水中硝基苯光降解研究

为研究硝基苯在水体中的光化学行为.建立基于液相色谱的硝基苯浓度的测定方法.分别以低压紫外汞灯、氙灯和自然阳光为光源,研究水中硝基苯的光降解规律,探讨光强、pH值、江水中可溶性物质等因素对硝基苯光解速率的影响.结果表明,硝基苯光降解反应符合一级反应动力学规律,反应速率常数k与初始入射光强,I0成正比,k=0.0014I0;紫外光辐射强度在水中呈指数衰减.2、3月份太阳辐射强度下,江水表层中(30～40mm厚)硝基苯光降解的半衰期约为2d.酸性条件下,硝基苯光降解反应速率有所提高,碱性条件下基本无变化.江水中的腐殖质和某些杂质对硝基苯的光降解有促进作用.研究为污染水体的自然修复提供理论依据.     

负载TiO2颗粒活性炭去除微囊藻毒素- LR的动力学

以活性炭为载体,采用溶胶凝胶法制备负载型的催化剂(TiO2/GAC),进行了有无紫外光降解和有无活性炭条件下的微囊藻毒素- LR( MCLR)降解试验.结果显示,在紫外光照射下,MCLR不会自身降解,且紫外光照对活性炭吸附性能无明显影响.此外,通过负载型催化剂对不同初始质量浓度的MCLR溶液的吸附和光催化降解试验,进行了Lagergreen准二级模型和颗粒内部扩散模型拟合催化剂的吸附去除动力学研究,应用Langmuir- Hinshelwood和Freundlich-Hinshelwood模型拟合光催化降解过程.结果表明,Lagergren准二级模型和Langmuir- Hinshdwood模型均能较好地描述TiO2/GAC对MCLR的吸附、光降解过程,Langmuir-H inshelwood模型中吸附平衡常数Kt值基本保持不变,约(0.057 0±0.0008)L/μg,降解速率常数k值随着初始质量浓度的增加有所下降.     

水质对UV/H2O2降解邻苯二甲酸二甲酯反应动力学的影响

研究了不同初始pH值、浊度与常见阴离子浓度等水质条件对UV/H2O2工艺降解邻苯二甲酸二甲酯(DMP)反应速率的影响,并进一步比较了去离子水和自来水中DMP的降解速率.结果表明,UV/H2O2对DMP的光降解过程符合一级反应动力学模型,不同水质条件对降解速率有不同程度的影响.酸性条件较碱性条件更有利于DMP降解; 水的浊度大于7 NTU时,光降解速率常数迅速下降; NO3-、Cl3-、HCO3-等阴离子对DMP降解有抑制作用,且随离子浓度增大,抑制作用增强,3种离子对DMP光降解的抑制程度顺序为HCO3-＞NO3-＞Cl3-.在5个30 W低压汞灯照射下,当H2O2的浓度为20 mg·L-1时,DMP在去离子水和自来水中光降解速率常数分别为0.042 8 min-1和0.031 5 min-1,自来水中的光降解速率常数较去离子水中的低,这可能是水中多种离子影响的结果.     

镍网负载纳米TiO2对甲苯降解的实验研究

采用溶胶-凝胶法制备负载纳米TiO2的泡沫镍网,并利用自制的间歇式光催化反应装置对甲苯废气降解进行实验研究.考察了光源波长、湿度、含氧量、甲苯初始浓度等因素对甲苯去除率的影响,并对光催化剂的失活和再生进行了实验研究.结果表明,在光源波长为185 nm条件下,体系相对湿度为45％、含氧量为21％、甲苯初始质量浓度为208 mg/m3,甲苯的去除率达97％以上,通过紫外光照射失活光催化剂12 h,其活性能基本恢复,对甲苯的去除率达87％以上.     

真空紫外光降解瓦斯反应动力学规律

为了研究真空紫外光降解瓦斯过程的反应动力学规律,在自制的真空石英光化学反应器中以含甲烷标准气体模拟矿井瓦斯,运用Langmuir-Hinshelwood(L-H)拟一级反应动力学模型对不同光照强度、氧气体积分数、甲烷初始体积分数和水分子体积分数下瓦斯(甲烷)的降解过程进行拟合.结果表明:真空紫外光降解瓦斯反应动力学规律符合一级反应动力学特性;光照强度、甲烷初始体积分数、氧气体积分数和水分子体积分数是影响真空紫外光降解瓦斯的主要因素;瓦斯(甲烷)降解的反应速率随光照强度和氧气体积分数增大而增大,随甲烷初始体积分数增大而减小,随水分子体积分数增大而先增大后减小.     

