In the radiant section of cracking furnace, the thermal cracking process is highly coupled with turbulent flow, heat transfer and mass transfer. In this paper, a three-dimensional simulation of propane pyrolysis reactor tube is performed based on a detailed kinetic radical cracking scheme, combined with a comprehensive rigorous computational fluid dynamics (CFD) model. The eddy-dissipation-concept (EDC) model is introduced to deal with turbulence-chemistry interaction of cracking gas, especially for the multi-step radical kinetics. Considering the high aspect ratio and severe gradient phenomenon, numerical strategies such as grid resolution and refinement, stepping method and relaxation technique at different levels are employed to accelerate convergence. Large scale of radial nonuniformity in the vicinity of the tube wall is investigated. Spatial distributions of each radical reaction rate are first studied, and made it possible to identify the dominant elementary reactions. Additionally, a series of operating conditions including the feedstock feed rate, wall temperature profile and heat flux profile towards the reactor tubes are investigated. The obtained results can be used as scientific guide for further technical retrofit and operation optimization aiming at high conversion and selectivity of pyrolysis process.

In the hydrogen network with the minimum hydrogen utility flow rate, the pinch appears at the point with zero hydrogen surplus, while the hydrogen surpluses of all the other points are positive. In the hydrogen purity profiles, the pinch can only lie at the sink-tie-line intersecting the source purity profile. According to the alternative distribution of the negative and positive regions, the effect of the purification to the hydrogen surplus is analyzed. The results show that when the purification is applied, the pinch point will appear neither above the purification feed nor between the initial pinch point and the purification feed, no matter the purification feed lies above or below the initial pinch point. This is validated by two case studies.

Based on frequency response and convex optimization, a novel optimal control system was developed for chemical processes. The feedforward control is designed to improve the tracking performance of closed loop chemical systems. The parametric model is not required because the system directly utilizes the frequency response of the loop transfer function, which can be measured accurately. In particular, the extremal values of magnitude and phase can be solved according to constrained quadratic programming optimizer and convex optimization. Simulation examples show the effectiveness of the method. The design method is simple and easily adopted in chemical industry.

Batch processes are important in chemical industry, in which operators usually play a major role and hazards may arise by their inadvertent acts. In this paper, based on hazard and operability study and concept of qualitative simulation, an automatic method for adverse consequence identification for potential maloperation is proposed. The qualitative model for production process is expressed by a novel directed graph. Possible operation deviations from normal operating procedure are identified systematically by using a group of guidewords. The proposed algorithm is used for qualitative simulation of batch processes to identify the effects of maloperations. The method is illustrated with a simple batch process and a batch reaction process. The results show that batch processes can be simulated qualitatively and hazards can be identified for operating procedures including maloperations. After analysis for possible plant maloperations, some measures can be taken to avoid maloperations or reduce losses resulted from maloperations.

The solubilities of some solid n-alkanes in supercritical ethane were correlated and predicted in this paper using the Carnahan-Starling-van der Waals model with a density-dependent parameter of a₁₂. At a given temperature, the linear fit of the parameter of a₁₂ and the density of the supercritical solvent was used for solubility correlation, resulting in an average absolute average relative deviation (AARD) of 8.68%, which was between the values of the semiempirical models and the other compressed gas models used in this article. In the linear fit of the parameter of a₁₂ and the density of the solvent, the regressed slope m and intercept n of the linear fit can be correlated with the carbon atom number of solid n-alkanes and then the solubilities of solid n-alkanes in supercritical ethane can be predicted with the intercept n and slope m. The average AARD in solubility prediction was 26.99%.

It is important to know how ILs (ionic liquids) influence organic reaction. In this paper, activity coefficients at infinite dilution of more than 80 organic compounds in ILs are collected and analyzed systematically. Through the study on typical organic reactions happened in ILs, such as Diels-Alder, esterification and Friedel-Crafts reaction, the ratio of activity coefficients at infinite dilution of products and reactants is employed to estimate different effects of different structural ILs on the rate and selectivity of reactions.

