Environmental Performance Assessment of a Novel Process Concept for Propanol Production from Widely Available and Wasted Methane Sources.

Currently, propanol production highly depends on conventional fossil resources. Therefore, an alternative production process, denoted as "C123", is proposed and evaluated in which underutilized and methane-rich feedstocks such as biogas (scenario BG), marginal gas (scenario MG), and associated gas (scenario AG) are converted into propanol. A first modular-scale process concept was constructed in Aspen Plus, based on experimental data and know-how of the C123 consortium partners. The environmental performance of the considered scenarios was compared at the life cycle level by calculating key performance indicators (KPIs), such as the global warming burden. The results showed that scenario BG is the least dependent on fossil fuels for energy use. Scenario AG seems the most promising one based on almost all selected KPIs when taking into account the avoided gas flaring emissions. The performance of the C123 process concept could be improved by applying heat integration in the process concept.

Quantification of the global and regional impacts of gas flaring on human health via spatial differentiation.

Globally, gas flaring caused 350 million tonnes of CO2 emissions in 2018. In addition to climate change, this burning practice also has other negative consequences for humans (e.g., respiratory problems) and the environment. The aim of this paper is to quantify the impact of flaring on human health (at the global and country level) via the calculation of the number of disability-adjusted life years (DALYs) caused by the combustion of associated gas. For this quantification, gas flaring emissions were linked with midpoint indicators (e.g., climate change) in life cycle assessment (LCA) for all selected countries. Regionalised characterisation factors (CFs) were applied in the impact assessment to allow for spatial differentiation. The global impact on human health caused by flaring was obtained by taking the sum for all countries. The results show that these flaring emissions globally cause 4.83 × 105 DALYs or 6.19 × 10-5 DALYs/person on an annual basis. This amounts to 0.12% of the total DALYs related to air pollution (from PM2.5) caused by all polluting sectors and 6.51% of the total DALYs related to climate change. To quantify these impacts, this study uses a country perspective rather than considering local characteristics. Thus, if more precise information at a more local level (e.g., city level) is sought, additional factors (e.g., meteorological conditions) should be taken into account. Finally, future research should also focus on the benefits of gas flaring reduction techniques to enable the selection of the most promising technologies for the elimination of gas flaring and its effects.

Design of a Mesoscale Continuous-Flow Route toward Lithiated Methoxyallene.

The unique nucleophilic properties of lithiated methoxyallene allow for C-C bond formation with a wide variety of electrophiles, thus introducing an allenic group for further functionalization. This approach has yielded a tremendously broad range of (hetero)cyclic scaffolds, including precursors to active pharmaceutical ingredients. To date, however, its valorization at scale is hampered by the batch synthesis procedure, which suffers from serious safety issues. Hence, the attractive heat- and mass-transfer properties of flow technology were exploited to establish a mesoscale continuous-flow route toward lithiated methoxyallene. An excellent conversion of 94 % was obtained, corresponding to a methoxyallene throughput of 8.2 g h-1 . The process is characterized by short reaction times, mild reaction conditions and a stoichiometric use of reagents.

Enhancing Zeolite Performance by Catalyst Shaping in a Mesoscale Continuous-Flow Diels-Alder Process.

In contrast to most lab-scale batch procedures, a continuous-flow implementation requires a thorough consideration of the solid catalyst design. In a previous study, irregular zeolite pellets were applied in a miniaturized continuous-flow reactor for the Diels-Alder reaction in the construction of norbornene scaffolds. After having faced the challenges of continuous operation, the aim of this study is to exploit catalyst structuring. To this end, microspheres with high uniformity and various sphere diameters were synthesized according to the vibrational droplet coagulation method. The influence of the use of these novel zeolite shapes in a mesoscale continuous-flow Diels-Alder process of cyclopentadiene and methyl acrylate is discussed. An impressive enhancement of catalyst lifetime is demonstrated, as even after a doubled process time of 14 h, the microspheres still exceeded the conversion after 7 h when using zeolite pellets by 30 %. A dual reason is found for this beneficial impact of catalyst shaping. The significant improvement in catalyst longevity can be attributed to the interplay of the chemical composition and the porosity structure of the microspheres.

