Pyrolysis and combustion of Aroclor 1254 contaminated dielectric fluids

Pyrolysis and combustion products were determined for several levels of PCB contamination in mineral oil and other dielectric fluids. Yields of PCDFs were roughly proportional to the quantity of PCB in the feed.     

介质阻挡放电氧化降解木质素磺酸钠的动力学研究

为了有效地处理难生物降解的造纸废水,采用气相介质阻挡放电产生氧化性物质,对木质素磺酸钠进行了氧化降解研究。在不同操作条件下,对其降解动力学及矿化程度进行了研究。结果表明,介质阻挡放电能有效地降解木质素磺酸钠,其氧化降解反应遵循准一级动力学反应。当峰值电压为20 kV,被水蒸气饱和的空气为气源,流量为7 L/min时,氧化处理60 min后,木质素磺酸钠降解率达到70％。其速率常数K随峰值电压、气源、气体流量和木质素磺酸钠的初始浓度的变化而不同。气体流量越大,木质素磺酸钠的初始浓度越低,速率常数K越大,降解效果越好。随着处理时间的增加,氧化性物质能将部分木质素磺酸钠矿化使溶液TOC降低,当被水蒸气饱和的空气作为气源时,氧化处理120min,21.38%的TOC被去除。     

气相介质阻挡放电氧化降解酸性红88的机理

为了有效处理难生物降解的染料废水,采用气相介质阻挡放电产生以羟基自由基为主的氧化性物质,对偶氮染料酸性红88（AR88）进行了氧化降解,并对放电过程中各化学效应对AR88降解的作用机理进行了分析。结果表明,当用相对湿度100％的空气为气源时,放电过程中生成的活性物种如OH·、O,和H2O2是引起放电过程中AR88氧化降解反应的主体,其中OH·在AR88的降解过程中起主要作用,O3参与了对AR88的氧化降解,H2O2对AR88的降解没有明显作用。采用GC／MS分析AR88的主要降解中间产物为萘磺酸、1,2-萘醌、1,2-苯并吡喃酮、萘酚和邻苯二甲酸。通过产物测定和前线电子密度理论,推测了降解途径。     

Thermally induced formation of PCDD and PCDF from tri- and tetrachlorobenzene in dielectric fluids

The thermal behavior of dilute (5000-50 ppm) solutions of tri- and tetrachlorobenzene in mineral oil, silicone oil, and tetrachloroethylene (TCE) has been investigated. Although pyrolyses or combustion of neat chlorobenzenes readily forms significant yields of PCDDs/PCDFs, corresponding treatment of dilute solutions was generally non-productive. This result is consistent with the proposition that, under the conditions studied, the rate-limiting step for PCDD/PCDF formation is bimolecular in chlorobenzene. In contrast, earlier studies of PCBs implied a rate-limiting step that was unimolecular in chloroaromatics. Combustion of dilute solutions of chlorobenzenes in tetrachloroethylene did produce detectable concentrations of PCDF; this result reflects combination of chlorobenzene and TCE- or TCE-derived species.     

电晕-介质阻挡协同放电降解连续流丙酮

利用自制等离子体反应器开展电晕-介质阻挡协同放电降解连续流丙酮研究,利用均匀设计法获得适宜的丙酮降解参数及其相互关联性,通过解析电晕-介质阻挡协同放电机理,结合丙酮降解热力学性能分析,获得影响丙酮降解的主要因素。结果表明：丙酮降解的适宜条件为反应器电压9.60 kV、空气流量1.4 L·min-1、在丙酮气体流量20 mL·min-1的连续流体系下,电晕-介质阻挡协同放电3 min、初始质量浓度为1.807 mg·L-1的丙酮单次循环降解率可达35.01%。解析等离子体放电过程和热力学性质发现,丙酮降解受协同放电活性粒子与反应温度的双重影响。     

