties. Upon treating the ICANs with dilute hydrochloric acid at room temperature, the valuable monomers can be easily chemically recycled in almost quantitative yield. This work demonstrates the great potential of spiroborate bonds as a novel dynamic ionic linkage for development of new reprocessable and recyclable ionomer thermosets.

Microwave-driven upcycling of single-use plastics using zeolite catalyst

The chemical upcycling of plastic represents an attractive approach of using plastic waste as feedstock in promoting the circular economy and decarbonizing the chemical industry. Here we report a one-step microwave-assisted heterogeneous catalysis approach for the deconstruction of plastic into valuable monomers. A high BTX aromatics (benzene, toluene, and xylene) yield of 44.7% was achieved using ZSM-5 catalyst at a low temperature of 300 °C under atmospheric pressure. The very nature of microwave initiation enhances the transformation of intermediates via the desirable cyclization/aromatization routes whilst preventing the random thermal cracking of plastic. This proof-of-concept heralds an exciting new era of applications for the responsible and sustainable recycling of waste plastic, in which plastic are efficiently converted back to high-value petrochemical products.

Electrocatalytic Upcycling of Biomass and Plastic Wastes to Biodegradable Polymer Monomers and Hydrogen Fuel at High Current Densities.

Transformation of biomass and plastic wastes to value-added chemicals and fuels is considered an upcycling process that is beneficial to resource utilization. Electrocatalysis offers a sustainable approach; however, it remains a huge challenge to increase the current density and deliver market-demanded chemicals with high selectivity. Herein, we demonstrate an electrocatalytic strategy for upcycling glycerol (from biodiesel byproduct) to lactic acid and ethylene glycol (from polyethylene terephthalate waste) to glycolic acid, with both products being as valuable monomers for biodegradable polymer production. By using a nickel hydroxide-supported gold electrocatalyst (Au/Ni(OH)2), we achieve high selectivities of lactic acid and glycolic acid (77 and 91%, respectively) with high current densities at moderate potentials (317.7 mA/cm2 at 0.95 V vs RHE and 326.2 mA/cm2 at 1.15 V vs RHE, respectively). We reveal that glycerol and ethylene glycol can be enriched at the Au/Ni(OH)2 interface through their adjacent hydroxyl groups, substantially increasing local concentrations and thus high current densities. As a proof of concept, we employed a membrane-free flow electrolyzer for upcycling triglyceride and PET bottles, attaining 11.2 g of lactic acid coupled with 9.3 L of H2 and 13.7 g of glycolic acid coupled with 9.4 L of H2, respectively, revealing the potential of coproduction of valuable chemicals and H2 fuel from wastes in a sustainable fashion.

Correlations between product distribution and feedstock composition in thermal cracking processes for mixed plastic waste

Thermal conversion can transform the carbon-based waste into valuable chemicals to be further used in the petrochemical industry for a polymeric carbon circular economy. This work’s aim was to identify chemical correlations between the thermal-cracking products and the feedstock polymer composition when using highly blended waste streams. The challenges addressed were to: (i) access a pool of experimental data on the monomer recovery potential of real-life, highly blended waste streams; (ii) estimate the polymer constituents of the mixed waste streams; and (iii) formulate a generic and systematic method to identify correlations between feedstock constituents and cracking products. Different post-consumer waste streams were investigated, including cardboard, automotive shredder residues, cable stripping waste, and textile waste. The cracking experiments were performed in a 2–4MWth industrial-scale Dual Fluidized Bed system at 800 °C using steam as fluidization agent. The polymeric constituents of the feedstocks were estimated using a numerical convex optimization method. To identify correlations between the feedstocks and products, a carbon bond-based classification was introduced. The experimental monomer yield ranged from 0.08 kg/kgf to 0.3 kg/kgf (f = feedstock) for the evaluated materials, corresponding to a carbon feedstock conversion rate between 14 % and 44 %. High yields of valuable monomers were obtained for the materials with the highest polyolefin content. The olefin monomer production correlated positively to the amount of aliphatic carbon in the original material and negatively to the carbon contents of the aromatic rings. From the trends observed, it was concluded that a framework based on carbon bond types is a promising approach to identify such correlations, which could serve as predictive tools for monomer recovery based on material’s composition and overall process conditions.

CuF2/DMAP-Catalyzed N-Vinylation: Scope and Mechanistic Study.

