Thermal analyses of home-made zeolite by DSC and TG

Volatile organic compounds (VOCs) and greenhouse gases are the main factors involved in pollution control and global warming. Various treatment methods involving incineration, adsorption, etc., have been employed to reduce VOCs and greenhouse gases concentration in the operating environment and atmosphere. Activated carbon, zeolite, silica gel, and alumina have been broadly used to adsorb pollutants in various industrial applications. Based on the promising effect of adsorption, we analyzed and identified the thermal phenomena of home-made zeolite using various instruments. The endothermic reaction under 100?°C of home-made zeolite was identified as steam adsorption, which is an important discovery. The optimal adsorption temperatures of home-made zeolite have been determined at 200?C550?°C.     

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。     

生物质炭的制备、改性以及在挥发性有机物吸附方面的应用

挥发性有机物（VOCs）是大气中重要的污染源之一,对环境和人类健康产生严重的危害。吸附法是工业中最常用的去除VOCs的方法,吸附剂是吸附技术的关键,生物质炭是一种由生物质基材料在高温下热解活化等工艺制得的炭材料,具有较高的比表面积、丰富的孔隙结构和化学活性表面,在环境污染控制领域具有广泛应用。基于最近的研究,本文系统地综述了常用于去除VOCs的生物质炭的制备和改性方法,以及生物质炭在吸附VOCs的应用研究。本文首要目标是评估生物质炭去除VOCs的能力,特别是经过各种改性和活化工艺后,评价生物质炭作为吸附剂去除VOCs的适用性;确定改性和活化后对VOCs吸附能力的影响;揭示生物质炭对VOCs可能存在的吸附机理。最后,文章也对生物质炭的再生提出了建议和展望。     

Thermal analyses of four adsorption materials for environmental pollution by DSC and TG

In view of loss prevention and hazard control, traditional engineers use adsorbents to adsorb volatile organic compounds (VOCs) in the semiconductor, photonics, and petrochemical industries. To save funds and promote green energy application, industries usually apply a zeolite processing desorption step under high temperature in the zeolite rotor-wheel system. Many thermal runaway accidents and flame incidents have occurred in the desorption step. Zeolite has been used to adsorb VOCs and applied in the processing desorption step in a reactor without considering oxygen concentration situation, which could easily lead to a flame followed by thermal explosion. Nitrogen is a critically important purge gas regarding passive action for avoiding an accident. Home-made zeolite was investigated for the best manufacturing ratio, which was 20. Brunauer–Emmett–Teller of zeolite (Si/Al = 20) was analyzed to be 400 m² g^?1, which is easy for adsorbing pollutants. According to our previous studies, home-made zeolite has prominent adsorption capacities on VOCs. Zeolite rotor-wheel system was developed to desorb the pollutants of interest. Zeolite was applied to analyze the thermal stability, runaway reaction under various oxygen concentrations, reuse rates, etc. Zeolite is a thermally stable material under room temperature to 650 °C. An endothermic reaction (30–100 °C) of home-made zeolite was analyzed by differential scanning calorimetry and thermogravimetric analyzer. Clearly, water has a significant effect on deteriorating for the zeolite adsorption. Home-made zeolite is a suitable adsorbent and catalyst in the petrochemical and environmental industries. As far as pollution control and loss prevention are concerned, versatility in the analysis of recycled adsorbents is required and is useful for various industrial applications.     

Application Potential of Bacterial Volatile Organic Compounds in the Control of Root-Knot Nematodes

Plant-parasitic nematodes (PPNs) constitute the most damaging group of plant pathogens. Plant infections by root-knot nematodes (RKNs) alone could cause approximately 5% of global crop loss. Conventionally, chemical-based methods are used to control PPNs at the expense of the environment and human health. Accordingly, the development of eco-friendly and safer methods has been urged to supplement or replace chemical-based methods for the control of RKNs. Using microorganisms or their metabolites as biological control agents (BCAs) is a promising approach to controlling RKNs. Among the metabolites, volatile organic compounds (VOCs) have gained increasing attention because of their potential in the control of not only RKNs but also other plant pathogens, such as insects, fungi, and bacteria. This review discusses the biology of RKNs as well as the status of various control strategies. The discovery of VOCs emitted by bacteria from various environmental sources and their application potential as BCAs in controlling RKNs are specifically addressed.     

