Hydrate phase equilibrium and structure for (methane + ethane + tetrahydrofuran + water) system

The separation of methane and ethane through forming hydrate is a possible choice in natural gas, oil processing, or ethylene producing. The hydrate formation conditions of five groups of (methane + ethane) binary gas mixtures in the presence of 0.06 mole fraction tetrahydrofuran (THF) in water were obtained at temperatures ranging from (277.7 to 288.2) K. In most cases, the presence of THF in water can lower the hydrate formation pressure of (methane + ethane) remarkably. However, when the composition of ethane is as high as 0.832, it is more difficult to form hydrate than without THF system. Phase equilibrium model for hydrates containing THF was developed based on a two-step hydrate formation mechanism. The structure of hydrates formed from (methane + ethane + THF + water) system was also determined by Raman spectroscopy. When THF concentration in initial aqueous solution was only 0.06 mole fraction, the coexistence of structure I hydrate dominated by ethane and structure II hydrate dominated by THF in the hydrate sample was clearly demonstrated by Raman spectroscopic data. On the contrary, only structure II hydrate existed in the hydrate sample formed from (methane + ethane + THF + water) system when THF concentration in initial aqueous solution was increased to 0.10 mole fraction. It indicated that higher THF concentration inhibited the formation of structure I hydrate dominated by ethane and therefore lowered the trapping of ethane in hydrate. It implies a very promising method to increase the separation efficiency of methane and ethane.     

C2 and C3 hydrocarbon separations in poly(1,5-naphthalene-2,2′-bis(3,4-phthalic) hexafluoropropane) diimide (6FDA-1,5-NDA) dense membranes

The transport of olefin and paraffin namely ethane, ethylene, propane and propylene in aromatic poly(1,5-naphthalene-2,2′-bis(3,4-phthalic) hexafluoropropane) diimide (6FDA-1,5-NDA) dense membranes was investigated. The gas permeability coefficients were measured at pressures from 2.5 to 16 atm for the C₂ hydrocarbon gases and pressures up to 8.4 atm for C₃ systems at 35 °C. This membrane exhibits permeabilities of 0.15, 0.87, 0.023 and 0.24 Barrer with respect to pure ethane, ethylene, propane and propylene, and shows an ideal selectivity of 5.8 for the separation of ethylene/ethane, 10 for propylene/propane, 7.6 for nitrogen/ethane and 50 for nitrogen/propane. The olefins showed a preferred permeability to paraffins and discussion were drawn to the permeability, diffusivity and solubility coefficients. The activation energies of permeation, diffusion and solution were also reported and the effect of temperature on the permeation properties was discussed for the pure gas permeability data obtained from 30 to 50 °C. The plasticisation effect was also found for propane and propylene, respectively, although it was neither detected in the saturated nor unsaturated C₂ hydrocarbons at pressures up to 16 atm.     

Low-temperature performance of LiFePO4/C cathode in a quaternary carbonate-based electrolyte

The low-temperature performance of LiFePO₄/C cathode in a quaternary carbonate-based electrolyte (1.0 M LiPF₆/EC+DMC+DEC+EMC (1:1:1:3, v/v)) was studied. The discharge capacities of the LiFePO₄/C cathode were about 134.5 mAh/g (20 °C), 114 mAh/g (0 °C), 90 mAh/g (−20 °C) and 69 mAh/g (−40 °C) using a 1C charge–discharge rate. Cyclic voltammetry measurements show obviously sluggish of the lithium insertion–extraction process of the LiFePO₄/C cathode as the operation temperature falls below −20 °C. Electrochemical impedance analyses demonstrate that the sluggish of charge-transfer reaction on the electrolyte/LiFePO₄/C interface and the decrease of lithium diffusion capability in the bulk LiFePO₄ was the main performance limiting factors at low-temperature.     