Tunable Large Pore Mesoporous Carbons for the Enhanced Adsorption of Humic Acid.

Tunable large pore soft templated mesoporous carbons (SMC) were obtained via the organic self-assembly of resorcinol/formaldehyde with the triblock copolymer F127 and by investigating the effect of carbon precursor to surfactant (p/s) ratio and carbonization temperature on the material characteristics. The p/s ratio and carbonization temperature were varied respectively from 0.83 to 0.25 and from 400 to 1200 °C. The resulting SMCs had various average pore sizes, tunable from 7 up to 50 nm. At lower p/s ratios, the pore size increased, pore size distributions broadened, and pore volumes increased. An increase of hydrophobicity was observed at elevated carbonization temperatures. A 2D hexagonal ordered SMC with a narrow pore size distribution was obtained at a ratio of 0.83. Lower ratios (0.5 and 0.25) transformed into disordered porous carbons containing micropores, mesopores, and even macropores. The SMCs were tested for adsorption of a large organic molecule, humic acid (HA), from water. The material characteristics that significantly affected HA adsorption capacity were pore size and mass % (wt %) carbon. The novel SMCs showed an unprecedented high adsorption of HA in the entire molecular weight distribution range. SMCs with large mesopores resulted in higher maximum adsorption capacities and improved HA adsorption kinetics compared to activated carbon.

Insights into the Reaction Mechanism of Ethanol Conversion into Hydrocarbons on H-ZSM-5.

Ethanol dehydration to ethene is mechanistically decoupled from the production of higher hydrocarbons due to complete surface coverage by adsorbed ethanol and diethyl ether (DEE). The production of C3+ hydrocarbons was found to be unaffected by water present in the reaction mixture. Three routes for the production of C3+ hydrocarbons are identified: the dimerization of ethene to butene and two routes involving two different types of surface species categorized as aliphatic and aromatic. Evidence for the different types of species involved in the production of higher hydrocarbons is obtained via isotopic labeling, continuous flow and transient experiments complemented by UV/Vis characterization of the catalyst and ab initio microkinetic modeling.

Characterization and Comparison of Fast Pyrolysis Bio-oils from Pinewood, Rapeseed Cake, and Wheat Straw Using 13C NMR and Comprehensive GC × GC.

Fast pyrolysis bio-oils are feasible energy carriers and a potential source of chemicals. Detailed characterization of bio-oils is essential to further develop its potential use. In this study, quantitative 13C nuclear magnetic resonance (13C NMR) combined with comprehensive two-dimensional gas chromatography (GC × GC) was used to characterize fast pyrolysis bio-oils originated from pinewood, wheat straw, and rapeseed cake. The combination of both techniques provided new information on the chemical composition of bio-oils for further upgrading. 13C NMR analysis indicated that pinewood-based bio-oil contained mostly methoxy/hydroxyl (≈30%) and carbohydrate (≈27%) carbons; wheat straw bio-oil showed to have high amount of alkyl (≈35%) and aromatic (≈30%) carbons, while rapeseed cake-based bio-oil had great portions of alkyl carbons (≈82%). More than 200 compounds were identified and quantified using GC × GC coupled to a flame ionization detector (FID) and a time of flight mass spectrometer (TOF-MS). Nonaromatics were the most abundant and comprised about 50% of the total mass of compounds identified and quantified via GC × GC. In addition, this analytical approach allowed the quantification of high value-added phenolic compounds, as well as of low molecular weight carboxylic acids and aldehydes, which exacerbate the unstable and corrosive character of the bio-oil.

Tuning the Pore Geometry of Ordered Mesoporous Carbons for Enhanced Adsorption of Bisphenol-A.

Mesoporous carbons were synthesized via both soft and hard template methods and compared to a commercial powder activated carbon (PAC) for the adsorption ability of bisphenol-A (BPA) from an aqueous solution. The commercial PAC had a BET-surface of 1027 m²/g with fine pores of 3 nm and less. The hard templated carbon (CMK-3) material had an even higher BET-surface of 1420 m²/g with an average pore size of 4 nm. The soft templated carbon (SMC) reached a BET-surface of 476 m²/g and a pore size of 7 nm. The maximum observed adsorption capacity (qmax) of CMK-3 was the highest with 474 mg/g, compared to 290 mg/g for PAC and 154 mg/g for SMC. The difference in adsorption capacities was attributed to the specific surface area and hydrophobicity of the adsorbent. The microporous PAC showed the slowest adsorption, while the ordered mesopores of SMC and CMK-3 enhanced the BPA diffusion into the adsorbent. This difference in adsorption kinetics is caused by the increase in pore diameter. However, CMK-3 with an open geometry consisting of interlinked nanorods allows for even faster intraparticle diffusion.

