单臂冠醚—金属卟啉配合物的合成与表征

利用磺酰氯键将苯并15-冠-5和5-(2-羟基苯基)- 10,15,20-三(4-硝基苯基)交联,合成了单臂冠醚一卟啉配体(CNTPP)及其金属配合物(CNIPPMn和CNTPPCo).通过红外光谱、紫外吸收光谱与光电子能谱对化合物和配合物进行结构分析表明,在489cm-1和480cm-1出现M-N键的吸收蜂,在1360cm-1和1363cm-1处有S=O键吸收峰.配位中心离子进入卟啉环后引起配合物CNTPPM分子的对称性提高,使Sorct带发生位移,且N原子与金属离子形成配位键后,其中一对N电子结合能升高,另外一对N原子下降,且导致配合物中M2p3/2的电子结合能变大.     

道化学指数评价法在淮化集团某合成氨厂的应用

化工企业由于工艺装置复杂、产品危险性高等特点极易发生事故,极小的安全隐患往往导致重大事故给企业甚至国家带来严重损失。为探求潜在事故的危险性和总损失,在对淮化集团的合成氨厂生产工序流程分析基础上划分三个评价单元,应用美国道化学公司火灾爆炸指数评价法对此三个评价单元分别进行评价并量化可能造成的损失。评价结果显示各评价子单元的危险等级分别为非常大、很大和最轻,采取安全补偿措施后危险等级降为较轻、较轻和最轻,说明采取措施后若发生事故损失将会减少,通过对比补偿前后的财产损失可以说明这一结论。从另一角度来看,表明合成氨厂有较大的安全隐患需有关管理者采取措施以保障安全生产。采用的道化学指数法比较准确地反映出了被评价单位的实际情况,为化工企业的安全生产、安全管理提供了一定参考。     

CTAB作用下绿色合成纳米铁的制备及降解孔雀绿

化学合成纳米铁存在成本高和二次污染等问题,探寻低成本、环境友好的合成方法是纳米技术在环境修复中的研究热点之一.本课题组前期采用绿茶提取液(GTE)还原Fe2+合成纳米铁颗粒(Fe NPs),发现GTE合成的Fe NPs易被氧化和团聚.本文采用阳离子表面活性剂十六烷基三甲基溴化铵(CTAB)对绿色合成纳米铁形貌和粒径进行改善,提高了纳米铁颗粒的分散性和抗氧化性.通过SEM、XRD、FT-IR、UV-vis等表征手段对GTE合成的Fe NPs和CTAB作用下合成的Fe NPs的微观结构表征以及对孔雀绿降解效果对比表明:CTAB作用下合成的Fe NPs分散均匀,CTAB的包覆提高了Fe NPs的稳定性,从而提高了Fe NPs的反应活性.GTE合成的Fe NPs对孔雀绿的去除率为75.66%,而CTAB作用下绿色合成的Fe NPs的去除率高达91.06%.最后,提出了CTAB作用下GTE合成Fe NPs的可能机理.     

Thermal risk in batch reactors: Theoretical framework for runaway and accident

Thermal safety and risk of accidents are still challenging topics in the case of batch reactors carrying exothermic reactions. In the present paper, the authors develop an integrated framework focusing on defining the governing parameters for the thermal runaway and evaluating the subsequent risk of accident. A relevant set of criteria are identified in order to find the prior conditions for a thermal runaway: failure of the cooling system, critical temperature threshold, successive derivatives of the temperature (first and second namely) vs. time and no detection in due time (reaction time) of the runaway initiation. For illustrative purposes, the synthesis of peracetic acid (PAA) with hydrogen peroxide (HP) and acetic acid (AA) is considered as case study. The critical and threshold values for the runaway accident are identified for selected sets of input data. Under the conditional probability of prior cooling system failure, Monte Carlo simulations are performed in order to estimate the risk of thermal runaway accident in batch reactors. It becomes then possible to predict the ratio of reactors, within an industrial plant, potentially subject to thermal runaway accident.     

棱形十二面体Ag_3PO_4微晶的辅助合成及其可见光催化性能

以六次甲基四胺(HMTA)和聚乙烯吡咯烷酮(PVP)为混合辅助剂,采用沉淀法合成了立方晶相棱形十二面体Ag3PO4微晶,对其进行了表征,并通过降解罗丹明B考察了其可见光催化活性。实验结果表明:以0.10g(25 g/mol(以Ag NO3计))HMTA和0.10 g PVP为混合辅助剂合成的棱形十二面体Ag3PO4微晶,其禁带宽度为2.17e V,对罗丹明B有较好的可见光催化活性;在8 mg/L罗丹明B溶液中加入0.4 g/L Ag3PO4,可见光照射12 min时,未添加辅助剂以及分别添加0.10 g PVP、0.10 g HMTA、0.10 g HMTA和0.10 g PVP混合辅助剂制备的Ag3PO4对罗丹明B的降解率分别为67.59%,76.25%,91.88%,99.64%;棱形十二面体Ag3PO4微晶重复使用4次后,罗丹明B的降解率仍达91.59%,说明该光催化剂具有较好的重复使用性能。     