Measurements of methane hydrate equilibrium in systems inhibited with NaCl and methanol

Natural gas hydrates are ice-like inclusion compounds that form at high pressures and low temperatures in the presence of water and light hydrocarbons. Hydrate formation conditions are favorable in gas and oil pipelines, and their formation threatens gas and oil production. Thermodynamic hydrate inhibitors (THIs) are chemicals (e.g., methanol, monoethylene glycol) deployed in gas pipelines to depress the equilibrium temperature required for hydrate formation. This work presents a novel application of a stepwise differential scanning calorimeter (DSC) measurement to accurately determine the methane hydrate phase boundary in the presence of THIs. The scheme is first validated on a model (ice + salt water) system, and then generalized to measure hydrate equilibrium temperatures for pure systems and 0.035 mass fraction NaCl solutions diluted to 0, 0.05, 0.10, and 0.20 mass fraction methanol. The hydrate equilibrium temperatures are measured at methane pressures from (7.0 to 20.0) MPa. The measured equilibrium temperatures are compared to values computed by the predictive hydrate equilibrium tool CSMGem.     

Partial oxidation of ethane to syngas in an oxygen-permeable membrane reactor

A perovskite-type oxide of Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ (BSCFO) with mixed electronic and oxygen ionic conductivity at high temperatures was used as an oxygen-permeable membrane. A tubular membrane of BSCFO made by extrusion method has been used in the membrane reactor to exclusively transport oxygen for the partial oxidation of ethane (POE) to syngas with catalyst of LiLaNiO/γ-Al₂O₃ at temperatures of 800–900 °C. After only 30 min POE reaction in the membrane reactor, the oxygen permeation flux reached at 8.2 ml cm⁻² min⁻¹. After that, the oxygen permeation flux increased slowly and it took 12 h to reach at 11.0 ml cm⁻² min⁻¹. SEM and EDS analysis showed that Sr and Ba segregations occurred on the used membrane surface exposed to air while Co slightly enriched on the membrane surface exposed to ethane. The oxygen permeation flux increased with increasing of concentration of C₂H₆, which was attributed to increasing of the driving force resulting from the more reducing conditions produced with an increase of concentration of C₂H₆ in the feed gas. The tubular membrane reactor was successfully operated for POE reaction at 875 °C for more than 100 h without failure, with ethane conversion of ∼100%, CO selectivity of >91% and oxygen permeation fluxes of 10–11 ml cm⁻² min⁻¹.     

Thermal stability of fatty acids in subcritical water

In this work, hydrolytic reaction conditions of various temperatures (300–370 °C) and times (0–30 min) at a constant pressure of 20 MPa were applied to the thermal decomposition of three kinds of fatty acids (FAs), stearic acid, oleic acid, and linoleic acid, in subcritical water. The degradation characteristics were investigated from the derived data, and the thermal stability of FAs in subcritical water was estimated. The primary reactions we observed were isomerization and pyrolysis of FAs. The main pathway of degradation was deduced by analyzing the contents of pyrolyzed products. We found that more saturated FAs have greater thermal stability in subcritical water. All FAs remained stable at 300 °C or below. Based on these results, we recommend that hydrolysis of vegetable oils and fats using subcritical water should be carried out below 300 °C (at 20 MPa) and for less than 30 min to obtain high-yield FA production.     

Solubility of carbon dioxide,methane, and ethane in 1-butanol and saturated liquid densities and viscosities

A designed pressure–volume–temperature (PVT) apparatus has been used to measure the (vapor + liquid) equilibrium properties of three binary mixtures (methane +, ethane +, and carbon dioxide + 1-butanol) at two temperatures (303 and 323) K and at the pressures up to 6 MPa. The solubility of the compressed gases in 1-butanol and the saturated liquid densities and viscosities were measured. In addition, the density and viscosity of pure 1-butanol were measured at two temperatures (303 and 323) K and at the pressures up to 10 MPa. The experimental results show that the solubility of the gases in 1-butanol increases with pressure and decreases with temperature. The dissolution of gases in 1-butanol causes a decline in the viscosity of liquid phase. The saturated liquid density follows a decreasing trend with the solubility of methane and ethane. However, the dissolution of carbon dioxide in 1-butanol leads to an increase in the density of liquid phase. The experimental data are well correlated with Soave–Redlich–Kwong (SRK) and Peng–Robinson (PR) equations of state (EOSs). SRK EOS was slightly superior for correlating the saturated liquid densities.     

Determination of Henry’s law constant of light hydrocarbon gases at low temperatures

The solubility of i-butane in water at the low temperatures was measured (274 K to 293 K). Additionally, Henry’s law constants of light hydrocarbons (methane, ethane, propane, i-butane, and n-butane) in water at the low temperatures are reported. A modified equation based on Krichevsky–Kasarnovsky equation is proposed to consider the effect of pressure and temperature on the equation parameters. Results show that Henry’s law constant of the selected components depends on temperature. It is deduced that pressure has a considerable effect on Henry’s law constant for methane, ethane, and propane, whereas this dependency for butanes is negligible.     

