Decomposition Of Ethylene Research Articles

A mechanistic and kinetic investigation on the oxidative thermal decomposition of decabromodiphenyl ether

The thermal processes of materials containing decabromodiphenyl ether (BDE-209) normally result in the exposure of BDE-209 to high-temperature environments, generating a series of hazardous compounds. However, the evolution mechanisms of BDE-209 during oxidative thermal processes remain unclear. Thus, this paper presents a detailed investigation on the oxidative thermal decomposition mechanism of BDE-209 by utilizing density functional theory methods at the M06/cc-pVDZ theoretical level. The results show that the barrierless fission of the ether linkage dominates the initial degradation of BDE-209 at all temperatures, with branching ratio over 80%. The decomposition of BDE-209 in oxidative thermal processes is mainly along BDE-209 → pentabromophenyl and pentabromophenoxy radicals → pentabromocyclopentadienyl radicals → brominated aliphatic products. Additionally, the study results on the formation mechanisms of several hazardous pollutants indicate that the ortho-phenyl-type radicals created by ortho-C-Br bond fission (branching ratio reached 15.1% at 1600 K) can easily be converted into octabrominated dibenzo-p-dioxin and furan, which require overcoming the energy barriers of 99.0 and 48.2 kJ/mol, respectively. The O/ortho-C coupling of two pentabromophenoxy radicals also acts as a non-negligible pathway for the formation of octabrominated dibenzo-p-dioxin. The synthesis of octabromonaphthalene involves the self-condensation of pentabromocyclopentadienyl radicals, followed by an intricately intramolecular evolution. Results presented in this study can enhance our understanding of the transformation mechanism of BDE-209 in thermal processes, and offer an insight into controlling the emissions of hazardous pollutants.

Preparation of water‐based flexography printing ink by KMnO4 modified activated carbon for fruit ripening control application

AbstractEthylene is a type of gas that fruits and vegetables can produce naturally. The release of ethylene gas from fruits and vegetables causes them to ripen and undergo physical, chemical and biological changes, such as changes in the appearance in terms of shape and colour, changes in firmness and texture, changes in taste and changes in nutritional value. Furthermore, it also facilitates the growth of microorganisms. These changes lead to spoilage if the fruit or vegetables are left to over ripen. Therefore, the prevention and reduction of damage caused by the ripening of fruits and vegetables entail reducing or slowing down the release of ethylene gas produced by them. This research project aimed to study the properties of activated carbon and potassium permanganate (KMnO4) modified activated carbon, applied as a printing layer on plastic materials for bananas, in terms of their adsorption and decomposition of ethylene. Active and water‐based flexography printing inks were prepared from water‐based binder and ethylene adsorbing and scavenging agents (activated carbon and KMnO4 modified activated carbon) at various concentrations of active agents, that is, 0.0, 5.0, 7.5 and 10.0%w/v. Then, those inks were printed on polypropylene plastic substrate. The delayed ripening of fruits results showed that the plastic materials coated with modified activated carbon inks delayed the physiology disorder (colour and firmness changing about 250% and 226%) and prolonged the storage time up to 14 days when compared with control. In addition, the functional ink layer also presented a high efficiency of abrasion resistance of about 75 cycles of rubbing at 1.8 kg. The products that stem from this research can be applied as packaging for fruits and vegetables in the form of bags, stickers and product pads that can help extend the life and slow the ripening of fruits and vegetables.

Mapping of operating windows for methane and ethane pyrolysis in the pulsed compression reactor by experiments and modelling

By modelling and experiments optimal operating conditions for methane (between 1000 and 3000 K, 300 bar) and ethane pyrolysis (between 800 and 3200 K, 400 bar) in the pulsed compression reactor (PCR) were evaluated. The PCR is a free piston reactor that can compress a gas from atmospheric pressure up to 600 bar in a single pulse. A differential internal energy balance was used for solving the temperature and pressure during the compression. The GERG-2008 equation of state was used to account for non-idealities. To predict the reaction products, both chemical equilibrium (EQ) and kinetic models available from literature were evaluated. The kinetic models (GRI-mech, Holmen et al., 1995 etc.) did not predict part of the experiments well. The EQ model predicts trends well. Therefore, the EQ model was used to map the operating domains. The aim is to reach a maximum concentration of products (olefins and aromatics) in the product gas and a conversion of 20% or more. For methane pyrolysis at 1600 K and 320 bar with nitrogen as diluent and an initial gas temperature of 588 K, the model analysis led to an experimentally observed factor 5.2 increase in ethylene in the outlet (1.4%mol) compared to a previous optimum point (Slotboom et al., 2021). With ethane pyrolysis 9% of ethylene was obtained at a conversion of 66% with an ethylene selectivity of 61% around 1480 K and 400 bar. Further analysis with the EQ model showed that for the thermal coupling of methane with an initial gas temperature of 773 K, conversion is possible without diluting with nitrogen. For ethane decomposition nitrogen is always needed as a diluent up to 773 K.