建立数学模型分析UV-Fenton对金属切削液废水的降解

采用UV/Fenton技术处理金属切削液废水,并通过正交实验和单因素实验得到了最佳工作条件为:pH=2.5,H2O2(浓度30%)投加量=127.5 mL/L,Fe2+投加量=24.8 mmol/L,总反应时间=3 h,投加次数6次,此条件下金属切削液废水COD去除率达到95%。最后,通过正交实验数据和单因素模型方程利用1st Opt进行多元非线性拟合建立UV/Fen-ton对金属切削液废水COD降解率的数学模型方程,然后进行分析讨论。     

Main products and kinetics of the thermal degradation of polyamides

The thermal degradation of the polyamides (PA) 6, 12, 66 and 612 was investigated by means of thermal analysis/mass spectrometry (TA-MS) and pyrolysis in a german standard oven. Sample masses were about 20 and 40 mg. The heating rates used in the dynamic studies were 1, 5 and 10 K min(-1). Both air and nitrogen atmospheres were utilized. The kinetic parameters were calculated from the TA-MS measurements and the main decomposition products were registered online. The evolved products from the pyrolysis oven were captured and analyzed off-line by GC/MS.     

Mechanisms of product formation from the pyrolytic thermal degradation of catechol

Catechol has been identified as one of the most abundant organic products in tobacco smoke and a major molecular precursor for semiquinone type radicals in the combustion of biomass material. The high-temperature gas-phase pyrolysis of catechol under hydrogen-rich and hydrogen-lean conditions was studied using a fused-silica tubular flow reactor coupled to an in-line GC/MS analytical system. Thermal degradation of catechol over temperature range of 250-1000 degrees C with a reaction time of 2.0s yielded a variety products including phenol, benzene, dibenzofuran, dibenzo-p-dioxin, phenylethyne, styrene, indene, anthracene, naphthalene, and biphenylene. Ortho-benzoquinone which is typically associated with the presence of semiquinone radicals was not observed and is proposed to be the result of fast decomposition reactions that lead to a variety of other reaction products. This is in contrast to the decomposition of hydroquinone that produced para-benzoquinone as the major product. A detailed mechanism of the degradation pathway of catechol is proposed.     

催化剂协同介质阻挡放电等离子体对不同VOCs的催化选择性

为考察混合气体中各组分对VOCs降解的影响,以及催化剂在协同低温等离子体降解多组分VOCs气体中的表现,选取甲苯、丙酮及乙酸乙酯组成混合VOCs进行低温等离子体降解,进而研究混合降解方式对混合VOCs气体各组分降解效果的影响。先制备了Mn₂O₃/γ-Al₂O₃催化剂,采用催化剂后置方式研究催化剂在协同低温等离子体降解多组分混合VOCs气体过程中的表现。结果表明：多组分混合VOCs降解时,甲苯和乙酸乙酯的降解率相较单独降解时都有所提升,当特定输入能量（SIE）为700 J∙L⁻¹时,提升率分别为69.1%和12.64%,而丙酮的降解率相较单独降解时却发生了明显下降,下降了40.74%;多组分混合VOCs降解时的臭氧产量相较3种VOCs单独降解时均有微弱下降;多组分混合VOCs相较单种VOCs降解时的碳平衡均略有下降;在协同低温等离子体降解多组分VOCs气体过程中,Mn₂O₃/γ-Al₂O₃催化剂对混合VOCs中甲苯、乙酸乙酯及丙酮降解率有明显提升,且随VOCs降解难度的上升而更加明显,并使得各条件下VOCs降解的碳平衡均得到了提升。本研究结果可为低温等离子体降解VOCs的实际应用提供参考。     

Laboratory evaluations of the thermal degradation properties of toxic organic materials in sewage sludge

