悬浮床加氢裂化油溶性催化剂与沥青质的作用

在高压釜反应器中对添加了油溶性 Ni 催化剂(UPC-O)和水溶性 Ni 催化剂(UPC-W)的辽河稠油常压渣油(LHAR)进行了悬浮床加氢裂化实验。通过元素分析和傅里叶变换红外光谱(FTIR)分析对抑制反应生焦效果好的 UPC-O 与 LHAR 沥青质的作用进行了研究。元素分析结果显示,在 LHAR 中加入 UPC-O1000μg/g,沥青质和脱沥青质油中 Ni 含量分别出476μg/g和110μg/g 增加到7 559μg/g 和1 024μg/g,表明 UPC-O 在沥青质中有富集的趋势。FTIR 表征结果显示,UPC-O 和沥青质发生了相互作用。UPC-O 可在沥青质原位硫化为活性组分,对沥青质在悬浮床加氢裂化反应中的缩合起到好的抑制作用。     

Syngas production via combined oxy-CO2 reforming of methane over Gd2O3-modified Ni/SiO2 catalysts in a fluidized-bed reactor

In this research, Ni/SiO₂ catalyst was modified with different amount of Gd₂O₃ and characterized with temperature-programmed desorption of CO₂ (CO₂-TPD) and NH₃ (NH₃-TPD), temperature-programmed reduction with H₂ (H₂-TPR) and X-ray diffraction (XRD). It was found that Gd₂O₃-modified Ni/SiO₂ catalysts possessed higher CO₂ adsorption and activation ability due to the formation of surface carbonate species. H₂-TPR and XRD characterizations found that the strong interaction among nickel, Gd₂O₃ and SiO₂ took place, which improved the dispersion of Ni. Gd₂O₃-modified Ni/SiO₂ catalysts exhibited higher activity and stability for the combined oxy-CO₂ reforming of methane in fluidized-bed reactor. The H₂/CO ratio in produced syngas could be controlled via controlling reaction temperature and CO₂/O₂ ratio in feed.     

Effect of carbon surface oxidation on platinum supported carbon particles on the performance of gas diffusion electrodes for the oxygen reduction reaction

The effect of carbon surface oxidation on platinum supported carbon particles (Pt/C) with nitric acid was investigated by cyclic voltammetry, electrochemical impedance spectroscopy, polarization experiments and chronoamperometry. Cyclic voltammograms, polarization curves and electrochemical impedance spectra showed that the treated catalyst had much larger active surface area and higher ionic conductivity than the untreated catalyst, and provided enhanced performance for oxygen reduction. The formation of acidic groups was examined by IR spectra. The Pt/C surface oxidation had a large effect on the performance of a gas diffusion electrode for oxygen reduction reaction.     

Surface modification of starch nanocrystals through ring‐opening polymerization of ε‐caprolactone and investigation of their microstructures

Bionanoparticles of starch obtained by submitting native potato starch granules to acid hydrolysis conditions. The resulted starch nanoparticles were used as core or macro initiator for polymerization of ε‐caprolactone (CL). Starch nanoparticle‐g‐polycaprolactone was synthesized through ring‐opening polymerization (ROP) of CL in the presence of Sn(Oct)₂ as initiator. The detailed microstructure of the resulted copolymer was characterized with NMR spectroscopy. Thermal characteristic of the copolymer was investigated using DSC and TGA. By introducing PCL, the range of melting temperature for starch was increased and degradation of copolymer occurred in a broader region. X‐ray diffraction and TEM micrographs confirmed that there was no alteration of starch crystalline structure and morphology of nanoparticles, respectively. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Restraining the associations of anthracene fluorophore by chemically linking to poly(methyl methacrylate)

Associations (dimer or aggregate) of anthracene (An) fluorophores tend to interrupt the monomer emission and reduce the quantum yield (Φ_PL); therefore, poly(methyl methacrylate) (PMMA) chain was used in this study to chemically link to anthracene and to block the mutual associations among the anthracene fluorophores. With this aim, the target polymers were prepared by anionic polymerizations with 9,10‐dibromoanthracene/s‐butyllithium as initiating system to proceed polymerizations of methyl methacrylate (MMA) directly or in the presence of 1,1‐diphenylethylene (DPE). Use of DPE before addition of MMA produces stable initiating anionic species and avoids potential side reactions during polymerization; however, it also introduces four β‐phenylene rings around the central anthracene ring, which interfere with the corresponding emission pattern and reduce the Φ_PL (32%) value due to potential interactions between phenylene rings and anthracene. On the contrast, polymerization without participation of DPE results in polymer with central anthracene ring directly connected to two PMMA chains, which gives clean vibronic emission pattern with limited association emissions and enhanced Φ_PL (52%) value. Physical blending of anthracene by PMMA is less efficient to restrain the associations and results in a film of lower Φ_PL (20%). © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation of branched polyacrylonitrile through self‐condensing vinyl copolymerization

