Emission characteristics of volatile organic compounds from semiconductor manufacturing

A huge amount of volatile organic compounds (VOCs) is produced and emitted with waste gases from semiconductor manufacturing processes, such as cleaning, etching, and developing. VOC emissions from semiconductor factories located at Science-Based Industrial Park, Hsin-chu, Taiwan, were measured and characterized in this study. A total of nine typical semiconductor fabricators (fabs) were monitored over a 12-month period (October 2000-September 2001). A flame ionization analyzer was employed to measure the VOC emission rate continuously in a real-time fashion. The amount of chemical use was adopted from the data that were reported to the Environmental Protection Bureau in Hsin-chu County as per the regulation of the Taiwan Environmental Protection Administration. The VOC emission factor, defined as the emission rate (kg/month) divided by the amount of chemical use (L/month), was determined to be 0.038 +/- 0.016 kg/L. A linear regression equation is proposed to fit the data with the correlation coefficient (R2)=0.863. The emission profiles of VOCs, which were drawn using the gas chromatograph/mass spectrometer analysis method, show that isopropyl alcohol is the dominant compound in most of the fabs.     

CPB改性沸石对磷酸盐的吸附-解吸性能研究

采用溴化十六烷基吡啶(CPB)对天然沸石进行改性,并考察了CPB改性沸石对磷酸盐的吸附-解吸性能。结果表明,CPB改性沸石对磷酸盐具备一定的吸附能力,且吸附行为满足Langmuir等温吸附模型;粒径、改性剂投加量、反应温度、pH值及共存阴离子等因素均会影响CPB改性沸石对磷酸盐的吸附能力;减小粒径和降低反应温度均有利于CPB改性沸石对磷酸盐的吸附去除;粒径≤0.18 mm CPB改性沸石吸附磷酸盐较优的改性剂投加量为250 mmol/kg;当溶液的初始pH值位于4~10之间时CPB改性沸石对磷酸盐的吸附能力随pH值的增加而增强;SO42-的存在会明显降低CPB改性沸石对磷酸盐的吸附效率,而提高溶液的pH值有助于消除SO42-存在对CPB改性沸石吸附磷酸盐的负面影响;HCO3-的存在会一定程度上抑制CPB改性沸石对磷酸盐的吸附去除,而提高溶液的pH值无法消除HCO3-存在对CPB改性沸石吸附磷酸盐的负面影响;CPB改性沸石吸附磷酸盐后一定条件下可以重新解吸出来,且随着解吸液SO42-浓度的增加解吸率明显增大。     

室内空气总挥发性有机物检测的热解吸参数优化

总挥发性有机物(TVOC)是评价室内空气质量最重要的指标。为了提高TVOC检测的准确度,选取解吸气流量、热解吸温度、进样时间和热解吸时间四项因素设计正交实验,以热解吸率作为指标,对TVOC的热解吸过程进行了优化。并讨论在优化后参数的控制下,TVOC各组分的检测准确度。实验结果表明,优化的热解吸条件下各参数指标分别为解吸气流量40 mL/min、热解吸温度280℃、进样时间120 s、热解吸时间30 s。检测准确度的结果表明,在优化热解吸参数的控制下,各组分的回收率在90.3%～97.3%之间,满足TVOC的实际检测需求。     

吸附浓缩-催化燃烧工艺处理低浓度大风量有机废气

对已运行的有机废气治理工程运行情况的进行分析研究,并对采用吸附浓缩-催化燃烧工艺处理低浓度大风量的有机废气工程中的各项数据进行监测,得出其最佳条件为:吸附时间18 h,空床气速0.8 m/s,吸附容量1.9%;解吸温度100~120℃,解吸时间4 h。该工程实例的监测结果表明,催化燃烧的TVOC去除效率保持在99%以上,同时,该工艺对废气中甲苯、二甲苯和TVOC的总去除率分别能达到98.3%、99.6%和97.7%。     