Density functional theory investigation on selective adsorption of VOCs on borophene

In the field of volatile organic compounds (VOCs) pollution control, adsorption is one of the major control methods, and effective adsorbents are desired in this technology. In this work, the density functional theory (DFT) calculations are employed to investigate the adsorption of typical VOCs molecules on the two-dimensional material borophenes. The results demonstrate that both structure of χ₃ and β₁₂ borophene can chemically adsorb ethylene and formaldehyde with forming chemical bonds and releasing large energy. However, other VOCs, including ethane, methanol, formic acid, methyl chloride, benzene and toluene, are physically adsorbed with weak interaction. The analysis of density of states (DOS) reveals that the chemical adsorption changes the conductivity of borophenes, while the physical adsorption has no distinct effect on the conductivity. Therefore, both χ₃ and β₁₂ borophene are appropriate adsorbents for selective adsorption of ethylene and formaldehyde, and they also have potential in gas sensor applications due to the obvious conductivity change during the adsorption.     

Industrial standardization of thermal analysis in Japan

To satisfy the needs for industrial standards for thermal analysis in the Japanese polymer industry, round-robin tests of differential scanning calorimetry (DSC), thermogravimetry (TG), thermomechanical analysis (TMA) and thermodilatometry (TD) have been carried out recently. The results are discussed in this short review. The DSC applications tested were not only for determination of transition temperature but also for measurements of the transition heat and heat capacity. The TG task group did not aim at longterm thermal endurance studies, but relative thermal stability in molding and estimation of filler content, residual solvent content, etc. TMA was found to be a useful tool for measuring softening temperature and heat distortion temperature, especially for high-temperature engineering plastics, instead of the Vicat test which has temperature limitations. For temperature calibration of DSC and TG, ICTA-NIST certified reference materials were used together with other potential temperature standards; some inorganic substances and alloys were not found to be preferable to pure metals. For TMA and TD metal plates were found to be very useful for temperature calibration. Analysis of the round-robin test results also clarified present status of practical applications of thermal analysis, such as reproducibility and causes of errors. Plenary lecture     

Environmental applications for thermal analysis

A review is presented of the applications of thermoanalytical techniques to problems encountered in the measurement and control of air pollution. A number of suggestions are offered regarding new or extended applications of these techniques.     

热脱附-气相色谱-三重四极杆串联质谱法测定环境空气中的挥发性有机物

采用热脱附(TD)结合气相色谱-三重四极杆串联质谱(GC-MS/MS)建立了环境空气中23种挥发性有机物(VOCs)同时检测的分析方法。空气样品通过主动采样的方式富集到装有Tenax-TA填料的热脱附管中,热解吸后在选择反应监测(SRM)模式下用GC-MS/MS进行检测,内标法定量。结果表明,23种VOCs在0.01~1 ng和1~100 ng低、高两个范围内线性关系良好,相关系数(r²)均大于0.99,方法定量限为0.00008~1 μ g/m³。加标水平为2、10和50 ng时,23种VOCs的平均回收率为77%~124%。除了最低加标水平的氯苯,相对标准偏差(RSD, n=6)均小于20%。对市内3个采样点的环境空气进行测定,其中苯、甲苯、乙苯、二甲苯、苯乙烯、1,2,4-三甲基苯和六氯丁二烯均有检出。实验证明,该TD和GC-MS/MS相结合的检测方法具有准确、可靠、灵敏度高等优点,适用于环境空气中VOCs的同时测定。     

Development of a Water Matrix Certified Reference Material for Volatile Organic Compounds Analysis in Water

Water matrix certified reference material (MCRM) of volatile organic compounds (VOCs) is used to provide quality assurance and quality control (QA/QC) during the analysis of VOCs in water. In this research, a water MCRM of 28 VOCs was developed using a “reconstitution” approach by adding VOCs spiking, methanol solution into pure water immediately prior to analysis. The VOCs spiking solution was prepared gravimetrically by dividing 28 VOCs into seven groups, then based on ISO Guide 35, using gas chromatography-mass spectrometry (GC-MS) to investigate the homogeneity and long-term stability. The studies of homogeneity and long-term stability indicated that the batch of VOCs spiking solution was homogeneous and stable at room temperature for at least 15 months. Moreover, the water MCRM of 28 VOCs was certified by a network of nine competent laboratories, and the certified values and expanded uncertainties of 28 VOCs ranged from 6.2 to 17 μg/L and 0.5 to 5.3 μg/L, respectively.     

