金属卟啉检测室内空气挥发性有机污染物浓度的性能研究

以四苯基卟啉(TPP)为起始物,通过金属插入反应,获得FeTPP、ZnTPP、CoTPP、MnTPP。以合成的金属卟啉为检测器,测定了其检测甲苯、三乙胺、丙醛、异丙醇等浓度的检测限及灵敏度。结果表明,CoTPP检测甲苯、丙醛较好,而FeTPP检测三乙胺、异丙醇较好,MnTPP、ZnTPP对4种物质都有响应,但特异性不强,且灵敏度都较低;CoTPP只对甲苯和丙醛有响应,特异性强,且灵敏度高。     

甲苯对两相厌氧系统的影响及降解特性研究

采用两相厌氧工艺处理含甲苯模拟废水,研究了甲苯浓度变化对两相厌氧系统的影响。低浓度甲苯对厌氧微生物具有一定的刺激作用,较高浓度甲苯具有抑制作用,高浓度甲苯具有毒害作用。厌氧系统在投加不同浓度的甲苯前后挥发性脂肪酸(VFA)表现出不同的变化趋势,并对厌氧发酵方式产生影响。甲苯的浓度变化影响其降解效率。     

两亲接枝共聚物PS-g-N-PEO的合成及表面性能研究——铸膜溶剂及浓度的影响

采用大分子单体法合成了一系列聚苯乙烯接枝壬基酚聚氧乙烯 (PS g NPEO)两亲共聚物 ,采用溶液铸膜法将其在PET表面制膜 ,并利用扫描电子显微镜 (SEM) ,X射线光电子能谱 (XPS) ,衰减全反射红外光谱(ATR)和水接触角 (CA)等手段研究了共聚物组成、铸膜溶剂及浓度对共聚物膜表面形貌、组成及水浸润性能的影响 .结果表明 ,两亲接枝共聚物在不同条件下可形成规则的表面微孔 ,共聚物中NPEO含量越高 ,共聚物膜表面微孔孔径越大 ,对应的水接触角越小 .以THF为铸膜溶剂时 ,制膜浓度越大 ,共聚物膜表面微孔孔径越大 ,对应的水接触角越小 ;而以甲苯为溶剂时 ,制膜浓度对共聚物膜表面形貌影响不大 ,但水接触角要较THF体系显著降低 ,水接触角与浓度关系与THF体系相反 ,制膜浓度越大 ,对应的水接触角越大 .制膜浓度相同时 ,THF作溶剂 ,共聚物膜微孔较大 ,表面亲水组分含量较低 ;以甲苯为溶剂 ,微孔较密 ,表面亲水组分较高 .     

TiO2光催化降解苯和甲苯的动力学研究

利用溶胶-凝胶法制备了粒径约为13nm、晶型为锐钛矿相和金红石相混晶的TiO2光催化剂,并利用此催化剂对挥发性有机污染物苯和甲苯进行了光催化降解研究,对不同的催化剂用量、光源、污染物的初始浓度以及氧气对光催化反应速率的影响进行了研究。结果表明,光催化降解甲苯和苯的反应均符合假一级动力学方程,光强与光催化降解甲苯的反应的速率常数之间呈指数关系,光波长对光催化降解苯的影响也很显著;随着甲苯和苯初始浓度的增加,光催化反应速率常数降低;氧气加快了光催化降解甲苯和苯的速率;对于光催化降解初始浓度为37.6μmol/L的甲苯而言,催化剂的最佳使用量为0.30g,对于光催化降解初始浓度为9.0μmol/L的苯来说,催化剂的最佳用量为0.10g。     

