Oxidative coupling of methane over strontium-doped neodymium oxide: Parametric evaluations

Since its discovery in 1982, oxidative coupling of methane (OCM) has been considered one of the most promising approaches for the on-purpose synthesis of ethylene. The development of more selective catalysts is essential to improve process economics. In this work, undoped neodymium oxide as well as neodymium oxide doped with high (20%) and low (2.5%) levels of strontium were tested in a high-throughput fashion covering a wide range of operating conditions. The catalysts were shown to be able to achieve greater than 18% C₂+ yield. Space velocity was shown to play a significant role in C₂+ selectivity. For a methane to oxygen feed ratio of 3.5, selectivity increased with increasing space velocity, reaching a maximum of 62% at a methane conversion of 30% at an optimal space velocity of ~250,000 ml/h/g. The difference in activity between the three samples was linked to the contribution of different oxygen centers.     

Metathesis of 1‐Hexene over Heterogeneous Tungsten‐Based Catalysts

1‐Hexene metathesis was performed over standard and potassium‐doped WO₃/SiO₂ catalysts. The samples were tested at various reaction temperatures, molar feed compositions, and space times. Under the applied reaction conditions, doping with potassium reduced the isomerization and cracking activity of the catalyst by at least half and improved the yield of detergent‐range alkenes twofold. However, increasing the potassium loading to a higher amount resulted in a significant reduction in the metathesis activity as both Brønsted and Lewis acid sites were affected. Optimum operating conditions for the yield of detergent‐range alkenes were identified using response surface methodology.     

Effect of a chemical synthesis‐based pharmaceutical wastewater on performance,acetoclastic methanogenic activity and microbial population in an upflow anaerobic filter

The performance of an upflow anaerobic filter (UAF) treating a chemical synthesis‐based pharmaceutical wastewater was evaluated under various operating conditions. During start‐up, the UAF was initially fed by glucose till an organic loading rate (OLR) of approximately 7.5 kg COD m^?3 day^?1 with a hydraulic retention time of 2.3 days. A soluble COD removal efficiency of 98% was achieved before the addition of the wastewater. Initially, the filter inertia was acclimatized to the wastewater by sequential feeding of 10% (w/v), 30% (w/v) and 70% (w/v) of the pre‐aerated wastewater mixed with glucose followed by a 100% (w/v) pre‐aerated wastewater. During the operation, the COD removal efficiency and methane yield decreased to 75% and 0.30 m³ CH₄ kg^?1 COD_removed respectively. As the UAF became accustomed to the pre‐aerated wastewater, raw wastewater was fed in increasing ratios of 20% (w/v), 60% (w/v) and 80% (w/v) with the pre‐aerated wastewater as the remaining part. During this stage of the operation, a COD removal efficiency in a range of 77–86% was achieved and the methane yield decreased to 0.24 m³ CH₄ kg^?1 COD_removed. Finally, 100% (w/v) raw wastewater was fed and a COD removal efficiency of 65% was achieved with a methane yield of 0.20 m³ CH₄ kg^?1 COD_removed. At the end of the operation, acetoclastic methanogenic activity was only measured in the bottom section of the UAF, this showed a 90% reduction in comparison with activity of inoculation sludge. Microscopic examinations revealed that rod‐shaped methanogens remained as the dominant species whereas Methanosarcina‐like species and filaments were present only in insignificant numbers along the UAF. © 2002 Society of Chemical Industry     

Copolymerization of ethylene/5‐ethylidene‐2‐norbornene with bis (2‐phenylindenyl) zirconium dichloride catalyst: I. Optimization of the operating conditions by response surface methodology

In this study, the copolymerization of ethylene with nonconjugated diene (5‐ethylidene‐2‐norbornene) was carried out with a bis(2‐PhInd) ZrCl₂ metallocene catalyst. Some polymerization factors that were considered affective on the catalyst activity, including comonomer content in the feed, ethylene pressure, and polymerization temperature, were investigated via response surface methodology to determine the optimum polymerization conditions. We found that the comonomer content in the feedstock had no enormous effect on the catalyst activity depression. Also, the polymerization temperature increment through the scrutinized range decreased the copolymerization activity. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis and properties of novel organosoluble bismaleimides and polyaspartimides containing bis(4‐maleimido‐3, 5‐dimethyl phenyl) halo phenyl methane