Experimental and kinetic modeling study of low-temperature oxidation of n-pentane

Attractiveness in advanced low-temperature combustion engines drives a constantly updated understanding of low-temperature oxidation chemistry. In this work, the low-temperature oxidation chemistry of n-pentane in two jet-stirred reactors at atmospheric pressure and in the temperature range of 500–825 K was investigated using combined analysis methods of synchrotron vacuum ultraviolet photoionization mass spectrometry, gas chromatography, and Fourier transform infrared spectroscopy. Furthermore, the gaseous mixture from JSR was collected in acetonitrile for subsequent product characterization using flow injection analysis, high-pressure and ultra-high-pressure liquid chromatography coupled to a Thermo Scientific™ Orbitrap® Q-Exactive high-resolution mass spectrometry. Numerous intermediate species were identified by these analytical methods, which contributed to unraveling the low-temperature oxidation reaction network of n-pentane. A detailed n-pentane model was tentatively developed to reduce deviations between experimental measurements and model predictions by updating the rate constants of C5 keto-hydroperoxide decomposition, C5 hydroperoxy cyclic ether decomposition, and Korcek reactions of C5 keto-hydroperoxide, and by introducing pressure-dependent rate constants for the reaction classes of Q˙OOH + O2, Q˙OOH decompositions, concerted HȮ2-elimination of RȮ2, C5 keto-hydroperoxide decomposition, C5 hydroperoxy cyclic ether decomposition, and Korcek reactions of C5 keto-hydroperoxide, and by adding more detailed sub-mechanisms for C5 cyclic ethers and C5 keto-hydroperoxides. This updated model was validated against a set of available experimental data, including jet-stirred reactor species data and ignition delay times. These exploratory updates of the kinetic model reveal the considerable influence of the rate constants of hydroperoxide decomposition and the pressure-dependent rate constants of key reaction classes on the kinetic model predictions, highlighting the future demands for high-precision quantum chemistry calculations of the pressure-dependent rate constants of the aforementioned reaction classes to reduce mechanism uncertainties and to develop accurate and robust chemical kinetic models.

Decomposition of Ethane as a Hydrogen Rich Molecule on the Aluminum-Doped Boron Nitride Nanotube: A DFT Approach

It is predictable that hydrogen gas will be used as the common main energy supply instead of fossil fuels in the near future. Studying hydrogen-production by using hydrogen-rich materials as a source of hydrogen on metal-free catalysts may be worthwhile. We studied the adsorption of ethane, as a hydrogen-rich molecule, on the one, two and three aluminum-doped boron nitride nanotubes using density functional theory. The interactions between any possible sides of ethane and any possible sites on Al[Formula: see text]-doped BNNT were studied. The only adsorption has occurred from the carbon atom side of the ethane molecule on the doped aluminum atom site of the BNNT. After the adsorption process, the possible configurations of the intermediates and transition states to receive the decomposition reaction pathway of the ethane molecule were surveyed. The results showed that the ethane molecule was decomposed only on the two aluminum-doped BNNT to four hydrogen atoms.

DFT studies of the adsorption and decomposition of dimethyl ether on copper surface

Polyethers are excellent lubricants in reducing friction and wear between tribological counterfaces. However, they may decompose at the high temperatures due to the friction. Besides, the metal surfaces or metal abrasives of the machines will act as catalysts in accelerating the degradation of polyethers. Dimethyl ether (DME) is the simplest ether and may act as a model for polyethers. In this work, the catalytic mechanism of copper surface, Cu(111), on the degradation of adsorbed DME on the Cu(111) surface (DME*) was studied theoretically, by using the density functional theory. The energetics and kinetics of the reactions of DME* decomposition on the Cu(111) surface were calculated. The results showed that there are three main routes dominating the decomposition of DME* on the Cu(111) surface, all initiated by the breakage of C H bond. These three routes may lead to the production of CO*, CH*, and H*, which are all tightly adsorbed on the Cu(111) surface and hence may deteriorate the performance of the machines. Kinetic analysis indicates that the C H bond connecting the C O bond in ether-based lubricants should be strengthened to improve the thermal stability of the lubricant.

