化学事故救援方舱舱室环境安全性模拟研究

运用计算流体动力学(CFD)方法,对具有超压防护功能的某化学事故应急救援手术方舱室内气体污染物运动扩散的规律以及对人员安全的影响进行了数值模拟,其研究结果表明:当大气环境中氢氰酸(HCN)浓度为5mg/L时,前10s从常规进风口进入舱室的HCN在滤毒通风装置开启后,随气流运动逐渐向整个舱室扩散,经净化空气的混合稀释作用,绝大部分通过舱体缝隙排出舱室,30min内舱室HCN浓度的总量下降了95.1%,说明超压防护很好地保证了舱室环境的安全性。     

氰化物测定机理的研究

研究了酒石酸-硝酸锌法提取易释放氰化物,磷酸-EDTA提取总氰的机理;对异烟酸-吡唑啉酮光度法测定氰化物的条件作了探讨。     

化学法处理高浓度电镀废水

分析、总结了采用化学法处理高浓度电镀废水中的含氰废水、含镍废水、含铬废水和含酸废水的工程设计、调试和实际运行情况。实践表明,化学法处理高浓度电镀废水是行之有效的,而用PH／ORP计控制好废水处理中的化学反应是稳定运行的关键。     

Cyanide Removal by Chinese Vegetation. Quantification of the Michaelis-Menten Kinetics (6 pp)

Background Little is known about metabolism rates of environmental chemicals by vegetation. A good model compound to study the variation of rates among plant species is cyanide. Vascular plants possess an enzyme system that detoxifies cyanide by converting it to the amino acid asparagine. Knowledge of the kinetic parameters, the half-saturation constant (Km) and the maximum metabolic capacity (vmax), is very useful for enzyme characterization and biochemical purposes. The goal of this study is to find the enzyme kinetics (KM and vmax) during cyanide metabolism in the presence of Chinese vegetation, to provide quantitative data for engineered phytoremediation, and to investigate the variation of metabolic rates of plants. Methods Detached leaves (1.0 g fresh weight) from 12 species out of 9 families were kept in glass vessels with 100 mL of aqueous solution spiked with potassium cyanide at 23°C for 28 h. Four different treatment concentrations of cyanide were used, ranging from 0.44 to 7.69 mg CN/L. The disappearance of cyanide from the aqueous solution was analyzed spectrophotometrically. Realistic values of the half-saturation constant (KM) and the maximum metabolic capacity (vmax) were estimated by a computer program using non-linear regression treatments. As a comparison, Lineweaver-Burk plots were also used to estimate the kinetic parameters. Results and Discussion The values obtained for KM and vmax varied with plant species. Using non-linear regression treatments, values of vmax and KM were found in a range between 6.68 and 21.91 mg CN/kg/h and 0.90 to 3.15 mg CN/L, respectively. The highest vmax was by Chinese elder (Sambucus chinensis), followed by upright hedge-parsley (Torilis japonica). The lowest vmax was demonstrated by the hybrid willow (Salix matssudana x alba). However, the highest KM was found in the water lily (Nymphea teragona), followed by the poplar (Populus deltoides Marsh). The lowest KM was demonstrated by corn (Zea mays L.). The values of vmax were normally distributed with a mean of 13 mg CN/kg/h. Conclusions Significant removal of cyanide from aqueous solution was observed in the presence of plant materials without phytotoxicity, even at high doses of cyanide. This gives rise to the conclusion that the Chinese plant species used in this study are all able to efficiently metabolize cyanide, although with different maximum metabolic capacities. A second conclusion is that the variation of metabolism rates between species is small. All these plants had a similar KM, indicating the same enzyme is active in all plants. Recommendations and Outlook Detoxification of cyanide with trees seems to be a feasible option for cleaning soils and water contaminated with cyanide. For phytoremediation projects, screening appropriate plant species adapted to local conditions should be seriously considered. More chemicals should be investigated to find common principles of the metabolism of environmental chemicals by plants.     

沉淀-电解氧化法处理高铁氰化废水

采用沉淀-电解氧化联合技术处理高铁氰化提金废水,重点考察了沉淀剂添加量、沉淀时间、温度、电解电压、电解时间等因素对总氰、游离氰和铁氰络合物去除率的影响。结果表明,随着CuCl₂加入量的增大,氰化废水中各主要离子的沉淀率逐步增加。常温下向100 mL含氰废水中加入3.0 g CuCl₂并搅拌40 min后,总氰(CN_T)、CN⁻、Fe离子的去除率分别可达到95.29%、98.00%与100%。以钛板为阴阳极,采用一阴两阳体系对沉淀后液进行电解氧化实验,当电压为6 V、极间距为15 mm、电解时间为5 h、初始浓度为60%的条件下,CN_T和CN⁻的去除率最高可达到99.76%和99.90%。XRD分析表明,沉淀过程中铜氰、铁氰络合离子的去除主要归因于CuCN、Cu₂Fe(CN)₆、CuSCN等沉淀的形成。电解氧化过程中随着外加电压与氯离子浓度的增大,废水中残存的游离氰与金属氰络合离子的去除率逐渐增加,这主要是阳极反应产生的Cl₂/ClO⁻等强氧化剂作用的结果。以上研究结果可为高铁氰化提金废水的综合处理提供参考。     

