工业甲醛生产节能的基本途径

甲醛生产在化学工业生产中属于能耗较多的产品之一，回收甲醛生产过程中的化学反应热量不但节省大量能源，对于降低甲醛生产成本，改善生产环境都具有现实意义。     

光热催化氧化VOCs的研究进展

挥发性有机污染物（volatile organic compounds,VOCs）是加重大气复合污染的重要前体物之一。催化氧化技术是在催化剂的作用下,将VOCs氧化分解为无毒的CO₂和H₂O,是目前最有效的治理手段之一。综述了国内外VOCs催化氧化技术的研究进展,针对传统的热催化氧化技术的高能耗和光催化净化技术的低效率等问题,重点总结了光热催化剂的设计理念和对其作用机制的认知,展望了VOCs光热催化氧化技术未来的发展应用方向。     

Fenton试剂氧化偶合混凝法处理含酚废水的机理研究

氧化偶合混凝法处理废水,是使其中的有机污染物在氧化剂的诱导作用下,发生偶合或聚合而被混凝过滤去除。本文采用低剂量Fenton试剂诱导氧化偶合混凝法处理苯酚及其衍生物模拟废水,取得良好效果。通过对苯酚氧化过程的分析及分子量分布的测定,证实了反应过程中确有偶合产物生成,并通过顺磁共振波谱（ESR）的研究及偶合产物结构的质谱（GC/MS）鉴定,推测了偶合反应的机理。该偶合反应为自由基偶合反应,偶合产物是由C－C键或C－O键联接而成的。     

甲苯的光氧化降解试验研究

以气相甲苯为对象,研究其在波长为254 nm紫外光下的光氧化降解反应.同时,考察了甲苯初始浓度、光强和相对湿度对甲苯转化率的影响,分析了甲苯降解中间产物的生成机理.结果表明,随着甲苯初始浓度的增加,甲苯转化率缓慢下降;随着光照强度的增强,甲苯转化率逐渐增加;而提高相对湿度,甲苯转化率则为先升高后降低.在甲苯降解动力学分析中发现其光氧化降解过程符合伪一级反应动力学,且表观速率常数与光照强度成正比.通过对甲苯降解中间产物的分析,发现随着光照强度的增加,含苯环物质的降解更为充分,乙醇、乙酸等的相对含量逐渐增加,苯甲醇、苯甲醛缩二甲醇等的含量逐渐降低,在此基础上提出了甲苯生成含苯环产物及开环生成2-戊酮等的降解机理.     

Characterization of products from photooxidation of toluene

Photooxidation reaction of toluene in smog chamber systems was initiated by the UV radiation of tolucne/CH5ONO/NOx mixtures. The products of the photooxidation reaction of toluene and its subsequent reactions were analyzed directly utilizing Fourier transform infrared spectrometer （FTIR）. Detailed assignments to FTIR spectrum of gas-phase products were given. The information of some important functional groups in the products, such as, carbonyl groups （C-O）, hydroxyl groups （-OH）, carboxylic acid （- COOH）, C-C bonding, N O bonding and C-H bonding （C H）, was got from this analysis. These results were compared to those analyzed by aerosol time of flight mass spectrometer （ATOFMS）. It was found that there are some differcnccs between FTIR analysis of gas-phase products and that of particle-phase, for example, the products with carbonyl groups, which were connected to unsaturated chemical bonds, was relatively higher in the gas phase, while kctoncs, aldehydes, carboxylic acid and organonitrates were the dominant functional groups in the aerosol-phase reaction products. The possible reaction pathways of some important products in the gas phase were also discussed.     

脉冲放电处理苯酚废水降解过程的分析

由于水中脉冲放电产生等离子体通道,水会发生复杂的等离子体化学反应,产生各种自由基,本文检测到放电形成的羟基自由基.对苯酚废水进行放电降解研究,利用紫外分光计、有机碳分析仪、液相质谱联用仪和气相质谱仪等仪器对降解产物进行检验.结果表明,苯酚废水在放电作用下生成的中间产物为:多羟基苯酚、酮、醛和酯等,最终产物为二氧化碳和水.此结果对苯酚废水在脉冲放电,甚至直流或交流电下的苯酚降解机理的进一步研究有参考价值.     

