Robust Microporous Metal–Organic Frameworks for Highly Efficient and Simultaneous Removal of Propyne and Propadiene from Propylene

Simultaneous removal of trace amounts of propyne and propadiene from propylene is an important but challenging industrial process. We report herein a class of microporous metal–organic frameworks ( NKMOF‐1‐M ) with exceptional water stability and remarkably high uptakes for both propyne and propadiene at low pressures. NKMOF‐1‐M separated a ternary propyne/propadiene/propylene (0.5 : 0.5 : 99.0) mixture with the highest reported selectivity for the production of polymer‐grade propylene (99.996 %) at ambient temperature, as attributed to its strong binding affinity for propyne and propadiene over propylene. Moreover, we were able to visualize propyne and propadiene molecules in the single‐crystal structure of NKMOF‐1‐M through a convenient approach under ambient conditions, which helped to precisely understand the binding sites and affinity for propyne and propadiene. These results provide important guidance on using ultramicroporous MOFs as physisorbent materials.     

High pressure pyrolysis of toluene. 1. Experiments and modeling of toluene decomposition

The pyrolysis of toluene, the simplest methyl-substituted aromatic molecule, has been studied behind reflected shock waves using a single pulse shock tube. Experiments were performed at nominal high pressures of 27 and 45 bar and spanning a wide temperature range from 1200 to 1900 K. A variety of stable species, ranging from small hydrocarbons to single ring aromatics (principal soot precursors such as phenylacetylene and indene) were sampled from the shock tube and analyzed using standard gas chromatographic techniques. A detailed chemical kinetic model with 262 reactions and 87 species was assembled to simulate the stable species profiles (specifically toluene, benzene and methane) from the current high-pressure pyrolysis data sets and shock tube-atomic resonance absorption spectrometry (ARAS) H atom profiles obtained from prior toluene pyrolysis experiments performed under similar high-temperature conditions and lower pressures from 1.5 to 8 bar. The primary steps in toluene pyrolysis represent the most sensitive and dominant reactions in the model. Consequently, in the absence of unambiguous direct experimental measurements, we have utilized recent high level theoretical estimates of the barrierless association rate coefficients for these primary reactions, C6H5 + CH3 --> C6H5CH3 (1a) and C6H5CH2 + H --> C6H5CH3 (1b) in the detailed chemical kinetic model. The available data sets can be successfully reconciled with revised values for deltaH0f(298K)(C6H5CH2) = 51.5 +/- 1.0 kcal/mol and deltaH0f(298K)(C6H5) = 78.6 +/- 1.0 kcal/mol that translate to primary dissociation rate constants, reverse of 1a and 1b, represented by k(-1a,infinity) = (4.62 x 10(25))T(-2.53)exp[-104.5 x 10(3)/RT] s(-1) and k(-1b,infinity) = (1.524 x 10(16))T(-0.04)exp[-93.5 x 10(3)/RT] s(-1) (R in units of cal/(mol K)). These high-pressure limiting rate constants suggest high-temperature branching ratios for the primary steps that vary from 0.39 to 0.52 over the temperature range 1200-1800 K.     

Numerical Investigation on 1,3-Butadiene/Propyne Co-pyrolysis and Insight into Synergistic Effect on Aromatic Hydrocarbon Formation

A numerical investigation on the co-pyrolysis of 1,3-butadiene and propyne is performed to explore the synergistic effect between fuel components on aromatic hydrocarbon formation.A detailed kinetic model of 1,3-butadiene/propyne co-pyrolysis with the sub-mechanism of aromatic hydrocarbon formation is developed and validated on previous 1,3-butadiene and propyne pyrolysis experiments.The model is able to reproduce both the single component pyrolysis and the co-pyrolysis experiments,as well as the synergistic effect between 1,3-butadiene and propyne on the formation of a series of aromatic hydrocarbons.Based on the rate of production and sensitivity analyses,key reaction pathways in the fuel decomposition and aromatic hydrocarbon formation processes are revealed and insight into the synergistic effect on aromatic hydrocarbon formation is also achieved.The synergistic effect results from the interaction between 1,3-butadiene and propyne.The easily happened chain initiation in the 1,3-butadiene decomposition provides an abundant radical pool for propyne to undergo the H-atom abstraction and produce propargyl radical which plays key roles in the formation of aromatic hydrocarbons.Besides,the 1,3-butadiene/propyne co-pyrolysis includes high concentration levels of C3 and C4 precursors simultaneously,which stimulates the formation of key aromatic hydrocarbons such as toluene and naphthalene.     