UV-Fenton 体系氧化降解苯酚废水反应动力学研究

利用UV-Fenton高级氧化技术对苯酚废水进行了处理研究.通过半衰期法对苯酚的反应级数进行了探讨,确定其在UV-Fenton体系降解过程中的表观反应级数为3/2,并初步建立了苯酚UV-Fenton降解的动力学模型,并从反应速率系数着手探讨了污染物初始浓度、双氧水加入量、亚铁离子浓度及pH值对反应降解速率的影响.     

鱼藤酮在不同类型土壤中的降解

利用高效液相色谱法(HPLC)研究鱼藤酮在不同类型土壤(稻田土、菜田土和果园土)中的降解,并探讨土壤微生物、土壤含水量、紫外光照和土壤理化性质等因子对鱼藤酮降解的影响.结果表明,鱼藤酮在不同类型土壤中的降解符合一级动力学方程.避光条件下,鱼藤酮在稻田土(pH=5.5)、菜田土(pH=5.64)和果园土(pH=4.78)中的降解速率常数分别为0.164 5、0.147 8和0.120 3;鱼藤酮在灭菌菜田土中的半衰期为10.51 d,而在未灭菌菜田土中的降解半衰期为4.76 d.避光条件下,鱼藤酮在烘干的土壤中稳定.其半衰期为15,16 d;土壤含水量为田间饱和含水量的60%时,鱼藤酮半衰期为4.03 d;厌氧条件下,鱼藤酮半衰期为3.51 d.紫外光照也是加速鱼藤酮降解的重要因素,未接受紫外照射的土壤中的鱼藤酮半衰期为67.28 h,接受照射时仅为10.51 h.研究表明,鱼藤酮在土壤中的降解受微生物、紫外光照及土壤含水量的影响较大;土壤pH值越小,鱼藤酮滞留时间越长;此外,土壤理化性质也是影响鱼藤酮在土壤中滞留性的重要因子.本研究为正确评估鱼藤酮的环境安全性提供了依据.     

饮用水中微囊藻毒素臭氧降解效能及影响因素研究

对臭氧氧化去除饮用水中微囊藻毒素RR及LR的降解效能、反应动力学进行了试验研究,讨论了藻毒素初始质量浓度、pH值、羟基自由基(·OH)抑制剂(HCO-3)、溶解性有机碳(DOC)质量浓度对降解的影响.结果表明:整个降解过程符合一级动力学反应方程,降解速率常数与藻毒素初始质量浓度无关;pH值的升高、HCO-3和DOC的存在都会降低藻毒素的降解效率.在液相臭氧质量浓度为8.20 mg·L-1,pH=7.0,温度为(25±1) ℃,反应时间30 min的条件下,MC-RR降解速率常数k=7.80×102 min-1,去除率达90.0%;MC-LR降解速率常数k=1.06×101 min-1,去除率达96.3%.     

基于纳米二氧化钛光催化的邻苯二甲酸二(2-乙基)己酯的光降解研究

以锐钛型纳米二氧化钛为催化剂,研究了Ti O2投加量、底物初始浓度、溶液的p H值、光源种类以及降解时间等因素对废水中邻苯二甲酸二(2-乙基)己酯(DEHP)光催化降解的影响。研究结果表明,DEHP的光催化降解率随着纳米Ti O2投加量的增加先增大后减小,纳米Ti O2的最佳投加量为0. 30 g/L。随着DEHP初始浓度的增大,DEHP的光催化降解率减小,当DEHP初始浓度小于50 mg/L时,降解率降幅较小,而当DEHP初始浓度大于50 mg/L后,降解率急剧减小。随着p H的增大,DEHP的光催化降解率先增大后减小,呈现单峰型,当p H为7时,DEHP的降解率达到最大,酸性和碱性条件下,均不利于DEHP的光催化降解。紫外光照射下,DEHP光催化降解率有了大幅提高,降解率大小顺序为η(UVC)>η(UVB)>η(UVA); DEHP的紫外光催化降解符合一级动力学方程,降解半衰期为2. 15~25. 99 h。     

UV/H2O2催化氧化去除微囊藻毒素-LR

研究了UV/H2O2氧化降解微污染水体中微囊藻毒素MC-LR的效果,探讨了各种因素如H2O2浓度、pH值、光强、MC-LR浓度及反应时间对降解的影响.UV和H2O2氧化去除MC-LR具有协同作用,H2O2在UV照射下产生的羟基自由基对MC-LR有很强的氧化能力.MC-LR的降解过程可用准一级反应速率方程和二级反应速率方程拟合.反应速率常数随MC-LR的起始浓度增加而减少,反应半衰期随MC-LR的起始浓度增加而延长.在H2O2浓度为1.0 mmol/L、反应温度为(25.5±1)℃、pH值为6.8、光强2.5×104 lux及反应时间60 min的条件下,质量浓度为0.203 mg/L的MC-LR的去除率可以达到80.8%.结果表明,UV/H2O2氧化体系能有效地降解MC-LR.     

