二氧化钛光催化降解甲醛反应动力学研究

以钛酸丁酯为前驱体，应用溶胶一凝胶法制备TiO2粉体和负载TiO2薄膜，考察了不同活化温度和活化时间对TiO2光催化降解甲醛性能的影响，并对TiO2薄膜光催化降解甲醛的反应动力学进行了研究。试验结果表明，在活化温度450℃、活化时间5h条件下，所得TiO2粉体及薄膜的光催化活性较好。不同初始浓度下甲醛光催化降解率与时间关系的动力学研究表明，一级反应动力学模型与试验数据拟合较好，方差R^2大于或等于0．99。     

太阳能光催化降解法去除水中罗丹明染料的研究

在太阳光的紫外线辐射下，应用载有ＴｉＯ２薄层的平板式光催化反应器，进行了光催化降解法去除水中罗丹明染料的试验，结果表明，当紫外线辐射强度平均为３３Ｗ／ｍ＾２，反应时间为１８ｍｉｎ时，水中罗丹明染料浓度由１０ｍｇ／Ｌ降至０．０１ｍｇ／Ｌ，在室国家排放标准，探讨了太阳能光催化反应系统的改进方向及工业化应用的有关问题。     

纳米TiO2在有机废水处理方面的研究进展

综述了光催化材料纳米TiO2的制备、光催化降解水中有机污染物的机理、动力学规律及其研究现状和发展方向。     

不同光照度下活性艳红X-3B的光催化降解动力学研究

以活性艳红X-3B为模型化合物，以TiO2为光催化剂，研究了不同光照度下污染物的多相光催化降解动力学。结果表明，活性艳红X-3B的光催化降解动力学符合Langmiur—Hinshelwood动力学模型，其中的表观反应速率常数(k)随入射光照度的增加而增大，吸附平衡常数(KA)却随入射光照度的增加而减小，在实验的光照度范围内，k和KA^-1与光照度的平方根成比。     

二氧化钛薄膜光催化性能的影响因素及提高途径

TiO2薄膜光催化技术有广阔的应用前景,在国内外得到了广泛的研究。介绍了TiO2薄膜光催化降解的研究现状,指出了影响薄膜光催化性能的若干因素和提高薄膜光催化效率的相应手段。另外,对金属复合、半导体复合对TiO2薄膜光催化性能的影响和可见光催化的研究现状进行了评述。     

TiO2-PTFE光催化膜的制备及性能

以聚四氟乙烯（PTFE）乳液和纳米TiO2粉末为原料,采用无水乙醇为溶剂,经辊压后与不锈钢网结合,制备了多孔固定化TiO2-PTFE光催化膜。膜性能研究结果表明,m（TiO2）：m（PTFE）=4时,光催化反应处理质量浓度为20mg／L的苯甲酸溶液,2h内TOC去除率高达81．3％。通过扫描电子显微镜观察,TiO2-PTFE光催化膜表面平整,且孔隙分布均匀。TiO2最佳负载量为15mg／cm2。在优化反应条件下同悬浮态TiO2光催化反应体系相比,TiO2-PTFE光催化膜对光源有更高的利用率,表现出更佳的催化活性。     

二氧化钛纳米材料的合成及其在环保领域的应用研究进展

综述了近年来纳米TiO2光催化剂在制备方法、表面改性、光催化氧化机理及应用方面的研究进展，提出了半导体催化剂的研究发展的方向。     

纳米二氧化钛光催化降解水中有机污染物的研究进展

TiO2在光催化降解水中有机污染物方面具有明显的优势。综述了pH、TiO2表面改性、载体、外加氧化剂及其他因素对TiO2光催化降解水中有机污染物催化活性的影响，讨论了光电催化 、太阳能利用等对光催化领域的推动作用，展望了这方面工作的发展方向。     

固定相光催化氧化技术的研究与进展

叙述了近年来国内外固定相光催化氧化技术的研究成果，讨论了光催化氧化技术的机理和动力学规律、催化剂载体及催化剂固定方法、影响因素等，并对固定相光催化氧化技术的发展方向进行了探讨。     

二氧化钛光催化降解处理染料废水

研究了TiO2的添加量，粒径大小，作用时间对3种染料废水脱色率的影响及TiO2薄膜对染料废水的处理效果。对于汽巴克染绿和直接大红染料溶液，适宜的TiO2添加量均为5g/L，紫外灯照射60min，其脱色率大于85％。对于阳离子红染料溶液，适宜的TiO2添加量为3g/L，其脱色率为83．5％。粒径小的TiO2作用效果优于粒径大的效果。在室温和适宜的TiO2添加量的条件下，随照射时间的延长，太阳光的光催化降解效果渐渐接近于紫外光的光催化降解效果。将TiO2薄膜固定在陶瓷睛上，有利于TiO2的重复使用。     

Review of the kinetics of alkaline degradation of cellulose in view of its relevance for safety assessment of radioactive waste repositories