A series of bismaleimides was synthesized from bis(4‐amino‐3, 5‐dimethylphenyl) (X) phenyl methane (X = 3′chloro, 3′‐bromo, 3′‐benzyloxy, 4′‐chloro, 4′‐fluoro) and maleic anhydride. The bismaleimides were subsequently polymerized with various diamines by Michael addition to yield novel polyaspartimides. All the polymers exhibited good solubility in organic solvents and the inherent viscosity of the polymers were in the range of 0.40–0.56 dL/g, which is good enough to fabricate composites and films. The temperature at which 10% weight loss occurred was in the range of 390–441°C. The polymers had high glass transition temperature in the range of 205–275°C and left about 31.95–84.20% char yield at 800°C indicating that they have good self‐extinguishing property. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Modification of bismaleimide resin by poly(ethylene phthalate‐co‐ethylene terephthalate), poly(ethylene phthalate‐co‐ethylene 4,4′‐biphenyl dicarboxylate), and poly(ethylene phthalate‐co‐ethylene 2,6‐naphthalene dicarboxylate)

Aromatic polyesters were prepared and used to improve the brittleness of bismaleimide resin, composed of 4,4′‐bismaleimidodiphenyl methane and o,o′‐diallyl bisphenol A (Matrimid 5292 A/B resin). The aromatic polyesters included PEPT [poly(ethylene phthalate‐co‐ethylene terephthalate)], with 50 mol % of terephthalate, PEPB [poly(ethylene phthalate‐co‐ethylene 4,4′‐biphenyl dicarboxylate)], with 50 mol % of 4,4′‐biphenyl dicarboxylate, and PEPN [poly(ethylene phthalate‐co‐ethylene 2,6‐naphthalene dicarboxylate)], with 50 mol % 2,6‐naphthalene dicarboxylate unit. The polyesters were effective modifiers for improving the brittleness of the bismaleimide resin. For example, inclusion of 15 wt % PEPT (MW = 9300) led to a 75% increase in fracture toughness, with retention in flexural properties and a slight loss of the glass‐transition temperature, compared with the mechanical and thermal properties of the unmodified cured bismaleimide resin. Microstructures of the modified resins were examined by scanning electron microscopy and dynamic viscoelastic analysis. The toughening mechanism was assessed as it related to the morphological and dynamic viscoelastic behaviors of the modified bismaleimide resin system. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2352–2367, 2001     

Gas Hydrate Formation by Methane‐Helium Mixtures

Equilibrium conditions for gas hydrates formed by methane‐helium mixtures with helium concentrations of 31.9, 63.9, and 74.6 mol.‐% have been studied at pressures up to 160 bar. The data obtained indicate that in the studied range of helium concentrations and pressures helium hardly contributes to the stability of the gas hydrate formed. The shift of equilibrium conditions to lower temperatures and higher pressures is caused by dilution of methane in the gas phase and, consequently, the decrease in the chemical potential of methane in the gas phase.     

High-yield synthesis of carbon nano-onions in counterflow diffusion flames

High-yield synthesis of carbon nanotubes (CNTs) and nano-onions (CNOs) on a catalytic nickel substrate using counterflow diffusion flames was investigated. With ethylene fixed at 5%, methane varied from 15% to 45% in the upper flow, and air supplied in the lower flow, only a moderate CH₄ concentration (25%) could yield high density CNTs. However, when oxygen was increased to 50% in the lower flow, only CNOs were synthesized. An increase in methane concentration from 15% to 45% led to a higher yield and a greater diameter (ranging from 5 to 60 nm) of CNOs. To examine the role of mixed fuel, it was observed that as ethylene was removed and only 45% methane and nitrogen were supplied in the upper flow, no CNOs could be generated. While, as methane was increased to 50% or 55%, high-yield CNOs were synthesized and the yield increased with methane concentration. Note that the key parameters influencing the formation and yield of CNOs are both the oxygen and fuel concentrations. There was a critical threshold value of oxygen concentration, 30%, for onset of CNOs synthesis. Also, the critical threshold value of methane concentration for onset of CNOs formation decreased with increasing oxygen concentration or ethylene concentration.     