CuF2/DMAP has been established as an excellent catalytic system for vinylsilane-promoted N-vinylation of amides and azoles at room temperature without an external fluoride source. A mechanism has been proposed on the basis of the isolation of reactive intermediate [Cu(DMAP)4Cl2], fluoride ion-assisted transmetalation, and ultraviolet-visible spectroscopic studies. The catalytic efficiency of the synthesized and structurally characterized [Cu(DMAP)4Cl2] complex has been demonstrated. The valuable monomers for water-soluble polymers, viz., NVP, NVC, and NVIBA, were synthesized on a gram scale.

Ruthenium Catalyzed Oxidative Cleavage of High Oleic Sunflower Oil: Considerations Regarding the Synthesis of a Fully Biobased Triacid

AbstractTricarboxylic acids are molecules of interest for the synthesis of highly cross‐linked polymers, for instance, for the curing of epoxy resins. Herein, a synthesis route to a novel high oleic sunflower oil based triacid is described by applying a ruthenium catalyzed oxidative cleavage of its double bonds. A statistical concept is devised for the prediction of the yields of mono‐, di‐, and trifunctional derivatives that can be formed from high oleic sunflower oil, depending on the overall conversion of double bonds into this functional group and the overall oleic acid content of the used oil. This concept proved to be highly useful for the explanation of seemingly moderate triacid yields, which are inherently dependent on the unsaturated fatty acid content of the used oil. All obtained sunflower oil based polyacids are fully analyzed by attenuated total reflection infrared spectroscopy (ATR‐IR), electrospray ionization mass spectrometry (ESI‐MS), 1H, 13C, and quantitative 31P nuclear magnetic resonance (NMR) spectroscopy. In addition, a more sustainable purification procedure is developed to obtain a polymerizable mixture of polyacids containing more than 2.0 carboxylic acids per molecule in average.Practical applications: Tricarboxylic acids are valuable monomers for the synthesis of cross‐linked polymers. The herein reported procedure represents a hitherto unknown synthesis route towards a new triacid and polyacid mixture directly from high oleic sunflower oil.

Technoeconomic evaluation of recent process improvements in production of sugar and high-value lignin co-products via two-stage Cu-catalyzed alkaline-oxidative pretreatment

BackgroundA lignocellulose-to-biofuel biorefinery process that enables multiple product streams is recognized as a promising strategy to improve the economics of this biorefinery and to accelerate technology commercialization. We recently identified an innovative pretreatment technology that enables of the production of sugars at high yields while simultaneously generating a high-quality lignin stream that has been demonstrated as both a promising renewable polyol replacement for polyurethane applications and is highly susceptible to depolymerization into monomers. This technology comprises a two-stage pretreatment approach that includes an alkaline pre-extraction followed by a metal-catalyzed alkaline-oxidative pretreatment. Our recent work demonstrated that H2O2 and O2 act synergistically as co-oxidants during the alkaline-oxidative pretreatment and could significantly reduce the pretreatment chemical input while maintaining high sugar yields (~ 95% glucose and ~ 100% xylose of initial sugar composition), high lignin yields (~ 75% of initial lignin), and improvements in lignin usage.ResultsThis study considers the economic impact of these advances and provides strategies that could lead to additional economic improvements for future commercialization. The results of the technoeconomic analysis (TEA) demonstrated that adding O2 as a co-oxidant at 50 psig for the alkaline-oxidative pretreatment and reducing the raw material input reduced the minimum fuel selling price from $1.08/L to $0.85/L, assuming recoverable lignin is used as a polyol replacement. If additional lignin can be recovered and sold as more valuable monomers, the minimum fuel selling price (MFSP) can be further reduced to $0.73/L.ConclusionsThe present work demonstrated that high sugar and lignin yields combined with low raw material inputs and increasing the value of lignin could greatly increase the economic viability of a poplar-based biorefinery. Continued research on integrating sugar production with lignin valorization is thus warranted to confirm this economic potential as the technology matures.

Valorization of Hazardous Organic Solid Wastes towards Fuels and Chemicals via Fast (Catalytic) Pyrolysis