Removal of ethylene by synthesized Ag/TiO2 photocatalyst under visible light irradiation

Photocatalysts based on titanium dioxide (TiO2) were widely applied to solve environmental problems such as water and air pollution treatment. Currently, the application of these compounds for food packaging is increasing. This study prepared silver (Ag) doped TiO2 photocatalyst (Ag/TiO2) for the decomposition of gas ethylene (Eth), which is the main factor that causes fruits to over-ripen and damage or decay. It found that the doping of Ag could improve the optical property and light adsorption ability of Ag/TiO2 photocatalyst, which directly enhanced the photocatalytic decomposition of Eth performance.Under visible light, Ag/TiO2 could depredate 91.2% of Eth, while the removal performance by using the original TiO2 was 43.9%. The increased initial concentration of Eth from 5 to 30 ppm could inhibit the photocatalytic efficiency of Ag/TiO2 from 98.6 to 69.2%. Besides, the relative humidity and gas flow rate are roles in the Eth decomposition process. The recycling experiment confirmed that Ag/TiO2 had good reusability with a slight loss in photocatalytic performance (18.6%) after ten cycles tested. The future protective application of Ag/TiO2 for food protection during storage and transportation is discussed. This work provides a potential method to remove gas ethylene, reduce the ripening process and extend the shelf life of fruits.

Fine‐Tuning Texture of Highly Acidic HZSM‐5 Zeolite for Efficient Ethanol Dehydration

AbstractAchieving high and stable ethylene yield from (bio)ethanol dehydration over highly active acidic zeolite remains challenging due to undesired side‐reactions. To overcome this issue, the fine‐tuned textural property of the HZSM‐5 catalyst with a hierarchical structure is crucial to overcome diffusion restrictions and limit undesired side‐reactions. Herein, the texture of high acid catalysts obtained via hydrothermal synthesis was simply tuned in the presence of tetrabutylammonium hydroxide as a meso‐ and micropore directing agent and the controlled molar ratio of NaF‐to‐Al2O3. The hierarchically designed HZSM‐5 with the small nanosheet size of 6.5 nm exhibits a high external surface area and mesopores, largely enhancing the catalytic performance of ethanol dehydration up to 95 % ethylene yield as well as preventing the formation of heavy hydrocarbons. To gain insights into the mechanistic points of view, the in situ DRIFTS study revealed that ethylene could form through ethoxy‐mediated mechanism or decomposition of diethyl ether (DEE). The catalyst deactivation caused by polyaromatics obtained from side‐reactions is the reason for low ethanol conversion and high DEE selectivity. Reducing the crystal size of highly acidic zeolite to ultra‐thin nanosheet can shorten the residence time of ethanol, intermediates, and products in porous structures, substantially suppressing the transformation of coke precursors into heavy hydrocarbons to achieve high and stable ethylene yield.

Ruthenium Metal–Organic Frameworks as Stable Nanostructures for Selective Hydrogen Production from Acetaldehyde and Water under Mild Conditions

Hydrogen is a promising energy carrier because it is a wide and sustainable source. However, it is still extremely difficult to store and transport hydrogen safely because of its active chemical properties and harsh explosion limits. Organic liquid is a popular research field for hydrogen production and storage. Inspired by its biological metabolism, here acetaldehyde is innovatively used for hydrogen production. The hydrogen content of an acetaldehyde–water solution is 10.2 wt %, which is slightly lower than that of a methanol–water solution but much higher than that of formic acid and formaldehyde. For the first time, we prepared several ruthenium metal–organic frameworks (MOFs) as stable nanostructures for selective hydrogen production from acetaldehyde and water under mild conditions (∼60 °C). Ru-MOFs all have nanoscale pores, and the turnover frequency of ruthenium 2,3,5,6-tetramethyl-1,4-phenylenediamine for acetaldehyde decomposition is up to 223 h–1 in water at 90 °C. Because C–C bond cleavage is an inevitable step for hydrogen or energy production from C2 organics, ion chromatography, high-performance liquid chromatography, 1H NMR spectroscopy, and mass spectrometry were employed to propose a catalytic process of hydrogen production from acetaldehyde decomposition. We evidently prove that water participates in acetaldehyde decomposition, thereby claiming an acetaldehyde–water reforming process. Additionally, we confirm that formic acid and acetic acid are the intermediates during the hydrogen production process. This research not only holds great promise for hydrogen production from C2 organics at low temperatures, as well as catalytic technology for C–C bond cleavage, but it also provides certain profound scientific insights for hydrogen or energy production from multicarbon organics, such as biomass.

