由维尼纶厂废液合成乙酸乙酯

本文以维尼纶厂废液中提取的乙醛为原料，通过缩合反应合成乙酸乙酯，乙醛转化率达９１．５％，选择性达９３．０％，并对乙醛的提取、催化剂合成及缩合反应进行了探讨。     

介质阻挡等离子放电臭氧氧化乙醛废水

对介质阻挡等离子体放电产生臭氧以及臭氧氧化乙醛模拟废水(乙醛水)的过程特性进行了研究。纯氧的介质阻挡等离子放电产生含有一定臭氧浓度的氧气流,含臭氧的氧气流通入模拟乙醛废水中对乙醛进行臭氧氧化。研究发现,乙醛可以被臭氧深度氧化成CO和CO2,CO2的选择性为66%~80%。乙醛去除反应是臭氧浓度的一级反应和乙醛浓度的一级反应。臭氧氧化乙醛的能量效率随能量密度的增加而降低。研究还表明,如能循环使用未能和废水中的乙醛发生反应的臭氧有望降低臭氧处理废水的成本。     

粉煤灰合成分子筛及处理含氟废水的研究

实验利用工业废渣——循环流化床粉煤灰合成出较高结晶度的X型和P型分子筛,合成过程无须高温焙烧预处理.通过XRD分析表征,发现该法合成分子筛结晶度较高,X型和P型分子筛相对结晶度分别达68%～75%和55%.实验应用合成分子筛进行载铁改性,并对NaF模拟的工业含氟废水进行了除氟实验.结果表明,载铁X型分子筛处理工业含氟废水效果良好,除氟率可达74%～98%,除氟容量达25.0～30.0 mg/g.在处理含氟废水过程中,载铁合成分子筛与其他除氟剂相比较,具有除氟率高、除氟容量大、反应迅速的特点.     

微波辐射加热合成蒽醌的清洁生产正交实验研究

微波辐射加热合成蒽醌反应,速度快、产率高、无污染,是一种很有应用价值的清洁生产方法。观测了微波辐照条件下蒽醌产率的变化情况及影响因素,着重研究了邻苯甲酰苯甲酸环化脱水缩合生成蒽醌的最佳反应条件及蒽醌产率与影响因素间的关系。     

乙醛生产废水碱解脱毒预处理

对乙醛生产废水进行碱解预处理,研究碱投加量、反应温度、反应时间对脱毒效果的影响。结果表明,乙醛生产废水经碱解预处理后,废水中有毒物质降解明显,且厌氧生物毒性和好氧活性污泥毒性显著下降。碱投加量、反应温度和反应时间是影响乙醛生产废水碱解预处理效果的重要因素,在反应时间为0.5 h,碱投加量为1.2 g/L,反应温度为30℃,好氧活性污泥毒性即可有大幅下降;产甲烷抑制率在反应时间为3 h以上,反应温度为60℃、碱投加量为2 g/L以上,有大幅下降。     

精醛中三氯乙醛快速测定法

精醛是生产DDT的主要中间产品,也是一些合成药物、有机磷农药的原料。它的主要成分是三氯乙醛(共含量大于93～95％)。在精醛中除了占极大多数的三氯乙醛外也存在有二氯乙醛、乙醛、二氯乙酸乙酯、三氯乙酸乙酯等付产物。所以寻找精醛中三氯乙醛的分析方法不仅对精醛的工艺过程合理控制DDT的质量,而且对DDT生产过程的废水中氯醛的排放量都有     

Fe-MCM-41催化氧化2,4-二氯苯氧乙酸

采用水热法合成了Fe-MCM-41中孔分子筛,紫外、红外及XRD表征显示铁离子已进入中孔分子筛骨架。以H2O2为氧化剂形成类Fenton试剂,实验结果表明,在催化剂加入量为1 g/L、H2O2体积分数为6%、pH为4、反应时间为10h、反应温度为35℃的条件下,处理质量浓度为50 mg/L的2,4-D废水的降解率达94.95%。宏观动力学研究显示,该反应近似为一级反应,反应速率常数、表观活化能分别为0.21667 min-1和26.65 kJ/mol。     

