化工生产事故预防信息系统研究

为指导操作人员正确地处理化工生产过程中的问题,防范人为误操作导致的事故发生,开发了以化工生产的危险与可操作性分析结果和典型事故原因分析结果为知识库的事故预防信息系统.系统实时在线监测化工生产过程中的关键变量,通过判定变量间的影响关系,实现对化工生产过程潜在危险的辨识、预警并给予实时操作指导,以确保生产安全,提高装置的生产效率.最后,以丙烯聚合工艺为例,在多功能过程试验控制平台上进行了验证,探讨了事故预防信息系统的应用方法.     

Dyes adsorption using a synthetic carboxymethyl cellulose-acrylic acid adsorbent

Removal of noxious dyes is gaining public and technological attention. Herein grafting polymerization was employed to produce a novel adsorbent using acrylic acid and carboxymethyl cellulose for dye removal. Scanning electron microscopy and Fourier-transform infrared spectroscopy verified the adsorbent formed under optimized reaction conditions. The removal ratio of adsorbent to Methyl Orange, Disperse Blue 2BLN and malachite green chloride reached to 84.2%, 79.6% and 99.9%, respectively. The greater agreement between the calculated and experimental results suggested that pseudo second-order kinetic model better represents the kinetic adsorption data. Equilibrium adsorptions of dyes were better explained by the Temkin isotherm. The results implied that this new cellulose-based absorbent had the universaiity for removal of dyes through the chemical adsorption mechanism.     

金属氧化物降解六氯苯的活性比较及催化机理研究

以氧化铝(α-Al_2O_3、γ-Al_2O_3)、氧化钙(CaO)、过渡金属氧化物(Mn O_2、α-Fe_2O_3、γ-Fe_2O_3、Ni_2O_3、CuO)为催化剂,考察了催化剂种类、添加比例等因素对六氯苯(Hexachlorobenzene,HCB)降解效果和产物组分的影响.结果表明,催化效果随催化剂添加比例的提高显著增加.在反应温度为350℃,反应时间1 h,金属氧化物添加比例为100∶1的条件下,碱土金属氧化物CaO及过渡金属氧化物中的α-Fe_2O_3和Ni_2O_3降解活性较好,这3种氧化物对HCB的降解率分别达到65.5%、100.0%和100.0%,脱氯率D_1分别为54.4%、81.9%和77.5%.HCB降解有机产物分析结果显示,8种金属氧化物与HCB样品反应产物中均存在低氯代苯,在α-Fe_2O_3和Ni_2O_3的催化作用下有2~4氯代低氯苯检出,说明在降解过程中存在明显的逐级脱氯/加氢反应;与CaO反应后的产物中低氯代苯较少,经拉曼光谱定性分析,有无序碳的检出,说明除了脱氯/加氢还存在脱氯缩合反应.     

铝铁锡共聚物的合成及其特性研究

合成制备了铝铁锡共聚物，测定分析了其水解共聚合和熟化过程中的pH变化，并通过扫描电镜和混凝实验对共聚物的晶形貌像和絮凝作用进行了研究。结果表明：Sn^4 具有比Fe^3 ，Al^3 更强的水解活性，它有使共聚物的分子趋于均一的作用；铝铁锡共聚物的最佳配比为：NAl∶NFe∶NSn=5∶5∶3,最佳水解度B^*＝2．0,此共聚物具有比CPAFC更优良的絮凝性能。     

Determination of direct and fugitive PM emissions in a Mediterranean harbour by means of classic and novel tracer methods

Remodelling works are frequent in harbour areas, given that they must adapt to rapidly changing market requirements. Depending on their nature (construction, demolition, etc.), these works may be carried out during long periods of time and thus exert a significant impact on the air quality at the harbours and their surroundings. The air quality at the Valencia harbour was studied during an enlargement project. Four sampling stations aimed to cover the major dust-emitting activities in the harbour. In addition, a sampling campaign was carried out to collect dust materials at their emission sources (e.g., loading and unloading of clinker and petroleum coke, as well as the enlargement works). Differences obtained between PM levels at the monitoring sites were correlated with the distance between sampling stations and enlargement works and/or harbour operations, as well as with the preferential wind direction. In all cases, the days with the highest PM_10 levels were linked to wind directions coinciding with the location of the enlargement works or the clinker and petroleum coke stocks. Classic source apportionment methodologies (PCA and CMB) were applied to the data, but their interpretation was complex due to the similar chemical signatures of PM originating from direct and fugitive emissions from stocked materials (e.g., clinker), and the enlargement works. To overcome this difficulty, a novel non-statistical approach was used to obtain quantitative estimations of the contributions from sources (petroleum coke and clinker), based on the correlation between specific PM components (e.g., carbonaceous species) and source tracers (e.g., V). Finally, a qualitative test using phenolphthalein was devised to identify the presence of clinker on the filters, which provided positive results. This novel tracer approach is thus recommended for harbour authorities.     