Seasonal characteristics of ambient volatile organic compounds in Seoul,Korea

The measurements of C₂–C₉ volatile organic compounds (VOC) were carried out at a site in Seoul, the capital of Korea from August 1998 to July 1999. Air samples were collected for 24 h in 6 l SUMMA canisters every 6 days. The canister samples were quantitatively analyzed by a GC/FID and GC/MS. The species with the highest mean concentration among the 70 identified was propane (7.8 ppb), followed by toluene (6.4 ppb) and ethylene (5.9 ppb). The high concentration of propane was mainly attributed to the emissions by liquefied petroleum gas (LPG) usage for cooking and heating, and butane fuel for transportation. The general trend of the seasonal variation shows higher concentrations in winter and lower ones in summer. This behavior was mainly caused by the variations of temperature, and resultant VOC source strengths, coupled with the variations of the mixing depth. According to the analysis of concentration ratios, the seasonal contributions of the major emission sources to the VOC concentrations were influenced by ambient temperature. Further, it was identified that the contributions by the use of solvents, natural gas, LPG, and butane fuel were closely related to the variations of consumption pattern according to seasons. Through the analysis of the concentration correlations between less reactive compound and highly reactive ones for summer and winter months, it was found that photochemical reactivity affects relative concentration of reactive compound.     

Adsorption and desorption characteristics of several herbicides on sediment

The objective of this study was to clarify the adsorption and desorption characteristics of several herbicides in sediment. Five herbicides, esprocarb, thiobencarb, dimethametryn, pretilachlor, and simetryn were examined in this study. The adsorption ratio on the sediment increased in the following order: pretilachlor < dimethametryn < simetryn < thiobencarb < esprocarb. On the other hand, the adsorption ratio on the sediment without organic matter increased in the following order: thiobencarb < esprocarb < pretilachlor < dimethametryn < simetryn. Furthermore, the amounts of simetryn, dimethametryn, and pretilachlor adsorbed on the sediment without organic matter increased, while those of esprocarb and thiobencarb decreased in comparison to the original sediment. These results strongly suggested that the mineral surface in the sediment was very important as the adsorption site for the herbicide, especially in the case of simetryn, dimethametryn, and pretilachlor. All the adsorption and desorption data fitted well with the Freundlich equation. The hysteresis in the adsorption-desorption phenomena in the sediment was observed for all the herbicides, and it was affected by the organic matter in sediment, especially in the case of dimethametryn and pretilachlor.     

印刷环节挥发性有机物无组织排放特征测定研究

对使用溶剂型油墨的凹版印刷设备和使用水性油墨的柔版印刷设备无组织排放的挥发性有机物(VOCs)浓度进行了实际监测,并采用计算流体动力学模拟无组织排放VOCs的收集效率。结果表明：(1)使用溶剂型油墨的凹版连续印刷过程非甲烷总烃(NMHC)最高均值达到5 975.67 mg/m³,约为使用水性油墨的柔版印刷(191.67 mg/m³)的31.2倍。虽然使用水性油墨可明显降低NMHC的排放,但其操作空间的浓度依然存在超过《工作场所有害因素职业接触限值第1部分：化学有害因素》(GBZ 2.1—2019)的现象。(2)印刷车间应该设置专门的调墨室,能缓解印刷车间内挥发性污染气体浓度的波动。(3)计算流体动力学模拟显示,设置合理的集气罩可有效降低VOCs的无组织排放,收集效率为70%～75%。     

各类VOCs在蜂窝陶瓷型La0.8Sr0.2MnO3催化剂上的催化燃烧性能

以涂有CeO2-ZrO2固溶体的堇青石蜂窝状陶瓷为载体,用浸渍法制备堇青石蜂窝陶瓷型整体La0.8Sr0.2MnO3催化剂,测试了该催化剂催化燃烧各类VOCs的特性。研究表明,VOCs催化燃烧的难易程度为：含氯烃〉烷烃〉酸〉芳烃〉酮〉酯〉醇〉醛。La0.8Sr0.2MnO3催化剂对含氧有机化合物具有较好的催化活性,完全燃烧温度均在280℃之内。通过关联VOCs的理化性质,发现VOCs在La0.8Sr0.2MnO3催化剂上的反应活性与VOCs分子中最弱C—H键键能和VOCs分子极性密切联系。     

