Study of phase behavior and Congo red dye partitioning in aqueous two-phase systems composed of hydrophilic alcohols (1-propanol/ 1-butanol) and sodium salts

ABSTRACT

The partitioning of the Congo red dye in ATPSs formed by alcohols (1-butanol, 1-propanol)/sodium salts was considered. Binodal and the LLE data were experimentally determined at 298.15 K. The salting-out abilities of the salts follow the order Na₃C₆H₅O₇ > NaH₂PO₄ > C₂H₃ O₂Na. The phase-forming abilities of the alcohols follow the order: 1-butanol > 1-propanol. The four-parameter equation was applied to correlate the binodal curves data. Therefore, The Bancroft and Othmer-Tobias equations were used to prove the reliability of the corresponding LLE data. ATPS composed of 6.5% of 1-butanol and 20% of Na₃C₆H₅O₇ had the highest values of extraction by the yield of 98.54%.     

Swelling and plastic properties of coal devolatilized at elevated pressures of H2 and He: Influence of potassium and silicon additives

The influences of SiO₂ and potassium additives on the swelling and plastic properties of a low volatile bituminous coal have been characterized at elevated pressures of H₂ and He using a high-pressure microdilatometer. The results suggest that non-porous SiO₂ serves as a ‘diluent’ as it has only a minor influence on the nature of the thermoplastic properties of coal. In marked contrast, K₂CO₃ or KOH significantly reduced the swelling of coal at low pressures (< 1.0 MPa). The effectiveness of K₂CO₃ and KOH as de-caking additives increased with the increase in loading of the additives. In addition, the effectiveness of potassium additives depended on the type of anions present. While K₂CO₃ or KOH served as strong decaking additives, KCl showed little effect. At elevated pressures of H₂ or He (>2.0 MPa), the swelling behaviour of K₂CO₃ or KOH loaded coal was reduced only slightly compared with the behaviour without additives. The influence of potassium additives is a function of coal particle size, heating rate and mode of addition (dry-mixed or solution impregnation). The presence of K₂CO₃ or KOH resulted in increased coke yield (i.e., reduced weight loss of coal during pyrolysis). This increase in coke yield was accompanied by a slight reduction in total light gases monitored (primarily C₂C₄). It is suggested that char-forming crosslinking reactions that can be catalysed by K₂CO₃/KOH facilitate increased thermosetting solid yield. At elevated pressures of H₂, the maximum swelling parameter in the presence of these potassium compounds was further increased compared with that noted in He. This behaviour is explained by suggesting that a hydrogen atmosphere reduces the extent of cross-linking reactions.     

13C CP/MAS and2H NMR study of tert-butyl alcohol dehydration on H-ZSM-5 zeolite. Evidence for the formation of tert-butyl cation and tert-butyl silyl ether intermediates

The dehydration reaction of tert-butyl alcohol, selectively labelled with¹³C in CH₃ or C-O groups (t-BuOH[2–¹³C₂] andt–BuOH[1-¹³C]), as well as selectively deuterated in methyl groups (t-BuOH[2-²H₉]), was studied on H-ZSM-5 zeolite simultaneously with¹³ C CP/MAS and²H solid state NMR. When adsorbed and dehydrated on zeolite at 296 K,t-BuOH[2–¹³C₁] andt-BuOH[1–¹³C] give rise to identical₁₃C CP/MAS NMR spectra of oligomeric aliphatic products. This is explained in terms of the fast isomerization of the tert-butyl hydrocarbon skeleton via the formation of tert-butyl cation as the key reaction intermediate. An alkoxide species, most probably tert-butyl silyl ether (t-BuSE), was also detected as the side reaction intermediate. This intermediate was stable within the temperature range 296–373 K and decomposed at 448 K to produce additional amounts of final reaction products, i.e. butene oligomers. NMR data point to the existence of equilibria between the initial tert-butyl alcohol, tert-butyl cation and butene that is formed from the intermediate carbocation.     