膜的改性及其在环境领域应用研究进展

膜改性由于具有清洁、廉价、节能等特点，近年来得到快速发展，是解决膜污染的有效方法之一。本文综合介绍了膜的基体改性、表面改性这两种改性类型和目前常用的改性方法包括表面涂覆、表面活性剂改性、化学修饰改性、仿生改性等等，并简单介绍了膜改性在环境领域的应用，探讨了膜改性今后的发展。     

Novel Polymeric Materials from Biological Oils

A variety of novel polymeric materials ranging from elastomers to tough, rigid plastics have been prepared by the cationic copolymerization of regular soybean oil, low-saturation soybean oil, or conjugated low-saturation soybean oil with various alkene commonomers. Using appropriate compositions and reaction conditions, 70–100% of the soybean oil is covalently incorporated into the cross-linked polymer networks, contributing significantly to cross-linking during copolymerization. The resulting thermosets exhibit thermophysical and mechanical properties that are competitive with those of their petroleum-based counterparts. In addition, good damping and shape memory properties have been obtained by controlling the degree of cross-linking and the rigidity of the polymer backbone. New materials with similar characteristics have also been produced from other biological oils, including tung, and fish oils using the same technique. The new, more valuable properties of these bioplastics suggest numerous promising applications of these novel polymeric materials.     

Development of Stream Water Chemistry during Spring Melt in a Northern Hardwood Forest

The role of snowmelt and subsurface hydrology in determiningthe chemistry of a small headwater stream in the TurkeyLakes Watershed (TLW) was evaluated for the spring meltperiods 1992 to 1996. Spring runoff is the dominanthydrological event at the TLW each year. Processesoccurring within the snowpack during snowmelt wereprincipally responsible for the above-ground changes inchemical fluxes relative to bulk deposition (the effect ofwinter throughfall was minimal). Large changes in chemicalfluxes occurred below ground. Organic matter decomposition,weathering, nitrification, and element cycling are some ofthe more important below-ground processes that operateduring the snow accumulation and ablation season and controlthe composition of the water ultimately appearing in thestream. Maximum stream discharge was accompanied byelevated concentrations of H⁺, NO₃ ^-, K⁺,NH₄ ⁺, DOC, Al and Mn, but reduced levels ofCa²⁺, Mg²⁺, SO₄ ^2- and SiO₂. Theconcentration-discharge relationships were consistent withwater movement through and above the forest floor duringpeak discharge, a flowpath facilitated by rapid infiltrationof meltwater and the existence of a relatively impermeablelayer in the mineral soil creating a perched water table. Averaged over the five periods of snow accumulation andablation, it was estimated that pre-melt stream flow, andwater routed through the forest floor and through the uppermineral soil contributed 9, 28 and 63%, respectively, ofthe discharge measured at the outlet of the catchment. Theforest floor contribution would be greater at peak dischargeand at higher elevations. An end-member mixing modelestimated concentrations of SO₄ ^2-, NO₃ ^-,Cl^-, Ca²⁺, Mg²⁺, Na⁺ and Al that werecomparable to average values measured in the stream. Othervariables (NH₄ ⁺, H⁺, K⁺ and DOC) wereover-estimated implying retention mechanisms operatingoutside the model assumptions.     

Ring-Opening Polymerization of Cyclic Esters onto Liquefied Biomass

Ring-opening polymerization of cyclic esters (-caprolactone, -valerolactone, and l-lactide) onto liquefied biomass (LB) was conducted to obtain the polyester-type polyol and to regulate the characteristics of LB. IR and ¹H-NMR spectra of the obtained polyol showed that the polymerization was successfully conducted in the presence of acid catalyst, which is used in liquefaction. The molecular weight (M_w), hydroxyl value, and viscosity were controllable by changing the reaction conditions. Polyester-type polyurethane foams with a wide range of properties were prepared from the obtained polyol with the appropriate combinations of foaming agents.     

Ethoxylated Soybean Polyols for Polyurethanes

Soybean polyols prepared by ring opening reactions of epoxidized soybean oil with hydrogen active compounds (water, alcohols, organic or inorganic acids, thiols, hydrogen etc.) have a low reactivity in the reaction with isocyanates because the hydroxyl groups are secondary. This paper presents a simple and convenient method to increase the reactivity of soybean polyols with secondary hydroxyl groups by ethoxylation reactions with the preservation of triglyceride ester bonds. The method uses mild reaction conditions: low alkoxylation temperature of 35–45 °C, low pressure of 0.1–0.2 MPa (15–30 p.s.i.) and a superacid as catalyst (HBF₄). The new soybean polyols have a higher reactivity toward isocyanates in polyurethane formation due to the high percentage of primary hydroxyl groups. The primary hydroxyl content was determined by the second order kinetics of polyol reaction with phenyl isocyanate.