Small Hydrocarbons Research Articles

A TG-MS study on the coupled pyrolysis and combustion of oil sludge

Integrated thermal treatment (coupled pyrolysis and combustion) is considered to be an effective method for the utilization of oil sludge (OS). Characteristics of OS pyrolysis, OS combustion and OS char combustion were comprehensively investigated with a thermogravimetry-mass spectrum (TG-MS) system in this work. Small molecule hydrocarbons like CH4 were main components in OS pyrolysis gas. Nitrogen and sulfur containing compounds, H2O, and CO2 were detected out during OS and OS char combustion. The maximum intensities of NH3, HCN and NO all appeared in the OS combustion. H2S was the main precursor of SO2, and the peak of H2S occurred earlier with an increase in the pyrolysis temperature between 500 and 700 °C. Besides, with an increase in the pyrolysis temperature, NO2 and SO2 emissions increased during OS char combustion.

Correlation between pyrolysis behaviors of the components and the overall pyrolysates from pulping spent liquor

The pyrolysis behaviors of the three major organic components of eucalyptus alkaline peroxide mechanical pulping (APMP) spent liquor including alkali lignin (AL), lignin-carbohydrate complexes (LCC), and polysaccharide (PLS) were studied with emphasis on the effect and contributions of components on the overall pyrolysates of APMP spent liquor solid (ASLS). Profound differences on product properties from each component pyrolysis were illustrated. The results indicated that the bio-oil during ASLS pyrolysis was mainly attributed to AL, while the bio-gas and char were mostly affected by PLS. Small molecule hydrocarbons released during ASLS pyrolysis mainly came from AL and LCC, and CO and CO2 mainly produced from PLS. As for bio-oils, AL generated the largest proportion of monomeric phenols and aromatic hydrocarbons (AHs), while PLS and LCC mainly contributed to the production of ketones, furans and acids. The correlation shown here is of interest for further studies on pulping spent liquor grading utilization.

Catalytic Pyrolysis of Municipal Plastic Film Wastes Over Nanoporous Al-MCM-41.

A mesoporous material, Al-MCM-41, was applied to the catalytic pyrolysis of municipal plastic film waste (MPFW) to produce large amounts of valuable hydrocarbons. Compared to non-catalytic pyrolysis, the catalytic pyrolysis of MPFW over Al-MCM-41 revealed a lower decomposition temperature and activation energy upon thermogravimetric analysis. Heavy aliphatic hydrocarbons, which are the major products of non-catalytic pyrolysis, were cracked into small hydrocarbons and converted efficiently to aromatic hydrocarbons by catalytic pyrolysis over Al-MCM-41. The activity of catalytic conversion was enhanced by increasing the catalyst to reactant ratio.

Catalytic Pyrolysis of Organosolv and Klason Lignin Over Al-SBA-15.

The catalytic pyrolysis of two types of lignin, organosolv and klason lignin, which were extracted from miscanthus, over Al-SBA-15 was carried out using a thermogravimetric (TG) analyzer and a pyroyzer-gas chromatography/mass spectrometry (Py-GC/MS). Although Al-SBA-15 has weak acidity, the large molecular phenolic pyrolyzates of lignin were converted effectively into small molecular phenols and aromatic hydrocarbons due to the large pore size of Al-SBA-15. Compared to klason lignin, organosolv lignin produced larger amounts of valuable chemicals, such as mono-phenol, mono-aromatics, and furans, by catalytic pyrolysis over Al-SBA-15.

Sustainable Steel Carburization by Using Snack Packaging Plastic Waste as Carbon Resources

In recent years, the research regarding waste conversion to resources technology has attracted growing attention with the continued increase of waste accumulation issues and rapid depletion of natural resources. However, the study, with respect to utilizing plastics waste as carbon resources in the metals industry, is still limited. In this work, an environmentally friendly approach to utilize snack packaging plastic waste as a valuable carbon resources for steel carburization is investigated. At high temperature, plastic waste could be subject to pyrolytic gasification and decompose into small molecular hydrocarbon gaseous products which have the potential to be used as carburization agents for steel. When heating some snack packaging plastic waste and a steel sample together at the carburization temperature, a considerable amount of carbon-rich reducing gases, like methane, could be liberated from the plastic waste and absorbed by the steel sample as a carbon precursor for carburization. The resulting carburization effect on steel was investigated by optical microscopy, scanning electron microscopy, electron probe microanalyzer, and X-ray photoelectron spectrometer techniques. These investigation results all showed that snack packaging plastic waste could work effectively as a valuable carbon resource for steel carburization leading to a significant increase of surface carbon content and the corresponding microstructure evolution in steel.