Effect of Sr Substitution on the Novel La1-xSrxCo0.5Ni0.5O3-δ Perovskite-Type Catalysts for Hydrogen Production in Ethanol Steam Reforming

La1-xSrxCo0.5Ni0.5O3-δ perovskites with different substitution of La by Sr have been firstly synthesized and applied as catalysts for ethanol steam reforming (ESR). The effect of partial Sr substitution on the performance and stability of La1-xSrxCo0.5Ni0.5O3-δ for ESR was investigated. The synthesized samples were characterized by XRD, SEM, BET, and EDS techniques. The results show that with the increase of substitution of La by Sr, the pore size and surface area of La1-xSrxCo0.5Ni0.5O3-δ perovskite increase. The doping of Sr causes changes in the specific surface area, pore volume, and pore size of the catalyst, which in turn causes changes in its catalytic activity. Meanwhile, La0.1Sr0.9Co0.5Ni0.5O3-δ with a highest SBET presents the highest ethanol conversion rate among all the samples. The modifications of catalyst characteristics caused by the Sr substitution in La1-xSrxCo0.5Ni0.5O3-δ directly affect its catalytic performance in the ESR. What is more, the influences of operating parameters on the catalytic activity of La0.1Sr0.9Co0.5Ni0.5O3-δ were studied in detail, and the optimum conditions were determined and applied for stability experiments. When the temperature is lower than 500°C, the selectivity of gas products is most likely affected by the dehydrogenation of ethanol and the decomposition of acetaldehyde. Meanwhile, the improving hydrogen selectivity and reducing the formation of by-products can be achieved by increasing the reaction temperature. The best catalytic performance for hydrogen production was achieved with La0.1Sr0.9Co0.5Ni0.5O3-δ which presented the highest ethanol conversion (98.7%) under the optimal reaction conditions. La0.1Sr0.9Co0.5Ni0.5O3-δ perovskites with higher strontium degree of substitution exhibited an excellent activity and stability of the catalysts derived.

Core/Shell Nitrogen-Doped TiO2@SiO2 Nano-Catalyst as an Additive in Photocatalytic Paint for Gaseous Acetaldehyde Decomposition

A nitrogen-doped TiO2@SiO2 core/shell nano-photocatalyst (N-TiO2@SiO2) was used as an additive in photocatalytic paint and applied for the photocatalytic degradation of gaseous acetaldehyde under light-emitting diode (LED) visible light irradiation. N-TiO2 was synthesised via the solvothermal method and then encapsulated by SiO2 via the sol-gel method. The incorporation of the N atom into the TiO2 structure was observed by X-ray photoelectron spectroscopy. The N-TiO2@SiO2 core/shell structure was determined by TEM images. The photodegradation of gaseous acetaldehyde using the prepared N-TiO2@SiO2 photocatalytic paint was examined in a closed chamber under LED light irradiation. The photodegradation of acetaldehyde by N-TiO2@SiO2 photocatalytic paint (31%) was significantly higher than that of TiO2 paint (5%) and N-TiO2 paint (20%) within 16 h. The chemical resistance and adhesion ability of N-TiO2@SiO2 photocatalytic paint were investigated following Thai Industrial Standards (TIS) no. 2321 and standard test methods for rating adhesion by tape test (ASTM D 3359-22). The N-TiO2@SiO2 paint showed good acid and alkali resistance, as well as high adhesion ability comparable with commercial paint (without a photocatalyst).