Amphiphilic linear–hyperbranched polymer poly(ethylene glycol)–branched polyethylenimine–poly(ϵ‐caprolactone): synthesis,self‐assembly and application as stabilizer of platinum nanoparticles

Amphiphilic linear–hyperbranched polymer poly(ethylene glycol)–branched polyethylenimine–poly(?‐caprolactone) (PEG‐PEI‐PCL) was synthesized by progressively conjugating PEG (one chain) and PCL (multi‐chains) to PEI (hyperbranched architecture) with a yield of 87%. PEG‐PEI‐PCL forms nano‐sized uniform spherical micelles by self‐assembly in water. The micelles had an average diameter of 56 nm determined using dynamic light scattering and 35 nm observed from transmission electron microscopy images. PEG‐PEI‐PCL was used as a stabilizer of platinum nanoparticles (PtNPs) for the first time. The particle diameter of PEG‐PEI‐PCL‐stabilized PtNPs was 7.8 ± 1.4 nm. Amphiphilic (hydrophilic–hydrophilic–hydrophobic) and hyperbranched (linear–hyperbranched–grafted) structures enabled PtNPs to effectively stabilize and disperse in liquid‐phase synthesis. The highly disperse PtNPs in PEG‐PEI‐PCL micelles improved the catalytic activity for the reduction of 4‐nitrophenol with a catalytic yield of near 100%. © 2016 Society of Chemical Industry     

Hydrogenation of dimethyl oxalate to ethylene glycol over mesoporous Cu‐MCM‐41 catalysts

The synthesis and utilization of mesoporous Cu‐MCM‐41 catalysts for hydrogenation of dimethyl oxalate to ethylene glycol is described in this article. Physicochemical properties of these Cu‐MCM‐41 catalysts have been investigated by N₂‐physisorption, X‐ray diffraction, inductively coupled plasma, N₂O titration, transmission electron microscopy, temperature programmed reduction, Fourier transform infrared spectroscopy, and X‐ray photoelectron spectroscopy. It was found that the copper loading significantly influenced the pore structure and copper surface area of the catalyst. High catalytic performance is obtained over a 20Cu‐MCM‐41 catalyst with a full DMO conversion and EG yield of 92% at a LHSV of 3.0 h^?1. The catalytic performance of optimized 20Cu‐MCM‐41 catalyst could be attributed to the fine copper dispersion and large copper surface areas. © 2013 American Institute of Chemical Engineers AIChE J, 59: 2530–2539, 2013     

Synthesis and characterization of biodegradable block copolymers of poly(propylene fumarate‐co‐sebacate)‐co‐poly(ethylene glycol) and poly(ethylene fumarate‐co‐sebacate)‐co‐poly(ethylene glycol)

The synthesis of two low molecular weight linear unsaturated oligoester precursors, poly(propylene fumarate‐co‐sebacate) (PPFS) and poly(ethylene fumarate‐co‐sebacate) (PEFS), are described. PPFS, PEFS, and poly(ethylene glycol) are then used to prepare poly(propylene fumarate‐co‐sebacate)‐co‐poly(ethylene glycol) (PPFS‐co‐PEG) and poly(ethylene fumarate‐co‐sebacate)‐co‐poly(ethylene glycol) (PEFS‐co‐PEG) block copolymers. The products thus obtained are investigated in terms of the molecular weight, composition, structure, thermal properties, and solubility behavior. A number of design parameters including the molecular weights of PPFS, PEFS, and PEG, the reaction time in the polymer synthesis, and the weight ratio of PEG to PPFS or to PEFS are varied to assess their effects on the product yield and properties. The hydrolytic degradation of PPFS‐co‐PEG and PEFS‐co‐PEG in an isotonic buffer (pH 7.4, 37°C) is investigated, and it is found that the fumarate ester bond cleaves faster than does the sebacate ester bond. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 295–300, 2004     

Fixed‐Bed Multi‐Tubular Reactors for Oxidative Dehydrogenation in Ethylene Process

An industrial‐scale reactor for ethylene production was modeled using the oxidative dehydrogenation of ethane (ODHE) in a multi‐tubular reactor system, examining a variety of parameters affecting reactor performance. The model showed that a double‐bed multi‐tubular reactor with intermediate air injection scheme was superior to a single‐bed design, due to the increased ethylene selectivity while operating under lower oxygen partial pressures. The optimized reactor length for 100 % oxygen conversion was theoretically determined for both reactor designs. The use of a distributed oxygen feed with a limited number of injection points indicated a significant improvement on the reactor performance in terms of ethane conversion and ethylene selectivity. This concept also overcame the reactor runaway temperature problem and enabled operations over a wider range of conditions to obtain enhanced ethylene production.     