Effect of an H2O2 additive on hydrogen ignition and combustion in a supersonic air flow

The effect of small amounts of inert and reacting additives (such as hydrogen peroxide, its decomposition products,CO ₂, etc.) on the ignition and combustion of hydrogen in a high-temperature supersonic air flow was studied experimentally. It is shown that direct doping of the fuel has little effect on the combustion ofH ₂, whereas injection of hydrogen peroxide or small amounts of pure hydrogen ahead of the nozzle decreases suddenly the ignition delay, indicating the profound effect of the reaction products. Comparative experiments with inert additives showed that these additives only lead to a decrease in the air-flow temperature. Institute of Theoretical and Applied Mechanics, Siberian Division, Russian Academy of Sciences, Novosibirsk 630090. Translated from Fizika Goreniya i Vzryva, Vol. 33, No. 3, pp. 70–75, May–June, 1997.     

Mixed micelles of hexadecylpyridinium bromide + tetradecyltrimethylammonium bromide in aqueous glycol oligomers

Conductances of hexadecylpyridinium bromide (HPyBr) + tetradecyltrimethylammonium bromide (TTAB) mixtures over the entire mole fraction range of HPyBr (α_HPyBr) were measured in pure water as well as in the presence of various aqueous ethylene glycol oligomers containing 10 and 30 wt% of each additive in their respective binary mixtures at 30°C. Each conductivity curve shows two breaks corresponding to two critical micelle concentrations (cmc; C₁ and C₂ over the whole mole fraction range of HPyBr + TTAB mixtures except in the presence of pure HPyBr and TTAB, where a single break was observed. From the conductivity data, various micellar paramelers in the absence and presence of glycol additives were computed. A variation in the micellar parameters in the presence of additive showed that additive introduction mainly influence the medium properties and therefore the micellar properties. However, no significant micelle-glycol interactions were observed even with an increase in the number of repeating units from ethylene glycol to polyethylene glycol 600. The mixing behavior of HPyBr + TTAB is close to nonideal and is identical in pure water and in the presence of various glycols. This has been attributed to the presence of synergistic interactions between unlike monomers at C₁ that are not influenced even by the presence of additives. The appearance of the second cmc is mainly attributed to structural transitions of the mixed micelles at C₁ with a further increase in surfactant concentration.     

LIQUID - LIQUID DISTRBUTION EQUILIBRIUM IN THE TERNARY SYSTEM : CITRIC ACID - 2-BUTANOL - WATER 298.15 K

Partition of citric acid, 2-butanol and water between the aqueous and alcoholic phases is reported. Distribution of citric acid is expressed in terms of, H₃Cit (2-BuOH)₅, complex formation in the organic phase. Detailed thermodynamic analysis of the investigated system is presented.     

Effect of the vapors of organometallic compounds on the processes of ignition and combustion of hydrogen, propylene, and natural gas

It is established that small additions (～10^?1%) of hexacarbonyls of chromium and molybdenum promote combustion of the stoichiometric 2H₂ + O₂ mixture, which manifests itself in a decrease in the lower limit of initiated ignition by the pressure and in an increase in the visible propagation rate of the flame. However, inhibition of oxidation of propylene by these additives takes place. This fact means that the role of hydrogen atoms in the development of chains during flame propagation in hydrocarbon-air mixtures is not determining. Therefore, the kinetic mechanism inhibiting combustion of hydrocarbons by carbonyls based on accounting for termination of hydrogen atoms, which is suggested in the literature, should be refined. In the flame of oxidation of hydrogen in the presence of chromium hexacarbonyl, excited chromium atoms are found. Comparison of the inhibiting efficiency of the vapors of ferrocene Fe(C₅H₅)₂, butyrylferrocene C₁₄H₁₆FeO, carbonyls of metals and their mixture with the vapors of sulfur hexafluoride SF₆, and a series of halogen-substituted hydrocarbons (CF₂Cl₂, C₄H₉J, CCl₄, CHCl₃) on combustion of mixtures of natural gas with air is performed.     