Application of a Self-developed Proton Transfer Reaction-Mass Spectrometer to On-line Monitoring Trace Volatile Organic Compounds in Ambient Air

Real-time and on-line monitoring volatile organic compounds(VOCs) are valuable for real-time evalua- ting air quality and monitoring the key source of pollution. A self-developed proton transfer reaction-mass spectrometer(PTR-MS) was constructed and applied to on-line monitoring trace VOCs in ambient air in Hefei, China. With the help of a self-developed catalytic converter, the background signal of the instrument was detected and the stability of the instrument was evaluated. The relative standard deviation of signal at m/z 21 was only 0.74% and the detection limit of PTR-MS was 97 part per trillion(97×10^-12, volume ratio). As a case of the air monitoring in Hefei, the ambient air at Dongpu reservoir spot was on-line monitored for 13 d with our self-developed PTR-MS. Meanwhile, a solid-phase micro-extraction(SPME) technique coupled to gas chromatography-mass spectrometry/mass spectrometry (GC-MS/MS) was also used for the off-line detection of the air. The results show that our self-developed PTR-MS can be used for the on-line and long-term monitoring of VOCs in air at part per trillion level, and the change trend of VOCs concentration monitored with PTR-MS was consistent with that detected with the conventional SPME-GC-MS. This self-developed PTR-MS can fully satisfy the requirements of air quality monitoring and real-time monitoring of the key pollution sources.     

纳米材料在用于癌症诊断的呼出气挥发性有机物检测中的应用

细胞新陈代谢的变化会导致挥发性有机化合物（VOCs）类型及含量发生变化,因此可通过分析某些标志性VOCs简立起多种疾病早期诊断的模型. 人体呼出物中特征VOCs的检测作为一种非侵入性、无损的检测手段,近些年在疾病检测领域已成为世界范围内的研究热点. 其中,纳米材料可用于增强传感器性能,并使传感器便携式小型化,推进检测传感器进入临床. 在这篇综述中,作者将种类繁多的传感器中用到的纳米材料归纳总结为金属、金属氧化物、碳基、复合物和MOFs基纳米材料等几类,并讨论了不同类纳米材料在VOCs检测中的优劣势. 本文所建立起的分析方法及讨论有助于进一步了解检测技术的优越性与局限性. 最后,作者对利用VOCs的检测实现癌症早期筛选的研究及发展提出了个人观点.     

Lightweight Polymer Composites from Waste Materials: A Solution to Environmental Pollution

Several new lightweight polymer concretes derived from industrial, agricultural, and naturally occurring waste materials were investigated. Various physicomechanical properties of these materials were studied. Such inexpensive and lightweight polymer composites, which have properties superior to ordinary reinforced cement concrete, may find wide applications in building technology and related areas and may serve as better substitutes for cement. Furthermore, recycling of such wastes from various sources may help to solve the present environmental pollution problems.     

离子液体中的聚合反应研究进展

室温离子液体是一种新兴的可替代挥发性有机化合物（VOCs）的绿色溶剂和高效的反应介质，为减少或消除化学反应和过程工程中的环境问题提供了重要的途径。以离子液体为反应介质进行聚合反应，可消除或减小VOCs的危害，也可实现催化剂的有效回收利用和聚合物的纯化，更好地控制聚合反应及聚合产物的结构与性质、乃至直接用作高效的聚合催化剂。本文综述近年来离子液体中聚合反应的研究现状及最新进展，分析现存的问题，并展望今后的发展方向。     

Near-infrared spectroscopy and multivariate calibration for the quantitative determination of certain properties in the petrochemical industry

Near-infrared (NIR) spectroscopy in conjunction with chemometric techniques allows on-line monitoring in real time, which can be of considerable use in industry. If it is to be correctly used in industrial applications, generally some basic considerations need to be taken into account, although this does not always apply. This study discusses some of the considerations that would help evaluate the possibility of applying multivariate calibration in combination with NIR to properties of industrial interest. Examples of these considerations are whether there is a relation between the NIR spectrum and the property of interest, what the calibration constraints are and how a sample-specific error of prediction can be quantified. Various strategies for maintaining a multivariate model after it has been installed are also presented and discussed.     