Caffeic acid phenethyl ester (CAPE) is a rare, naturally occurring phenolic food additive. This work systematically reported fundamental data on conversion of caffeic acid (CA), yield of CAPE, and reactive selectivity during the lipase-catalyzed esterification process of CA and phenylethanol (PE) in ionic liquids (ILs). Sixteen ILs were selected as the reaction media, and the relative lipase-catalyzed synthesis properties of CAPE were measured in an effort to enhance the yield of CAPE with high selectivity. The results indicated that ILs containing weakly coordinating anions and cations with adequate alkyl chain length improved the synthesis of CAPE. [Emim][Tf₂N] was selected as the optimal reaction media. The optimal parameters were as follows by response surface methodology (RSM): reaction temperature, 84.0 ℃; mass ratio of Novozym 435 to CA, 14:1; and molar ratio of PE to CA, 16:1. The highest reactive selectivity of CAPE catalyzed by Novozym 435 in [Emim][Tf₂N] reached 64.55% (CA conversion 98.76% and CAPE yield 63.75%, respectively). Thus, lipase-catalyzed esterification in ILs is a promising method suitable for CAPE production.

In situ capping is an attractive and cost-effective method for remediation of contaminated sediments, but few studies on enhancing contaminant degradation in sediment caps have been reported, especially for chlorinated benzenes. Electrically enhanced bioactive barrier is a new process for in situ remediation for reducible compounds in soil or sediments. The primary objective of this study is to determine if electrodes in sediment could create a redox gradient and provide electron acceptor/donor to stimulate degradation of chlorinated contaminant. The results demonstrate that graphite electrodes lead to sustainable evolution of hydrogen, displaying zero-order kinetics in the initial stages with different voltages. The constant rates of hydrogen evolution at 3, 4, and 5 V are 1.05, 2.54, and 4.3 nmol·L^-1·d^-1, respectively. Even higher voltage can produce more hydrogen, but it could not keep long time because the over potentials on electrode surfaces prevent its function. The study shows that 4 V is more appropriate for hydrogen evolution. The measured and evaluated concentration of 1,2,3,5-tetrachlorobenzene in pore water of sediment and concentration of sulfate show that dechlorination is inhibited at higher concentration of sulfate.

Parent coal tar pitch (CTP) was modified with boric acid (BA), cinnamaldehyde (CMA) and the mixture of BA and CMA, respectively. The parent CTP and three modified CTPs were characterized by elemental analysis, thermogravimetric analysis, Fourier transform infrared (FT-IR) spectroscopy and scanning electron microscopy. The four samples were carbonized at different temperatures and resultant carbonized products were characterized by FT-IR spectroscopy, X-ray diffraction and polarized-light microscopy. The results show that the morphologies and carbonization behaviors of the parent CTP and modified CTPs are quite different. The carbonization yield of the CTP modified with the mixture of BA and CMA is higher than that of CTP modified with BA or CMA only. In addition, the modification of CTP with 7 g of BA and 10 ml of CMA results in an increase in carbonization yield by 5.64%. During the pyrolysis of modified CTPs, the dehydration of BA or the distillation of CMA occurs at the temperature lower than 300 ℃, and methyl and methylene groups of the modified CTPs disappear gradually as temperature rises. Furthermore, the modification of CTP by the mixture of BA and CMA results in more intensive mesophase spheres than other modified CTPs, and the modified CTP is easier to be carbonized to form graphitic carbon.

The electrodeposition behavior of nickel at glassy carbon (GC) and stainless steel (SS) electrodes in low temperature urea-acetamide-NaBr-KBr melt was investigated using cyclic voltammetry, chrono-amperometric current-time transients and scanning electron microscopy. Cyclic voltammograms and dimensionless chronoamperometric current-time transients analysis show that the electrodeposition of nickel is an irreversible process and proceeds via three-dimensional progressive nucleation with diffusion-controlled growth on both GC and SS substrates. Scanning electron microscopic analysis indicates the nickel deposits obtained on SS electrode are generally uniform, dense, and adherent to the substrate with rounded crystallites in the nanometer size regime. It is also found that the crystal structure of the electrodeposited nickel is independent on the deposition potential. The nickel deposits produced from the melt at higher cathodic potential exhibit larger grain size.