富镧稀土镍储氢合金催化甲苯液相加氢反应的动力学研究

研究了由富镧稀土镍储氢合金与甲苯组成浆液储氢体系 ,储氢合金催化甲苯液相加氢反应的动力学特性。考察了反应温度、液相氢浓度等因素对浆液体系内部传质 反应过程的影响。结果表明 ,在实验条件下富镧稀土镍 甲苯浆液体系中甲苯的液相加氢反应速率随反应温度的升高而升高 ,并在 4 90K左右达到最大 ,当温度超过 5 10K后反应速率迅速下降。富镧稀土镍 甲苯浆液体系中甲苯的液相加氢反应为反应控制过程 ,体系中气 液界面和液相主体到催化剂表面的传质阻力完全可以忽略。表现反应速率对甲苯表现为零级 ,对液相氢浓度为一级 ,得到反应动力学模型 ,该模型与实验结果有很好的一致性 ,富镧稀土镍催化的甲苯加氢反应的活化能为 4 1 0 1kJ·mol- 1。     

室内空气中甲醛浓度的测定

目的为了快速准确的测定高校室内空气中甲醛浓度。方法采用乙酰丙酮分光光度法,对计算机房、物理实验室、化学实验室三个房间的甲醛浓度进行了测定分析。结果相对于化学实验室来说,计算机房的甲醛浓度多了0.77倍;物理实验室的甲醛浓度比化学实验室的多了0.98倍。结论室内空气质量可能会受新房对甲醛的释放时间以及室内新家具的存放时间影响;乙酰丙酮分光光度法具有简便、易控制、成本低等优点,可以广泛使用于普通室内甲醛浓度的测定。     

Fenton试剂增强电晕放电技术降解甲苯

通过气溶胶分散技术将芬顿(Fenton)试剂引入气相反应体系来增强电晕放电对污染物甲苯的降解.含Fe2 、Co2 和Mn2 等过渡金属离子的催化剂溶液以微液滴形式添加入反应器电晕区,考察了催化剂对甲苯蒸气降解速率的影响,发现甲苯平均降解速率均有显著提高.在这三种金属离子溶液浓度均为0.05mol/L,电极气流量为0.6m3/h和极间电压为23kV时,甲苯(初始浓度为900mg/m3)降解速率增强因子β分别为1.29,1.28和1.51.气相和液相中降解产物的分析表明,微液滴内发生的电Fenton反应将电晕放电产生的H2O2转化为具有更强氧化性的羟基自由基(HO.),而甲苯的中间产物溶解在微液滴中,增强了甲苯的降解速率.     

深度探究浓度对化学平衡的影响

就Fe3++SCN-Fe(SCN)2+平衡而言,向该平衡体系中加入一定浓度的FeCl3溶液,通过改进浓度对化学平衡影响的实验和对实验的深入探究,借助实验的功能解决了平衡移动的方向、Fe(SCN)2+的浓度和溶液的颜色是如何变化的等问题,进而使学生对“外界条件对化学平衡的影响”有了更全面的认识.     

高聚物溶液中大分子链尺寸的研究——旋转半径R_G与浓度C的关系

根据Flory等效流体力学球模型及其粘度理论,对溶液中大分子链尺寸进行了研究,导出了一个能在整个溶液浓度范围内适用的形式简单的大分子链尺寸与溶液浓度间定量关系新方程。由该方程计算分子量为1.1×10~5的聚苯乙烯在不同浓度的甲苯溶液中的R_G值与Hayashi等人的小角X散射实验值很接近;也与King等人由中子散射法测得的实验值基本一致。相比较,由本模型所得的预言结果比其它理论模型所得的结果更为满意。     