Study on miscibility of poly(vinyl chloride) and polyepichlorohydrin by viscometric and thermal analysis

Viscometric analysis was carried out to study the miscibility of poly(vinyl chloride) (PVC) and polyepichlorohydrin (PECH) in various solvents, tetrahydrofuran (THF), methyl ethyl ketone (MEK) and dimethylformamide (DMF). The Krigbaum–Wall criterion is used here to evaluate the miscibility of the two components, and Δb is introduced which can be calculated from the viscosity curves. The results show that their attractive forces are predominant when dissolved in THF, while in MEK and DMF repulsive forces play a leading role. This is attributed to different solubilities of the two polymers in the three solvents and to different influences of the solvents on the conformation of the polymers. Thermal measurement was performed by differential scanning calorimetry to investigate the glass transition temperature (T_g) of the blends prepared from the three solvents. Phase separation is observed for the samples made from MEK and DMF, while for THF the sample exhibits a single phase.     

First principles studies of thermal decomposition of anhydrous zinc oxalate

The highly reactive and unstable exothermal features of methyl ethyl ketone peroxide (MEKPO) have led to a large number of thermal explosions and runaway reaction accidents in the manufacturing process. To evaluate the self-accelerating decomposition temperature (SADT) of MEKPO in various storage vessels, we used differential scanning calorimetry (DSC) and vent sizing package 2 (VSP2). The thermokinetic parameters were, in turn, used to calculate the SADT from theoretical equations based on the Semenov model. This study aimed at the SADT prediction value of various storage vessels in Taiwan compared with the UN 25 kg package and UN 0.51 L Dewar vessel. An important index, such as SADT, temperature of no return (T _NR) and adiabatic time maximum rate (TMR_ad), was necessary and useful to ensure safe storage or transportation for self-reactive substances in the process industries.     

Analytical strategies for the quality assessment of recycled high-impact polystyrene: a combination of thermal analysis, vibrational spectroscopy, and chromatography

Various analytical techniques (thermal analysis, vibrational spectroscopy, and chromatographic analysis) were used in order to monitor the changes in polymeric properties of recycled high-impact polystyrene (HIPS) throughout mechanical recycling processes. Three key quality properties were defined and analysed; these were the degree of mixing (composition), the degree of degradation, and the presence of low molecular weight compounds. Polymeric contaminations of polyethylene (PE) and polypropylene (PP) were detected in some samples using differential scanning calorimetry (DSC). Vibrational spectroscopy showed the presence of oxidised parts of the polymeric chain and gave also an assessment of the microstructure of the polybutadiene phase in HIPS. The presence of low molecular weight compounds in the HIPS samples was demonstrated using microwave-assisted extraction followed by gas chromatography-mass spectrometry (GC-MS). Several volatile organic compounds (VOCs), residues from the polymerisation, additives, and contaminations were detected in the polymeric materials. Styrene was identified already in virgin HIPS; in addition, benzaldehyde, α-methylbenzenaldehyde, and acetophenone were detected in recycled HIPS. The presence of oxygenated derivates of styrene may be attributed to the oxidation of polystyrene (PS). Several styrene dimers were found in virgin and recycled HIPS; these are produced during polymerisation of styrene and retained in the polymeric matrix as polymerisation residues. The amount of these dimers was highest in virgin HIPS, which indicated that emission of these compounds may have occurred during the first life-time of the products. This paper demonstrates that a combination of different analytical strategies is necessary to obtain a detailed understanding of the quality of recycled HIPS.     

饮用水中挥发性有机物(VOCs)的GC-MS分析

用顶空－毛细管气相色谱－质谱联用仪测定了北京主要区域的自来水,北京目前市场销售的瓶装饮用水（包括天然矿泉水,纯净水等）中２３种挥发性有机物（ＶＯＣｓ）（包括有机氯化物,有机溴代物及苯系物等）的浓度,并与其它城市（如天津,上海,兰州等地）的自来水中ＶＯＣｓ的浓度进行了比较,结果表明北京市区内自来水及大多数市售瓶瓶饮用水中ＶＯＣｓ含量很低。