Tetrahedral homonuclear organoelement clusters and subhalides of aluminium,gallium and indium

This review is focused on the synthesis and the reactivity of tetrahedral organoelement clusters of the heavier elements of third main-group aluminium, gallium, and indium, which have been known for about a decade. They possess the elements in an unusually low oxidation state of +1 and have direct element–element interactions between their four constituents. Each cluster atom is further attached to one terminal and in most cases a bulky organic substituent, which prevents disproportionation by steric shielding. The synthesis of these compounds succeeds by different methods such as the reduction of suitable organoelement(III) halides with alkali metals and magnesium or the treatment of element(I) halides with lithium organyls. They are deeply coloured, and their bonding situation may best be described by delocalized molecular orbitals. They show a singular chemical reactivity, which results in the formation of many secondary products possessing unprecedented structures and properties. The synthesis of organoelement subhalides still containing the elements in low oxidation states is discussed in more detail in the second part of this review. These compounds are easily accessible by the careful oxidation of the clusters with halogen donors such as hexachloroethane or with AlX₃/X₂ mixtures. They produce dimers via halogen bridges, but in certain cases monomers were observed even for the solid state. They are very effective starting compounds for secondary reactions and the generation of new products containing the elements in unusual oxidation states by salt-elimination reactions, for instance.     

分子模拟方法在爆炸反应机理方面的应用进展

针对爆炸过程反应机理异常复杂,实验检测手段对其认识匮乏的现状,综述了量子化学、反应分子动力学等分子模拟方法的特点及研究进展,分析了分子模拟技术在燃爆机理研究中的应用进展,包括量子化学方法对于燃料热解/燃烧、瓦斯等可燃体系爆炸过程的微观基元反应步骤、反应能垒及热力学参数的计算,以及反应分子动力学(ReaxFF MD)在含能材料、可燃混合气等复杂爆炸体系获取可能的反应路径及中间自由基变化的应用。对分子模拟方法在爆炸领域研究的应用提出了建议及展望,指出ReaxFF MD和密度泛函理论(DFT)相结合是一种研究复杂爆炸体系微观反应机理极具潜力的方法,借助先进的分析检测手段对模拟方法的验证及修正,能获取更准确、全面的微观反应动力学模型。     

Size distribution and chemical composition of secondary organic aerosol formed from Cl-initiated oxidation of toluene

Secondary organic aerosol (SOA) formed from Cl-initiated oxidation of toluene was investigated in a home-made smog chamber. The size distribution and chemical composition of SOA particles were measured using aerodynamic particle sizer spectrometer and the aerosol laser time-of-flight mass spectrometer (ALTOFMS), respectively. According to a large number of single aerosol diameter and mass spectra, the size distribution and chemical composition of SOA were obtained statistically. Experimental results showed that SOA particles created by Cl-initiated oxidation of toluene is predominantly in the form of fine particles, which have diameters less than 2.5 m (i.e., PM2.5), and glyoxal, benzaldehyde, benzyl alcohol, benzoquinone, benzoic acid, benzyl hydroperoxide and benzyl methyl nitrate are the major products components in the SOA. The possible reaction mechanisms leading to these products are also proposed.     

污水厂污泥低温热化学转化过程机理研究

污水厂污泥低温热化学转化是可望达到能量平衡的污泥处理新技术。借助污泥与其转化产物的元素分析、污泥的热重分析和衍生油的GC/MS分析等手段,对该转化反应过程的元素转移、转化特征温度和反应机理进行了研究。认为过程的主要反应是脂肪族化合物的蒸发、蛋白质肽键断裂和基团转移反应,参与反应的主要成份是脂肪族化合物和蛋白质,其中前者参与反应的温度低于后者,而糖类化合物参与反应的温度最高。     

干法加氨脱除SO2中的温度效应

研究了在ＮＨ３参与下，干法脱除ＳＯ２中的温度效应，实验结果表明，在ＳＯ２与ＮＨ３的热化学反应中，反应程度随温度上升呈线性下降，然而，在脉冲电晕条件下，ＳＯ２脱率却随温度上升呈现非线性变化，通过测定不同温度下的产物组成，揭示了在脉８冲电晕放电条件，干法脱除ＳＯ２存在两条平反应途径；（１）先成盐后氧化；（２）先氧化后成盐，在较高温度下反应主要按第（２）条途径进行。     

Influence of water contained in porous limestone on corrosion

The chemical degradation of porous limestone due to its reaction with sulphur dioxide was investigated by determining amounts and distributions of sulphur-containing corrosion products in samples collected from historic buildings. Water vapour adsorption equilibria have been determined for limestones of varying petrology, and correlated with sulphur dioxide uptakes measured in artificial weathering experiments. Out of several possible routes of the corrosive reaction, dissolution of sulphur dioxide in bulk water present in the stone may be related to the prevailing mechanism leading to stone deterioration. The bulk water may appear in the limestone as water condensed in the capillaries, or absorbed by hygroscopic salts.     