Laboratory thermal decomposition studies were performed to evaluate potential emissions from sewage sludge incinerators. Precisely controlled thermal decomposition experiments were conducted on sludge spiked with mixtures of hazardous organic compounds, on mixtures of pure compounds without sludge, and on unspiked sludge. Experiments were conducted in nitrogen and air atmospheres with gas phase reaction times of 2.0 seconds over the temperature range 300 degrees C-1000 degrees C. It was found that sludge inhibited the decomposition of moderately stable spiked contaminants but accelerated the decomposition of the most stable components. This effect was attributed to radical scavengers produced by the sludge matrix at lower temperatures which then decomposed at higher temperatures. A multiple hearth simulation study suggested that most of the organic material present in the sludge matrix is vaporized within the upper hearths that are held at lower temperatures and may consequently escape from such incinerators undestroyed. A number of stable byproducts resulted from the sludge decomposition that may be of environmental concern.     

Investigation on thermal degradation kinetics and mechanisms of chicken manure,lignite, and their blends by TGA

Environmental Science and Pollution Research - In this study, thermogravimetric analysis (TGA) was performed under the air environment for four different heating rates (10, 20, 30, and 40 °C...     

介质特性对DBD降解苯的影响

为了提高介质阻挡放电（dielectric barrier discharge，DBD）等离子体的处理效率，研究了内外介质组成分别为：（1）石英＋石英；（2）陶瓷＋石英；（3）陶瓷＋陶瓷这3种情况下苯的降解情况。试验结果表明，在处理低浓度含苯废气时，陶瓷＋陶瓷效果最好；陶瓷（内管）＋石英（外管）在处理高浓度含苯废气时显示出优势。通过对气相产物和固相结焦产物的分析验证了DBD能有效降解苯，降解产物不会带来新的污染。进一步分析了实验条件和介质材料的变化对DBD降解苯的影响机理。     

介质特性对DBD降解苯的影响

为了提高介质阻挡放电(dielectric barrier discharge,DBD)等离子体的处理效率,研究了内外介质组成分别为:(1)石英 石英;(2)陶瓷 石英;(3)陶瓷 陶瓷这3种情况下苯的降解情况.试验结果表明,在处理低浓度含苯废气时,陶瓷 陶瓷效果最好;陶瓷(内管) 石英(外管)在处理高浓度含苯废气时显示出优势.通过对气相产物和固相结焦产物的分析验证了DBD能有效降解苯,降解产物不会带来新的污染.进一步分析了实验条件和介质材料的变化对DBD降解苯的影响机理.     

Discrimination and thermal degradation of toxaphene compounds in capillary gas chromatography when using split/splitless and on-column injection

Technical toxaphene and a 22-component Reference Mixture were analyzed using capillary gas chromatography with split/splitless injection (SSL) and on-column injection (OC). In both techniques, electron-capture, negative ionization mass spectrometry (ECNI-MS) was used for detection of chlorobornanes, chlorocamphenes and related compounds. Significant discrimination of highly chlorinated congeners was observed as a result of incomplete transfer of these compounds from the vaporizer to the analytical column when using SSL. This resulted in a much lower response for nona- and decachloro congeners than when using OC. In addition, several toxaphene components, especially the chlorobornanes with gem dichloro substitution on the six-member carbon ring, undergo thermal degradation when using SSL. Some of these congeners are major components of technical toxaphene, but generally are not present, except at low concentrations, in environmental and biological samples. Therefore, technical toxaphene may be discriminated and/or degraded differently than toxaphene compounds in environmental samples when using SSL. This results in significant bias of the quantitative data when using the technical material as a reference. OC suffers much less from these deficiencies and, therefore, is a preferable technique for toxaphene analysis.     

Advances with supercritical fluids

In the last decade, supercritical fluids more and more have been proved as environmentally benign media for chemical and related processes. Many new processes and products have been developed, using the inherent physical and chemical properties of supercritical fluids. Moreover, these processes also promise economic effects. The prerequisites for this success however, are a sound knowledge of physico-chemical properties of--and phenomena in--supercritical mixtures and the availability of other chemical engineering data. This requires an effective exchange of knowledge between a large number of branches of science. In the following, a lot of recent papers will be cited, which should give an overview of actual results on fundamentals and their applications.     