The degradation of cellulose (a substantial component of low- and intermediate-level radioactive waste) under alkaline conditions occurs via two main processes: a peeling-off reaction and a basecatalyzed cleavage of glycosidic bonds (hydrolysis). Both processes show pseudo-first-order kinetics. At ambient temperature, the peeling-off process is the dominant degradation mechanism, resulting in the formation of mainly isosaccharinic acid. The degradation depends strongly on the degree of polymerization (DP) and on the number of reducing end groups present in cellulose. Beyond pH 12.5, the OH^- concentration has only a minor effect on the degradation rate. It was estimated that under repository conditions (alkaline environment, pH 13.3-12.5) about 10% of the cellulosic materials (average DP = 1000-2000) will degrade in the first stage (up to 10⁵ years) by the peeling-off reaction and will cause an ingrowth of isosaccharinic acid in the interstitial cement pore water. In the second stage (10⁵-10⁶ years), alkaline hydrolysis will control the further degradation of the cellulose. The potential role of microorganisms in the degradation of cellulose under alkaline conditions could not be evaluated. Proper assessment of the effect of cellulose degradation on the mobilization of radionuclides basically requires knowing the concentration of isosaccharinic acid in the pore water. This concentration, however, depends on several factors such as the stability of ISA under alkaline conditions, sorption of ISA on cement, formation of sparingly soluble ISA-salts, etc. A discussion of all the relevant processes involved, however, is far beyond the scope of the presented overview.     

Study of Aging Characteristics of Ternary Blends of Polyethylenes—II

Six film samples of low-density polypropylene (LDPE)/linear LDPE (LLDPE)/high-density polypropylene (HDPE) with varying ratios of LDPE (20–45 ... wt%) and LLDPE (25–50 wt%) having a fixed amount of HDPE at 30 wt% were prepared by blown film extrusion technique. The samples were aged at four different temperatures, 55°, 70°, 85°, and 100°C, for four different time periods in the interval of between 150 hours and up to 600 hours. The change in the structure of various constituents and the formation of various oxygenated (peroxy and hydroperoxy) and unsaturated groups during thermo-oxidative degradation was discussed by infrared spectroscopy. The visiosity-average molecular weight was found to have decreased slowly in the initial aging hours and temperatures, whereas it decreased by 10% with its previous value tensile strength that is, 100°C when aged for 600 hours. The tensile strength of the sample first increased by 67% at 55°C and 89% at 70°C up to 450 hours, whereas the values increased by 52.5% at 85°C and 33.9% at 100°C when aged for 150 hours and then decreased. The percentage elongation at break increased by 2.7% at 55°C and 10.7% at 70°C for 150 and 300 hours of aging, respectively, whereas the percentage decreased when aged at 85°C and 100°C for up to 600 hours of aging. The values of gel content (percent) increased and initial degradation temperature decreased with aging time and temperature.     

Determination of the Burning Characteristics of a Slick of Oil on Water

The burning rate of a slick of oil on a water bed is characterized by three distinct processes, ignition, flame spread and burning rate. Although all three processes are important, ignition and burning rate are critical. The former, because it defines the potential to burn and the latter because of the inherent possibility of boilover. Burning rate is calculated by a simple expression derived from a one-dimensional heat conduction equation. Heat feedback from the flame to the surface is assumed to be a constant fraction of the total energy released by the combustion reaction. The constant fraction (χ) is named the burning efficiency and represents an important tool in assessing the potential of in situ burning as a counter-measure to an oil spill. By matching the characteristic thermal penetration length scale for the fuel/water system and an equivalent single layer system, a combined thermal diffusivity can be calculated and used to obtain an analytical solution for the burning rate. Theoretical expressions were correlated with crude oil and heating oil, for a number of pool diameters and initial fuel layer thickness. Experiments were also conducted with emulsified and weathered crude oil. The simple analytical expression describes well the effects of pool diameter and initial fuel layer thickness permitting a better observation of the effects of weathering, emulsification and net heat feedback to the fuel surface. Experiments showed that only a small fraction of the heat released by the flame is retained by the fuel layer and water bed (of the order of 1%). Ignition has been studied to provide a tool that will serve to assess a fuels ease to ignite under conditions that are representative of oil spills. Two different techniques are used, piloted ignition when the fuel is exposed to a radiant heat flux and flash point as measured by the ASTM D56 Tag Closed Cup Test. Two different crude oils were used for these experiments, ANS and Cook Inlet. Crude oils were tested in their natural state and at different levels of weathering, showing that piloted ignition and flash point are strong functions of weathering level.     