掺混含氧燃料的柴油替代物部分预混火焰中多环芳香烃的荧光光谱和碳烟浓度

为研究不同含氧燃料与柴油掺混后碳烟降低机理, 本文在自行设计的燃烧器上构建部分预混层流火焰, 采用甲苯和正庚烷混合物(T20, 20%(体积分数)甲苯、80%正庚烷)作为柴油替代物,并分别添加甲醇、乙醇、正丁醇、丁酸甲酯和2,5-二甲基呋喃(DMF), 且保证混合燃料的含氧量均为4%. 进而应用激光诱导荧光法和激光诱导炽光法分别测量不同混合燃料的火焰中多环芳香烃(PAHs)的荧光光谱和碳烟浓度. 结果表明: 通过PAHs的荧光光谱可测量不同燃料火焰中PAHs的生成和增长历程. 四环芳香烃(A4)的生成氧化规律和碳烟基本一致, 说明通过分析A4变化可以预测碳烟变化. 添加含氧燃料后, T20燃料中甲苯含量降低是导致PAHs的荧光光谱强度降低和碳烟生成量减少的主要原因; 同时不同含氧燃料本身对多环芳香烃的生成贡献能力也是影响PAHs的荧光强度和碳烟生成的重要原因. 含氧量相当时, 掺混正丁醇后PAHs的荧光光谱强度和碳烟浓度比添加甲醇、乙醇、丁酸甲酯和DMF这四种含氧燃料的更低. 因此从含氧燃料结构来讲, 正丁醇掺混入T20燃料中降低PAHs和碳烟作用最显著.     

Low energy electron beam treatment of VOCs

Research on electron beam decomposition of volatile organic compounds (VOCs) in air was carried out to establish an advanced treatment technology for industrial off-gases. Benzene, toluene and o-xylene were selected as aromatic VOCs and dichloro-, trichloro- and tetrachloro-ethylene as chloroethenes. The experimental results showed that G-values of decomposition ranged from 1.0–2.2 in aromatic compounds and 30–60% of decomposed compounds were converted into aerosols. On the other hand, G-values of decomposition of chloroethenes increased with the initial concentration and number of chlorine atoms in a molecule, for example, the G-value at 180 and 1580 ppm of tetrachloroethylene were 22 and 172, respectively. The formation of aerosol was not observed in the decomposition of chloroethenes. An application of low energy electron accelerator for treatment of exhaust gases containing VOCs was also discussed.     

在线质谱仪在车内VOCs现场快速监测中的应用

挥发性有机物(VOCs)影响车内空气质量和驾乘者的身心健康。自主研发的在线挥发性有机物质谱仪(SPI-MS 2000),实现了有机物分子的单光子电离,产生无碎片的分子离子,可实现秒级响应,仪器的质量分辨率优于800 FWHM,质量精度优于0.02 amu,对甲苯的测定限优于3μg/m^3,且在3~8000μg/m^3范围内有良好的线性关系。将该仪器应用于某客车车内空气的在线检测:在5 s内检测到20多种微克~毫克每立方米量级的有机物。该仪器在车内VOCs现场快速监测方面有广泛的应用前景。     

Simultaneous determination of odorous volatile organic compounds with gas chromatography and a thermal desorber: A case study on methyl ethyl ketone, methyl isobutyl ketone, butyl acetate, toluene, and xylene

In this study, a series of experiments were conducted to examine the feasibility of the gas chromatographic approach for the quantification of several odorous volatile organic compounds (VOCs) in environmental samples which included methyl ethyl ketone, isobutyl alcohol, methyl isobutyl ketone, and butyl acetate plus benzene, toluene, and xylene (namely, BTX). The gaseous working standards (WS) of seven compounds were initially calibrated at varying concentration ranges by direct injection (DI) into GC injector. The detection properties of these compounds were then tested with a thermal desorber (TD). The relative sensitivities of three aromatic VOCs differed greatly between DI and TD methods. In contrast, four polar VOCs tend to consistently exhibit relative enhancement in response factors with increasing molecular mass (an exception of butyl acetate), regardless of method. The TD-based analysis was reliable enough to detect all target VOCs below their odor threshold values with their detection limit (DL) values. This TD method, when tested against a number of environmental samples collected from several industrial facilities, confirmed the presence of these odorous VOCs at a wide concentration range.     