Toward rational design of amines for CO2 capture: Substituent effect on kinetic process for the reaction of monoethanolamine with CO2

Amines have been considered as promising candidates for post-combustion CO₂ capture. A mechanistic understanding for the chemical processes involved in the capture and release of CO₂ is important for the rational design of amines. In this study, the structural effects of amines on the kinetic competition among three typical products (carbamates, carbamic acids and bicarbonate) from amines + CO₂ were investigated, in contrast to previous thermodynamic studies to tune the reaction of amines with CO₂ based on desirable reaction enthalpy and reaction stoichiometry. We used a quantum chemical method to calculate the activation energies (E_a) for the reactions of a range of substituted monoethanolamines with CO₂ covering three pathways to the three products. The results indicate that the formation of carbamates is the most favorable, among the three considered products. In addition, we found that the E_a values for all pathways linearly correlate with pK_a of amines, and more importantly, the kinetic competition between carbamate and bicarbonate absorption pathways varies with pK_a of the amines, i.e. stronger basicity results in less difference in E_a. These results highlight the importance of the consideration of kinetic competition among different reaction pathways in amine design.     

Toxics Use Reduction in the Home: Lessons Learned from Household Exposure Studies

Workers and fence-line communities have been the first to benefit from the substantial reductions in toxic chemical use and byproducts in industrial production resulting from the Massachusetts Toxics Use Reduction Act (TURA). As TURA motivates reformulation of products as well as retooling of production processes, benefits could extend more broadly to large-scale reductions in everyday exposures for the general population. Household exposure studies, including those conducted by Silent Spring Institute, show that people are exposed to complex mixtures of indoor toxics from building materials and a myriad of consumer products. Pollutants in homes are likely to have multiple health effects because many are classified as endocrine disrupting compounds (EDCs), with the ability to interfere with the body’s hormone system. Product-related EDCs measured in homes include phthalates, halogenated flame retardants, and alkylphenols. Silent Spring Institute’s chemical analysis of personal care and cleaning products confirms many are potential sources of EDCs, highlighting the need for a more comprehensive toxics use reduction (TUR) approach to reduce those exposures. Toxics use reduction targeted at EDCs in consumer products has the potential to substantially reduce occupational and residential exposures. The lessons that have emerged from household exposure research can inform improved chemicals management policies at the state and national levels, leading to safer products and widespread health and environmental benefits.     

Occurrence and formation of disinfection by-products in the swimming pool environment: A critical review

Disinfection of water for human use is essential to protect against microbial disease; however, disinfection also leads to formation of disinfection by-products (DBPs), some of which are of health concern. From a chemical perspective, swimming pools are a complex matrix, with continual addition of a wide range of natural and anthropogenic chemicals via filling waters, disinfectant addition, pharmaceuticals and personal care products and human body excretions. Natural organic matter, trace amounts of DBPs and chlorine or chloramines may be introduced by the filling water, which is commonly disinfected distributed drinking water. Chlorine and/or bromine is continually introduced via the addition of chemical disinfectants to the pool. Human body excretions (sweat, urine and saliva) and pharmaceuticals and personal care products (sunscreens, cosmetics, hair products and lotions) are introduced by swimmers. High addition of disinfectant leads to a high formation of DBPs from reaction of some of the chemicals with the disinfectant. Swimming pool air is also of concern as volatile DBPs partition into the air above the pool. The presence of bromine leads to the formation of a wide range of bromo- and bromo/chloro-DBPs, and Br-DBPs are more toxic than their chlorinated analogues. This is particularly important for seawater-filled pools or pools using a bromine-based disinfectant. This review summarises chemical contaminants and DBPs in swimming pool waters, as well as in the air above pools. Factors that have been found to affect DBP formation in pools are discussed. The impact of the swimming pool environment on human health is reviewed.     