APCI(+)FT-ICR MS Analysis of Hydrocarbons Using Isooctane as Ionizing Reagent - A Comparison with HTGC-FID, GC×GC-MS and NMR

Hydrocarbons present in saturated fractions of crude oils can be assessed by atmospheric pressure chemical ionization (APCI) using small hydrocarbons as ionizing reagents in a Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR MS). In this work, five paraffin standards of different average molar mass distributions (Mw) were easily ionized by APCI(+)FT-ICR MS using isooctane as the reagent gas. Data of Mw, carbon number and double bond equivalent (DBE) distributions corresponding to linear and cyclic hydrocarbons (HCs) were compared to results obtained from analysis of high temperature gas chromatography with a flame ionization detector (HTGC-FID), comprehensive two-dimensional gas chromatography coupled to mass spectrometry (GC×GC-MS) and 1H and 13C nuclear magnetic resonance (NMR) spectroscopy. APCI(+)FT-ICR MS data showed good agreement with those of analytical techniques. Furthermore, the ability of APCI(+) to assess n-paraffin, even in blends with polyaromatic hydrocarbon molecules such as coronene (Mw = 301 Da) at concentrations from 2.5 to 25 µg mL-1, was demonstrated. The typical MS paraffin profile (containing repeating mass units of 14 Da) was clearly confirmed, being totally suppressed when a concentration of 25 µg mL-1 of coronene was used. This phenomenon was also evidenced in one of two saturated fractions produced using saturates, aromatics and polar (SAP) compound fractionation methodology.

Dissociative ionisation of adamantane: a combined theoretical and experimental study.

Diamond nanoparticles, or nanodiamonds, are intriguing carbon-based materials which, maybe surprisingly, are the most abundant constituent of presolar grains. While the spectroscopic properties of even quite large diamondoids have already been explored, little is known about their unimolecular fragmentation processes. In this paper we characterise the dissociative ionisation of adamantane (C10H16) - the smallest member of the diamondoid family - utilising imaging Photoelectron Photoion Coincidence (iPEPICO) spectroscopy and Density Functional Theory (DFT) calculations. We have found adamantane to dissociatively photoionise via several parallel channels of which H, C3H7 and C4H8 losses are the most important ones. Calculations confirm the existence of a rate-limiting transition state for the multiple C-loss channels, which is located at 10.55 eV with respect to neutral adamantane. In addition, we found dissociation channels leading to small cationic hydrocarbons, which may be relevant in the interstellar medium.

Untangling the methane chemistry in interstellar and solar system ices toward ionizing radiation: a combined infrared and reflectron time-of-flight analysis.

Pure methane (CH4/CD4) ices were exposed to three ionizing radiation sources at 5.5 K under ultrahigh vacuum conditions to compare the complex hydrocarbon spectrum produced across several interstellar environments. These irradiation sources consisted of energetic electrons to simulate secondary electrons formed in the track of galactic cosmic rays (GCRs), Lyman α (10.2 eV; 121.6 nm) photons simulated the internal VUV field in a dense cloud, and broadband (112.7-169.8 nm; 11.0-7.3 eV) photons which mimic the interstellar ultra-violet field. The in situ chemical evolution of the ices was monitored via Fourier transform infrared spectroscopy (FTIR) and during heating via mass spectrometry utilizing a quadrupole mass spectrometer with an electron impact ionization source (EI-QMS) and a reflectron time-of-flight mass spectrometer with a photoionization source (PI-ReTOF-MS). The FTIR analysis detected six small hydrocarbon products from the three different irradiation sources: propane [C3H8(C3D8)], ethane [C2H6(C2D6)], the ethyl radical [C2H5(C2D5)], ethylene [C2H4(C2D4)], acetylene [C2H2(C2D2)], and the methyl radical [CH3(CD3)]. The sensitive PI-ReTOF-MS analysis identified a complex array of products with different products being detected between experiments with general formulae: CnH2n+2 (n = 4-8), CnH2n (n = 3-9), CnH2n-2 (n = 3-9), CnH2n-4 (n = 4-9), and CnH2n-6 (n = 6-7) from electron irradiation and CnH2n+2 (n = 4-8), CnH2n (n = 3-10), CnH2n-2 (n = 3-11), CnH2n-4 (n = 4-11), CnH2n-6 (n = 5-11), and CnH2n-8 (n = 6-11) from broadband photolysis and Lyman α photolysis. These experiments show that even the simplest hydrocarbon can produce important complex hydrocarbons such as C3H4 and C4H6 isomers. Distinct isomers from these groups have been shown to be important reactants in the synthesis of polycyclic aromatic hydrocarbons like indene (C9H8) and naphthalene (C10H8) under interstellar conditions.