Fluorometric analysis on physicochemical properties of phosphatidylcholine-based W/O microemulsion involved with enzymatic reactivity in phospholipid hydrolysis

Interfacial tension and fluorometric analysis were employed for the investigation of the interfacial local fluidity and the hydrophobicity of the micro water pool in the PC-based water-in-oil (W/O) microemulsion. These microenvironment properties strongly influenced the phospholipase A₂ reactivity for phospholipid hydrolysis in the W/O microemulsion. The organic phase was prepared by mixing of isooctane as a main solvent and 1-butanol as a co-solvent. The critical micelle concentration (CMC) was dramatically decayed from 9mM to 0.025mM by the increasing of the 1-butanol content. The local interfacial fluidity of the micro water pool was measured by using fluorescence polarity indicated by 1,6-Diphenyl-1,3,5-hexatriene-4′-trimethylammonium tosylate (TMA-DPH) and Coumarin 343 (C343). It was apparently increased with increasing the molar ratio of additive 1-butanol. In contrast, the hydrophobicity of the water pool measured by C343 was almost constant throughout the molar ratio of additive 1-butanol. Additive alcohol influenced the micro fluidity and enhanced reactivity of phospholipase A₂ in lipid hydrolysis. This work was presented at 13 ^th YABEC symposium held at Seoul, Korea, October 20–22, 2007.     

Roles of Pt and alumina during the combustion of coke deposits on propane dehydrogenation catalysts

Temperature programmed oxidation of coke deposited on Pt based propane dehydrogenation catalysts reveals that the deposited coke can be categorised into three groups according to their burning temperatures. When coke was separated from the catalyst, however, only one TPO peak could be observed. Experimental results suggest that γ-Al₂O₃ enhances the coke burning process by increasing coke surface area contacts to oxygen. Pt may also act as a catalyst for the coke combustion reaction. Experiments also show that changing dehydrogenation reaction temperature, variation of H₂/HC ratios, addition of only Sn or Sn and an alkali metal (Li, Na and K) can significantly affect the amount of each coke formed. Sample weight used in the temperature programmed oxidation (TPO) experiment also affects the resolution of TPO spectrum.     

Role of Oxalic Acid in Promoting Ignition and Combustion of Boron: an Experimental and Theoretical Study

Boron is an attractive fuel for propellants and explosives because of its high energy density. However, its combustion is inhibited by the oxide layer that covers the particles. The use of oxalic acid as an additive was shown to promote boron oxidation. In this study, the thermodynamic model FactSage 6.2 and a laser ignition facility were used to investigate the effect of oxalic acid on the burning characteristics of boron particles. The results of the thermodynamic analyses show that oxalic acid can reduce B₂O₃(l) production during boron combustion. This enables removal of the the oxide film and promotes the burning of boron. However, only at high temperatures (>1500 K) H₂O(g) (produced from H₂C₂O₄) can react with B₂O₃ and remove the oxide film. The evolution of boron combustion flame takes place in three stages: ignition, stable combustion, and extinction; the bright yellow color in the flame indicates boron ignition, the bright white color indicates boron combustion, and the bright green color is interpreted as BO₂ emission. Addition of oxalic acid into boron powders can significantly promote boron ignition and combustion. The ignition delay time of the resulting mixture is reduced by 42.4 %, the combustion intensity is raised by 16.7 %, and the combustion efficiency of boron is increased by 21.5 percentage points. The mechanism of action of oxalic acid on enhancing the combustion of boron was studied by scanning electron microscopy.     