The electrochemical properties of thermophilic cytochrome P450 CYP119A2 at extremely high temperatures in poly(ethylene oxide)

The electrochemical measurements were carried out by using thermophilic cytochrome P450 CYP119A2 (P450st) modified with poly(ethylene oxide) (PEO) in PEO₂₀₀ as an electrochemical solvent. The PEO modified P450st gave clear reduction–oxidation peaks by cyclic voltammetry in oxygen-free PEO₂₀₀ up to 120 °C. The midpoint potential measured for the P450st was −120 mV vs. [Fe(CN)₆]⁴⁻/[Fe(CN)₆]³⁻ at 120 °C. The peak separation, ΔE, was 16 mV at 100 mV/s. The estimated electron transfer rate of PEO-P450st at 120 °C was 35.1 s⁻¹. The faster electron transfer reaction was achieved at higher temperatures. The electrochemical reduction of dioxygen was observed at 115 °C with the PEO-modified P450st system.     

New dicationic piperidinium hexafluorophosphate ILs,synthesis, characterization and dielectric measurements

A new class of dicationic ionic liquids (ILs) were synthesized for electrochemical applications at high temperatures. The syntheses are based on a dialkylation reaction of N-alkylpiperidine followed by anion exchange. The structures of ILs, based on piperidinium combined with hexafluorophosphate anion, were identified by using ¹H, ¹³C, ¹⁹F, ³¹P NMR and FT-IR spectroscopy. ILs’ thermal properties were investigated in the temperature range from −50 to 350 °C by using differential scanning calorimetry (DSC). In the frequency of 10⁻²–10⁶ Hz range, dielectric measurements were performed on ILs’ samples at various temperatures from −80 to 20 °C, i.e. around the glass transition temperature. The peak relaxation was observed near to this temperature. Also, the conductivity was investigated and the energy activation determined. The temperature dependence of the relaxation times was shown to be governed by the Arrhenius equation.     

Kinetic and thermodynamic behaviour of CF4 clathrate hydrates

This study presents experimental kinetic and thermodynamic data for CF₄ clathrate hydrates. Experimental measurements were undertaken in a high pressure equilibrium cell with a 40 cm³ inner volume. The measurements of experimental hydrate dissociation conditions were performed in the temperature range of (273.8 to 278.3) K and pressures ranging from (4.55 to 11.57) MPa. A thermodynamic model based on van der Waals and Platteeuw (vdW–P) solid solution theory was used for prediction and comparison of hydrate dissociation conditions and the Langmuir constant parameters for CF₄ based on Parrish and Prausnitz equation are reported. For the kinetics, the effect of initial pressure and temperature on the induction time, CF₄ hydrate formation rate, the apparent rate constant of reaction, storage capacity, and water to hydrate conversion during the hydrate formation were studied. Kinetic experiments were performed at initial temperatures of (275.3, 276.1 and 276.6) K and initial pressures of (7.08, 7.92, 9.11, 11.47 and 11.83) MPa. Results show that increasing the initial pressure at constant temperature decreases the induction time, while CF₄ hydrate formation rate, the apparent rate constant of reaction, storage capacity, and water to hydrate conversion increase. The same trends are observed with a decrease in the initial temperature at constant pressure.     

Characterization of the different fractions obtained from the pyrolysis of rope industry waste

A study of the possibilities of pyrolysis for recovering wastes of the rope's industry has been carried out. The pyrolysis of this lignocellulosic residue started at 250 °C, with the main region of decomposition occurring at temperatures between 300 and 350 °C. As the reaction temperature increased, the yields of pyrolyzed gas and oil increased, yielding 22 wt.% of a carbonaceous residue, 50 wt.% tars and a gas fraction at 800 °C. The chemical composition and textural characterization of the chars obtained at various temperatures confirmed that even if most decomposition occurs at 400 °C, there are some pyrolytic reactions still going on above 550 °C. The different pyrolysis fractions were analyzed by GC–MS; the produced oil was rich in hydrocarbons and alcohols. On the other hand, the gas fraction is mainly composed of CO₂, CO and CH₄. Finally, the carbonaceous solid residue (char) displayed porous features, with a more developed porous structure as the pyrolysis temperature increased.     