Pd/MCM-41对乙醇汽油车尾气排放乙醛的吸附和催化氧化性能

以正硅酸乙酯(TEOS)为硅源,十六烷基三甲基溴化铵(CTAB)为模板剂,采用水热合成法制备了MCM-41分子筛,以其为载体采用等体积浸渍法制得Pd/MCM-41催化剂,并用于乙醇汽油车冷启动排放乙醛的净化。采用氮气吸附脱附法(BET)、X射线衍射仪(XRD)、透射电子显微镜(TEM)对Pd/MCM-41理化性能进行表征,并用原位傅里叶变换红外技术研究了Pd/MCM-41在空气氛围下对乙醛的净化机理。结果表明:Pd/MCM-41具有规整的六方孔道、孔径分布均匀、比表面积大的特点;常温下,Pd/MCM-41催化剂可快速吸附乙醛,吸附容量可达105 mg·g~(-1),而吸附在Pd/MCM-41上的乙醛在180~220℃之间即可发生氧化而生成CO2和乙酸。     

TiO2光催化氧化降解乳酸的工艺及机理研究

以TiO2为催化剂、紫外灯为光源对乳酸进行光催化降解实验,考察了乳酸初始浓度、TiO2用量、反应时间、曝气方式等因素对乳酸降解率的影响,并在此基础上应用正交实验对降解条件进行优化,同时对乳酸的降解机理进行了探索研究。实验结果表明：以300 W紫外汞灯为光源,在乳酸初始浓度为0.5 g/L、TiO2量为0.20 g/L、反应时间120 min、持续通入空气鼓泡的条件下,乳酸降解效果最佳,乳酸降解率为99.9%;降解12 h总有机碳去除率达91.2%。乳酸光催化降解的反应途径为：乳酸脱羧生成乙醇,乙醇被氧化生成乙醛,进而氧化为乙酸,所有的中间产物被继续降解,最终矿化为CO2和H2O等小分子物质。     

酚醛树脂胶粘剂生产废水的物化前处理

采用酸性二步缩合-混凝法，对ρ(CODcr)=70224mg／L，ρ(挥发酚)=14200mg,／L，P(甲醛)=7480mg/L的酚醛树脂胶粘剂生产废水进行了物化前处理试验研究。第一步采用酚醛缩合方法，第二步采用脲醛缩合方法，通过试验确定了各步的缩合剂用量和工艺条件，经物化前处理的废水，CODcr去除率达79％以上，挥发酚和甲醛去除率达到99％以上，为后续处理创造了条件；缩合处理每吨废水可回收树脂16．25kg，有效地降低了处理费用。     

Carbonyl compounds in the urban environment of Athens,Greece

The concentration levels of 15 selected carbonyl compounds in 62 samples were determined at two sites in Athens basin from June to December 2000. Formaldehyde was the most abundant species (0.05-39 microg m(-3)), which comprised from 22% to 37% of the total measured compounds, followed by acetaldehyde (4.32-49 microg m(-3)), acetone/acrolein (0.64-198 microg m(-3)) and butanal (0.79-140 microg m(-3)). The mean formaldehyde/acetaldehyde and acetaldehyde/propanal molar ratios were calculated. No significant seasonal differences were observed for all the carbonyls. Photochemical production was found to weigh upon atmospheric levels for 83-93% in summer days, dropping below 33% in the winter. The importance of formaldehyde and acetaldehyde as a source of hydroxyl radicals in Athens was also assessed.     

