大气臭氧损耗中双自由基反应机理的量子化学研究

用量子化学ＲＨＦ理论方法研究了单重态双自由基ＮＨ,ＣＨ２、ＣＣＬ２与大气臭氧Ｏ３的反应机理。在３－２１Ｇ水平上用梯度解析技术优化了上述瓜在的反应物、中间体和产物构型,６－３１Ｇ或６－２１Ｇ计算能量,得到了各构型的有关结构数据。计算表明：上述反应分２步进行,双自由基先与Ｏ３反应生成稳定的中间体,然后在光照条件下中间体分解为ＮＨＯ、Ｈ２Ｃ烽ＣＬ２ＣＯ等稳定分子。从动力学看,２步反应分别为「π４ｓ＋Ｗ２     

三维电催化氧化处理难生化降解有机废水研究进展

难降解有机废水成分复杂、危害大,易导致癌变、畸变,对人类健康产生重大影响,是需要优先治理的环境问题.在许多情况下,采用传统生物法和物理化学法来处理难生化处理有机废水很难达到理想的处理效果,并且其操作工艺复杂,成本相对较高.三维电催化氧化技术的出现为难降解有机废水的处理提供了一种绿色环保高效的方法.三维电催化氧化体系具有...     

突发事件下多种信息交互传播的动力机制与调控策略

针对突发事件下多种信息共存情境中信息交互传播的调控问题,首先界定了该情境中“涌现→传播”过程的组成要素,建立了信息交互关系框架及其系统动力学模型;其次,通过设计和仿真基础情景,将仿真结果与案例进行对比,检验模型的模拟趋势与现实状况的一致性;最后,通过设计和仿真实验情景,考查决策者的关键可控因素对系统演化的影响。研究结果表明:官方渠道所发布信息的可信度、平均个体传播量及群体的立场认知水平,与相信和传播官方渠道信息的人数均正相关,而与相信和传播民间渠道信息的人数均负相关;对各群体数量演化影响的显著性而言,官方渠道信息的平均个体传播量最高,官方渠道信息的可信度次之,群体的立场认知水平较低。     

瓦斯抽采二次膨胀封孔材料膨胀机理及应用研究

为降低瓦斯抽采漏气,开发了1种具备后期膨胀的二次膨胀材料（DE）,以水泥基材料为对比样,利用自制的膨胀力测试装置,以XRD和SEM分别表征其膨胀力及微观结构。研究结果表明:相比水泥基材料,DE材料的膨胀力明显,并表现出显著的时间效应,且DE材料的膨胀力随约束刚度增大而增大;水化1 d时, DE材料较水泥基材料生成更多的钙矾石（AFt）晶体;随着DE材料水化,AFt晶体不断增多,且水化7 d后AFt晶体发生延迟膨胀,这是引起DE材料后期膨胀的主要因素;工程应用表明DE材料可提高瓦斯抽采浓度及纯量,有效改善抽采效果。     

关于促进社区居民垃圾分类习惯养成的研究

社区是生活垃圾排放的主要源头场所。本研究以社区为中心,从习惯养成的角度出发,以斯金纳强化理论为依据,综合分析多方面影响因素,为社区垃圾分类管理及居民垃圾分类投放习惯的养成提出合理化建议。     

Diphenylarsinic acid sorption mechanisms in soils using batch experiments and EXAFS spectroscopy

• DPAA sorption data was found to fit the Freundlich equation. • K_f was significantly positive correlated with oxalate-extractable Fe₂O₃. • Ligand exchange was the main mechanism for DPAA sorption on soils. • Bidentate binuclear and monodentate mononuclear DPAA bonds were identified. Diphenylarsinic acid (DPAA) is a phenyl arsenic compound derived from chemical warfare weapons. Macroscopic and microscopic work on DPAA sorption will provide useful information in predicting the partitioning and mobility of DPAA in the soil-water environment. Here, batch experiments and extended X-ray absorption fine structure (EXAFS) spectroscopy were used to investigate the sorption mechanisms of DPAA. The DPAA sorption data from 11 soil types was found to fit the Freundlich equation, and the sorption capacity, K_f, was significantly and positively correlated with oxalate-extractable Fe₂O₃. The K_f values of eight of the 11 untreated soils (1.51–113.04) significantly decreased upon removal of amorphous metal (hydr)oxides (0.51–13.37). When both amorphous and crystalline metal (hydr)oxides were removed from the untreated soils, the K_f values either decreased or slightly increased (0.65–3.09). Subsequent removal of soil organic matter from these amorphous and crystalline metal (hydr)oxide-depleted samples led to further decreases in K_f to 0.02–1.38, with only one exception (Sulfic Aquic-Orthic Halosols). These findings strongly suggest that ligand exchange reactions with amorphous metal (hydr)oxides contribute most to DPAA sorption on soils. EXAFS data provide further evidence that DPAA primarily formed bidentate binuclear (²C) and monodentate mononuclear (¹V) coring-sharing complexes with As-Fe distances of 3.34 and 3.66 Å, respectively, on Fe (hydr)oxides. Comparison of these results with earlier studies suggests that ²C and ¹V complexes of DPAA may be favored under low and high surface coverages, respectively, with the formation of ¹V bonds possibly conserving the sorption sites or decreasing the steric hindrance derived from phenyl substituents.     