In the absence of catalyst, 70% hydrogen peroxide was used to oxidize succinic anhydride to solid monoperoxysuccinic acid (PSA). Then PSA was applied to synthesis of ε-caprolactone (ε-CL) by oxidation of cyclohexanone in the heterogeneous system. In order to achieve material recycle, solid precipitated in the process of synthesizing ε-CL was dehydrated via reactive distillation followed by recrystallization to prepare succinic anhydride, which was characterized by IR (infrared spectra) and ¹HNMR (¹H nuclear magnetic resonance). Effects of molar ratio of PSA to cyclohexanone, acetic acid dosage, reaction temperature, reaction time on conversion of cyclohexanone, yield and selectivity of ε-CL were investigated respectively. The results indicated that conversion of cyclohexanone, yield and selectivity of ε-CL were upto 98.1%, 97.5% and 99.4% respectively under the optimal conditions. In addition, in the process of synthesizing succinic anhydride, the optimal yield of succinic anhydride reached 67.4%.

Most of traditional linear poly(ethylene terephthalate) (PET) resins of relatively low molecular mass and narrow molecular mass distribution have low melt strength at foaming temperatures, which are not enough to support and keep cells. An in-situ polymerization-modification process with esterification and polycondensation stages was performed in a 2 L batch stirred reactor using pyromellitic dianhydride (PMDA) or pentaerythritol (PENTA) as modifying monomers to obtain PETs with high melt strength. The influence of amounts of modifying monomers on the properties of modified PET was investigated. It was found that the selected modifying monomers could effectively introduce branched structures into the modified PETs and improve their melt strength. With increasing the amount of the modifying monomer, the melt strength of the modified PET increased. But when the amount of PENTA reached 0.35% or PMDA reached 0.9%, crosslinking phenomenon was observed in the modified PET. Supercritical carbon dioxide (ScCO₂) was employed as physical foaming agent to evaluate the foaming ability of modified PETs. The modified PETs had good foaming properties at 14 MPa of CO₂ pressure with foaming temperature ranging from 265 ℃ to 280 ℃. SEM micrographs demonstrated that both modified PET foams had homogeneous cellular structures, with cell diameter ranging from 35 μm to 49 μm for PENTA modified PETs and 38 μm to 57 μm for PMDA modified ones. Correspondingly, the cell density had a range of 3.5×10⁷ cells·cm^-3 to 7×10⁶ cells·cm^-3 for the former and 2.8×10⁷ cells·cm^-3 to 5.8×10⁶ cells·cm^-3 for the latter.

In this work, we describe a novel facile method to prepare long one-dimensional hybrid nanofibers by using hydrated bacterial cellulose nanofibers (BCF) as a template. Silver (Ag) nanoparticles with an average diameter of 1.5 nm were well dispersed on BCF via a simple in situ chemical-reduction between AgNO₃ and NaBH₄ at a relatively low temperature. A growth mechanism is proposed that Ag nanoparticles are uniformly anchored onto BCF by coordination with BC-containing hydroxyl groups. The bare BCF and as-prepared Ag/BCF hybrid nanofibers were characterized by several techniques including transmission electron microscopy, X-ray diffraction, thermogravimetric analyses, and ultraviolet-visible (UV-Vis) absorption spectra. The antibacterial properties of Ag/BCF hybrid nanofibers against Escherichia coli (E. coli, Gram-negative) and Staphylococcu saureus (S. saureus, Gram-positive) bacteria were evaluated by using modified Kirby Bauer method and colony forming count method. The results show that Ag nanoparticles are well dispersed on BCF surface via in situ chemical-reduction. The Ag/BCF hybrid nanofiber presents strong antibacterial property and thus offers its candidature for use as functional antimicrobial agents.

In this work we investigated the effect of nitric acid concentration on the pore structure, surface chemistry and liquid phase adsorption of olive stone based activated carbon prepared by mixing process using phosphoric acid and steam as activating agents. Chemicals and textural characterization show that the increase of HNO₃ concentration increases considerably the total acidic groups but decreases specific surface area and pore volume. The study of adsorption in aqueous solutions of two organics, phenol and methylene blue, on raw and oxidized activated carbon indicates that the treatment of mixed activated carbon with different concentrations of nitric acid improves the adsorbent capacity for methylene blue at HNO₃ concentrations less or equal to 2 mol·L^-1, while it has a negative effect on phenol adsorption.