Simulations of hydrogen, carbon dioxide, and small hydrocarbon sorption in a nitrogen-rich rht-metal-organic framework.

Grand canonical Monte Carlo (GCMC) simulations of gas sorption were performed in Cu-TDPAH, also known as rht-MOF-9, hereafter [1], a metal-organic framework (MOF) with rht topology consisting of Cu2+ ions coordinated to 2,5,8-tris(3,5-dicarboxyphenylamino)-1,3,4,6,7,9,9b-heptaazaphenalene (TDPAH) ligands. This MOF is notable for the presence of open-metal copper sites and high nitrogen content on the linkers. [1] Exhibits one of the highest experimental H2 uptakes at 77 K/1 atm within the extant rht-MOF family (ca. 2.72 wt%) and also has strong affinity for CO2 (5.83 mmol g-1 at 298 K/1 atm). Our simulations, which include explicit many-body polarization interactions, accurately modeled macroscopic thermodynamic properties (e.g., sorption isotherms and isosteric heats of adsorption (Qst)) as well as the binding sites for H2, CO2, CH4, C2H2, C2H4, and C2H6 in the MOF. Four different binding sites were observed through analysis of the radial distribution function (g(r)) about the two chemically distinct Cu2+ ions, simulated annealing calculations, and examination of the three-dimensional histogram showing the sites of occupancy: (1) at the Cu2+ ion facing toward the center of the linker (CuL), (2) at the Cu2+ ion facing away from the center of linker (CuC), (3) nestled between three [Cu2(O2CR)4] units in the corner of the truncated tetrahedral (T-Td) cage and (4) straddling the copper nuclei parallel to the axis of the Cu-Cu bond within the T-Td cage. The low-loading (initial) binding site in the MOF is highly sensitive to the partial charges of the Cu2+ ions that were used for parametrization. It was discovered that most sorbates prefer to sorb onto or near the Cu2+ ions that exhibit the greater partial positive charge (i.e., at site 1). The simulated H2 and CO2 sorption results obtained using a polarizable potential for the respective sorbates are in good agreement with the corresponding experimental data, especially near ambient pressure. Simulations of gas sorption were also performed in [1] using nonpolarizable potentials for the individual sorbates; these include potentials from the TraPPE force field for most sorbates.

Potential of polarizable force fields for predicting the separation performance of small hydrocarbons in M-MOF-74.

The separation of light olefins from paraffins via cryogenic distillation is a very energy intensive process. Solid adsorbents and especially metal-organic frameworks with open metal sites have the potential to significantly lower the required energy. Specifically, M-MOF-74 has drawn considerable attention for application in olefin/paraffin separation. To investigate how the separation proceeds on a molecular level and to design better materials, molecular simulation can be a useful tool. Unfortunately, it is still a challenge to model the adsorption behavior of many adsorbates in metal-organic frameworks with open metal sites. Previously, the inclusion of explicit polarization has been suggested to improve the quality of classical force fields for such systems. Here, the potential of polarizable force fields for the description of olefins and paraffins in metal-organic frameworks with open metal sites is investigated. In particular, heats of adsorption, binding geometries, and adsorption isotherms are calculated for C2H4, C2H6, C3H6, and C3H8 in M-MOF-74 (with M = Co, Mn, Fe, and Ni). In this study, no force field parameters are adjusted to improve the model. The results show that including explicit polarization significantly improves the description of the adsorption in comparison to non-polarizable generic force fields which do not consider explicit polarization. The study also reveals that simulation predictions are sensitive to the assigned repulsive potential and framework charges. A fully re-parametrized polarizable force field may have the capability to improve the predictions even further.