Sources and photodecomposition of formaldehyde and acetaldehyde in Rome ambient air

Atmospheric levels of formaldehyde and acetaldehyde as well as their diurnal and seasonal variations were investigated from 1994 to 1997 in downtown Rome during sunny and wind calm days. Hourly concentrations of formaldehyde ranged from 8 to 28 ppbV in summer and 7 to 17 ppbv in winter; acetaldehyde concentrations varied correspondingly within the 3–18 and 2–7 ppbv intervals. Percentages of both aldehydes photochemically produced were estimated through a simple relationship based upon the comparison of individual ratios of formaldehyde and acetaldehyde to toluene in ambient air and automobile emission. Photochemical production was found to weigh upon atmospheric levels for 80–90% in summer days. It dropped below 35% in the winter period, when direct emission from traffic largely predominated. Photochemical summer source was more efficient for acetaldehyde than for formaldehyde, especially in the early morning. The importance of formaldehyde as the major source of hydroxyl radicals in Rome was also assessed.     

Trends of ambient carbonyl compounds in the urban environment of Hong Kong

The concentrations of C₁–C₈ carbonyl compounds were measured at two urban sites in Hong Kong from October 1997 to September 2000. The daily total carbonyl concentrations were found to range from 2.4 to 37 μg m⁻³. Formaldehyde was the most abundant species, which comprised from 36 to 43% of the total detected carbonyls, followed by acetaldehyde (18–21%) and acetone (8–20%). The highest 24-hour average concentrations measured were 10 and 7.7 μg m⁻³ for formaldehyde and acetaldehyde, respectively. Seasonal and temporal variations in the concentrations of formaldehyde and acetaldehyde were not obvious, but lowest concentrations often occurred from June to August. The mean formaldehyde/acetaldehyde molar ratios at the two sites in summer (2.8±1.1 and 2.5±1.2) were significantly higher (p⩽0.01) than those in winter periods (1.9±0.6 and 2.0±0.6). The phenomena were explained by influences of both photochemical reactions and local meteorological conditions. Better correlations between formaldehyde and acetaldehyde, and between NO_x and each of the two major carbonyls were obtained in winter periods indicating direct vehicular emissions were the principal sources. The ambient formaldehyde and acetaldehyde concentrations in the urban atmosphere of Hong Kong were within the normal ranges reported in the literature for other urban sites world-wide.     

Speciated hydrocarbon and carbon monoxide emissions from an internal combustion engine operating on methyl tertiary butyl ether-containing fuels

In the present work, engine and tailpipe (after a three-way catalytic converter) emissions from an internal combustion engine operating on two oxygenated blend fuels [containing 2 and 11% weight/weight (w/w) methyl tertiary butyl ether (MTBE)] and on a nonoxygenated base fuel were characterized. The engine (OPEL 1.6 L) was operated under various conditions, in the range of 0-20 HP. Total unburned hydrocarbons, carbon monoxide, methane, hexane, ethylene, acetaldehyde, acetone, 2-propanol, benzene, toluene, 1,3-butadiene, acetic acid, and MTBE were measured at each engine operating condition. As concerns the total HC emissions, the use of MTBE was beneficial from 1.90 to 3.81 HP, which were by far the most polluting conditions. Moreover, CO emissions in tailpipe exhaust were decreased in the whole operation range with increasing MTBE in the fuel. The greatest advantage of MTBE addition to gasoline was the decrease in ethylene, acetaldehyde, benzene, toluene, and acetic acid emissions in engine exhaust, especially when MTBE content in the fuel was increased to 11% w/w. In tailpipe exhaust, the catalyst operation diminished the observed differences. Ethylene, methane, and acetaldehyde were the main compounds present in exhaust gases. Ethylene was easily oxidized over the catalyst, while acetaldehyde and methane were quite resistant to oxidation.     