Effects of airborne volatile organic compounds on plants

Routine measurements of volatile organic compounds (VOCs) in air have shown that average concentrations are very much smaller than those used in laboratory experiments designed to study the effects of VOCs on plants. However, maximum hourly concentrations of some VOCs can be 100 times larger than the average, even in rural air. Experimental studies have rarely extended for longer than a few days, so there is little information on potential long-term effects of exposure to small concentrations. This review considers the available evidence for long-term effects, based on laboratory and field data. Previous reviews of the literature from Germany and the USA are cited, prior to an assessment of the effects of individual VOCs. Although hydrocarbons from vehicle exhausts have been implicated in the observed effects on roadside vegetation, the evidence suggests that it is the nitrogen oxides in the exhaust gases that are mostly responsible. There is evidence that aromatic hydrocarbons can be metabolised in plants, although the fate of the metabolites is not known. There is a large literature on the effects of ethylene, because of its role as a plant hormone. Effects have been reported in the field, in response to industrial emissions, and dose-response experiments over several weeks in laboratory studies have clearly identified the potential for effects at ambient concentrations. The main responses are morphological (e.g. epinasty), which may be reversible, and on the development of flowers and fruit. Effects on seed production may be positive or negative, depending on the exposure concentration. Chlorinated hydrocarbons have been identified as potentially harmful to vegetation, but only one long-term experiment has studied dose-response relationships. As for ethylene, the most sensitive indication of effect was on seed production, although long-term accumulation of trichloroacetic acid in tissue may also be a problem. There is little evidence of the direct effects of oxygenated hydrocarbons on plants. Plants are a significant emission source of short-chain alcohols, aldehydes and ketones. Peroxyacetyl nitrate (PAN) has a well-documented history as damaging to vegetation. There have been few long-term experimental studies despite the field evidence for damaging effects. Early studies in California have been followed by more recent data from east Asia, but there is still a dearth of information on the potential for effects of PAN and related peroxyacyl nitrates on vegetation typical of regions around tropical and sub-tropical cities where PAN pollution is increasingly important. The lack of long-term measurements, coupled with the available evidence that effects are not linearly related to 'dose' measured as the product of exposure concentration and time, means that the possibility of adverse effects of VOCs on vegetation cannot be safely rejected, particularly in urban and industrial areas. Although reproductive processes (flowering, seed production) appear to be most sensitive, there have been no experimental studies on subsequent seed viability and the consequences at the ecosystem level of changes to plant phenology. The potential for VOC metabolites to accumulate in plant tissue has been demonstrated, but any subsequent effects on herbivores and phytophagous insects have yet to be investigated.     

