Electrocatalysis of chlorine evolution on different materials and its influence on the performance of an electrochemical reactor for indirect oxidation of pollutants

Two different Ti/Pt–Ir materials (commercial and home made) and Ti/PdO + Co₃O₄ were investigated for their electrocatalytic properties versus Cl₂ evolution reaction. The materials were used in a batch electrochemical reactor to treat biologically recalcitrant di-azo compound. An electrochemically driven oxidation, mediated by a Cl₂/Cl⁻ couple, proved efficient for destruction of this complex organic molecule, causing cleavage of the conjugated double bonds and destruction of unsatured bonds. Both Ti/Pt–Ir materials performed well; lower kinetics obtained with the Ti/PdO + Co₃O₄ anode was caused by adsorption of the model compound, evidenced in preliminary voltammetric measurements. The dye oxidation reaction followed the second order kinetics with partial orders in the model compound and (time varying) chlorine concentrations equal to one. Specific energy consumption of 3.12 kWh m⁻³ proved the process more economic than the homogeneous phase oxidation.     

氯离子导体及其应用开发

本文围绕有希望实现实用化的PbCl_2基氯离子导体,着重从材料研制、应用探索及应用前景这三个方面概述了氯离子导体研究的状况和今后动向。     

间接原子吸收分光光度法测定聚丙烯、聚乙烯中的微量(?)

介绍用原子吸收分光光度法测定PE、PP氯含量。该方法采用氧气燃烧法处理样品,用Ag~+沉淀Cl~-,经分离后用原子吸收光谱测溶液中剩余Ag~+浓度,从而得到样品中氯含量。讨论了仪器参数、操作条件对测定结果的影响,结果表明,在分离前存放4～30分钟对测试结果无影响。火焰法的测定条件为波长328.1nm、灯电流7.5mA、狭缝宽度0.4nm、C_2H_2压力0.025MPa、空气压0.16MPa、燃烧器高度7.5mm。实验采用的离心转速2000r/min、时间5分钟、HNO_3浓度1%。该法灵敏度可达0.1μg/ml、相对标准误差<2%。     

液氨装置工艺计算及改造总结

介绍我公司液氯装置由活塞式氨气压缩机氨-CaCl2盐水系统改为带经济器的螺杆式氯气液化机组的工艺计算,新建装置特点以及改造后的装置在我公司运行情况和使用效果。经改造后的液氯装置每年可节约电费73万余元,同时提高了装置的安全可靠性。     

Photocatalytic degradation of gaseous perchloroethylene in continuous flow reactors: Rate enhancement by chlorine radicals

The degradation of perchloroethylene (PCE) by UV/TiO₂ photocatalysis in gas phase was studied. The degradation efficiency has been compared in different continuous flow reactors: a photocatalytic tangential reactor (PTR) where the air flows tangentially over the catalytic medium and two photocatalytic filtering reactors (PFR) where the air flows through the porous catalytic medium. The degradation rate shows a linear dependence with the concentration of pollutants (up to 350 mg PCE/N m³) for the PTR, but the degradation was negligible for the PFR. The degradation rate was enhanced by accelerating the chlorine radicals’ formation (by adding HCl in catalytic quantity in the air flow or by PCE over-heating). In these conditions, the oxidation rate constant of PCE in the PFR was about five times higher than that in the PTR, although the mass of catalyst involved in the PFR was about 10 times lower and the contact time was about a 1000 times shorter than that of the PTR. Thus, the catalyst is globally more efficiently used in the PFR, as the mass transfer is not limiting. As a result, a degradation mechanism of PCE, involving the generation of free chlorine radicals, as the first limiting step, has been confirmed.     

