Ring hydrogenation of naphthalene and 1-naphthol over supported metal catalysts in supercritical carbon dioxide solvent

Catalytic ring hydrogenations of naphthalene and 1-naphthol were studied over several supported metal catalysts in supercritical carbon dioxide solvent at low temperature. Higher concentration of hydrogen in supercritical carbon dioxide and lower reaction temperature were responsible for higher catalyst activity and selectivities to the desired partial ring hydrogenated products as compared with those observed in organic solvent for the same catalyst.     

煤气初冷器喷洒洗萘工艺的改进

针对初冷器喷洒洗萘存在的堵塞和阻力大等问题，相应采取了改进工艺和调整操作参数等措施，即确保了出厂煤气的质量，又提高了生产的安全性。     

Synthesis and properties of liquid crystalline polymers with low Tm and broad mesophase temperature ranges

Novel thermotropic liquid crystalline polymers (TLCP) with improved processability and lower cost than Vectra^® were synthesized by esterification and melt polycondensation. Aromatic compounds, 6-hydroxyl-2-naphthoic acid, 2,6-naphthlenedicarboxylic acid, 4-hydroxybenzoic acid or terephthalic acid, were used as polycyclic stiff rod-like mesogenic groups. Aliphatic diol, ethylene glycol or 1,4-butanediol was used as flexible spacers to form semi-flexible main chain TLCP. The LCP products were characterized by FT-IR and ¹H NMR to identify their chemical structures. The analytical results showed the polymers had inherent viscosities of 0.35-0.54 dL/g. The crank shaft structure of the naphthalene decreased the melting temperature (T_m) of LCP (181-272 °C) to facilitate extrusion or injection molding, and maintained relatively high heat deflection temperature for high performance engineering plastics applications. The 5% weight loss decomposition temperatures were above 400 °C. LCPs have good solvent resistance and low hygroscopicity. The SEM morphology showed strong orientation on the surface in the flow direction and many micro-fibers structure in a sectional drawing. The optical textures of polymers observed by POM revealed a strong birefringence in the melts and indicated that they form nematic mesophase. All polymers have broad mesophase temperature (ΔT_meso) ranges.     

国内外石油萘生产技术进展

介绍了近年来国内外萘的主要生产技术及发展状况 ,尤其是石油萘的生产技术。指出了我国石油萘发展应解决的问题     

Liquid crystal polyarylates containing 2,6-naphthalene dicarbonyl group (I): Effects of kinky monomers on thermal and anisotropic behaviors

A series of copolyarylates primarily based upon 2,6-naphthalene dicarboxylic acid, hydroxybenzoic acid and 4,4-biphenol were prepared by slurry-melt polymerization with Santotherm 66 as a heat exchange medium. The frequently used kinky monomer, resorcinol or isophthalic acid, was introduced into these copolyarylates to modify the chemical strcture. The relationship of the thermal behavior and the crystalline structures for these copolymers was studied by means of DSC and wide angle X-rays diffraction. The amount of mcorporated kinky modifier was found to produce a significant effect on the liquid crystalline phase and the melting temperature of the copolyarylates. All of these liquid crystal polymers exhibited nematic textures; shreaded and/or Schlieren type, depending upon the incorporated kinky monomer. The liquid crystal polymers modified by isophthalic acid (up to 40 mole % of 2,6-naphthalene dicarboxylic acid replaced by isophthalic acid) possessed shreaded texture however high the temperatures of the polymer melts were. The liquid crystal polymers modified by resorcinol (60 to 100 mole % of 4, 4-biphenol replaced by resorcinol), however, would have two types of nematic textures: the shreaded texture occurred when the temperature of the polymer melt was between the melting temperature and the anisotropic transition temperature; the Schlieren texture existed when the temperature of the polymer melt was high above the anisotropic transition temperature. The Schlieren texture formed only when a liquid crystal polymer revealed good flowability and lower rigidity. The polydomain concepts could be utilized to explain the observed textures of these copolyarylates clearly.     

A naphthalene sublimation study on heat/mass transfer for flow over a flat plate

It is important to completely understand heat/mass transfer from a flat plate because it is a basic element of heat/mass transfer. In the present study, local heat/mass transfer coefficient is obtained for two flow conditions to investigate the effect of boundary layer using the naphthalene sublimation technique. Obtained local heat/mass transfer coefficient is converted to dimensionless parameters such as Sherwood number, Stanton number and Colburnj-factor. These also are compared with correlations of laminar and turbulent heat/mass transfer from a flat plate. According to experimental results, local Sherwood number and local Stanton number are in much better agreement with the correlation of turbulent region rather than laminar region, which means analogy between heat/mass transfer and momentum transfer is more suitable for turbulent boundary layer. But average Sherwood number and average Colburnj-factor representing analogy between heat/mass transfer and momentum transfer are consistent with the correlation of laminar boundary layer as well as turbulent boundary layer.     