Vapor-phase chemical equilibrium for the hydrogenation of benzene to cyclohexane from reaction-ensemble molecular simulation

The reaction-ensemble Monte-Carlo (REMC) molecular simulation method was used to study the vapor-phase chemical equilibrium for the reaction of hydrogenation of benzene to cyclohexane. A one-center modified Buckingham exponential-6 (1CMBE6) effective pair potential model (that had already been used to predict thermodynamic properties and liquid–liquid equilibria of helium+hydrogen mixtures) was used for hydrogen. Six-center modified Buckingham exponential-6 (6CMBE6) effective pair potential models (that had already been used to reproduce the saturated liquid and vapor densities, vapor pressures, second virial coefficients, and critical parameters of the six-membered ring molecules), were used for benzene and cyclohexane. No binary adjustable parameters were needed to compute the unlike-pair Buckingham exponential-6 interactions in the ternary system. Simulation results were obtained for the effect of some operating variables such as temperature (from 500 to 650 K), pressure (from 1 to 30 bar), and hydrogen to benzene feed mole ratio (from 1.5:1 to 6:1) on the reaction conversion, molar composition, and mass density of the ternary system at equilibrium. These results were found to be in excellent agreement with calculations using the predictive Soave–Redlich–Kwong (PSRK) group contribution equation of state.     

An experimental and modeling study of the oxidation of n-heptane,ethylbenzene, and n-butylbenzene in a jet-stirred reactor at pressures up to 10 bar

In the context of better understanding pollutant formation from internal combustion engines, new experimental speciation data were obtained in a high-pressure jet-stirred reactor for the oxidation of three molecules, which are considered in surrogates of diesel fuel, n-heptane, ethylbenzene, and n-butylbenzene. These experiments were performed at pressures up to 10 bar, at temperatures ranging from 500 to 1 100 K, and for a residence time of 2 s. Based on results previously obtained close to the atmospheric pressure for the same molecules, the pressure effect on fuel conversion and product selectivity was discussed. In addition, for the three fuels, the experimental temperature dependence of species mole fractions was compared with simulations using recent literature models with generally a good agreement. For n-heptane, the obtained experimental data, at 10 bar for stoichiometric mixtures, included the temperature dependence of the mole fractions of the reactants and those of 21 products. Interestingly, the formation of species previously identified as C₇ diones was found significantly enhanced at 10 bar compared with lower pressures. The oxidation of ethyl- and n-butylbenzenes was investigated at 10 bar for equivalence ratios of 0.5, 1, and 2. The obtained experimental data included the temperature dependence of the mole fractions of the reactants and those of 13 products for the C₈ fuels and of 19 products for the C₁₀ one. For ethylbenzene under stoichiometric conditions, the pressure dependence (from 1 to 10 bar) of species mole fraction was also recorded and compared with simulations with more deviations obtained than for temperature dependence. For both aromatic reactants, a flow rate analysis was used to discuss the main pressure influence on product selectivities.     

Evidence for cyclohexyl as a reactive surface intermediate during high-pressure cyclohexane catalytic reactions on Pt(111) by sum frequency generation vibrational spectroscopy

Sum frequency generation (SFG) surface vibrational spectroscopy has been used to identify reactive surface intermediates in situ during catalytic dehydrogenation reactions of high-pressure cyclohexane (C(6)H(12)) on the Pt(111) crystal surface in the presence and absence of high-pressure hydrogen. These experiments provide the first spectroscopic evidence of cyclohexyl (C(6)H(11)) as a reactive surface intermediate during the cyclohexane catalytic conversion to benzene at high pressure in the presence of excess hydrogen. In addition, it was proposed from temperature-dependent SFG experiments that dehydrogenation of cyclohexyl is a rate-limiting step in the cyclohexane catalytic conversion to benzene.     

Adsorption of hexane, cyclohexane, and benzene on microporous carbon obtained by pyrolysis of hypercrosslinked polystyrene

The relationships of adsorption of hexane, cyclohexane, and benzene on a D4609 microporous carbon adsorbent obtained by the pyrolysis of hypercrosslinked polystyrene are compared. It is shown that in the range of relative pressures corresponding to the filling of ultramicropores, the adsorption behaviors of cyclohexane and benzene are essentially identical, in contrast to hexane, which is characterized by higher adsorption values and isosteric heat of adsorption. The observed relationships are explained by the steric features of the distribution of molecules of various structures in ultramicropores.     

