无烟煤型焦反应性的研究

以无烟粉煤为主配料,分别添加ＲＳＬ和ＲＳＦ两种热塑性粘结剂。采用冷压成型高温干留制备型焦的工艺,获得几种无烟煤型焦样品,并对其进行了反应性测试。重点研究了无烟煤煤阶和粘结剂对型焦反应性的影响,为便于分析,同时对粘结剂和原料无烟煤的反应性进行了研究。研究结果表明,煤阶和粘结剂性质是影响型焦反应性的主要因素。型焦反应性随煤阶变化规律与其原料无烟煤一致,说明煤的性质可决定其型焦的反应性;另外,由两种粘结     

Study on monomer reactivity ratios of acrylonitrile/itaconic acid in aqueous deposited copolymerization system initiated by ammonium persulfate

A single water-soluble initiator-ammonium persulfate (APS), not containing alkali metal ions, was first utilized to initiate copolymerization of acrylonitrile (AN)/itaconic acid (IA) in aqueous deposited copolymerization system. Monomer reactivity ratios of this polymerization system were investigated using element analysis method and Q–e schemes. It was found that the monomer reactivity ratios of AN/IA calculated from Q–e schemes are 0.505 (r _AN) and 1.928 (r _IA), while the monomer reactivity ratios of AN/IA in aqueous deposited copolymerization system at 60 °C are 0.64 (r _AN) and 1.37 (r _IA) calculated from Kelen–Tüdõs method, 0.61 (r _AN) and 1.47 (r _IA) from Fineman–Ross method. The three pairs of monomer reactivity ratios are in good agreement. With the increase of the polymerization temperature, the monomer reactivity ratios of AN and IA approach to unity, indicating that the aqueous deposited copolymerization of AN/IA has a tendency to ideal copolymerization. At lower polymerization conversion, the monomer reactivity ratios of AN and IA have hardly any changes. When the polymerization conversion is more than 5%, the monomer reactivity ratio of AN increases, while that of IA decreases.     

Activation of glassy carbon electrodes by photocatalytic pretreatment

This paper describes a simple and rapid photocatalytic pretreatment procedure that removes contaminants from glassy carbon (GC) surfaces. The effectiveness of TiO₂ mediated photocatalytic pretreatment procedure was compared to commonly used alumina polishing procedure. Cyclic voltammetric and chronocoulometric measurements were carried out to assess the changes in electrode reactivity by using four redox systems. Electrochemical measurements obtained on photocatalytically treated GC electrodes showed a more active surface relative to polished GC. In cyclic voltammograms of epinephrine, Fe(CN)₆^3−/4− and ferrocene redox systems, higher oxidation and reduction currents were observed. The heterogeneous electron transfer rate constants (k^o) were calculated for Fe(CN)₆^3−/4− and ferrocene which were greater for photocatalytic pretreatment. Chronocoulometry was performed in order to find the amount of adsorbed methylene blue onto the electrode and was calculated as 0.34 pmol cm⁻² for photocatalytically pretreated GC. The proposed photocatalytic GC electrode cleansing and activating pretreatment procedure was more effective than classical alumina polishing.     

The characterization and chemical reactivity of powdered wool

Wool powders with various particle sizes have been produced using different milling techniques. Scanning electron microscopy (SEM) showed gradual breakdown of the fibre as it was progressively converted into powder form. Chlorination enhanced the effectiveness of subsequent air-jet milling. X-ray photoelectron spectroscopy (XPS) revealed an increase in the surface concentrations of oxygen and nitrogen, and a decrease in carbon and sulphur on conversion of the fibres into powders, as the cortex became exposed on the powder surface. An increased surface concentration of cysteic acid was observed for the chlorinated powder. Rapid uptake of dye by wool powders was observed in situations where there was virtually no uptake by the original fibre. Hydrophobic dyes were more readily sorbed than were hydrophilic dyes. The chlorination treatment led to a decrease in the sorption of acid dyes. Confocal microscopy, used in conjunction with a fluorescent stain, showed that chemicals were able to penetrate wool particles, even at room temperature. The rate and extent of uptake of dye by the finer powders were comparable to that obtained with activated charcoal, even though the surface area of the charcoal was 100 times greater.     