液体高铁酸钠同时去除电镀废水中氰化物和重金属

采用自制的电化学装置在线制备液体高铁酸钠,然后将制得的高铁酸钠投加到电镀废水中进行处理,考察不同pH值和不同高铁酸钠投加量对废水中总氰化物、Cu2+、Ni2+去除率的影响;对比研究了高铁酸钠氧化法和次氯酸钠氧化法在处理低浓度含氰电镀废水的效果。结果表明,当pH为9~10,高铁酸钠的最佳投加量为0.024~0.048 mmol·L-1时,总氰化物、Cu2+和Ni2+的同时去除率均在90%以上;在处理低浓度含氰电镀废水时,高铁酸钠对总氰化物、Cu2+和Ni2+的同时去除率均明显高于次氯酸钠。这是因为高铁酸钠能够有效地氧化多种络合态的氰化物,包括Cu（CN）43-、Cu（CN）42-、Ni（CN）42-等,使废水中的重金属转变为离子态;然后在碱性条件下,在高铁酸盐还原产物-Fe（OH）3助凝和絮凝作用下,反应生成沉淀,达到同时去除氰化物和重金属的目的。     

絮凝-电解氧化联合处理氰化提金废水

采用絮凝-电解氧化联合技术处理氰化废水,主要研究了聚硅酸铝铁 (PSAF) 添加量、絮凝时间、pH、电压、电解时间、极板间距对总氰(CN_T)、游离氰(CN⁻)、Cu、Zn离子去除率的影响,并对其反应机制做了分析。研究表明,当PSAF添加量为2 g·L⁻¹,絮凝时间为30 min,pH为9条件下,CN_T、CN⁻、Zn、Cu离子的去除率分别可达42.97%、100%、84.40%、34.88%。Zn(CN)₄²⁻、Cu(CN)₃²⁻、CN⁻的吸附量分别为567.88、89.76、439.74 mg·L⁻¹。以钛板为阴极,石墨板为阳极,采用一阴两阳体系对絮凝后液进行电解氧化实验,在电压为3 V、电解时间为2 h、极板间距为10 mm条件下,CN_T、CN⁻、Zn、Cu离子的去除率可达91.70%、100%、99.15%、94.49%。絮凝过程中Zn(CN)₄²⁻、Cu(CN)₃²⁻、CN⁻的去除是由电荷中和和化学吸附共同作用的,其中电荷中和起主要作用。Zn(CN)₄²⁻、Cu(CN)₃²⁻、CN^-的化学吸附主要归因于其与PSAF水解产生的羟基阳离子发生交换反应。XRD分析表明,加入酸性絮凝剂PSAF的瞬间,部分Zn(CN)₄^2-反应为Zn(CN)₂沉淀。电解氧化过程中Zn(CN)₄²⁻、Cu(CN)₃²⁻破络释放的氰根会被阳极表面产生的O₂、·OH完全氧化为N₂和CO₂,Zn、Cu离子在阴极板电沉积而被去除。     

电解氧化法处理黄金冶炼厂选冶废水

采用电解氧化法处理同时含有高浓度氰化物与COD的黄金冶炼厂选冶废水,主要考查了外加电压、溶液pH、电解时间及极板间距等因素对氰化物和COD去除率的影响,充分利用原水中Cl^-的阳极氧化效应,深入探讨了电化学氧化过程及污染物氧化去除机理。结果表明,随着外加电压和电解时间的增大,氰化物和COD去除率逐渐增大。以石墨为阳极,钛合金为阴极,采用一阴两阳电解体系对废水进行氧化,当电压为4.5 V、初始pH为7、电解时间为3 h、极板间距为1.5 cm的条件下,总氰化物 (CN_T) 、COD、SCN^-及Cu的去除率最高可达99.6%、96%、99.9%与99.2%。电解过程中体系pH逐渐降低,电场作用下定向迁移至阳极附近的污染物去除主要归因于HClO及ClO^-的间接氧化作用,当pH大于5.0时以HClO的氧化为主,ClO^-的氧化为辅,而pH小于5.0时则主要是HClO的氧化。电解氧化过程中约有36.17%的Cu与SCN^-形成CuSCN沉淀而被除去,剩余的铜则扩散至阴极沉积析出。GC-MS分析表明,烷烃类、酯类、酮类等大分子的C=C键、酯基、羰基等化学键和官能团被氧化断链成小分子物质,随后继续被氧化为H₂O、CO₂和N₂。     

Detoxification of ferrocyanide in asoil–plant system

The detoxification of iron cyanide in a soil–plant system was investigated to assess the total cyanide extracted from contaminated soil and allocated in the leaf tissue of willow trees(Salix caprea). They were grown in soil containing up to 1000 mg/kg dry weight(dw) of cyanide(CN),added as ~(15)N-labeled potassium ferrocyanide and prepared with a new method for synthesis of labeled iron cyanides. CN content and ~(15)N enrichment were monitored weekly over the exposure in leaf tissue of different age. The ~(15)N enrichment in the young and old leaf tissue reached up to 15.197‰ and 9063‰, respectively; it increased significantly over the exposure and with increasing exposure concentrations(p 0.05). Although the CN accumulation in the old leaf tissue was higher, compared to the young leaf tissue(p 0.05), the ~(15)N enrichment in the two tissue types did not differ statistically. This indicates a non-uniform CN accumulation but a uniform ~(15)N allocation throughout the leaf mass. Significant differences were detected between the measured CN content and the C~(15)N content, calculated from the ~(15)N enrichment(p 0.05), revealing a significant CN fraction within the leaf tissue, which could not be detected as ionic CN. The application of labeled iron CN clearly shows that CN is detoxified during uptake by the willows. However, these results do not exclude other detoxification pathways, not related to the trees. Still, they are strongly indicative of the central role the trees played in CN removal and detoxification under the experimental conditions.     

丙烯腈含量的测定改进

总结了常用测定丙烯腈原料含量方法存在的不足，提出了以１００减去水分和有机杂质的方法来确定丙烯腈含量。并对瓣老测定方法进行对比验证，结果表明，改进的方法操作简单，数据准确，可行。