Branched polyacrylonitrile (PAN) was prepared through a self‐condensing vinyl copolymerization of acrylonitrile and 2‐(2‐bromopropionyloxy)ethyl acrylate (BPEA). The branched architecture of the product was confirmed by NMR spectra and the average degree of branching (DB ) was estimated. Through a comparison of the intrinsic viscosity of the product with that of its linear analogue, the contraction factor g′ was calculated. It was found that the viscosity of the branched PAN was obviously lower that that of linear PAN. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effects of three crosslinkers on colored pH‐responsive core–shell latexes

Environmentally responsive hydrogels have become attractive research subjects for many applications. In this work, a series of pH‐sensitive and color‐changing nanoparticles (nanogels) with core–shell structures were synthesized. The cores were blue latex particles synthesized by a miniemulsion technique with styrene and methacrylic acid as monomers and Neozapon Blue 807 as a dye. The shell was a pH‐sensitive polymer that was precipitation‐polymerized onto the core from 2‐(diethylamino) ethyl methacrylate with N,N′‐methylenebisacrylamide, poly(propylene glycol) diacrylate, and divinylbenzene as crosslinking agents. In the resultant latexes, the color was observed to change from deep blue to pale blue as the pH of the system was changed from a high of 10 to a low of 3. The synthesized latexes and particles (gels) were then characterized with an ultraviolet–visible spectrometer, dynamic light scattering, Fourier transform infrared, and nuclear magnetic resonance. Atomic force microscopy was also used to investigate the different morphologies of the particles after the synthesized latexes were dried at different pH values. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis of poly(methyl methacrylate)/silica nanocomposite through emulsion polymerization using dimethylaminoethyl methacrylate

Polymer/Silica nanocomposite latex particles were prepared by emulsion polymerization of methyl methacrylate (MMA) with dimethylaminoethyl methacrylate (DM). The reaction was performed using a nonionic surfactant and in the presence of silica nanoparticles as the seed. The polymer‐coated silica nanoparticles with polymer content and number average particle sizes ranged from 32 to 93 wt % and 114–310 nm, respectively, were obtained depending on reaction conditions. Influences of some synthetic conditions such as MMA, DM, surfactant concentration, and the nature of initiator on the coating of the silica nanoparticles were studied. Electrostatic attraction between anionic surface of silica beads and cationic amino groups of DM is the main driving force for the formation of the nanocomposites. It was demonstrated that the ratio of DM/MMA is important factor in stability of the system. The particle size, polymer content, efficiency of the coating reaction, and morphology of resulted nanocomposite particles showed a dependence on the amount of the surfactant. Zeta potential measurements confirmed that the DM was located at the surface of the nanocomposites particles. Thermogravimeteric analysis indicated a relationship between the composition of polymer shell and polymer content of the nanocomposites. The nanocomposites were also characterized by FTIR and differential scanning calorimetry techniques. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Kinetics study of Ti[O(CH2)4OCHCH2]4 initiated ring‐opening polymerization of ε‐caprolactone by differential scanning calorimetry

Chemical shrinkage was used for the in situ measurement of the progressing chemical stabilization reactions and the influence of ozone during the stabilization of polyacrylonitrile. A method for evaluating the activation energy through the sensitivity temperature is presented. The calculated results show that the activation energies were 161.57 kJ/mol in air and 181.23 kJ/mol in ozone-enriched air. Therefore, the chemical reactions were postponed during stabilization in ozone-enriched air. Ozone seemed to act in three ways: first, ozone promoted the formation of the serious skin–core structure. Second, ozone accelerated the chemical reactions and shortened the stabilization time at lower heating rates. Third, ozone postponed the chemical reactions. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Maghnite‐H+, a solid catalyst for the cationic polymerization of α‐methylstyrene

The polymerization of α‐methylstyrene (AMS) catalyzed by Maghnite‐H⁺ (Mag‐H) was investigated. Mag‐H is a montmorillonite sheet silicate clay, exchanged with protons. It was found that the cationic polymerization of AMS is initiated by Mag‐H at ambient temperature in bulk and in solution. The effect of the amount of Mag‐H, the temperature, and the solvent was studied. The polymerization rate increased with increase in the temperature and the proportion of catalyst, and it was larger in nonpolar solvents. These results indicated the cationic nature of the polymerization. It may be suggested that the polymerization is initiated by proton addition to monomer from Mag‐H. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008