Synthesis Gas and Zinc Production in a Noncatalytic Packed‐Bed Reactor

A noncatalytic packed‐bed reactor has been constructed for management of the reduction of ZnO by methane, which leads to co‐production of synthesis gas and zinc. The reactor consisted of a simple vertical pipe filled with ZnO pellets. These pellets underwent reaction with a pure methane flow. Experimental tests were conducted in the temperature range 860–995 °C at atmospheric pressure in an electrically heated reactor. The results showed complete chemical conversion of methane to synthesis gas in the aforementioned temperature range. In addition, analysis of the product solids indicated that the collected solids in the outlet of the reactor were entirely zinc. The maximum methane flow rates (149–744 mL min^–1) were adjusted to ensure complete chemical conversion of methane. These adjustments were performed for different bed heights at various operating temperatures. Analysis of the product gases revealed high quality synthesis gas production without the influence of methane cracking or other undesired side reactions in the experimental tests. Finally, the governing partial differential equations of the reactor modeling were solved by the finite element method. Consequently, the gaseous profiles along the reactor and the breakthrough curves were predicted and compared with the experimental tests.     

Dual Effect of Low‐Dosage Poly(Ethylene Oxides) on Methane Hydrate Formation

Time‐dependent isochoric formation of methane hydrate was investigated in the presence of low‐dose poly(ethylene oxides) (PEOs). The effect of different molecular weights of PEO on methane hydrate nucleation time and storage capacity was studied and compared. Kinetic measurements revealed a dual effect of PEO, including inhibition and stabilization effects, on methane hydrate formation. The nature and type of the effect arises from the difference in molecular weights and concentration ranges of PEOs. These parameters directly affect the nucleation time and storage capacity of methane hydrate. Generally, in comparison with pure water, PEO improved the storage capacity of methane hydrate. PEO (1000 kD) at a concentration of 0.5 wt % exhibits a significant kinetic inhibitory performance. However, it was an efficient low‐dosage hydrate stabilizer at a concentration of 0.25 wt %, along with producing gas‐rich methane hydrate suitable for gas fuel storage and transportation.     

Effect of dynamic crosslinking on tensile yield behavior of polypropylene/ethylene‐propylene‐diene rubber blends

Tensile yield behavior of the blends of polypropylene (PP) with ethylene‐propylene‐diene rubber (EPDM) is studied in blend composition range 0–40 wt % EPDM rubber. These blends were prepared in a laboratory internal mixer by simultaneous blending and dynamic vulcanization. Vulcanization was performed with dimethylol phenolic resin. For comparison, unvulcanized PP/EPDM blends were also prepared. In comparison to the unvulcanized blends, dynamically vulcanized blends showed higher yield stress and modulus. The increase of interfacial adhesion caused by production of three‐dimensional network is considered to be the most important factor in the improvement. It permits the interaction of the stress concentrate zone developed at the rubber particles and causes shear yielding of the PP matrix. Systematic changes with varying blend composition were found in stress‐strain behavior in the yield region, viz., in yield stress, yield strain, width of yield peak, and work of yield. Analysis of yield stress data on the basis of the various expressions of first power and two‐thirds power laws of blend compositions dependence and the porosity model led to consistent results from all expression about the variation of stress concentration effect in both unvulcanized and vulcanized blend systems. Shapes and sizes of dispersed rubber phase (EPDM) domains at various blend compositions were studied by scanning electron microscopy. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 2104–2121, 2000     

Oxidative Dehydrogenation of Ethane Over Zirconia‐Supported Lithium Chloride Catalysts

A series of Li‐doped catalysts on zirconia or sulfated zirconia were prepared and investigated in the catalytic reaction of ethane oxidative dehydrogenation into ethylene. It is found that zirconia and sulfated zirconia supports prepared by different methods show varying nature and thus influence the catalytic performance of their supported Li catalysts in this reaction. Li catalysts doped on the sulfated zirconia prepared by a two‐step method can exhibit high ethane conversion, selectivity towards ethylene and ethylene yield as well as a stable catalytic performance. The Li precursors also affect the catalytic behavior. LiCl doped on sulfated zirconia can give high ethane conversion and ethylene selectivity. Addition of transitional and lanthanide metal oxides to the LiCl/SZ system significantly improves the activity and yield of ethylene in the oxidative dehydrogenation of ethane. Among the oxides studied, NiO and Nd₂O₃ demonstrate the best promoting effect in terms of catalytic conversion and ethylene yield.     