典型涂料制造企业VOCs排放量核算与排放特征分析

采集了上海地区8家不同类型的涂料制造企业中不同生产环节有组织排放的废气样本,分析其VOCs组分特征和活性VOCs物种,并应用3种实际排放量核算方法计算企业的VOCs年排放量,分析了其与排污许可排放量的关系。结果表明：1)涂料制造行业排放废气的特征组分为芳香烃、OVOCs、卤代烃,占全部VOCs质量浓度的56.2%~99.1%,乙酸乙酯、乙酸丁酯、4-乙基甲苯、间/对二甲苯、甲苯、甲乙酮是涂料制造行业VOCs排放的典型物种;2)基于MIR值法的计算结果,芳香烃和OVOCs是涂料制造行业排放VOCs的主要活性组分,累计OFP贡献率达36.0%~99.8%,其中,4-乙基甲苯(52.1%)、氯乙烯(48.1%)、乙酸丁酯(47.9%)、乙酸乙酯(42.6%)、间/对二甲苯(41.3%)是各类涂料工艺废气中OFP贡献率最高的物质,除苯系物、乙酸酯类化合物外,氯乙烯、甲乙酮、四氢呋喃也是涂料制造过程中值得关注的活性物质;3)涂料制造企业车间的有组织废气VOCs排放量占全厂VOCs排放量的75.0%以上,其次是实验室废气,VOCs排放量为3.5%~16.8%。在VOCs实际排放量核算中,使用实测法的核算结果与物料衡算法接近,且计算简便,在正常运行时均低于许可排放限值;而产污系数法所核算数值较许可排放限值更高,在现阶段可作为一项惩罚性计算方法。     

餐厨垃圾处理厂挥发性有机物释放特征

选择目前国内成功运营的餐厨垃圾处理厂为采样点,该厂以利用餐厨垃圾生产生物蛋白饲料和厌氧发酵为主要工艺,采用气相色谱/质谱联用(GC/MS)技术对挥发性有机物(VOCs)浓度较高的工段,如破碎室、湿热反应器、好氧发酵仓进行了定性和定量分析.结果表明,3个采样点共检测出65种物质,包括醇、醛、酮、酯、芳香烃、硫化物、卤代物、烯烃和烷烃9类.湿热反应器排放VOCs浓度最高且包含物质种类最多,其中酮、酯、芳香烃、硫化物、卤代物、烯烃及烷烃类物质浓度均高于其他检测点,需对该工段进行重点监测和控制.     

Qualitative analysis of volatile organic compounds on biochar

Qualitative identification of sorbed volatile organic compounds (VOCs) on biochar was conducted by headspace thermal desorption coupled to capillary gas chromatographic-mass spectrometry. VOCs may have a mechanistic role influencing plant and microbial responses to biochar amendments, since VOCs can directly inhibit/stimulate microbial and plant processes. Over 70 biochars encompassing a variety of parent feedstocks and manufacturing processes were evaluated and were observed to possess diverse sorbed VOC composition. There were over 140 individual chemical compounds thermally desorbed from some biochars, with hydrothermal carbonization (HTC) and fast pyrolysis biochars typically possessing the greatest number of sorbed volatiles. In contrast, gasification, thermal or chemical processed biochars, soil kiln mound, and open pit biochars possessed low to non-detectable levels of VOCs. Slow pyrolysis biochars were highly variable in terms of their sorbed VOC content. There were no clear feedstock dependencies to the sorbed VOC composition, suggesting a stronger linkage with biochar production conditions coupled to post-production handling and processing. Lower pyrolytic temperatures (?350 °C) produced biochars with sorbed VOCs consisting of short carbon chain aldehydes, furans and ketones; elevated temperature biochars (>350 °C) typically were dominated by sorbed aromatic compounds and longer carbon chain hydrocarbons. The presence of oxygen during pyrolysis also reduced sorbed VOCs. These compositional results suggest that sorbed VOCs are highly variable and that their chemical dissimilarity could play a role in the wide variety of plant and soil microbial responses to biochar soil amendment noted in the literature. This variability in VOC composition may argue for VOC characterization before land application to predict possible agroecosystem effects.     

二次热解吸-气相色谱-质谱分析室内挥发性有机化合物

采用二次热解吸-气相色谱.质谱法对室内空气进行了定量和定性分析,共检出挥发性有机物245种,包括烷烃、烯烃、芳香类化合物、卤代烃、醇、醛、酮、酯、醚等化合物,住宅类室内空气中挥发性有机化合物浓度平均值明显高于办公类室内这些物质的浓度平均值,对室内空气样品分析中的特例进行了可能的污染源解析,推测室内过量使用液体胶粘剂有可能是引起污染物严重超标的原因之一.     