Speciated Hydrocarbon and Carbon Monoxide Emissions from an Internal Combustion Engine Operating on Methyl Tertiary Butyl Ether-Containing Fuels

ABSTRACT

In the present work, engine and tailpipe (after a three-way catalytic converter) emissions from an internal combustion engine operating on two oxygenated blend fuels [containing 2 and 11% weight/weight (w/w) methyl tertiary butyl ether (MTBE)] and on a nonoxygenated base fuel were characterized. The engine (OPEL 1.6 L) was operated under various conditions, in the range of 0-20 HP. Total unburned hydrocarbons, carbon monoxide, methane, hexane, ethylene, acetaldehyde, acetone, 2-propanol, benzene, toluene, 1,3-butadiene, acetic acid, and MTBE were measured at each engine operating condition. As concerns the total HC emissions, the use of MTBE was beneficial from 1.90 to 3.81 HP, which were by far the most polluting conditions. Moreover, CO emissions in tailpipe exhaust were decreased in the whole operation range with increasing MTBE in the fuel.

The greatest advantage of MTBE addition to gasoline was the decrease in ethylene, acetaldehyde, benzene, toluene, and acetic acid emissions in engine exhaust, especially when MTBE content in the fuel was increased to 11% w/w. In tailpipe exhaust, the catalyst operation diminished the observed differences. Ethylene, methane,and acetaldehyde were the main compounds present in exhaust gases. Ethylene was easily oxidized over the catalyst,while acetaldehyde and methane were quite resistant to oxidation.     

Carbonyls in the metropolitan area of Mexico City: calculation of the total photolytic rate constants Kp(s(-1)) and photolytic lifetime (tau) of ambient formaldehyde and acetaldehyde

A great number of studies on the ambient levels of formaldehyde and other carbonyls in the urban rural and maritime atmospheres have been published because of their chemical and toxicological characteristics, and adverse health effects. Due to their toxicological effects, it was considered necessary to measure these compounds at different sites in the metropolitan area of Mexico City, and to calculate the total rate of photolytic constants and the photolytic lifetime of formaldehyde and acetaldehyde. Four sites were chosen. Sampling was carried out at different seasons and atmospheric conditions. The results indicated that formaldehyde was the most abundant carbonyl, followed by acetone and acetaldehyde. Data sets obtained from the 4 sites were chosen to calculate the total rate of photolysis and the photolytic lifetime for formaldehyde and acetaldehyde. Maximum photolytic rate values were obtained at the maximum actinic fluxes, as was to be expected.     

Measurements of carbonyls in a 13-story building

BACKGROUND, AIM AND SCOPE: Formaldehyde and acetaldehyde are emitted by many mobile and stationary sources and secondary aldehydes are intermediates in the photo-oxidation of organic compounds in the atmosphere. These aldehydes are emitted indoors by many materials such as furniture, carpets, heating and cooling systems, an by smoking. Carbonyls, mainly formaldehyde and acetaldehyde, have been studied because of their adverse health effects. In addition, formaldehyde is a suspected carcinogen. Therefore, the concentrations of formaldehyde and acetaldehyde were determined to assess the inhalation exposure doses to carbonyls for people who work in a 13-story building and in order to evaluate the cancer hazard. METHODS: Carbonyl compounds in indoor and outdoor air were measured at a 13-story building located in Mexico City. The mezzanine, fifth and tenth floors, and the third level-parking garage were selected for sampling. Samples were collected in two sampling periods, the first from April 20 to 29, 1998 and the second from December 1 to 20, 1998. Carbonyls were sampled by means of DNHP-coated cartridges at a flow rate of 1 l min(-1) from 9:00 to 19:00 hours, during 2-hour time intervals and analyzed by HPLC with hours, during 2-hour time intervals and analyzed by HPLC with UV/VIS detection. RESULTS: Mean carbonyl concentrations were highest in the 3rd level-parking garage, with the formaldehyde concentration being the highest ranging from 108 to 418 microg m(-3). In working areas, the highest carbonyl arithmetic mean concentrations (AM) were observed on the 5th floor. Acetone and formaldehyde concentrations were highest in April ranging from 161 to 348 microg m(-3) (AM = 226) and from 157 to 270 microg m(-3) (AM = 221), respectively. Propionaldehyde and butyraldehyde were present in smaller concentrations ranging from 2 to 25 and 1 to 28 microg m(-3), respectively, considering all the samples. Mean indoor/outdoor ratios of carbonyls ranged from 1.8 to 9.6. A reduction of inhalation exposure doses of 41% and 45% was observed in the fifth floor air after the air conditioning systems had been repaired. Formaldehyde and acetaldehyde concentrations were higher in smoking environments. CONCLUSION: Indoor carbonyl concentrations were significantly greater than outdoor concentrations. Tobacco smoke seems to be the main indoor source of formaldehyde. After the air conditioning system was maintained and repaired (as was recommended), an important reduction in the emission of formaldehyde and acetaldehyde was achieved on all floors, except for the 3rd level parking garage, thereby reducing the inhalation exposure doses. RECOMMENDATION: The results obtained in this research demonstrated that maintenance of air conditioning systems must be carried out regularly in order to avoid possible adverse effects on health. Additionally, it is mandatory that isolated smoking areas, with air extraction systems, be installed in every public building.     