Enzymatic Extract Fractionation of (Cymbopogon winterianus Jowitt) Citronella through Supercritical Carbon dioxide (SC-CO2)

Cymbopogon winterianus Jowitt or citronella is said to be an insect repellant and usually planted in the yard in the Philippines. In this study enzymatic extracts of citronella were fractionated using supercritical carbon dioxide extraction to have different oil extracts in three different parameters, 10 megapascal (10 MPa), 20 megapascal (20 MPa) and 30 megapascal (30 MPa) at constant temperature at 40° Celsius. The highest oil yield is at 20 MPa with an average of 10.21 for three trials of extraction, followed by 10 MPa and 30 MPa with 4.89 and 2.15. Oil extract at 10 MPa was subjected to gas chromatography- mass spectrometry (GC-MS) and found four components in which 2-methyl-5-(1-methylethyl)bicycle hexan 2-ol or trans sabinene hydrate and 4-methanol-o-Menth-8-ene or elemol was the major compounds. The pure crude enzymatic extract, 20 MPa and 30 MPa supercritical carbon dioxide extracts were subjected to fatty acid profiling, twelve free fatty acid were found at pure crude enzymatic extract, while nine free fatty acid were found at 20 MPa and 30 MPa supercritical carbon dioxide extracts. Lauric (C12) is consistently highest in terms of weight by weight in three extracts that were subjected to free fatty acid profiling. This study can be used as basis for agricultural applications in food and pharmaceutical since there is no thorough study of the fractionation of enzymatic extract of citronella.     

Hydrate phase equilibrium in the system of (carbon dioxide + 2,2-dimethylbutane + water) at temperatures below freezing point of water

The four-phase equilibrium conditions of (vapor + liquid + hydrate + ice) were measured in the system of (CO₂ + 2,2-dimethylbutane + water). The measurements were performed within the temperature range (254.2 to 270.2) K and pressure range (0.490 to 0.847) MPa using an isochoric method. Phase equilibrium conditions of hydrate formed in this study were measured to be at higher temperatures and lower pressures than those of structure I CO₂ simple hydrate. The largest difference in the equilibrium pressures of structure I CO₂ hydrate and the hydrate formed in the present study was 0.057 MPa at T = 258.3 K. On the basis of the four-phase equilibrium data obtained, the quintuple point for the (ice + structure I hydrate + structure H hydrate + liquid + vapor) was also determined to be T = 266.4 K and 0.864 MPa. The results indicate that structure H hydrate formed with CO₂ and 2,2-dimethylbutane is stable exclusively at the temperatures below the quintuple temperature.     

The effect of temperature oscillation on the passive corrosion properties of Alloy 22

A temperature-oscillating heated electrode technique (TOHET) was developed for investigating the temperature effect on the passive corrosion properties of Alloy 22 (UNS N06022, Ni–22Cr–13Mo–3W–3Fe), which has been selected as the corrosion-resistant material (CRM) of the waste package outer barrier for the high level nuclear waste (HLNW) repository at Yucca Mountain, NV, USA. Cyclic and potentiostatic polarization tests were conducted on a temperature-controlled hot surface of Alloy 22, which was immersed in simulated Yucca Mountain ground waters. The current recorded during cyclic polarization tests was sensitive to temperature changes when the temperature amplitude was greater than 2 °C. Corrosion potential increased from −293 mV to −256 mV (Ag/AgCl) when temperature was decreased from 102 °C to 72 °C. Current variation was also observed during a potentiostatic test at −150 mV over which temperature oscillated between 65 °C and 95 °C. The log–linear plot of passive current density vs. temperature exhibited a linear relationship. In summary, the TOHET method is a valuable technique for studying the effects of temperature on the corrosion rate of passive alloys.     

Characteristics study of clear polymethylmethacrylate dosimeter,Radix W,in several kGy range

Basic characteristics of Radix W, a commercially available undyed polymethylmethacrylate (PMMA) dosimeter conventionally used by readout at 320 nm, were studied in the dose range of 0.5–8 kGy, for its wide application especially for the evaluation of the sterilization dose and the quality assurance of food irradiation. The characteristics of dose response, the effect of irradiation temperature, and its stability after irradiation were examined over candidate readout wavelengths of 270–320 nm. The dose response readout at shorter wavelength is higher than that at longer wavelength, and 280 nm is the suitable readout wavelength for measurement of dose range of 0.5–8 kGy. The post-irradiation stability of dose response for 6 kGy is less than 1% within 24 h after irradiation at an irradiation temperature of 20 °C. Dose response is higher with temperature at irradiation temperatures in the range of −40 to 20 °C.     