氯气干燥工艺技术的改进

阐述原有氯气干燥工艺存在的问题,配合烧碱产能由100kt/a扩产至140kt/a,充分利用原有氯气冷却净化设备,将原氯气干燥用单台泡沫塔更改成填料—泡罩,填料两塔串联流程,将将干燥剂硫酸改为外循环冷却工艺。使氯气干燥主要工艺指标即氯气中含由原为的500~1000×10-6降低到100×10-6以下。     

Domestic and Industrial Wastewater Treatment with Ozonated Activated Sludge

Poor sludge settleability is a problem encountered in many activated sludge wastewater treatment plants. This study was aimed at combatting the unwanted biological growths at the root of this phenomenon with ozone. Ozone dosed directly into the aeration basins of small activated sludge pilot plants treating both domestic and synthetic fuel wastewaters led to a substantial reduction of the bulking problem even at dosages as low as 6 to 10 mg/L. Ozone did not interfere in the delicate nutrient removal processes and significantly enhanced effluent quality.     

Improvement of structural stability and electrochemical activity of a cathode material LiNi0.7Co0.3O2 by chlorine doping

In the process of Li⁺ intercalation-deintercalation, electron removal is accompanied simultaneously. Oxygen was found to compensate electron removal both in theoretical calculations and practical experiments. Chlorine addition to LiNi_0.7Co_0.3O₂ was expected to exchange electrons in that Cl⁻ was easier to lose electrons than O²⁻. LiNi_0.7Co_0.3O_2−xCl_x was identified as a pure hexagonal lattice of α-NaFeO₂ type by X-ray diffraction. X-ray photoelectron spectroscopy was used to analyze the influence of chlorine substitution on the oxidation state of transition-metal ions. Charge-discharge experiments and cyclic voltammetry confirmed that chlorine addition was an effective way to improve reversible capacity and structural stability in cycles.     

耐盐性树脂PAA的合成及应用研究

以丙烯酸-丙烯酰胺为单体，过硫酸钾为引发剂，N，N-亚甲基双丙烯酰胺为交联剂。水浴阶梯升温共聚合成耐盐性树脂，采用正交试验通过分析，研究了主要因素对产物性能的影响，确定较佳反应条件：T=50℃(2h)～65℃(3h)，单体配比nAM：nAA=1：11，单体中和度[N]=90％～95％。引发剂浓度[I]=0．3％，单体浓度[M]=30％～35％，交联剂浓度[C]=0．025％～0．03％，并将此树脂作为缓释剂应用于固载二氧化氯中，取得了良好的效果。     

Fate of the chlorine and fluorine in a sub-bituminous coal during pyrolysis and gasification

The fate of the chlorine and fluorine present in a sub-bituminous coal from Indonesia during pyrolysis and gasification has been studied with fixed and entrained bed reactors. The rate profile for HCl evolved in the temperature programmed pyrolysis exhibits the main and shoulder peaks at 480 and 600 °C, respectively. Model experiments and subsequent Cl 2p XPS measurements show that HCl reacts with metal impurities and carbon active sites at 500 °C to be retained as inorganic and organic chlorine forms, from which HCl evolves again at elevated temperatures. It is suggested that the HCl observed in the coal pyrolysis may originate from the above-mentioned chlorine functionalities formed by secondary reactions involving the nascent char. In the CO₂ gasification of the 900 °C char at 1000 °C and 2.5 MPa, any measurable amounts of HCl and HF could not be detected even at a high conversion of 75 wt% (daf), suggesting the accumulation of these halogens in the residual char. When the coal is injected into an O₂-blown, entrained bed gasifier at 1200-1400 °C under 2.6 MPa, the partial oxidation proceeds to a larger extent at a higher O₂/coal ratio, whereas the chlorine and fluorine are enriched in the remaining char, and the extent of the enrichment at the latter stage of gasification is larger with the fluorine. The XPS measurements of the chars reveal the presence of the broad F 1 s peak, which can cover a wide range of binding energies attributable to inorganic and organic fluorine. The halogen enrichment during gasification is discussed in terms of secondary reactions of HCl and HF with char.