Reaction kinetics and implications of the decomposition and formation of C2H4O isomers

Acetaldehyde, ethylene oxide, and vinyl alcohol are three C2H4O isomers that are ubiquitous in combustion over a wide temperature range. A comprehensive reaction kinetics study has been performed for reactions that occur on the same C2H4O potential energy surface, mainly including the unimolecular reactions of three C2H4O isomers and the recombination reaction of CH3 with HCO. Temperature- and pressure-dependent rate coefficients were updated or newly predicted by performing quantum chemical calculations coupled with RRKM/master equation simulations. The dominance of CC bond fission is reconfirmed for acetaldehyde decomposition at higher temperatures. The negligible contribution of CH4 + CO channel from usual tight intramolecular H-shift transition state provides indirect evidence for previously reported roaming mechanism that was proposed to explain the observation of CH4 + CO in acetaldehyde pyrolysis. For ethylene oxide pyrolysis, current experiment and kinetic prediction have a good consistency in branching ratios between the formation of acetaldehyde and vinyl alcohol products. The radicals of CH3 + HCO can also be directly generated from ethylene oxide through a well-skipping reaction mechanism especially at higher temperatures. For CH3 + HCO recombination, we highlight the importance of CH3CO + H channel that was often overlooked previously. Kinetic simulations show that the incorporation of updated rate coefficients and newly identified channels results in a measurable influence on C2 chemistry, indicating the possibility and necessity of further improvement of core mechanism in combustion kinetic models.

Low-Temperature Synthesis of Cu-Doped Anatase TiO2 Nanostructures via Liquid Phase Deposition Method for Enhanced Photocatalysis.

Titanium dioxide (TiO2) photocatalysis can harness the energy from sunlight, providing a solution to many green- and energy-related problems. In this study, we aimed to produce Cu doped TiO2 (Cu-TiO2) structures at a low temperature (~70 °C) under atmospheric pressure based on liquid phase deposition. The products prepared with Cu nitrate exhibited anatase-phase TiO2 with the presence of Cu, and the particles showed a waxberry-like structure. Changing the Cu nitrate concentration allowed control of the atomic concentration; we confirmed ~1.3 atm.% of Cu ions in the product when we applied 10 mM in the precursor solution. By doping Cu, the light absorption edge shifted to 440 nm (~2.9 eV), and we proved the photocatalytic reaction through action spectral measurement. We observed the decomposition of acetaldehyde into CO2 on Cu-TiO2 photocatalysts, which produced optimized improvements in photocatalytic activity at Cu dopant levels between 0.2 and 0.4 atm.%. This study demonstrates that the liquid phase deposition technique can be used for doping metallic ions into TiO2, which shows promise for preparing novel and unique nanomaterials as visible light photocatalysts.

Fluorinated ether decomposition in localized high concentration electrolytes

Localized high concentration electrolytes (LHCEs) are a promising class of battery materials to enable stable cycling of the lithium metal anode. Here, we report the use of operando nuclear magnetic resonance (NMR) spectroscopy to observe electrolyte decomposition during Li stripping/plating and identify the influence of individual components in LHCEs on Li metal battery performance. Data from operando19F solution NMR indicates that both bis(fluorosulfonyl)imide (FSI−) salt and bis(2,2,2-trifluoroethyl) ether (BTFE) diluent molecules play a key role in solid electrolyte interphase (SEI) formation. Three-electrode electrochemical impedance spectroscopy (EIS) of commercial pouch cells also shows differences in interfacial resistances between LHCE and standard high concentration electrolytes (HCEs) that may be explained by incorporation of BTFE and BTFE reaction products into the SEI. Based on solid-state NMR and X-ray photoelectron spectroscopic characterization, we find that BTFE diluents decompose to form CF2- and CF3-containing fragments within a LiF-rich SEI deposited on the anode surface. The CEI on the cathode (here, LiNi0.8Mn0.1Co0.1O2) side of the battery also contains higher quantities of LiF and trapped LiFSI after cycling in the LHCE compared to a HCE that are attributed to diluent decomposition and correlated with lower impedance at the cathode. Overall, this work provides a new framework to consider highly fluorinated ether molecules—instead of functioning purely as diluting agents in LHCEs, these fluorinated ethers exhibit tunable interfacial reactivity that can be leveraged to control Li deposition behavior.

Porous Co-Pt Nanoalloys for Production of Carbon Nanofibers and Composites.