不同吸附剂上动态吸附-脱附挥发性有机气体性能研究

采用气相色谱法和热重分析(TG)研究了活性炭以及5A、NaY、13X、ZSM-5(Si0_2/Al_2O_3=27、300)、Hβ和MCM-41分子筛对正己烷、甲苯和乙酸乙酯的动态吸附-脱附性能,系统考察了挥发性有机气体(VOCs)浓度与种类及体积空速对吸附容量的影响。结果表明,增加体积空速和VOCs浓度,一定程度上能够提升吸附容量;活性炭吸附剂对三种VOCs具有较高的单位质量吸附量,而13X与NaY对三种VOCs具有更大的单位体积吸附量。     

热脱附-气相色谱-质谱法应用于工业源废气中挥发性有机物的目标和非目标筛查

建立了固相吸附热脱附-气相色谱-质谱(TD-GC-MS)综合筛查工业源废气中挥发性有机物(VOCs)的方法。对两种型号的固相吸附管进行了比较,最终选择使用Tenax SS TD Tubes吸附管。气体样品以恒定流速通过吸附管,富集分析物,经热脱附后,用GC-MS进行检测,目标化合物以内标法定量,非目标化合物的含量以甲苯的响应系数计算。方法检出限为1.06~5.44 ng,以采样体积300 mL计算,目标化合物的检出限为0.004~0.018 mg/m~3。吸附管平均加标回收率为78.4%~89.4%,相对标准偏差为3.9%~14.4%(n=7)。应用该方法对大连市某垃圾焚烧发电厂排放的废气进行VOCs目标及非目标化合物综合筛查,共检出29种VOCs,其中仅5种VOCs为预先设定的目标化合物,另外24种为非目标化合物,5种目标化合物含量仅占所有检出物总量的26.7%。证明了工业源废气VOCs分析中非目标化合物筛查的重要性,该研究思路对完整测定工业源挥发性有机污染物分布具有一定的借鉴意义。     

顶空固相微萃取-气相色谱-质谱联用分析纺织品中挥发性有机物

建立了顶空固相微萃取（HSSPME）-气相色谱（GC）-质谱（MS）联用测定纺织品中甲苯、4-乙烯基环己烯、苯乙烯、萘和1-苯基环己烯5种挥发性有机物（VOCs）的分析方法。选择聚二甲基硅氧烷（PDMS）作为萃取涂层,优化了SPME的萃取条件,包括平衡时间、萃取时间、萃取温度、顶空体积、离子强度、搅拌速度、解吸温度和时间以及GC—MS仪器条件。对于甲苯、4-乙烯基环己烯、苯乙烯、萘和1-苯基环己烯方法线性范围分别为0．087～870、3．32～3320、2．28～2280、0．015～150和0．050～50．0ng／g;检出限分别为0．005、0．042、0．670、0．008和0．011ng／g。实际样品加标回收率在80．1％～122％之间,RSD在0．8％～8．6％之间。方法符合纺织品中痕量VOCs的快速分析要求。     

Degradation of toluene gas at the surface of ZnO/SnO2 photocatalysts in a baffled bed reactor

To eliminate volatile organic compounds (VOCs) from contaminated air, a novel medium-scale baffled photocatalytic reactor was designed and fabricated, using immobilized ZnO/SnO₂ coupled oxide photocatalysts. Toluene was chosen as a representative pollutant of VOCs to investigate the degradation mechanism and the parameters affecting photocatalytic degradation efficiency. The preliminary experimental results indicate that the degradation efficiency of toluene increased with the increase of the light irradiation dosage, while it decreased with the increase of concentrations of toluene. The degradation efficiency increased rapidly with the increase of the relative humidity in a low humidity range from 0 to 35%, but decreased gradually in a high relative humidity (i.e., >35%). The optimum experimental conditions for toluene degradation is a toluene concentration of 106 mg m^?3, a relative humidity of 35%, and an illumination intensity of ca. 6 mW cm^?2 at the surface of ZnO/SnO₂ photocatalysts. The intermediates produced during the gaseous photocatalytic degradation process were identified using the GC–MS technique. Based on these identified intermediates, the photocatalytic mechanism of toluene into ZnO/SnO₂ coupled oxide catalyst was also deduced.     