PCDD/DF formations by the heterogeneous thermal reactions of phenols and their TiO2 photocatalytic degradation by batch-recycle system

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/DFs) formation by the thermal reactions of phenols with CuCl2 under oxygen flux were carried out in relation to their formation mechanisms. To evaluate the effect of photocatalytic degradation of titanium dioxide (TiO2) thin film prepared by the sol-gel method, the photocatalysis of PCDD/DFs in acetonitrile/water solution by batch-recycle system was conducted. For the thermal reaction system of powder mixtures of 2,4,5-trichlorophenol (2,4,5-TCP) and CuCl2, the formation rates were 8.1 microg/g-2,4,5-TCP/min for total PCDD/DFs and 6.9 microg/g-2,4,5-TCP/min for PCDDs, and total PCDD/DF rate was higher by approximately 40 fold compared to phenol vapor/oxygen/CuCl2 powder system. For the system of 2,4,5-TCP, PCDDs were mainly formed via ortho-phenoxyphenols (POP) intermediate by the condensation of 2,4,5-trichlorophenate. For PCDD/DF photocatalytic degradations, most PCDD congeners photodecomposed rapidly and the rates presented more than 70% (as dechlorination rates of 76% for PCDDs) at 24 h after irradiation, using PCDD/DFs formed with 2,4,5-TCP. The rate constants were in the order of 4.8-6.1 x 10(-3) min(-1), assuming the pseudo-first-order reactions for their low levels.     

一株苯酚降解菌的筛选及降解动力学特性

利用富集驯化的培养方法,从首钢焦化厂废水处理系统中的二沉池出水中,分离筛选出一株能够高效降解苯酚的菌株B3对其16S rDNA序列进行分析,并选择Monod方程和Andrews方程分别研究该菌在不同苯酚浓度条件下的降酚动力学模式。结果表明,B3为蜡状芽孢杆菌(Bacillus cereus);苯酚浓度较低时,苯酚对菌株的生长基本不产生抑制作用,用Monod模型对B3降酚动力学过程进行拟合,其动力学参数V max=0.03 h-1,K s=25.53 mg/L;苯酚浓度较高时,按照Andrews模型对B3降酚动力学过程进行非线性最小二乘曲线拟合,其动力学参数V max=0.08 h-1,K s=147.52 mg/L,K i=384.96 mg/L。根据动力学方程,推论菌株B3降解对于浓度238.30 mg/L的苯酚具有最佳降解效果。     

烟酰胺降解菌的筛选及其降解特性

采用HPLC对某烟酰胺生产废水的主要成分进行分析,并模拟废水中的主要成分烟酰胺(nicotinamide)的浓度,对以烟酰胺为唯一碳源配制的培养基进行降解实验,获得有较佳降解率和生长能力的菌株YSI-1和YSI-2.结果表明,YSI菌株的混合菌降解效果优于单株菌,混合菌在初始OD600值为0.4,pH为7.0时,对浓度为2000 mg/L的烟酰胺降解2 d的降解率可达32.8%.延长处理时间或提高菌种的初始OD600值,烟酰胺的去除率均有较大的增加.     

烟酰胺降解菌的筛选及其降解特性

采用HPLC对某烟酰胺生产废水的主要成分进行分析，并模拟废水中的主要成分烟酰胺（nicotinamide）的浓度，对以烟酰胺为唯一碳源配制的培养基进行降解实验，获得有较佳降解率和生长能力的菌株YSI-1和YSI-2。结果表明．YSI菌株的混合菌降解效果优于单株菌，混合菌在初始OD600值为0．4，pH为7．0时，对浓度为2000mg／L的烟酰胺降解2d的降解率可达32．8％。延长处理时间或提高菌种的初始OD600值，烟酰胺的去除率均有较大的增加。