HYDROPHOBE Challenge: A Joint Experimental and Computational Study on the Host-Guest Binding of Hydrocarbons to Cucurbiturils, Allowing Explicit Evaluation of Guest Hydration Free-Energy Contributions.

The host-guest complexation of hydrocarbons (22 guest molecules) with cucurbit[7]uril was investigated in aqueous solution using the indicator displacement strategy. The binding constants (103-109 M-1) increased with guest size, pointing to the hydrophobic effect and dispersion interactions as driving forces. The measured affinities provide unique benchmark data for the binding of neutral guest molecules. Consequently, a computational blind challenge, the HYDROPHOBE challenge, was conducted to allow a comparison with state-of-the-art computational methods for predicting host-guest affinity constants. In total, three quantum-chemical (QM) data sets and two explicit-solvent molecular dynamics (MD) submissions were received. When searching for sources of uncertainty in predicting the host-guest affinities, the experimentally known hydration energies of the investigated hydrocarbons were used to test the employed solvation models (explicit solvent for MD and COSMO-RS for QM). Good correlations were obtained for both solvation models, but a rather constant offset was observed for the COSMO data, by ca. +2 kcal mol-1, which was traced back to a required reference-state correction in the QM submissions (2.38 kcal mol-1). Introduction of the reference-state correction improved the predictive power of the QM methods, particularly for small hydrocarbons up to C5.

Triptycene-Based Microporous Cyanate Resins for Adsorption/Separations of Benzene/Cyclohexane and Carbon Dioxide Gas.

Triptycene-based cyanate monomers 2,6,14-tricyanatotriptycene (TPC) and 2,6,14-tris(4-cyanatophenyl)triptycene (TPPC) that contain different numbers of benzene rings per molecule were synthesized, from which two microporous cyanate resins PCN-TPC and PCN-TPPC were prepared. Of interest is the observation that the two polymers have very similar porosity parameters, but PCN-TPPC uptakes considerably higher benzene (77.8 wt %) than PCN-TPC (17.6 wt %) at room temperature since the higher concentration of phenyl groups in PCN-TPPC enhances the π-π interaction with benzene molecules. Besides, the adsorption capacity of benzene in PCN-TPPC is dramatically 7 times as high as that of cyclohexane. Contrary to the adsorption of organic vapors, at 273 K and 1.0 bar, PCN-TPC with more heteroatoms in the network skeleton displays larger uptake of CO2 and higher CO2/N2 selectivity (16.4 wt %, 60) than those of PCN-TPPC (14.0 wt %, 39). The excellent and unique adsorption properties exhibit potential applications in the purification of small molecular organic hydrocarbons, e.g., separation of benzene from benzene/cyclohexane mixture as well as CO2 capture from flue gas. Moreover, the results are helpful for deeply understanding the effect of porous and chemical structures on the adsorption properties of organic hydrocarbons and CO2 gas.

Enhanced effects of large-scale CO 2 transportation on oil accumulation in oil-gas-bearing basins — Implications from supercritical CO 2 extraction of source rocks and a typical case study

Abstract Large-scale mantle-derived CO2 emplacement and co-accumulation of CO2 and crude oil have been discovered in oil-gas bearing basins in eastern China and many other areas worldwide. To investigate the effect of the natural supercritical CO2 on the migration of crude oil as well as on the formation of oil reservoirs, experiments on supercritical CO2 extraction (SCE) and traditional chloroform extraction (CE) of hydrocarbon source rocks were carried out and the geochemical characteristics of the Huangqiao CO2-oil reservoir in the Subei Basin, eastern China were investigated. The SCE yielded a large proportion of the hydrocarbons in the Permian mudstone source rocks at 110 °C under 30 MPa. Compared with the traditional chloroform extraction (CE), the SCE-retrieved organic compounds are dominated by saturated hydrocarbons and contain a relatively higher concentration of small molecular mass compounds. Many wells in the Huangqiao reservoir yielded large amounts of CO2 from several formations, such as the Triassic Qinglong Formation (T1q) and the Permian Longtang Formation (P2l). Accompanying the CO2 flow, a certain amount of oil is commonly recovered. The oil is mainly light oil or condensate oil with a relative density of 0.7933–0.8308, and it contains 90.06–97.37% saturated hydrocarbons. Compared with hydrocarbons in the Permian source rocks, the oil accompanying the CO2 in the Huangqiao reservoir contains more C20- hydrocarbons and less C21+ hydrocarbons. The oil accompanying the CO2 has a similar composition to the SCE extracts from the source rocks, namely, both contain a relatively high concentration of low molecular mass hydrocarbons. Therefore, it can be concluded that, in the Huangqiao area, during movement upward along deep faults and fractures or flow through source rocks, the deep supercritical CO2 naturally extracted hydrocarbons, especially small molecular hydrocarbons, from the source rocks, and then brought them to the shallow strata to form the CO2-oil coupling reservoirs.