Growth of non-English-language literature on biodiversity conservation

English is widely recognized as the language of science, and English-language publications (ELPs) are rapidly increasing. It is often assumed that the number of non-ELPs is decreasing. This assumption contributes to the underuse of non-ELPs in conservation science, practice, and policy, especially at the international level. However, the number of conservation articles published in different languages is poorly documented. Using local and international search systems, we searched for scientific articles on biodiversity conservation published from 1980 to 2018 in English and 15 non-English languages. We compared the growth rate in publications across languages. In 12 of the 15 non-English languages, published conservation articles significantly increased every year over the past 39 years, at a rate similar to English-language articles. The other three languages showed contrasting results, depending on the search system. Since the 1990s, conservation science articles in most languages increased exponentially. The variation in the number of non-English-language articles identified among the search systems differed markedly (e.g., for simplified Chinese, 11,148 articles returned with local search system and 803 with Scopus). Google Scholar and local literature search systems returned the most articles for 11 and 4 non-English languages, respectively. However, the proportion of peer-reviewed conservation articles published in non-English languages was highest in Scopus, followed by Web of Science and local search systems, and lowest in Google Scholar. About 20% of the sampled non-English-language articles provided no title or abstract in English; thus, in theory, they were undiscoverable with English keywords. Possible reasons for this include language barriers and the need to disseminate research in countries where English is not widely spoken. Given the known biases in statistical methods and study characteristics between English- and non-English-language studies, non-English-language articles will continue to play an important role in improving the understanding of biodiversity and its conservation.     

绿色合成纳米氧化铁对污染土壤中镉的钝化研究

虽然绿色合成纳米材料已成功地用于去除废水中的重金属,但利用绿色合成纳米材料钝化土壤中重金属的报道很少.本文利用植物叶提取液制备纳米氧化铁(GION),并将其用于钝化土壤中重金属镉的研究,观察中、短培养周期下对镉钝化的稳定性.实验室条件下设置50%田间最大持水量培养,对照、1%、3%、9%GION 4个处理.分别于第60、120 d采样分析土壤中镉、pH、铁、酶等相关指标的变化.结果表明,GION对土壤中镉有较好的钝化效果,60 d与120 d之间有效态镉的含量无显著差异,说明GION对土壤中镉的钝化作用随时间增长相对稳定.120 d的数据显示,相比对照组,1%、3%、9%GION处理下有效态Cd(0.1 mol·L~(-1) CaCl_2)分别降低了19.1%、16.7%、66.7%,交换态Cd(Tessier法)分别降低了12.5%、18.8%、56.3%.GION能够显著提高土壤的pH和铁的含量.pH提高能够显著降低Cd的有效性.(NH_4)C_2O_4-Fe则分别增加了0.7、1.1、1.9倍,DCB-Fe分别增加了0.4、2.9、6.0倍.另外,随培养时间的延长,(NH_4)C_2O_4-Fe和DCB-Fe增加而HCl-Fe~(2+)含量降低.说明GION影响土壤中铁物种的活性,增强其生物化学过程而转化为更加稳定的形态,该过程将改变镉在土壤中的赋存形态.通过扫描电镜-能谱(SEM-EDS)发现,GION处理残渣态中Fe的含量远高于对照组,说明镉可能随铁进入残渣态.土壤中脲酶和转化酶活性升高而过氧化氢酶则没有显著的变化.该结果说明GION降低了土壤中镉的生物有效性,土壤得以恢复,从而提升了土壤酶活性.综上所述,GION具有环境友好的特点,且对镉具有稳定的钝化作用,可作为一种良好的中低污染重金属污染土壤的修复剂.     

二氧化钛/累托石制备及其光催化性能研究

以累托石和四氯化钛为原料制备了二氧化钛／累托石复合材料,考察了各种制备条件如灼烧温度、复合反应温度、HCI／TiCl4等对光催化性能的影响。X射线衍射及红外光谱对材料的分析表明,反应中发生了聚合钛离子与累托石中阳离子的交换反应。酸性红B水溶液的脱色效率的结果表明,不同实验条件对复合材料的光催化性能都有不同程度的影响。初步探讨了影响光催化性能的机理及材料制备的最佳条件。     

防空导弹武器系统伪装能力综合评价研究

针对防空导弹武器系统的暴露特征,采用层次分析法,建立了防空导弹武器系统伪装能力多层次综合评价指标体系和综合评价模型,采用模糊聚类分析法对数据进行处理,得出各评价对象的综合评价结果。最后通过算例,验证了该模型的有效性。     

失活甲醇催化剂用于脱除硫化氢的研究

本文研究了失活甲醇催化剂用于脱除硫化氢的试验。结果表明,失活甲醇催化剂具有较好的脱硫性能,其重量硫容在室温和６２３Ｋ时稍低于工业氧化锌脱硫剂,在４２３Ｋ－５２３Ｋ的温度范围内则大于工业氧化锌脱硫剂,其体积硫容在室温下大于工业氧化锌脱硫剂,失活甲醇催化剂的工作硫容随着的升高而增长,而且在低反应空速时或者经过还原后具有更大的硫容。