Formation of ZSM-22 zeolite catalytic particles by fusion of elementary nanorods.

An ZSM-22 aluminosilicate zeolite was synthesized using the hydrothermal gel method at 150 degrees C. Products obtained after different synthesis times were characterized using various techniques and catalytic testing. Massive formation of ZSM-22 nanocrystals occurs after only a short synthesis time, appearing as isolated rods with a cross section of 12+/-4 nm. Nanorods have aluminum enriched at their external surface. Later in the crystallization process nanorods align and fuse sideways, whereby the external surface is systematically converted into an internal micropore surface. The formation of aluminum bearing micropores by the joining of nanorod surfaces is responsible for the enhanced catalytic activity. For this, the zeolite synthesis of nanoscale crystallites is ineffective for enhancing catalytic activity.

Development of an integrated informatics toolbox: HT kinetic and virtual screening.

We discuss thoroughly aspects and issues for the development of a bespoke, but generic, electronic infrastructure designed to cope with the dynamic in high-throughput experimentation and knowledge management, is applicable to large or contract research organizations. We present the first generation of an informatics platform developed for TOPCOMBI, a research project funded by the European Commission for Nanotechnology and Nanoscience. It is composed by an infrastructure and a collection of modules dealing with laboratory analytics, robotics, data handling and analytics, optimization, in-database processing and visualization, which are developed collegially by the partners of the Consortium. This best-of-breed informatics system enables the capture and the re-usage of processes and methodologies, i.e. process and data flows, using the workflow paradigm. Complex workflows designed by power users can be eventually used by either other domain experts or by novices through a web portal. Workflows can also be run interactively to allow visual analytics for instance, or automatically. We present two case studies dealing with the kinetic study of glycerol catalytic oxidation using parallel equipments, and a novel, fully integrated QSAR applied in heterogeneous catalysis, respectively.

A unified single-event microkinetic model for alkane hydroconversion in different aggregation states on Pt/H-USY-zeolites.

A single-event microkinetic model for the catalytic hydroconversion of hydrocarbons on Pt/H-US-Y bifunctional zeolite catalysts developed for low-pressure vapor phase conditions was extended to cover high-pressure vapor phase and liquid phase conditions. The effect of the density of the bulk hydrocarbon phase on the physisorption as well as on the protonation steps of the reaction network was accounted for explicitly and can be interpreted in terms of "compression" of the hydrocarbon sorbate inside the zeolite pores and "solvation" of the catalyst framework by the dense bulk hydrocarbon phase. The bulk phase density effect on the physisorbed state is described via a single excess free enthalpy of physisorption. A dense bulk hydrocarbon phase destabilizes the sorbate molecules inside the catalyst pores. An expression of the excess free enthalpy of physisorption involving the fugacity coefficient and a zeolite dependent factor allows description of physisorption data. Typical excess free enthalpy values are in the range 1.5-5.1 kJ mol(-1) increasing with carbon number in the series of C5-C16 alkanes. At high-pressure vapor phase and liquid phase conditions, the excess standard protonation enthalpy is estimated at -7.8 kJ mol(-1) leading to relatively more stable carbenium ions at dense bulk phase conditions. As a result of the excess physisorption and protonation properties, the lightest hydrocarbons in mixtures are more competitive at dense phase conditions and their conversion is enhanced compared to low-density conditions.

n-Alkane hydroconversion on Zeogrid and colloidal ZSM-5 assembled from aluminosilicate nanoslabs of MFI framework type.

n-Alkane hydroisomerisation and hydrocracking experiments reveal that ZSM-5 materials synthesized by self-assembly of nanoslabs show different molecular shape selectivity than ZSM-5 synthesized by hydrothermal methods.