The controllable synthesis of carbon nanofibers (CNF) and composites based on CNF (Metals/CNF) is of particular interest. In the present work, the samples of CNF were produced via ethylene decomposition over Co-Pt (0-100 at.% Pt) microdispersed alloys prepared by a reductive thermolysis of multicomponent precursors. XRD analysis showed that the crystal structure of alloys in the composition range of 5-35 at.% Pt corresponds to a fcc lattice based on cobalt (Fm-3m), while the CoPt (50 at.% Pt) and CoPt3 (75 at.% Pt) samples are intermetallics with the structure P4/mmm and Pm-3m, respectively. The microstructure of the alloys is represented by agglomerates of polycrystalline particles (50-150 nm) interconnected by the filaments. The impact of Pt content in the Co1-xPtx samples on their activity in CNF production was revealed. The interaction of alloys with ethylene is accompanied by the generation of active particles on which the growth of nanofibers occurs. Plane Co showed low productivity (~5.5 g/gcat), while Pt itself exhibited no activity at all. The addition of 15-25 at.% Pt to cobalt catalyst leads to an increase in activity by 3-5 times. The maximum yield of CNF reached 40 g/gcat for Co0.75Pt0.25 sample. The local composition of the active alloyed particles and the structural features of CNF were explored.

Shock-tube study on the influence of oxygenated co-reactants on ethylene decomposition under pyrolytic conditions

The influence of various oxygenated co-reactants on soot formation was addressed by studying the pyrolysis of gas mixtures using ethylene as a base fuel in the absence of molecular oxygen. Alcohols (methanol, ethanol, and n-butanol) and ethers (diethyl ether, dimethoxymethane, furan, and tetrahydrofuran) were selected as oxygenated co-reactants. The pyrolysis process was studied behind reflected shock waves at around 3 bar. Laser extinction at 633 nm was used to determine soot-inception times and the related optical densities as a function of reaction time. The temporal variation in temperature was measured via time-resolved two-color CO absorption using two quantum-cascade lasers at 4.73 and 4.56 µm. Soot particle sizes were determined by time-resolved laser-induced incandescence using a Nd:YAG laser at a wavelength of 1064 nm. The major finding is that based on C2H4 as soot precursor, only CH3OH does not have a soot-promoting effect, whereas the addition of all other oxygenated hydrocarbons results in increased soot yields. The measured temperatures were compared with simulations based on a detailed chemical kinetics mechanism from the CRECK Modeling Group (Pejpichestakul et al. Proc. Combust. Inst. (2019)). In addition, kinetics modeling of hydrocarbon pyrolysis, PAH formation and soot growth was performed in OpenSMOKE++ software to give qualitative insight in the experimental results using the CRECK mechanism and an assembled mechanism composed of the CRECK and the recent PAH sub-mechanism (Sun et al. Proc. Combust. Inst. (2021)). The simulation reveals that the observed promotion of soot formation in presence of oxygenated co-reactants is associated with the release of CH3 and C3H3 during the thermal decomposition resulting in acceleration of C6H6 ring formation.

On the Elucidation of Polymer Fouling Mechanisms and Ethylene Decomposition in High‐Pressure LDPE Tubular Reactors

AbstractIn high‐pressure free‐radical ethylene polymerization tubular reactors, fouling often occurs due to polymer deposition onto the reactor's wall surface. This results in a decrease in the overall heat transfer coefficient. Note that a high‐pressure tubular reactor must be capable of removing about half of the generated polymerization heat to the cooling water flowing into the reactor's jackets. Therefore, reactor fouling can have serious implications including decrease of heat removal rate and monomer conversion, increase in the overall initiator(s) consumption, change of polymer quality, decline of reactor's safe operation, and significant economic losses due to lower plant productivity and longer reactor maintenance periods. In rare cases, the loss of reactor's heat removal capacity may result in the appearance of local hot spots that eventually can trigger ethylene decomposition. In the present review paper, the fundamental physical and chemical phenomena regarding polymer fouling and ethylene decomposition in high‐pressure low density polyethylene (LDPE) reactors are critically discussed. The effects of shear rate, polymer molecular weight, and wall surface energy on polymer adsorption and desorption are analyzed. Moreover, the effect of characteristic initiator decomposition and micromixing times and process conditions on initiator dispersion, polymer fouling, and ethylene decomposition are assessed.