A simple method of electrochemical lithium intercalation within graphite from a propylene carbonate-based solution

Electrochemical lithium intercalation within graphite from 1 mol dm^− 3 solution of LiClO₄ in propylene carbonate (PC) was investigated at 25 and − 15 °C. Lithium ions were intercalated into and de-intercalated from graphite reversibly at − 15 °C despite the use of pure PC as the solvent. However, ceaseless solvent decomposition and intense exfoliation of graphene layers occurred at 25 °C. The results of the Raman spectroscopic analysis indicated that the interaction between PC molecules and lithium ions became weaker at − 15 °C by chemical exchange effects, which suggested that the thermodynamic stability of the solvated lithium ions was an important factor that determined the formation of a solid electrolyte interface (SEI) in PC-based solutions. Charge–discharge analysis revealed that the nature of the SEI formed at − 15 °C in 1 mol dm^− 3 of LiClO₄ in PC was significantly different from that formed at 25 °C in 1 mol dm^− 3 of LiClO₄ in PC containing vinylene carbonate, 3.27 mol kg^− 1 of LiClO₄ in PC, and 1 mol dm^− 3 of LiClO₄ in ethylene carbonate.     

Methane hydrate dissociation above 0 °C and below 0 °C

The kinetic data of methane hydrate dissociation at various temperatures and pressures were measured in a sapphire cell apparatus by depressurizing method. When the temperature was higher than 0 °C, the experimental results showed that the hydrate dissociation rate was controlled by intrinsic dissociation reaction. When the temperature was lower than 0 °C, water generated from the hydrate dissociation would transform into ice rapidly at the surface of hydrate crystal. The released gas diffused from the hydrate and ice mixture to the bulk of gas phase. With the hydrate continuous dissociation, the boundary of ice–hydrate moved toward water/ice phase. The hydrate dissociation was controlled by gas diffusion, and the hydrate dissociation process was treated as a moving boundary problem. Corresponding kinetic models for hydrate dissociation were established and good agreements with experimental data were achieved.     

Dyed polyvinyl chloride films for use as high-dose routine dosimeters in radiation processing

Characteristics of the polyvinyl chloride (PVC) films containing 0.11 wt% of malachite green oxalate or 6GX-setoglausine and about 100 μm in thickness were studied for use as routine dosimeters in radiation processing. These films show basically color bleaching under irradiation with ⁶⁰Co γ-rays in a dose range of 5–50 kGy. The sensitivity of the dosimeters and the linearity of dose-response curves are improved by adding 2.5% of chloral hydrate [CCl₃CH(OH)₂] and 0.15% hydroquinone [HOC₆H₄OH]. These additions extend the minimum dose limit to 1 kGy covering dosimetry requirements of the quality assurance in radiation processing of food and healthcare products. The dose responses of both dyed PVC films at irradiation temperatures from 20°C to 35°C are constant relative to those at 25°C, and the temperature coefficients for irradiation temperatures from 35°C to 55°C were estimated to be (0.43±0.01)%/°C. The dosimeter characteristics are stable within 1% at 25°C before and 60 days after the end of irradiation.     

Effects of calcination and activation temperature on dry reforming catalysts

The effect of calcination temperatures on dry reforming catalysts supported on high surface area alumina Ni/γ-Al₂O₃ (SA-6175) was studied experimentally. In this study, the prepared catalyst was tested in a micro tubular reactor using temperature ranges of 500, 600, 700 and 800 °C at atmospheric pressure, using a total flow rate of 33 ml/min consisting of 3 ml/min of N₂, 15 ml/min of CO₂ and 15 ml/min of CH₄. The calcination was carried out in the range of 500–900 °C. The catalyst is activated inside the reactor at 500–800 °C using hydrogen gas. It was observed that calcination enhances catalyst activity which increases as calcination and reaction temperatures were increased. The highest conversion was obtained at 800 °C reaction temperature by using catalyst calcined at 900 °C and activation at 700 °C. The catalyst characterization conducted supported the observed experimental results.