Oxidative decomposition of naphthalene by supported metal catalysts

A fixed-bed reactor was utilized to investigate the activities of six metal catalysts (1% Pt, 1% Pd, 1% Ru, 5% Co, 5% Mo and 5% W on γ-Al₂O₃ support) in decomposing naphthalene, based on the production of carbon dioxide and the disappearance of naphthalene. The Pt and Pd catalysts were found to exhibit higher naphthalene oxidizing activity than other catalysts tested. The Co catalysts, whose activity is similar to that of the Ru catalysts, are promising for naphthalene oxidation. The kinetic results of naphthalene oxidation over 1% Pt/γ-Al₂O₃ catalysts are reported for the first time. A first-order reaction with respect to P_naphthalene was found, while the reaction order with respect to P_O2 decreased with increasing reaction temperatures. A Langmuir–Hinshelwood model was used to describe the observed kinetic behavior. Oxygen adsorption dominates at higher reaction temperatures (>140 °C), and consequently the oxidation of naphthalene over the Pt catalysts appeared to be insensitive to P_O2.     

集成煤气脱萘与冷凝液回用的终冷工艺

新的终冷工艺集成了煤气冷却、煤气脱萘与煤气冷凝液利用,使煤气净化单元实现煤气梯级冷却。利用终冷器上段冷凝液作为脱氨工序的软水,可以减少焦炉煤气净化单元的剩余氨水量。终冷器利用洗油脱除煤气中的萘,含萘洗油经加热、油水分离后,送往洗苯-脱苯工序再生。     

降低初冷工序后煤气含萘的措施

对初冷工序后煤气含萘高的原因进行了分析,针对存在的问题提出了解决方案,进行了技术改造。实践证明,改造方案经济、可行、有效。     

Thermal stability of metal-supported catalysts for reduction of cold-start emissions in a wood-fired domestic boiler

The aim of the present work is to develop a catalyst based on a mixture of manganese oxides and platinum supported on a metallic monolith for abatement of emissions from wood combustion, particularly during the cold-start phase. The activity and the thermal stability of the catalysts have been studied in the laboratory, before performing tests in a wood-stove. The effect of the hydrothermal treatment at 900°C on the adherence of the washcoat onto a metallic substrate was studied using scanning electronic microscope. It revealed well-adhering washcoat onto the metallic support due to the growth of the alumina whiskers during the treatment. The influence of the amount of washcoat, as well as the influence of the concentration of manganese oxides in it (Mn: 5 to 20 mol%/Al₂O₃) on the activity of fresh and hydrothermally-treated catalysts were studied. The activity tests were carried out using a mixture of carbon monoxide, naphthalene and methane in the presence of air, steam and carbon dioxide to resemble the flue gases from wood combustion. On the fresh catalysts, containing the same total amount of manganese, a high concentration of manganese oxides in the washcoat favoured the oxidation of carbon monoxide and naphthalene, whereas a lower concentration of manganese oxides in the washcoat gave higher activity for the oxidation of methane. An increased total amount of manganese oxides in the catalysts, which had the same amount of washcoat, resulted in an increase in activity for the oxidation of the three combustibles. After thermal treatment at 900°C for 270 h in steam, most of the manganese oxide catalysts were activated for the oxidation of carbon monoxide and naphthalene while only being slightly deactivated for the oxidation of methane. The addition of manganese oxides in the washcoat, however, lowers the temperature of the γ- to -alumina phase transformation. Platinum (0.5 mol%) was added to the manganese oxide (10 mol%) catalyst to improve its activity. A platinum catalyst was also tested for comparison. The platinum and the mixed catalysts showed similar activity for the oxidation of carbon monoxide and naphthalene, while the mixed catalysts were more active for the oxidation of methane. A similarly mixed MnO_x–Pt (10–0.5 mol%) catalyst supported on Al₂O₃ stabilised with 3% lanthanum, but at larger scale, was tested in a wood-stove. The possibility of pre-heating the catalyst during the start-up phase was studied. The tests revealed a strong decrease of the carbon monoxide and unburned hydrocarbons emissions during the start-up phase when the catalyst was pre-heated with hot air compared with no pre-heating or no catalyst.