Technology Focus: Offshore Production and Flow Assurance (November 2017)

Technology Focus Flow assurance and mitigation technical concerns are some of the more critical components in the engineering, design, cost, and operation of offshore production facilities. While gas-hydrate handling typically dominates the thermo-hydraulic design, the mitigation of waxes, emulsions, asphaltenes, corrosion, scale, and salt; solids handling; slugging; and operability of tubing, surface chokes, and pipelines are all challenging issues that demand attention and consider-able technical effort. Among these challenges, paraffin deposition (interchangeable with wax) in pipelines has gained importance in flow assurance. Reliable wax-deposition-prediction models based on specially designed flow-loop experiments are an available mitigation option. Alternative internal pipeline/flowline coatings or materials present another option to address flow-assurance problems. Addressing these challenges requires thorough technical investigation and development of advanced transient modeling. The three papers here discuss slightly different approaches to production continuity and oil/gas fluid-production assurance. All three have been scaled up either to demonstration stage or to actual field implementation and use. Subsea production faces both fluid and flow-based challenges that eventually lead to shutdown, safety concerns, or flow intermittency in production. The oil/gas production pipelines typically operate at a high Reynolds number and low-wall-shear-stress conditions; however, current wax-deposition models are based on laboratory flow-loop data obtained at low Reynolds number and high shear stress. Paper OTC 27757 discusses a present study that decouples the effect of the hydrodynamic parameters with specially designed flow-loop experiments. From the results, the Reynolds-number effects are more dominant on the deposited-wax-mass density compared with the shear stress and aid in scaleup from the laboratory to field conditions. Gas hydrates typically form at high-pressure and low-temperature conditions where free water and small hydrocarbon molecules exist together in sufficient concentrations. Once these thermodynamic conditions occur in oil/gas production flowlines/pipelines, solid hydrate plugs that greatly restrict flow usually form. One potential hydrate-mitigation technique involves using a low-adhesion, protective-surface internal coating to inhibit deposition. Paper OTC 27874 describes a study evaluating two different coatings, one a superhydrophobic, anti-icing coating and one an omniphobic and corrosion-resistant coating. Hydrate/ surface interactions were studied using micromechanical-adhesion-force measurements in both liquid and gas bulk phases. The initial results suggest that the use of these coatings may be an effective mitigation technique at low water content and in significantly corroded flowlines. The third paper presents the flow-assurance challenges and associated mitigation steps implemented in the high-pressure/high-temperature North Kuwait Jurassic (NKJ) fields. An offline transient-model adviser was built to mimic the hydrate mechanism and optimize the methanol injection. Paper SPE 182237 discusses the traditional methods of hydrate mitigation performed in the NKJ fields and the way the transient model was initially built and continually improved with more data. Currently, methanol is used for hydrate inhibition and an antiagglomerate is under trial. Mitigation of flow-assurance problems continues to drive new production-technology applications and approaches. The three papers highlighted here focus on minimizing costs while providing safe, effective, and reliable operations. I hope you find them as interesting as I did, and I greatly appreciate the opportunity to offer these new options to you in this and future Focus sections. Recommended additional reading at OnePetro: www.onepetro.org. SPE 181560 A Pigging Model for Wax Removal in Pipes by Qiyu Huang, China University of Petroleum, et al. SPE 183055 Multiphase-Flowmeter Performance: A Critical Piece of an Offshore-Well-Management Toolkit by V.U. Okotie, Abu Dhabi Marine Operating Company, et al.