Hydrogen–deuterium isotope effects in the reactions of chlorobenzene and benzene on a Pt/γ-Al2O3 catalyst

The kinetic isotope effect for combustion of a C₆H₅Cl/C₆D₅Cl mixture on Pt/-Al₂O₃ was found to be close to unity between 520 and 580 K. However, in the presence of an excess of heptane, an isotope effect of 1.5 was found between 460 and 490 K. For the combustion of a C₆H₆/C₆D₆ mixture the k_H/k_D value was around 2 between 404 and 439 K. The results show that in the combustion of chlorobenzene per se, C–H bond activation is not a rate-determining step. On Pt sites, C–Cl bond scission probably occurs already at low temperatures. The chlorine and the phenyl group cannot easily react further. Chlorine on the surface is active in chlorination, which is shown by the formation of C₆D₅Cl in an experiment with C₆H₅Cl and C₆D₆. Only at a certain temperature is the chlorine removed, partly as polychlorinated benzenes. The removal of chlorine from the catalyst allows oxygen to take part in the reaction, which determines the rate of the combustion of chlorobenzene. When heptane is present, Cl is removed from the surface and C–H bond scission can become rate determining, as is also the case in the combustion of C₆H₆/C₆D₆. Upon (partial) combustion of C₆H₅Cl/C₆D₅Cl and C₆H₆/C₆D₆ mixtures on a Pt/-Al₂O₃ catalyst, hydrogen–deuterium exchange occurs on the -Al₂O₃ support.     

Effect of temperature on the reaction of H2S with a coke

The effect of temperature on reaction of H₂S with carbon structures of a coke were studied in a fixed-bed quartz tube reactor coupled with two parallel detectors, flame photometric detector (FPD) and mass spectrum (MS). The uptake of H₂S with the coke matrix was studied through a sulfur uptake/temperature programmed desorption process (SU/TPD) and a temperature programmed oxidation process (TPO). The results show that the sulfur imbibed by a demineralized coke at elevated temperatures is very stable, which can only be decomposed and released to gas phase under combustion conditions. The chemical imbibition of sulfur takes place at an elevated temperature. At relatively lower temperatures, H₂S was adsorbed physically by the sample and then transformed to stable sulfur species. At higher temperatures, the chemical reactions between H₂S and DM-Coke led to the formation of more stable sulfur-containing forms and consequently increased H₂S uptake ability. This is essence of the temperature effect on the uptake of H₂S by a demineralized coke. The irregular behavior with the temperature was caused by the different interactions.     

Effect of temperature on the reaction of H2S with a coke

The effect of temperature on reaction of H₂S with carbon structures of a coke were studied in a fixed-bed quartz tube reactor coupled with two parallel detectors, flame photometric detector (FPD) and mass spectrum (MS). The uptake of H₂S with the coke matrix was studied through a sulfur uptake/temperature programmed desorption process (SU/TPD) and a temperature programmed oxidation process (TPO). The results show that the sulfur imbibed by a demineralized coke at elevated temperatures is very stable, which can only be decomposed and released to gas phase under combustion conditions. The chemical imbibition of sulfur takes place at an elevated temperature. At relatively lower temperatures, H₂S was adsorbed physically by the sample and then transformed to stable sulfur species. At higher temperatures, the chemical reactions between H₂S and DM-Coke led to the formation of more stable sulfur-containing forms and consequently increased H₂S uptake ability. This is essence of the temperature effect on the uptake of H₂S by a de-mineralized coke. The irregular behavior with the temperature was caused by the different interactions.     

Petroleum coke conversion behavior in catalyst-assisted chemical looping combustion

Efficiently using petroleum coke as fuel and reducing carbon emission meanwhile have become attractive in oil processing industry. The paper is focused on the application of Chemical Looping Combustion (CLC) with petroleum coke, with the purpose of investigating its combustion performance and effects of potassium. Some experiments were performed in a laboratory scale fluidized bed facility with a natural manganese-based oxygen carrier. Experimental results indicated that the coke conversion is very sensitive to reaction temperature. The present natural manganese-based oxygen carrier decorated by K has little effect on the improvement of coke conversion. XRD, SEM–EDX, and H₂-TPR were adopted to characterize the reacted oxygen carrier samples. After being decorated by K, the oxygen carrier's capacity of transferring oxygen was decreased. A calcination temperature above the melting point of K₂CO₃ (891 °C) shows better oxygen transfer reactivity in comparison to the one calcined at a lower temperature. The natural oxygen carrier used in the work has a high content of Si, which can easily react with K to form K(FeSi₂O₆). Further, irrespective of reaction temperature, the coke conversion can be significantly enhanced by decorating the coke with K, with a demonstration of remarkably shorter reaction time, faster average coke gasification rate and higher average carbon conversion rate.     