Calculation of carbon balances for evaluation of the biodegradability of polymers

Establishing carbon balances has been proven to be an applicable and powerful tool in testing biodegradability of polymers. In controlled degradation tests at a 4-L scale with the model polymer poly(-hydroxybutyrate) (PHB), it was shown that the degree of degradation could not be determined with satisfactory accuracy from CO₂ release alone. Instead, the course of degradation was characterized by means of establishing carbon balances for the degradation of PHB withAcidovorax facilis and a mixed culture derived from compost. Different analytical methods for determining the different carbon fractions were adapted to the particular test conditions and compared. Quantitative determination of biomass and residual polymer were the main problems in establishing carbon balances. Amounts of biomass derived from protein measurements depend strongly on assumptions of the protein content of the biomass. Selective oxidation of biomass with hypochlorite was used as alternative, but here problems arose from insoluble metabolic products. Determination of soluble components with the method of chemical oxygen demand (COD) also includes empirical assumptions but seems acceptable if the dissolved carbon fraction is in the range of some 10% total carbon. Results confirm both analytical assays and theoretical approaches, in ending up at values very close to 100%, within an acceptable standard deviation range under test conditions comparable to standard test practice.Paper presented at the Bio/Environmentally Degradable Polymer Society—Third National Meeting, June 6–8, 1994, Boston, Massachusetts.     

鼓泡式反应器高径比对氨法烟气脱碳性能的影响

以N2和CO2混合气模拟燃烧烟气,研究了鼓泡反应器的高径比以及反应条件对氨法烟气脱碳性能的影响。实验结果表明:在相同高径比的条件下,CO2吸收率随氨水质量分数的增加、反应温度的升高而逐渐增大,随进气CO2体积分数和模拟烟气流量的增加而逐渐减小;CO2吸收率随高径比的增加而增大,在高径比为3.98、氨水质量分数为28%、进气CO2体积分数为10%、模拟烟气流量为1.0L/min、反应温度为40℃的条件下,CO2吸收率最高可达100%。     

Model of technological alternatives of production of sodium chromate (VI) with the use of chromic wastes

This article presents a mathematical model which describes the sodium chromate (VI) production process with the use of chromic waste as a substitution of natural raw materials. This model is a function of selected process parameters common for all of the examined alternatives and based on equations of material balance. Optimization of the elaborated technological alternatives of the production process with use of recycling of chromic waste has been evaluated by determining the extreme value of the quality indicator WJ. This indicator defines the quantity of waste created in the process. Optimization results enabled the selection of the optimal technological solution from all of the alternatives possible for use in industrial practice. Negative values of the indicator prove that there is the possibility of introducing to the process a larger quantity of waste than the one obtained in the process and transported to the storage heaps.     

化学品生物降解性的评价与预测

介绍了有机化学物质生物降解性的测定方法及其预测方法研究概况，并讨论了生物降解性评价的发展前景。     

Structure-biodegradation relationships of polymeric materials. 1. Effect of degree of oxidation on biodegradability of carbohydrate polymers

The biodegradability of oxidized starch and inulin has been studied in relation to the degree of periodate oxidation to dialdehyde derivatives, by measuring oxygen consumption and mineralization to carbon dioxide. A higher degree of oxidation of dialdehyde starch and dialdchyde inulin results in a lower rate at which the polymers are biodegraded. It is demonstrated that the biodegradation rate of dialdehyde inulin derivatives decreases more than that of equivalent starch derivatives. The differences in biodegradation behavior between dialdehyde starch and dialdehyde inulin, resulting from comparable modifications, are discussed in terms of conformational structure.     

Mechanism of Microbial Degradation of Slow-Release Fertilizers

Methyleneureas are condensation products of urea and formaldehyde of different molecular mass and solubility; they are used in large amounts both as resins, binders, and insulating materials for industrial applications, as well as a slow-release nitrogen fertilizer for greens, lawns, or in bioremediation processes. In the present study, the microbial breakdown of these products was investigated. The nitrogen was released as ammonia and urea, and the formaldehyde released immediately oxidized via formiate to carbon dioxide. The enzymatic mechanism of metabolization of methyleneureas was studied in microorganisms isolated from soil, which were able to use these compounds as the sole source of nitrogen for growth. A strain of the Gram-negative bacterium Ralstonia paucula (formerly Alcaligenes sp. CDC group IVc-2) completely degraded methylenediurea and dimethylenetriurea to urea, ammonia, formaldehyde, and carbon dioxide. The enzyme initiating this degradation (methylenediurease) was purified and turned out to be different from the previously described enzyme from Ochrobactrum anthropi with regard to its regulation of expression and physicobiochemical properties. Fungal degradation of methyleneureas may occur via the formation of organic acids, thus leading to a nonenzymatic degradation of methyleneureas, which are unstable under acidic conditions.     

Effect of Degree of Substitution of Octenyl Succinate Starch on Enzymatic Degradation

Octenyl succinate starch of degree of substitution (ds) 0.03, 0.07, and 0.11 was synthesized in an aqueous medium. These compounds were then tested for the susceptibility to enzymatic degradation. The multiple-enzyme regime of -amylase, amyloglucosidase, and pullulanase was chosen for the evaluation. This combination of enzymes had been proven to degrade 99.5% of unmodified starch to glucose and hence was chosen for this study. It was found that even small amounts of subsituent caused a considerable decrease in the extent of degradation. The net extent of degradation decreased with increasing ds. Surprisingly, the amount of glucose from all three substituted substrates was quite similar, suggesting the effect small amounts of subtituent had on the enzymatic activity.