An Asymmetric Anion‐Pillared Metal–Organic Framework as a Multisite Adsorbent Enables Simultaneous Removal of Propyne and Propadiene from Propylene

The one‐step removal of multi‐component gases based on a single material will significantly improve the efficiency of separation processes but it is challenging, owing to the difficulty to precisely fabricate porous materials with multiple binding sites tailored for different guest molecules. Now a niobium oxide–fluoride anion‐pillared interpenetrated material ZU‐62 (NbOFFIVE‐2‐Cu‐i, NbOFFIVE=NbOF₅^2?) is presented. It features asymmetric O/F node coordination for the simultaneous removal of trace propyne and propadiene from propylene. The narrow distribution nanospace (aperture of Site I 6.75 Å, Site II 6.94 Å, Site III 7.20 Å) derived from the special coordination geometry within ZU‐62 customized the corresponding energy‐favorable binding sites for the propyne and propadiene that enable propadiene uptake (1.74 mmol g^?1) as well as excellent propyne uptake (1.87 mmol g^?1) under ultra‐low pressure (5000 ppm). The multisite capture mechanism was revealed by modeling studies.     

Experimental and modeling of oxidation of acetylene,propyne, allene and 1,3‐butadiene

The ignition delays of insaturated hydrocarbons‐oxygen‐argon mixtures were measured behind shock waves in the cases of acetylene, propyne, allene and 1,3‐butadiene. Reflected shock waves permitted to obtain temperatures from 1000–1650 K and pressures from 8.5 to 10.0 atm. A particular effort has been made to build a detailed mechanism of the reactions of C₃‐C₄ unsaturated species and benzene. This mechanism is based on the most recent kinetic data values published in the literature and is consistent with the thermochemistry. This mechanism has been validated by comparing the results of our simulations to the experimental results obtained in our shock tube experiments and to profiles of radicalar and molecular species measured in three premixed flames (acetylene [1–2] and 1,3‐butadiene [3]) coming from the literature. The main reaction pathways have been derived in the case of the oxidation of these four insaturated hydrocarbons and for the formation of benzene. © 1999 John Wiley & Sons, Inc. Int J Chem Kinet 31: 361–379, 1999     

Investigation on the performance,emissions and combustion characteristics of CRDI engine fueled with tallow methyl ester biodiesel blends with exhaust gas recirculation

This paper demonstrates the study of performance, combustion and emission characteristics of a common rail diesel injection (CRDI) engine with the influence of exhaust gas recirculation (EGR) (5, 15 and 25%) at various fuel injection pressures (400, 500 and 600 bar) under the effective load conditions (0, 25, 50, 75 and 100%). The experiments were carried out in a controlled manner using the CRDI engine fuelled with 80% (D80) diesel (98% purity) blended with 20% (B20) tallow biodiesel. The engine has been operated at a rated speed of 1500 rpm on all load conditions, fuel injection timings of 10°, 15° and 20° bTDC, fuel injection pressures of 400, 500 and 600 bar, respectively. Combustion-influenced performance characteristics such as variation of in-cylinder pressure and net heat release rate in J deg^?1 are also studied with the above operating conditions. It was observed that the usage of 20% biofuel blend shows considerable improvement in combustion, and it further enhances with an increase in the injection pressures. Besides, EGR (up to 25%) reduced significant pollutants at higher operating pressures (600 bar) at higher load conditions. It was also observed that CO₂ emission increased with increase in the % EGR with an increase in the load conditions. However, for CO emission increased up to 50% load condition and subsequently tends to decrease due to improved combustion at higher load; hence higher temperature. NO_x, smoke opacity continue to increase with the increase in pressure and the percentage increase in EGR due to its attainment of adiabatic temperature, which leads to the pathway for the Zeldovich mechanism. The present work shows light on the usage of tallow methyl ester produced from the wastes in the tannery industry as alternate biofuel operating the CRDI engines without compromising its combustion and emission characteristics to deliver the same power as petro-diesel.