Effect of metal on corona discharge plasma in a honeycomb catalyst and optimization of the critical parameters for ethylene removal

This work focused on the factors affecting the effective generation of corona discharge plasma in a honeycomb catalyst reactor. Pd, Co, and Ag were used as the active metal catalysts to investigate the plasma formation and decomposition of ethylene. Unlike the Ag-coated honeycomb catalyst, which resulted in excessive arcing, the Co-coated honeycomb monolith was able to generate stable plasma, but the discharge power was insufficient to decompose ethylene at an acceptable level. The incorporation of a small amount of Pd with Co significantly enhanced the discharge power and the ethylene removal performance. The catalytic activity of the prepared catalyst for the removal of ethylene was evaluated using plasma catalytic oxidation and thermal catalytic oxidation. ANOVA was used to assess the effect of single process factors and their relationships in the plasma process. All the process factors such as specific energy input (SEI), ethylene concentration, and flow rate were found to affect the ethylene conversion, CO2 selectivity, and energy efficiency (EE). Under the optimal conditions, i.e., an SEI of 80 J/L, an ethylene concentration of 20 ppm, and a flow rate of 20 L/min, the ethylene conversion was 85 %, CO2 selectivity was 70 %, and EE was 0.86 g/kW h.

Investigations of mechanism, surface species and support effects in CO hydrogenation over Rh

The Rh-catalyzed CO hydrogenation to hydrocarbons and C2-oxygenates over Rh/ZrO2 and Rh/SiO2 was studied. Catalytic reaction tests show a support effect with a faster steady state reaction rate over Rh/ZrO2 compared to Rh/SiO2. Temperature programmed hydrogenation (TPH) experiments reveal that the CO dissociation on the metal surface is rate limiting, and the support effect thus accelerates the CO dissociation on the metal. Combined TPH and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) studies after low-temperature CO pre-adsorption reveal a H-assisted C-O bond breakage through CH3O species on the Rh surface. Transient measurements indicate that this mechanism is also likely to be in operation during the steady state reaction at higher temperatures, although here the methoxide is too short-lived to be detected at steady state. This hydrogen-assisted CO activation can help to explain that previous studies have observed an inverse H/D isotope effect for Rh despite CO dissociation being the rate limiting step. TPH studies show that both CO pre-adsorption at 30 ℃ and CO/H2 exposure at 250 ℃ lead to so high CO coverages that it restricts the CO activation, which only starts once part of the CO has desorbed. The near-complete CO coverage on the working Rh surface is restricting the rate, but is essential for the selectivity towards oxygenates. Studies of acetaldehyde conversion in various atmospheres over Rh/SiO2 and Rh/ZrO2 catalysts show that acetaldehyde decomposes over a bare Rh surface with a rate that greatly exceeds the oxygenate formation rate in CO hydrogenation. In the presence of CO the acetaldehyde decomposition is strongly inhibited. The high CO coverage on the surface of the working Rh catalysts thus prevents oxygenate decomposition and is therefore essential for the ability to produce oxygenated products. The reaction temperature is observed to play a role for the establishment of the high coverage. During exposure to CO/H2 at reaction temperatures (>200 ℃) an activated process occurs whereby both the stability and coverage of the CO adlayer increases. This activated stabilization of the CO adlayer shifts the CO activation up in temperature in a subsequent TPH. The results contribute to a fundamental understanding of the reaction mechanism and support effects in the Rh-catalyzed CO hydrogenation, which can assist the formulation of improved Rh-based catalysts. The results, such as the identification of a H-assisted mechanism of CO hydrogenenation via methoxide, could also be of general relevance for the understanding of CO hydrogenation over other metals.

Detailed chemical effects of ammonia as fuel additive in ethylene counterflow diffusion flames

Ammonia is considered one of the most competitive fuels due to its carbon neutrality. The chemical effects of NH3 are distinguished by kinetic analysis via adding NH3 as reactive NH3 and fictitious inert NH3. The flame temperature and the mole fraction profiles affected by the chemical effects of NH3 addition for important species and soot are analyzed, with special emphasis on soot and its important precursor polycyclic aromatic hydrocarbons (PAHs). The results illustrate that NH3 addition inhibits the production of A1-A4. The chemical effects of ammonia decrease the hydrogen abstraction–C2H2–addition (HACA) surface growth rate and PAH condensation rate, which further reduces soot volume fraction and average particle diameter D63. The ammonia decomposition pathways interact with ethylene decomposition pathways via the four reactions: NH3 + C2H5 = C2H6 + NH2, HCN + C2H5 = C2H6 + CN, NH2 + C2H4 = C2H3 + NH3, and CH2CH2NH2 = C2H4 + NH2. The dilution and thermal effects of NH3 are dominant effects on soot reduction, while the chemical effects further inhibit soot formation.