TG-MS-FTIR study on pyrolysis behavior of superfine pulverized coal

Superfine pulverized coal as a new energy utilization method plays a significant role in alleviating pollutant emissions. The devolatilization behavior of superfine pulverized coal during pyrolysis was examined using TG-MS-FTIR. Gaseous products and mass loss were measured simultaneously. The results detected by MS are in good consistency with those obtained from FTIR. Mass loss is mainly caused by the release of moisture, decomposition of macromolecular, and polycondensation of aromatic. And NMG coal, with lower degree of coalification, has larger weight loss than HN coal. The main gaseous products are light hydrocarbons, such as small molecular alkane and unsaturated hydrocarbons, carbon monoxide, carbon dioxide and hydrogen. For both coals, as the particle size decrease, the release rate of CH4 increases initially then decreases. In addition, the influence of particle size and coal rank on the release characteristic of gaseous products is discussed in the work. The results provide new insights into the effect of particle size on gaseous products during pyrolysis, and are helpful for studying the variation of physicochemical properties during the comminution process.

Effect of Aldehyde and Carboxyl Functionalities on the Surface Chemistry of Biomass-Derived Molecules.

The adsorption and decomposition of acetaldehyde and acetic acid were studied on Rh(100) to gain insight into the interaction of aldehyde and carboxyl groups of biomass-derived molecules with the surface. Temperature-programmed reaction spectroscopy (TPRS) was used to monitor gaseous reaction products, whereas Reflection absorption infrared spectroscopy (RAIRS) was used to determine the nature of surface intermediates and reaction paths. The role of adsorbate interactions in oxygenate decomposition chemistry was also investigated by varying the surface coverage. Acetaldehyde adsorbs in an η2(C, O) configuration for all coverages, where the carbonyl group binds to the surface via the C and O atoms. Decomposition occurs below room temperature (180-280 K) via C-H and C-C bond breaking, which releases CO, H, and CHx species on the surface. At low coverage, CHx dehydrogenation dominates and surface carbon is produced alongside H2 and CO. At high coverage, about 60% of the CHx hydrogenates to form methane, whereas only 40% of the CHx decomposes further to surface carbon. Acetic acid adsorbs dissociatively on the Rh(100) surface via O-H bond scission, forming a mixture of mono- and bidentate acetate. The decomposition of acetate proceeds via two different pathways: (i) deoxygenation via C-O and C-C bond scissions and (ii) decarboxylation via C-C bond scission. At low coverage, the decarboxylation pathway dominates, a process that occurs at slightly above room temperature (280-360 K) and produces CO2 and CHx, where the latter decomposes further to surface carbon and H2. At high coverage, both decarboxylation and deoxygenation occur, slightly, above room temperature (280-360 K). The resulting O adatoms produced in the deoxygenation path react with surface hydrogen or CO to form water and CO2, respectively. The CHx species dehydrogenate to surface carbon for all coverages. Our findings suggest that oxygenates with a C═O functionality and an alkyl end react on the Rh(100) surface to produce synthesis gas and small hydrocarbons whereas CO2 and synthesis gas are produced when oxygenates with a COOH functionality and an alkyl end react with the Rh(100) surface. For both cases, carbon accumulation occurs on the surface.

Development of a ReaxFF Force Field for Cu/S/C/H and Reactive MD Simulations of Methyl Thiolate Decomposition on Cu (100).

It has been shown that the rate of decomposition of methyl thiolate species on copper is accelerated by sliding on a methyl thiolate covered surface in ultrahigh vacuum at room temperature. The reaction produces small gas-phase hydrocarbons and deposits sulfur on the surface. Here, a new ReaxFF potential was developed to enable investigation of the molecular processes that induce this mechanochemical reaction by using density functional theory calculations to tune force field parameters for the model system. Various processes, including volumetric expansion/compression of CuS, CuS2, and Cu2S unit cells; bond dissociation of Cu-S and valence angle bending of Cu-S-C; the binding energies of SCH3, CH3, and S atoms on a Cu surface; and energy for the decomposition of methyl thiolate molecular species on copper, were used to identify the new ReaxFF parameters. Molecular dynamics simulations of the reactions of adsorbed methyl thiolate species at various temperatures were performed to demonstrate the validity of the new potential and to study the thermal reaction pathways. It was found that reaction is initiated by C-S bond scission, consistent with experiments, and that the resulting methyl species diffuse on the surface and combine to desorb ethane, also as found experimentally.