Regulated and unregulated emissions from an internal combustion engine operating on ethanol-containing fuels

In the present work, the effect of ethanol addition to gasoline on regulated and unregulated emissions is studied. A 4-cylinder OPEL 1.6 L internal combustion engine equipped with a hydraulic brake dynamometer was used in all the experiments. For exhaust emissions treatment a typical three-way catalyst was used. Among the various compounds detected in exhaust emissions, the following ones were monitored at engine and catalyst outlet: methane, hexane, ethylene, acetaldehyde, acetone, benzene, 1,3-butadiene, toluene, acetic acid and ethanol. Addition of ethanol in the fuel up to 10% w/w had as a result an increase in the Reid vapour pressure of the fuel, which indicates indirectly increased evaporative emissions, while carbon monoxide tailpipe emissions were decreased. For ethanol-containing fuels, acetaldehyde emissions were appreciably increased (up to 100%), especially for fuel containing 3% w/w ethanol. In contrast, aromatics emissions were decreased by ethanol addition to gasoline. Methane and ethanol were the most resistant compounds to oxidation while ethylene was the most degradable compound over the catalyst. Ethylene, methane and acetaldehyde were the main compounds present at engine exhaust while methane, acetaldehyde and ethanol were the main compounds in tailpipe emissions for ethanol fuels after the catalyst operation.     

Indoor and outdoor carbonyl compounds in the hotel ballrooms in Guangzhou,China

Twenty-one carbonyl compounds were measured simultaneously at four hotel ballrooms in urban Guangzhou during the autumn, 2002. In each ballroom, measurements were carried out in business hours in the evening (20:30–24:00) on 7 consecutive days without any disturbance of the ballroom's normal operation. Nineteen out of the 21 target carbonyl compounds were identified in indoor and outdoor air. In the outdoor environment, formaldehyde was the most abundant carbonyl, followed by acetaldehyde, and there existed a strong correlation between formaldehyde and acetaldehyde. In the indoor air, however, acetaldehyde was the most abundant carbonyl, its concentrations seemed to be affected significantly by smoking. The indoor concentrations of carbonyls were found higher than their outdoor counterparts with only a few exceptions. Further studies concerning the indoor/outdoor ratios and mutual correlation of the carbonyls indicated that apart from direct emission from indoor materials and infiltration of outdoor air, other anthropogenic sources, e.g. tobacco smoke, also significantly contributed to carbonyl compounds. The possible sources of some high molecular weight carbonyls, e.g. nonanaldehyde, were also discussed briefly. Preliminary estimate of the exposures and risks due to carbonyls in the ballrooms was made, which indicated that long-term exposure in such places might cause increased chance of developing cancers.