Thermodynamic Equilibrium Analysis of Propane Dehydrogenation with Carbon Dioxide and Side Reactions

A thermodynamic analysis of propane dehydrogenation with carbon dioxide was performed using constrained Gibbs free energy minimization method. Different reaction networks corresponding to different catalytic systems, including non-redox and redox oxide catalysts, were simulated. The influences of CO₂/C₃H₈ molar ratio (1–10), temperature (700–1000 K), and pressure (0.5–5 bar) on equilibrium conversion and product composition were studied. In the presence of CO₂ with a molar ratio of CO₂/C₃H₈ = 1, the temperature of dehydrogenation can be 30 K lower than that of dehydrogenation in the presence of steam (H₂O/C₃H₈ = 1) and about 50 K lower than that of simple dehydrogenation without dilution to achieve 60% propane conversion. It was found that the occurrence of dry reforming of propane and coke-forming side reactions could strongly impact the equilibrium product composition of the multireaction system and, therefore, these reactions should be kinetically controlled. Comparison of the simulated reactant conversions with those reported in the literatures revealed that the experimental conversion levels of propane are far below the corresponding equilibrium values due to rapid catalyst deactivation by coke, implying that research efforts should be directed toward formulation of more active and selective catalysts.     

The promotional effect of K on the catalytic activity of Ni/MgAl<Subscript>2</Subscript>O<Subscript>4</Subscript> for the combined H<Subscript>2</Subscript>O and CO<Subscript>2</Subscript> reforming of coke oven gas for syngas production

A K-promoted 10Ni-(x)K/MgAl₂O₄ catalyst was investigated for the combined H₂O and CO₂ reforming (CSCR) of coke oven gas (COG) for syngas production. The 10Ni-(x)K/MgAl₂O₄ catalyst was prepared by co-impregnation, and the K content was varied from 0 to 5 wt%. The BET, XRD, H₂-chemisorption, H₂-TPR, and CO₂-TPD were performed for determining the physicochemical properties of prepared catalysts. Except under the condition of a K/Ni=0.1 (wt%/wt%), the Ni crystal size and dispersion decreased with increasing K/Ni. The coke resistance of the catalyst was investigated under conditions of CH₄: CO₂: H₂: CO:N₂=1 : 1 : 2 : 0.3 : 0.3, 800 °C, 5 atm. The coke formation on the used catalyst was examined by SEM and TG analysis. As compared to the 10Ni/MgAl₂O₄ catalyst, the Kpromoted catalyst exhibited superior activity and coke resistance, attributed to its strong interaction with Ni and support, and the improved CO₂ adsorption characteristic. The 10Ni-1K/MgAl₂O₄ catalyst exhibited optimum activity and coke resistance with only 1wt% of K.     

Ignition control of methane fueled homogeneous charge compression ignition engines using additives