Evaluation of septa quality for automatic SPME-GC-MS trace analysis

The vials used for the preparation of breath samples for automated solid-phase microextraction-gas chromatography-mass spectrometry analysis are crimped with septa. These septa often emit specific volatile organic compounds (VOCs) confounding the measurement results of breath samples. In the current paper, 14 different brands of magnetic caps with silicone-polytetrafluoroethylene (PTFE), butyl-PTFE, or butyl rubber septa were tested. The total emission of septa over a 4 h period was also evaluated. The tested septa emitted 39 different compounds, which are mainly hydrocarbons, alcohols, and ketones. Acetone and toluene are the most abundant out-gassing products. The concentration of acetone was in the range from 55 to 694 ppb for butyl-PTFE septum (brand 14) and butyl rubber (brand 10), respectively. The measured toluene amount was 69-1323 ppb for the septum brand 14 and brand 8 (silicone-PTFE), respectively. Generally, the butyl rubber septa released higher amounts of contaminants in comparison to the silicone ones.     

Product analysis and mechanism of toluene degradation by low temperature plasma with single dielectric barrier discharge

A single dielectric barrier discharge (DBD) low-temperature plasma reactor was set up, and toluene was selected as the representative substance for volatile organic compounds (VOCs), to study the reaction products and degradation mechanism of VOCs degradation by low-temperature plasma. Different parameters effect on the concentration of O₃ and NO_x during the degradation of toluene were studied. The exhaust in the process of toluene degradation was continuously detected and analyzed, and the degradation mechanism of toluene was explored. The results showed that the concentration of O₃ increased with the increase of the power density and discharge voltage of the plasma device. However, as the initial concentration of toluene increased, the concentration of O₃ basically keep steady. The concentration of NO_x in the by-products increased with the discharge voltage, power density, and initial concentration of toluene in the plasma device, and the concentration of NO₂ was much higher than the concentration of NO. The degradation process of toluene was detected and analyzed. The results showed that the degradation mechanism of toluene by plasma includes high energy electron bombardment reaction, active radical reaction and ion molecule reaction. Among them, the effect of high-energy electrons on toluene degradation is the largest, followed by the effect of free radicals, in which oxygen radicals participated in the reaction mainly through the formation of C–O bond, CO bond, (CO)–O– bond and –OH radical, while nitrogen radicals participate in the reaction mainly through the formation of C–NH₂, (CNH)- bond, CN bond and C–NO₂ bond. The results can provide some data supports for the study of low-temperature plasma degradation of VOCs.     

Humidity effect on the monolayer-protected gold nanoparticles coated chemiresistor sensor for VOCs analysis

Two gold-thiolate monolayer-protected nanoparticles were synthesized and used as interfacial layers on chemiresistor sensors for the analysis of violate organic compounds (VOCs). Toluene, ethanol, acetone and ethyl acetate were chosen as the target vapors. Both the resistance and capacitance were measured as the function of analyte concentrations. The effect of humidity on the sensor sensitivity to VOCs was investigated. The sensitivity decreases with humidity increasing, depending on the hydrophobicity of the target compounds. Less effect was observed on the higher hydrophobic compounds. While the relative humidity (RH) increased from 0 to 60%, the sensitivity to acetone decreased by 39 and 37%, respectively on the Au-octanethiol (C₈Au) and Au-2-phenylethanethiol (BC₂Au) coated sensors, while the sensitivity to toluene decreased by 12 and 14%, respectively. These results show that the sensors coated with hydrophobic compounds protected-metal nanoparticles can be employed in high humidity for hydrophobic compounds analysis. The resistance responses to VOCs are rapid, reversible, and linear, while the capacitance response is not sensitive and consequently not applicable for VOCs analysis. The response mechanism was also discussed based on the sensor response to water vapor. The capacitance response is not sensitive to the film swelling in dry environment.