     

Fuel pyrolysis through porous media: Coke formation and coupled effect on permeability

The development of hypersonic vehicles (up to Mach 10) leads to an important heating of the whole structure. The fuel is thus used as a coolant. It presents an endothermic decomposition with possible coke formation. Its additional permeation through the porous structure involves internal convection. This implies very complex phenomena (heat and mass transfers with chemistry). In this paper, the n-dodecane pyrolysis is studied through stainless steel porous medium up to 820 K and 35 bar (supercritical state). The longitudinal profiles of chemical compositions inside the porous medium are given thanks to a specific sampling technique with off-line Gas Chromatograph and Mass Spectrometer analysis. By comparison with previous experiments under plug flow reactor, the conversion of dodecane is higher for the present experimental configuration. The pyrolysis produces preferentially light gaseous species, which results in a higher gasification rate for a similar pyrolysis rate. The effects of the residence time and of the contact surface area are demonstrated. The transient changes of Darcy's permeability are related to the coke formation thanks to previous experimental relationship with methane production. A time shift is observed between coke chemistry and permeability change. This work is quite unique to the author's knowledge because of the complex chemistry of heavy hydrocarbon fuels pyrolysis, particularly in porous medium.     

Measurement of vapor-liquid equilibrium in systems with components of very different volatility by the total pressure static method

To make feasible the experimental study of vapor-liquid equilibrium (VLE) in the systems mentioned in the title, a static apparatus for accurate measurement of total vapor pressures of solutions was constructed. Mixtures of known composition are prepared synthetically in a thermostated equilibrium cell by weight from pure degassed components and the total pressure is measured by a quartz Bourdon gage. A procedure was developed for degassing pure liquids to a degree corresponding to the high precision of pressure determination required. The static assembly was tested by comparing obtained isothermal vapor pressures and calculated excess Gibbs free energies with literature data for the benzene - cyclohexane system at 14 and 20°C, respectively. Additional experimental vapor-pressure data are presented for pure cyclohexane, benzene, and N-methylpyrrolidone (abbreviated throughout this paper as NMP) at 6–24°C and for the binary systems of benzene-cyclohexane at 8°C and cyclohexane - NMP and benzene - NMP at 8, 14, and 20°C over the entire composition range. The binary data were reduced by a modified Barker's method to evaluate excess Gibbs free energies and vapor phase compositions.     

Impact of configuration and fluorination on the solubility of octyl ester benzoate dimers in CO2

Data are reported on the phase behavior of hydrocarbon and semifluoroinated octyl ester benzoate dimers in CO₂ to temperatures of 100 °C and pressures of 1 600 bar. The experimental data at 75 °C demonstrate that the non-fluorinated head-to-head (H–H) dimer dissolves in CO₂ at ∼400 bar lower pressures than the non-fluorinated tail-to-tail (T–T) dimer. Even though partially fluorinating the octyl tails of the H–H and T–T dimers renders them soluble in CO₂ at pressures near 200 bar, it still takes ∼40 bar more pressure to dissolve the fluorinated T–T dimer as compared to the H–H dimer. The difference in pressures needed to dissolve these dimers is attributed to steric constraints on the coplanarity of the benzene rings imposed by the H–H regiochemistry that do not exist with T–T dimers. Semi-empirical quantum mechanics calculations suggest that the H–H dimer has a twisted, non-coplanar conformation due to the steric effect of the octyl ester groups while the T–T dimer has a less twisted conformation. Steric hindrance in the H–H dimer reduces considerably resonance or conjugation between the π electrons of the aromatic groups which also reduces the dipole moments of the H–H dimers compared to those of the T–T dimers.     

Design of a Highly Active Pd Catalyst with P,N Hemilabile Ligands for Alkoxycarbonylation of Alkynes and Allenes: A Density Functional Theory Study

In the palladium-catalysed methoxycarbonylation of technical propyne, the presence of propadiene poisons the hemilabile Pd(P,N) catalyst. According to density functional theory calculations (B3PW91-D3/PCM level), a highly stable π-allyl intermediate is the reason for this catalyst poisoning. Predicted regioselectivities suggest that at least 11 % of propadiene should yield this allyl intermediate, in which the reaction gets stalled under the turnover conditions due to an insurmountable methanolysis barrier of 25.8 kcal mol⁻¹. The results obtained for different ligands and substrates are consistent with the available experimental data. A new ligand, (6-Cl-3-Me-Py)PPh₂, is proposed, which is predicted to efficiently control the branched/linear selectivity, avoiding rapid poisoning (with only 0.2 % of propadiene being trapped as the Pd allyl complex), and to tremendously increase the catalytic activity by decreasing the overall barrier to 9.1 kcal mol⁻¹.     