中国碳排放权交易促进低碳技术创新机制的研究

碳排放权交易已成为我国实施以市场为基础的重要环境规制之一,但此交易市场建设能否诱发我国低碳技术创新的有关研究仍然不足。以我国七个碳排放权交易试点为研究对象,采用合成控制法进行准自然实验,选取2004—2016年全国282个城市的面板数据,评估碳排放权交易试点政策对低碳技术创新的诱发效果,并使用排列检验法进行有效性检验;进而,定量分析碳排放权交易试点正式运行后对低碳技术创新的影响因素,探索七个试点效果差异的成因。研究发现:①碳排放权交易试点政策整体上诱发了试点地区的低碳技术创新活动。②各试点的政策效果存在一定差异,除重庆外的六个试点对政策响应较为迅速,其中北京、上海的诱发效果最显著,天津、广东、深圳和湖北次之,而重庆试点未能对政策作出充分的响应。③碳排放权交易对低碳技术创新作用中的政策"信号-预期"机制在我国首次得到验证,该机制在除重庆外的试点地区都得到了较好的构建。④碳排放权交易市场建设与区域产业结构升级产生了良好的协同作用,促进低碳技术创新,但其未能与外商直接投资形成相同作用;除重庆外,碳排放权交易这一市场型环境规制与控制型环境规制也呈现出协同作用。据此,应积极推进全国性碳排放权交易市场建设,以发挥其对低碳技术创新的诱发作用;但在统一市场建设过程中应重视地区差异,分步骤稳步推进;还应注重加强政府政策信号管理,引导企业开展低碳技术创新活动。     

Using soybean isoflavone to prevent hydrogen production reaction of aluminium dust and water in wet dust removal systems

Using a dry dust removal system used for aluminium dust collection presents a dust explosion risk, whereas a wet dust removal system presents a risk of hydrogen fire and explosion. Neither system can attain a sufficient level of safety for use at aluminium processing sites. In this paper, soybean isoflavone, a non-toxic and environmentally sustainable flavonoid, was investigated to inhibit hydrogen production from aluminium dust and water. Scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), and Fourier transform infrared spectroscopy (FTIR) were used to characterize aluminium particles before and after the reaction. Soybean isoflavone was found to inhibit hydrogen production from aluminium dust and water. At a soybean isoflavone solution concentration of 2.1 g L⁻¹, a dense protective film resulting from chemical adsorption on the surfaces of the aluminium particles isolated the aluminium particles from water molecules. This film blocked the reaction pathway between the aluminium particles and water to suppress hydrogen generation. This fundamental study addresses the problems of hydrogen fires and explosions in wet dust removal systems for aluminium dust collection and provides a novel, safe and effective method for aluminium dust removal.     

Low rate releases of hazardous light gases under semi-confined geometry: A consequence based approach and case-study application

As evidenced by accident statistics, an important factor when considering the safe operation of process plants is the effective mitigation of the effects of gaseous flammable releases, either by a prevention, or a protection approach. A detailed historical analysis was performed considering accidental scenarios associated with the use and management of light gases, starting from raw data selected from FACTS database and analysed by a causal multi-layer method. Results revealed that the major part of the accidental releases involving methane, hydrogen, ethene, ammonia can be attributed to organizational or process/plant immediate causes. As expected, the most frequent scenarios following the release are fire and explosion. We focus our attention on the development of a short-cut method allowing preliminary evaluation of the maximum gaseous build-up under semi-confined conditions, limiting the effects of the fire/explosion scenario to a tolerable level. The limitations of the model that is applied to selected case-studies and require further experimental validation are critically discussed. The results of the application of the model, which can boast of being safe but not disproportionately conservative, can be set as a maximum threshold in proper designing technical measures aiming at limiting the effects to a tolerable level by protection methods, e.g. isolation, venting, suppression and containment.