Laser diagnostics and chemical kinetic analysis of PAHs and soot in co-flow partially premixed flames using diesel surrogate and oxygenated additives of n-butanol and DMF

Effects of oxygenated fuels on soot reduction strongly depend on the base fuel. Interesting candidates from oxygenated fuels in this respect include both n-butanol and 2,5-dimethylfuran (DMF), because they have already been used in diesel engines recently. However, information is rather limited on n-butanol and DMF added into a diesel fuel surrogate in fundamental flames to investigate the mechanism of soot reduction. In the current work, both n-butanol and DMF was successively added into diesel surrogate (80% n-heptane and 20% toluene in volume, named as T20) in co-flow partially premixed flames. The effects of different oxygenated structures on polycyclic aromatic hydrocarbons (PAHs) and soot were investigated at the same oxygen weight fractions of 4% and the same volume fractions of 20%. The diagnostics on PAHs, soot volume fractions and soot sizes were conducted by using both laser-induced fluorescence (LIF) and two-color laser-induced incandescence (2C-LII). A combined detailed kinetic model (n-heptane/toluene/butanols/DMF/PAHs) has been obtained in order to clarify the chemical effects of the different oxygenated fuels on PAHs formation. Results show that the reduced toluene content due to the addition of oxygenated fuels is the dominant factor for the reduction of soot, as compared with the base fuel of T20. The oxygenated structure of n-butanol has a higher ability to reduce PAHs and soot as compared with the addition of DMF. This is due to the fact that the consumption of DMF leads to much formation of C5H5 which enhances the formation of PAHs and subsequent soot. However, the formation of PAHs can be inhibited remarkably as blending n-butanol because only small hydrocarbons like C2H2 and C3H3 etc. are formed. The formation rate of A4 is more similar to that of soot in comparison with the smaller ring aromatics. For the size of soot particles, the distribution range is shrunk from 19–70 nm for T20 to 20–40 nm for the addition of oxygenated fuels. As compared to the effects of oxygenated structures, DMF20 presents a little wider distribution on soot sizes than that of B16.8. Some larger soot particles are detected in DMF20 flame but cannot be found in B20 flame.

Evidence of Organic Luminescent Centers in Sol–Gel‐Synthesized Yttrium Aluminum Borate Matrix Leading to Bright Visible Emission

Yttrium aluminum borate (YAB) powders prepared by sol-gel process have been investigated to understand their photoluminescence (PL) mechanism. The amorphous YAB powders exhibit bright visible PL from blue emission for powders calcined at 450 °C to broad white PL for higher calcination temperature. Thanks to 13 C labelling, NMR and EPR studies show that propionic acid initially used to solubilize the yttrium nitrate is decomposed into aromatic molecules confined within the inorganic matrix. DTA-TG-MS analyses show around 2 wt % of carbogenic species. The PL broadening corresponds to the apparition of a new band at 550 nm, associated with the formation of aromatic species. Furthermore, pulsed ENDOR spectroscopy combined with DFT calculations enables us to ascribe EPR spectra to free radicals derived from small (2 to 3 rings) polycyclic aromatic hydrocarbons (PAH). PAH molecules are thus at the origin of the PL as corroborated by slow afterglow decay and thermoluminescence experiments.

Evidence of Organic Luminescent Centers in Sol–Gel‐Synthesized Yttrium Aluminum Borate Matrix Leading to Bright Visible Emission

AbstractYttrium aluminum borate (YAB) powders prepared by sol–gel process have been investigated to understand their photoluminescence (PL) mechanism. The amorphous YAB powders exhibit bright visible PL from blue emission for powders calcined at 450 °C to broad white PL for higher calcination temperature. Thanks to 13C labelling, NMR and EPR studies show that propionic acid initially used to solubilize the yttrium nitrate is decomposed into aromatic molecules confined within the inorganic matrix. DTA‐TG‐MS analyses show around 2 wt % of carbogenic species. The PL broadening corresponds to the apparition of a new band at 550 nm, associated with the formation of aromatic species. Furthermore, pulsed ENDOR spectroscopy combined with DFT calculations enables us to ascribe EPR spectra to free radicals derived from small (2 to 3 rings) polycyclic aromatic hydrocarbons (PAH). PAH molecules are thus at the origin of the PL as corroborated by slow afterglow decay and thermoluminescence experiments.