The management of municipal and industrial organic solid wastes has become one of the most critical environmental problems in modern societies. Nowadays, commonly used management techniques are incineration, composting, and landfilling, with the former one being the most common for hazardous organic wastes. An alternative eco-friendly method that offers a sustainable and economically viable solution for hazardous wastes management is fast pyrolysis, being one of the most important thermochemical processes in the petrochemical and biomass valorization industry. The objective of this work was to study the application of fast pyrolysis for the valorization of three types of wastes, i.e., petroleum-based sludges and sediments, residual paints left on used/scrap metal packaging, and creosote-treated wood waste, towards high-added-value fuels, chemicals, and (bio)char. Fast pyrolysis experiments were performed on a lab-scale fixed-bed reactor for the determination of product yields, i.e., pyrolysis (bio)oil, gases, and solids (char). In addition, the composition of (bio)oil was also determined by Py/GC-MS tests. The thermal pyrolysis oil from the petroleum sludge was only 15.8 wt.% due to the remarkably high content of ash (74 wt.%) of this type of waste, in contrast to the treated wood and the residual paints (also containing 30 wt.% inorganics), which provided 46.9 wt.% and 35 wt.% pyrolysis oil, respectively. The gaseous products ranged from ~7.9 wt.% (sludge) to 14.7 (wood) and 19.2 wt.% (paints), while the respective solids (ash, char, reaction coke) values were 75.1, 35, and 36.9 wt.%. The thermal (non-catalytic) pyrolysis of residual paint contained relatively high concentrations of short acrylic aliphatic ester (i.e., n-butyl methacrylate), being valuable monomers in the polymer industry. The use of an acidic zeolitic catalyst (ZSM-5) for the in situ upgrading of the pyrolysis vapors induced changes on the product yields (decreased oil due to cracking reactions and increased gases and char/coke), but mostly on the pyrolysis oil composition. The main effect of the ZSM-5 zeolite catalyst was that, for all three organic wastes, the catalytic pyrolysis oils were enriched in the value-added mono-aromatics (BTX), especially in the case of the treated wood waste and residual paints. The non-condensable gases were mostly consisting of CO, CO2, and different amounts of C1–C4 hydrocarbons, depending on initial feed and use or not of the catalyst that increased the production of ethylene and propylene.

Adsorption separation of liquid-phase C5-C6 alkynes and olefins using FAU zeolite adsorbents

Isoprene is of great importance as a valuable monomer for most chemical industries owing to the increasing demand for synthetic rubber. To obtain polymer-grade olefins, the removal of alkyne compounds from isoprene is mandatory and challenging. Adsorption separation using zeolites is one of the most promising alternatives for alkyne/olefin separation. Herein, a combination of batch, fixed bed column experiments and configurational-bias grand canonical Monte Carlo (CB-GCMC) simulations was applied to study alkyne’s selective adsorption from binary liquid-phase isoprene/1-pentyne mixtures in faujasite (FAU) zeolites. The adsorption separation performance, including the adsorption capacity and selectivity, was obtained based on the liquid-phase measurement method developed in this study. FAU zeolites exhibited 218 mg/g alkyne adsorption capacity and relatively high adsorption selectivity at low alkyne concentrations. Liquid adsorption separation of linear alkyne/olefin mixtures, covering 1-pentyne/1-pentene (C5) and 1-hexyne/1-hexene (C6), in FAU zeolites, was performed further to investigate the separation performance for alkynes and olefins. The binary isotherms for the 1-pentyne/isoprene system and extended studied olefin/alkyne systems were reproduced well by CB-GCMC simulations. The visualized average occupation profiles of adsorbate molecules in FAU zeolites showed that alkyne and olefin molecules were mainly distributed near the 4-rings and 6-rings. The concentrated areas were arranged perpendicular to each other.

One-Pot Cascade Catalysis of Dehydrochlorination of Greenhouse Gas HCFC-142b and Hydrochlorination of Acetylene for the Spontaneous Production of VDF and VCM

Hydrochlorofluorocarbon (HCFC) has been widely applied as the third-generation refrigerant globally, however, the global warming potential of such gases is often 100 and 1000 times higher than that of CO2. Dehydrochlorination reaction offers an encouraging strategy to transform the high-global-warming-potential gases of hydrochlorofluorocarbons (HCFCs) to low-global-warming-potential gases of hydrofluoroolefins (HFOs). However, the handling of a large amount of byproduct HCl remains one of the major challenges blocking the industrialization of dehydrochlorination of HCFC-142a for the production of vinylidene fluoride (VDF). A one-pot cascade reaction combining dehydrochlorination of HCFC-142b and hydrochlorination of acetylene was first proposed to spontaneously produce valuable monomers of VDF and vinyl chloride monomer (VCM) while eliminating the tedious HCl treatment step. Both thermodynamic calculations and experimental results validate the feasibility of the cascade reaction. Five different heterogeneous catalysts were screened for the proposed cascade reaction, including monocomponent catalyst BaF2, NAC, bifunctional BaF2/NAC catalyst, and bicomponent BaF2-NAC-S and BaF2-NAC-M catalysts. Among them, the mixed BaF2-NAC-M catalyst demonstrated the best catalytic performance, with BaF2 mainly acting as the dehydrochlorination site and NAC mainly acting as the hydrochlorination site. The corresponding reaction mechanism was also proposed.