三氯乙醛的光降解反应研究

研究了太阳光照下,水溶液中FeC l3-三氯乙醛的光化学反应速率,采用紫外分光光度计定时对含有不同浓度Fe（Ⅲ）的溶液进行实验测定,并根据三氯乙醛标准溶液曲线进行分析。实验结果表明,在波长为480nm的紫外光照射下：室内自然光下含有Fe（Ⅲ）和室外太阳光下不含Fe（Ⅲ）的三氯乙醛溶液中,三氯乙醛的浓度基本保持不变;但在室外太阳光下含有Fe（Ⅲ）的三氯乙醛溶液中,三氯乙醛的浓度随着Fe（Ⅲ）浓度的增加而减小。由此表明,Fe（Ⅲ）是三氯乙醛光化学反应的催化剂,FeC l3-三氯乙醛的光化学反应随着Fe（Ⅲ）浓度的增加而加快。     

Ammonium nitrate thermal decomposition with additives

Runaway reactions present a potentially serious threat to the chemical process industry and the community; such reactions occur time and time again often with devastating consequences. The main objective of this research is to study the root causes associated with ammonium nitrate (AN) explosions during storage. The research focuses on AN fertilizers and studies the effects of different types of fertilizer compatible additives on AN thermal decomposition. Reactive Systems Screening Tool (RSST) has been used for reactivity evaluation and to better understand the mechanisms that result in explosion hazards. The results obtained from this tool have been reported in terms of parameters such as “onset” temperature, rate of temperature and pressure rise and maximum temperature. The runaway behavior of AN has been studied as a solid and solution in water. The effect of additives such as sodium sulfate (Na₂SO₄) and potassium chloride (KCl) has also been studied. Multiple tests have been conducted to determine the characteristics of AN decomposition accurately. The results show that the presence of sodium sulfate can increase the “onset” temperature of AN decomposition thus acting as AN thermal decomposition inhibitor, while potassium chloride tends to decrease the “onset” temperature thus acting as AN thermal decomposition promoter.     

雾化-UV/O_3氧化硝基苯的实验研究

为了寻求一种经济有效的处理硝基苯废水的方法.通过雾化头把废水打成雾状,同时,在装置中通入O3引入紫外光,在装置中进行雾化-氧化.实验表明,整个体系中,液滴粒径、硝基苯浓度、pH值、反应时问等因素对硝基苯去除率影响最大,雾化-UV/O3氧化硝基苯法能够有效去除硝基苯.实验得到的最佳反应条件为:液滴粒径控制在50/μm.硝基苯质量浓度为50me/L,pH值为8.臭氧反应时间30min.采用雾化-UV/O3氧化硝基苯废水,取得了很好的去除效果,硝基苯去除率达到94.34%,二级雾化降解效率达到98.25%.     

障碍物条件下纳米SiO2粉体抑制瓦斯爆炸特性

为了研究障碍物条件下纳米SiO_2粉体对瓦斯爆炸的抑制特性,采用自行搭建的150 mm×150 mm×500 mm可视化瓦斯爆炸试验系统,分别对不同质量浓度和粒径的纳米SiO_2粉体抑爆特性进行了试验研究。结果表明:在障碍物条件下,纳米SiO_2粉体对瓦斯爆炸具有良好的抑制效果,0.10 g/L的30 nm SiO_2粉体可使9.5%瓦斯气体的最大火焰传播速度降低35%,爆炸超压降低34%;然而,纳米SiO_2粉体并非质量浓度越大抑爆效果越好,而是存在最佳抑爆质量浓度,即随纳米SiO_2粉体质量浓度上升,其抑爆性能先增大后减小,最佳抑爆质量浓度约为0.10 g/L;此外,纳米SiO_2粉体的抑爆性能与其粒径相关,且存在最佳抑爆粒径,相同质量浓度下30 nm SiO_2粉体比15nm和50 nm SiO_2粉体的抑爆效果好。     

城市污水再生处理工艺中发光细菌毒性变化的初步研究

保障再生水的生态安全是污水再生利用过程中非常关键的问题.本文采用发光细菌毒性测试方法测定了2个城市污水再生利用示范工程工艺流程中生物毒性的变化,尤其是可能生成有毒副产物的氯消毒过程中的毒性变化.结果表明,二级生物处理能显著降低污水的发光细菌毒性,但氯消毒显著提高了污水的毒性,并且脱氯后污水的毒性仍保持较高的水平,对生态安全造成了潜在威胁.同时,通过比较2种污水水质发现,DOC(溶解性有机碳含量)和UV254(254 nm处的紫外吸收值)较高的水样,消毒后的毒性较大,认为DOC和UV254可望作为预测污水消毒生态风险的水质指标,为污水消毒实践中确定安全合理的污水水质条件提供一定的依据.     