Homogeneous charge compression ignition is a new combustion technology that may develop as an alternative to diesel engines with high efficiency and low NO_x and particulate matter emissions. In this paper, the effect of additives such as dimethyl ether (DME), formaldehyde (CH₂O) and hydrogen peroxide (H₂O₂) for the control of ignition in natural-gas HCCI engines have been investigated numerically by adopting a single-zone zero-dimensional model. The chemical kinetic mechanism incorporated the GRI-3.0 mechanism that considers 53 species and 325 reactions together with the DME reaction scheme consisting of 79 species and 351 reactions. To simulate HCCI engine cycles, a variable volume computation has been performed by including a piston motion into the SENKIN code at a fixed equivalence ratio of 0.3 and initial mixture pressure of 1.5 bar. It was found that an additive-free mixture did not ignite for the intake temperature of 400 K. A mixture containing a small quantity of additives at the same temperature was ignited. For a fixed quantity of additive, it was found that H₂O₂ addition was effective in advancing the ignition timing as compared to the other two additives. It was found that the percentage of additives required to achieve a near TDC ignition timing increases linearly with the increase in the engine speed while decreases with the increase in the equivalence ratio with the superiority of H₂O₂. Furthermore, the addition of even 7% by volume of H₂O₂ could ignite a mixture at an intake temperature of 350 K, while at least the fractions of 12.5% and 35% by volume were needed for DME and CH₂O, respectively. It was also found that the mass fraction of NO with CH₂O addition was less than that with H₂O₂ addition. At the same time, however, a near TDC ignition timing resulted in a similar amount of NO for both additives. Overall, the enhanced reactivity of CH₄ in the presence of small amounts of additives could be used in HCCI engines fueled with methane to alleviate the high intake temperature requirements.     

Modelling of microporous diffusion of n-paraffins in zeolite 5A

Sorptive liquid-phase diffusion of two n-paraffins, C₁₀H₂₂ and C₁₁H₂₄, dissolved in isooctane, onto micropore of 5A zeolite was studied to assess multicomponent diffusion and competitive effects. Diffusion coefficients for adsorbing components are determined from experimental batch reactor data. The experimental data indicate that diffusion through the microporous zeolite crystals is the primary diffusional resistance. A mathematical model of the rate of adsorption of a solute from a liquid by micropore adsorbent in a batch system was developed. The equation describing the mass transport by diffusion in a micropore adsorbent has been solved in order to obtain theoretical uptake curves for systems when the adsorption equilibrium isotherm is the favourable and nonlinear one. A computer simulation of the microporous diffusion is performed by use of the ISIM-Interactive Simulation Language. The effect of main term and cross-term coefficients of micropore diffusion for the system considered is investigated.     

Effective Coke Removal in Methane to Benzene (MTB) Reaction on Mo/HZSM-5 Catalyst by H2 and H2O Co-addition to Methane

The catalytic dehydro-aromatization reaction over Mo/HZSM-5 catalyst was drastically stabilized by the co-addition of 5.4% H₂ and 1.8% H₂O to methane feed at 750 °C, 0.3 MPa and methane space velocity of 3000 mL g⁻¹ h⁻¹, suppressing the coke formation effectively, compared with single hydrogen or steam addition.     

Excess molar enthalpies for the binary and ternary mixtures of ether compounds (di-isopropyl ether, di-butyl ether, propyl vinyl ether) with ethanol and isooctane at 298.15 K

Excess molar enthalpy (H ^E ) data at 298.15 K are reported for the binary systems di-isopropyl ether (1)+ethanol (2), di-isopropyl ether (1)+isooctane (2), ethanol (1)+isooctane (2), di-butyl ether (1)+ethanol (2), di-butyl ether (1)+isooctane (2), propyl vinyl ether (1)+ethanol (2) and propyl vinyl ether (1)+isooctane (2). These data were obtained by using an isothermal flow calorimeter. The experimental binary H ^E data were well correlated with the Redlich-Kister model, and infinitely dilute partial excess molar enthalpies for each binary were calculated with the fitted Redlich-Kister parameters. Additionally, the isoclines of H ^E for ternary systems di-isopropyl ether (1)+ethanol (2)+isooctane (3), di-butyl ether (1)+ethanol (2)+isooctane (3) and propyl vinyl ether (1)+ethanol (2)+isooctane (3) at 298.15 K were calculated by using the Radojkovič equation. H ^E for all the measured systems in this work shows that mixing is endothermic.