Separation of benzene/cyclohexane mixtures using polyurethane–silica hybrid membranes

Mixed sols were prepared by dissolving polyurethane (a 30 wt% solution in n-propanol, PU) and tetraethylorthosilicate (TEOS) in ethanol at PU:TEOS mass ratios of 1:2, 1:1, 2:1 and 3:1. Each of the sols was coated on a porous α-alumina support tube by the dipping method, and green membranes were heat-treated at 200°C for 1 h in an atmosphere of nitrogen. A PU membrane was also prepared with PU alone. The membranes were 5–6 μm thick. The polyurethane–silica membranes were swollen in benzene but only slightly in cyclohexane at room temperature. The degree of swelling in benzene decreased with increasing fractions of TEOS in the hybrid sols. The selectivity of benzene to cyclohexane was improved due to the suppression of swelling as a result of hybridization with TEOS. The total permeation flux and benzene/cyclohexane selectivity in the membrane prepared with a sol of PU:TEOS=1:1 were 3×10⁻⁵ kg m⁻² s⁻¹ and 19, respectively.     

Shock tube pyrolysis of 1,2,4,5-hexatetraene

1,2,4,5-Hexatetraene (1245HT) is, according to theory, a key intermediate to benzene from propargyl radicals in a variety of flames; however, it has only been experimentally observed once in previous studies of the C3H3 + C3H3 reaction. To determine if it is indeed an intermediate to benzene formation, 1245HT was synthesized, via a Grignard reaction, and pyrolysized in a single-pulse shock tube at two nominal pressures of 22 and 40 bar over a temperature range from 540 to 1180 K. At temperatures T < 700 K, 1245HT converts efficiently to 3,4-dimethylenecyclobutene (34DMCB) with a rate constant of k = 10(10.16) x exp(-23.4 kcal/RT), which is in good agreement with the one calculated by Miller and Klippenstein. At higher temperatures, various C6H6 isomers were generated, which is consistent with theory and earlier experimental studies. Thus, the current work strongly supports the theory that 1245HT plays a bridging role in forming benzene from propargyl radicals. RRKM modeling of the current data set has also been carried out with the Miller-Klippenstein potential. It was found that the theory gives reasonably good predictions of the experimental observations of 1245HT, 1,5-hexadiyne (15HD), and 34DMCB in the current study and in our earlier studies of 15HD pyrolysis and propargyl recombination; however, there is considerable discrepancy between experiment and theory for the isomerization route of 1,2-hexadien-5-yne (12HD5Y) --> 2-ethynyl-1,3-butadiene (2E13BD) --> fulvene.     

Kinetics of the hydrogen atom reactions with benzene,cyclohexadiene and cyclohexene: hydrogenation mechanism and ring cleavage

The hydrogen atom reaction with benzene and the subsequent elementary reactions with H-atoms were studied in detail, using a fast gas flow in a linear reactor at pressures in the mbar region, with a mass spectrometer for the product analysis. The rate-constant determinations were based on a kinetic model, which includes the strong catalytic H-atom recombination on the wall, caused by adsorbed reactant molecules, and also corrects for the pressure drop within the reactor. The H-atom concentration was determined by scavenging with NO₂. The method was checked by determining the rate constant k(H + trans-butene-2) = (4.6 ± 1.2) × 10⁸ M^?1 s^?1, which agrees with the literature value of Daby et al. within experimental error limits. The rate constants determined are:

H + benzene is the rate determining step for benzene hydrogenation. From the rate constant for H + C₆D₆ it is concluded, that benzene is reformed from some intermediate reaction products (C₆H^*₇ and/or C₆H^*₈). These back reactions should be suppressed at high pressures, in agreement with results by Sauer and Ward (1–54 bar). The mass spectra show that H + benzene at mbar pressures predominantly initiates ring cleavage to form methyl radicals, methane, and C₂-hydrocarbons as the main products. However for H + cyclohexene 85% of the products is cyclohexane. The results for H + cyclohexadiene are intermediate to these extremes. It is argued that accumulation of vibrational energy over two consecutive reactions must be responsible for the ring cleavage, which most likely occurs from C₆H^**₈ and C₆H^**₁₀.     

Formation of isomeric terphenyls and triphenylene by pyrolysis of benzene

The pyrolysis of benzene has been investigated at 773, 923, and 1073 K and the mechanisms of formation of isomeric terphenyls and triphenylene have been studied, the results being compared with those obtained by pyrolysis of benzene solutions containing diphenyl and o=terphenyl. No differences in the mechanisms of the formation of terphenyls and triphenylene could be observed at the selected temperatures, even if ring fission and a higher degree of polymerization occurred at 1073 K. The addition of diphenyl and o-terphenyl showed that the reactions leading to the formation of isomeric terphenyls and triphenylene in the pyrolysis of pure benzene do not pass through stable intermediates.