中国工业产品国际贸易的污染足迹分析

从“污染足迹”的概念出发,利用官方统计数据和投入产出分析方法,分析了中国各工业部门的污染状况,核算了1994～2001年间中国工业产品国际贸易的污染成本和收益.结果表明,中国工业产品出口的污染密度要小于进口的污染密度;1999～2001年中国虽然存在工业产品贸易顺差,实际上却向国外转移了污染足迹;化学工业的净进口帮助中国转移了最多的污染足迹,污染足迹的流入主要来自纺织业和机械工业的净出口.     

焦化厂不同污染源作用下土壤PAHs污染特征

根据生产工序的不同将焦化场地划分为堆煤区、炼焦区、化产区,共采集40组土壤样品,分析各类污染源作用下场地PAHs污染程度、分布、影响途径及组成特征等.结果表明,场地处于严重污染水平且BaP是健康风险首要关注污染物.按ΣPAHs含量中位数排序,化产区（1733.87mg/kg）>炼焦区（32.86mg/kg）>堆煤区（21.21mg/kg）.对应污染途径依次为化工副产品的泄漏及填埋、烟粉尘大气沉降、煤粉（渣）降雨淋滤.异构体比值法判定的污染源不能明显区分各工序的土壤污染特点且存在偏差,利用ω（低环PAHs）/ω（高环PAHs）比值法进行排序,化产区深层（7.39）>化产区表层（1.33）>堆煤区（1.06）>炼焦区（0.39）,PAHs组成特征受污染源自身特性及外环境作用共同所致.4~5环PAHs是该焦化场地的特征污染物,化产区、堆煤区土壤中Nap、Phe占ΣPAHs比重较高,而炼焦区以BbF、Fla、Chry为主要组分.     

焦化厂不同污染源作用下土壤PAHs污染特征

根据生产工序的不同将焦化场地划分为堆煤区、炼焦区、化产区,共采集40组土壤样品,分析各类污染源作用下场地PAHs污染程度、分布、影响途径及组成特征等.结果表明,场地处于严重污染水平且BaP是健康风险首要关注污染物.按ΣPAHs含量中位数排序,化产区（1733.87mg/kg）>炼焦区（32.86mg/kg）>堆煤区（21.21mg/kg）.对应污染途径依次为化工副产品的泄漏及填埋、烟粉尘大气沉降、煤粉（渣）降雨淋滤.异构体比值法判定的污染源不能明显区分各工序的土壤污染特点且存在偏差,利用ω（低环PAHs）/ω（高环PAHs）比值法进行排序,化产区深层（7.39）>化产区表层（1.33）>堆煤区（1.06）>炼焦区（0.39）,PAHs组成特征受污染源自身特性及外环境作用共同所致.4~5环PAHs是该焦化场地的特征污染物,化产区、堆煤区土壤中Nap、Phe占ΣPAHs比重较高,而炼焦区以BbF、Fla、Chry为主要组分.     

含铝铁硅固废制备PSAF混凝剂RSM优化与结构表征

研究了以粉煤灰和氧化铁皮为原料制备聚硅酸铝铁混凝剂的影响因素及产品微观结构和形貌,选取碱化度、nAl：nFe、聚合温度、反应时间对透光率进行4因素3水平响应面实验.得出制备优化方案：碱化度为0.5,nAl：nFe为1.38,聚合温度为39.2℃,反应时间为1.36h,透光率预测值达90.24%,验证试验均值相对误差1.20%,表明RSM优化模型可靠.结合产品表征测试,XRD分析主要物相为氯化钠,大范围衍射驼峰预示着浸出液聚合形成了新的无定形物;FT-IR测试表明聚硅酸与Al³⁺、Fe³⁺之间存在较多金属-OH等非离子键络合态;TEM测试结果显示产品为高聚集度和枝化度的网状结构;TG分析表明产品在400℃以前失去结合水和羟基,700℃左右产品主要化学键断裂,对应DSC图中均出现较强吸热峰,产品具有较好的稳定性.     

农用化学品对农产品的污染及其对策

由于农业大量使用化学品 ,使农产品的农药残留量及其衍生物增加 ,从而对人体健康造成具大的危害性。本文的主要目的就是让人们进一步认识在农产品生产中使用农用化学品的危害 ,倡导我国农业走绿色农产品生产的道路