Gradient Composites of Alkaline Poly(6‐hexanelactam) with Graphite: One‐Step Synthesis,Structure, and Mechanical Properties

In a one‐step synthesis of gradient composites, molten monomer of 6‐hexanelactam was mixed with graphite (5 wt.‐%) and alkaline polymerization was performed under quasi‐isothermal conditions at about 170°C. The following initiator/activator system insensitive to traces of water and other low‐molecular‐weight compounds adsorbed on filler surface was used: the sodium salt was prepared through the reaction of sodium dicaprolactamobis(2‐methoxyethoxo)aluminate with 6‐hexanelactam; N‐acyllactam was formed in situ in molten monomer by solving flexible or rigid polyurethane foam consisting of either toluene diisocyanate or diphenylmethane‐4,4′‐diisocyanate, and a poly(propylene oxide) based polyol. To obtain gradient composites with a compositional variation between plane‐parallel surfaces, the incorporated filler underwent sedimentation due to gravity during initial stages of polymerization. The graphite‐free surface is suitable for treatment with adhesives, while the graphite‐rich surface layer (containing about 11 wt.‐% of graphite) possesses improved friction characteristics. Graphite slightly (i) reduces the polymer yield and the mean spherulite diameter; (ii) increases the crystallinity due to its nucleation activity; (iii) decreases the compliance, but does not affect its time dependence given by the matrix and (iv) reduces the yield strength, tensile strength and elongation at break. The friction coefficient of the graphite‐rich surface is reduced to almost 50% of that found for the graphite‐free surface; composites with cross‐linked matrix also show better wear properties.     

Penicillin Acylase‐Catalyzed Solid‐State Ampicillin Synthesis

The ability of immobilized penicillin acylase from E. coli to retain a remarkable catalytic activity in solid‐state systems has been demonstrated. Stabilization of immobilized penicillin acylase by inorganic salt hydrates allowed us to exploit nearly the whole catalytic activity of the enzyme at a very low water content. Using this technique, enzymatic synthesis of ampicillin in solid‐state systems was performed with high yields (up to 70% starting from equimolar mixture of reagents) and rates comparable to the corresponding values in homogeneous solutions and heterogeneous systems, “aqueous solution‐precipitate”. Peculiarities of the enzymatic solid‐state acyl transfer process, such as absence of the clear‐cut maximum on the ampicillin accumulation curves and dependence of the synthetic efficiency on the enzyme loading, have been observed. The space‐time yield of solid‐state enzymatic ampicillin synthesis was shown to be up to ten times higher compared to the homogeneous solutions and heterogeneous “aqueous solution‐precipitate” systems.     

Anaerobic digestion of waste activated sludge—comparison of thermal pretreatments with thermal inter‐stage treatments

BACKGROUND: Treatment methods for improved anaerobic digestion (AD) of waste activated sludge were evaluated. Pretreatments at moderate thermal (water bath at 80 °C), high thermal (loop autoclave at 130–170 °C) and thermo‐chemical (170 °C/pH 10) conditions prior to AD in batch vials (40 days/37 °C) were compared with inter‐stage treatments under the same conditions carried out between two separate steps of AD (19–21 days/37 °C). Combined treatment at 80 °C with CO₂/ NH₃‐stripping was also evaluated. RESULTS: Pretreatment at 80 °C had no effect on methane yield while inter‐stage treatment gave a 20% increase, compared with controls. Combining inter‐stage treatment with CO₂/ NH₃‐stripping gave an increase in pH (7.1 to 9.3), a drop in ammonia‐N concentration (910 mg‐N to 510 mg‐N) and a methane yield improvement of 31%. Pretreatment at 130 °C, 170 °C and 170 °C/pH 10 considerably increased the methane production within the first 4 days but the improvement following 40 days of digestion was only 13%, 9% and 2%, respectively. In comparison, inter‐stage treatment led to improvements of 9% (130 °C), 29% (170 °C) and 28% (170 °C/pH 10). All treatment processes increased sludge solubilization. CONCLUSION: Thermal treatment of waste activated sludge for improved anaerobic digestion seems more effective when applied as an inter‐stage treatment rather than a pretreatment. Copyright © 2010 Society of Chemical Industry     

Heterogeneous Palladium Catalysts Applied to the Synthesis of 2‐ and 2,3‐Functionalised Indoles

Heterogeneous palladium catalysts ([Pd(NH₃)₄]²⁺/NaY and [Pd]/SBA‐15) were applied to the synthesis of 2‐functionalised indoles, giving generally high conversions and selectivities (>89% yield) using only 1 mol % [Pd]‐catalyst under standard reaction conditions (polar solvent, 80 °C). For the synthesis of 2,3‐functionalised indoles by cross‐coupling arylation, the [Pd]/SBA‐15 catalyst was found to be particularly interesting, producing the expected compound with =35% yield after 12 days of reaction, which is comparable to the homogeneous catalyst, Pd(OAc)₂ (=48% yield). In the course of the study, the dual reactivity of the indole nucleus was demonstrated: aryl bromides gave clean C C coupling while aryl iodides led to a clean C N coupling.