FeSO4/H2O2/UV体系处理化纤厂棉浆粕黑液的研究

Fenton法是处理难降解有毒有机污染物的一种有效的方法.以棉浆粕黑液为研究对象,讨论了H2O2和FeSO4投加量、pH值、搅拌时间等因素对废水CODCr去除率的影响,将紫外光照引入Fenton试剂能提高废水中有毒有机污染物的降解速度,提高氧化能力 .实验确定了最佳工艺条件:pH=7,FeSO4投加量4 g/L,H2O2投加量为1.13%(V/V),搅拌时间15 min,此时CODCr去除率达到66.96%.     

Use of isoperibolic calorimetry for the study of the effect of water concentration,temperature and reactor venting on the rate of hydroxylamine thermal decomposition

Hydroxylamine, NH₂OH, thermal decomposition has been responsible for two serious accidents. However, its reactive behavior and the synergy of factors affecting the rate of its decomposition are not understood. In this work, isoperibolic calorimetric measurements were performed in a metal reactor, in the temperature range 130–150 °C, employing 30–80 ml solutions containing 1.4–20 g of pure hydroxylamine (2.8–40 g of the supplied reagent). The calorimetric measurements were performed in order to assess the effects that NH₂OH concentration, temperature and reactor venting has on NH₂OH rate of decomposition. The measurements showed that increased concentration or temperature, results in faster reactions and probably higher pressure generation per mass of reactant, with concentration having a more pronounced effect. However, when both factors work synergistically the result is dramatically worse in terms of reaction rate. The pressure generation is also different, thus indicating that different reaction pathways predominate each time. Venting the produced gases in stages resulted in the highest mass loss of the solution.     

The effect of environmental and design parameters on subjective road safety — a case study in Poland

In order to get a better insight into the safety effects of alternative road designs, the subjective safety experiment has been conducted. The experiment has been designed to test the effect of geometric design characteristics and road environment on the subjective safety of rural road curves. The method used here allows to investigate the effect of a real driving environment on safety in a complex way. The results have shown the importance of the composed effect of curve geometry and curve environment on the subjective safety of rural curves.     

Thermal decomposition of ethyl parathion

The thermal decomposition of ethyl parathion, an organophosphorus pesticide, has been studied by coupling calorimetric and chemical analysis. The decomposition process develops through two exothermic events with production of relevant amounts of uncondensible gases (final pressure 50 bar in an ARC run). A simple autocatalytic kinetic model has been adopted for simulating the first stage of the decomposition process.     

Decomposition of 1,4-dioxane by vacuum ultraviolet irradiation: Study of economic feasibility and by-product formation

We report the first use of vacuum ultraviolet (VUV) treatment to decompose 1,4-dioxane, a persistent organic contaminant that is difficult to remove by conventional drinking water treatment processes. The efficiency of VUV treatment was compared to that of VUV- and UV-based advanced oxidation processes (AOPs) (VUV/TiO₂, VUV/H₂O₂, UV/TiO₂, and UV/H₂O₂), and by-product formation was investigated. VUV treatment decomposed 1,4-dioxane more rapidly than did UV and UV/TiO₂ treatments. The decomposition rate was enhanced when VUV irradiation was combined with TiO₂ or H₂O₂. VUV/H₂O₂ decomposed 1,4-dioxane more rapidly than UV/H₂O₂ at a low H₂O₂ dose (1 mg/L), but the rate difference became small at a high H₂O₂ dose (5 mg/L). Electrical energy per order analysis revealed that VUV treatment, and the VUV- and UV-based AOPs, were economically feasible for 1,4-dioxane decomposition. Using raw water samples, we investigated by-product formation during VUV treatment and the effect of VUV irradiation on chlorinated disinfection by-product formation potential. Although the samples contained high concentrations of bromide, no bromate was produced by VUV treatment. VUV treatment slightly decreased trihalomethane formation potential (THMFP), whereas haloacetic acid formation potential (HAAFP) was unchanged, and total aldehyde concentration increased. The trend in HAAFP agreed with that had been reported for the VUV irradiation with much higher dose (Buchanan et al., 2006), whereas the trend in THMFP was different from that with much higher dose. THMFP, HAAFP, and aldehyde concentration were reduced by subsequent treatment with granular activated carbon (GAC) or biological activated carbon (BAC). Nitrite was produced by VUV treatment but disappeared after subsequent BAC treatment. These results suggest that VUV treatment should be combined with GAC or BAC treatment to suppress by-product formation.