低温固化聚酯卷材涂料的研制

选用合适单体合成高反应活性聚酯树脂,介绍了树脂的合成工艺,以高亚氨基部分醚化氨基树脂为交联剂,自制二壬基二磺酸为催化剂,制成低温固化卷材涂料。所制备的涂料具有很好的耐候性和加工成型性能。讨论了影响涂料性能的因素。     

钙基CO_2吸收剂循环活性衰减原因初探

对钙基CO2吸收剂的循环活性衰减进行了实验研究,考察了随着循环次数的增加,吸收剂的表面形态、吸收剂分子孔径及比表面积等微观结构的变化,分析了钙基CO2吸收剂循环活性衰减的原因。结果表明,随着循环次数的增加,吸收剂晶粒中的片状结构已经完全消失,取而代之的是正方体状的大晶粒,晶粒生长严重,大量空隙被封闭。而由此引起的吸收剂的比表面积的不断减小和孔容积的降低以及孔分布的改变,导致了吸收剂循环活性的衰减,吸收剂的循环转化率降低。     

硫杂质对焦反应性的影响及其机理(英文)

采用以低杂质沥青焦模拟石油焦和外掺杂的方式,研究硫杂质元素对焦反应性的影响,并通过XRD、SEM和EDS等检测手段探讨其作用机理。结果表明:在无其他杂质元素干扰的情况下,硫实际上是一种对焦的空气和CO2反应性都具有明显催化性的杂质元素。其催化作用可能是通过在焦的空气和CO2反应过程中分别引发有机硫→H2S→SO2→COS和单质硫(S x)→SO2和有机硫→H2S→COS→S x→C2S→COS两组可部分循环并具有增加碳耗和增大焦比表面积作用的反应体系来实现的。     

Copolymerization of methyl methacrylate with 4‐vinylpyridine initiated by a novel Ni(II)α‐Benzoinoxime complex

Copolymerizations of methyl methacrylate (MMA) with 4‐vinylpyridine (4VP) were performed from different monomer feed ratios in 1,4‐dioxan at 30°C under free radical initiation experimental conditions, using Ni(II)α‐Benzoinoxime complex as initiator. The obtained copolymers (PMMA4VP) were examined by FTIR and ¹H NMR spectroscopies. The composition of these copolymers was calculated, using ¹H NMR spectra and elemental analysis. Monomer reactivity ratios were estimated from Fineman–Ross (FR, r_m = 0.550, r_v = 1.165) and Kelen–Tudos (KT, r_m = 0.559, r_v = 1.286) linearization methods, as well as nonlinear error in variables model (EVM) method using the RREVM computer program (RREVM, r_m = 0.559, r_v = 1.264). These values suggest that MMA‐4VP pair copolymerizes randomly. ¹H NMR spectra provide information about the stereochemistry of the copolymers in terms of sequence distributions and configurations. These results showed that the age of the Ni complex has an impact not only on its activity towards polymerization reactions but also on the features of the corresponding copolymers, whereas the chemical composition was insensitive to this prominent factor. The mechanism of MMA‐4VP copolymerization is consistent with a radical process as supported by microstructure and molecular weight distribution studies. Thermal behaviours of these copolymers were investigated by differential scanning calorimetry and thermogravimetric analysis. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Decomposition of methane and its reaction with CO2 over Rh/ZSM-5 catalyst

The decomposition of methane, its conversion into higher hydrocarbons and the reaction between CH₄ and CO₂ have been investigated on Rh/ZSM-5 in a fixed bed continuous-flow reactor. Independently of the temperature at 523–973 K, the decomposition of methane gave hydrogen, surface carbon and a small amount of ethane: ethylene and benzene were not detected. The reactivity of surface carbon formed at different temperatures has been examined toward H₂, O₂ and CO₂. The carbon exhibited less reactivity toward CO₂. The reaction between CH₄ and CO₂ occurred rapidly above 673 K to give CO and H₂ with a ratio of 1.3–1.6. Very little carbon was deposited during the reaction. It is concluded that the facile reactions between CH_x and CO₂ are responsible for the lack of carbon deposition. However, a significant amount of carbon deposition and the deactivation of the catalyst occurred when more than 4–5% of ethane was added to the reacting gas mixture. The extent of deactivation can be decreased by using a large excess of CO₂. This revised version was published online in June 2006 with corrections to the Cover Date.     

Asymmetric bihomologous crosslinkers for bicomponent gels—The way to strongly increased elastic moduli

2‐Hydroxyethylmethacrylate (HEMA) and acrylamide (AA) have been copolymerized via free radical mechanism, in the presence of 5 mol % of four different crosslinker systems, the symmetric ethylenglycoldimethacrylate (EGDMA), bisacrylamide (BIS), a mixture of EGDMA and BIS, and the asymmetric acrylamideethylenmethacrylate (METAA). The polymerizations have been monitored with a rheometer, exhibiting the gel obtained with the asymmetric METAA, an elastic modulus that is dramatically increased compared with those of the gels prepared with the other three crosslinker systems. A kinetic analysis using the terminal model has been used to build probabilistic surfaces that give information about how the crosslinker is incorporated into the network. This analysis shows a high dissimilarity between the reactions using the asymmetric and the mixture of symmetric crosslinkers, what has been correlated to the difference in modulus. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010