绍兴市柯桥区工业园区挥发性有机物污染特征研究

为更好地管控和治理绍兴市柯桥区工业园区的挥发性有机物(VOCs),利用柯桥区现有的两工业园区VOCs监测站点(园区1站、园区2站)2019年3月至2020年2月的监测数据分析柯桥区工业园区VOCs污染特征并进行溯源.结果表明:园区1站每月VOCs质量浓度平均值为125μg/m3,园区2站为137μg/m3,都呈现出3月...     

Emission characteristics of ultrafine particles and volatile organic compounds in a commercial printing center

Laser printers are one of the common indoor equipment in schools, offices, and various other places. Laser printers have recently been identified as a potential source of indoor air pollution. This study examines the characteristics of ultrafine particles (UFPs, diameter <100 nm) and volatile organic compounds (VOCs) emitted from laser printers housed in a commercial printing center. The results indicated that apart from the printer type, the age of printers, and the number of pages printed, the characteristics of UFPs emitted from printers also depend on indoor ventilation conditions. It was found that at reduced ventilation rates of indoor air, there was a rise in the number concentration of UFPs in the printing center. Interestingly, the contribution of UFPs to the total number of submicrometer-sized particles was observed to be higher at a sampling point far away from the printer than the one in the immediate vicinity of the printer. Black carbon (BC) measurements showed a good correlation (rs = 0.82) with particles in the size range of 100-560 nm than those with diameters less than 100 nm (rs = 0.33 for 50-100 nm, and rs = -0.19 for 5.6-50 nm particles). Measurements of VOCs in the printing center showed high levels of m-, o-, and p-xylene, styrene, and ethylbenzenes during peak hours of printing. Although toluene was found in higher levels, its concentration decreased during peak hours compared to those during nonoperating hours of the printing center.     

Lysis of cyanobacteria with volatile organic compounds

One of bacteria collected from Lake Sagami, Japan, Brevibacillus sp., was found to have a lytic activity of cyanobacteria, but did not produce active compounds. Instead, the co-culturing of Microcystis with the Brevibacillus sp. enhanced the production of two volatile compounds, beta-cyclocitral and 3-methyl-1-butanol, and the former had a characteristic lytic activity. It was confirmed that these volatile compounds were derived from the cyanobacteria themselves. beta-Ionone, geosmin and 2-methylisoborneol derived from cyanobacteria and similar volatile compounds, terpenoids, produced by plants also had a lytic activity. The minimum inhibitory concentration values of the cyanobacterial metabolites were estimated to be higher than those of compounds from plants except for a few compounds. Among them, beta-cyclocitral only produced a characteristic color change of culture broth from green to blue. This color change is similar to the phenomenon observed when a sudden decline in growth of cyanobacteria begins in a natural environment.     

Simultaneous passive sampling of volatile organic compounds

In this paper, the results obtained in the simultaneous passive sampling of toluene, hexane, methyl ethyl ketone and ethyl acetate on activated charcoal are presented and compared with results obtained when the compounds were tested individually. Any observed deviations in the sampling rate are possibly due to the variations in the adsorption efficiency or in the coefficients of desorption caused by the presence of more than one adsorbate, though in all cases the values obtained are within the accepted margins recommended by NIOSH     

Microwave plasma conversion of volatile organic compounds

A microwave-induced, steam/Ar/O2, plasma "torch" was operated at atmospheric pressure to determine the feasibility of destroying volatile organic compounds (VOCs) of concern. The plasma process can be coupled with adsorbent technology by providing steam as the fluid carrier for desorbing the VOCs from an adsorbent. Hence, N2 can be excluded by using a relatively inexpensive carrier gas, and thermal formation of oxides of nitrogen (NOx) is avoided in the plasma. The objectives of the study were to evaluate the technical feasibility of destroying VOCs from gas streams by using a commercially available microwave plasma torch and to examine whether significant byproducts were produced. Trichloroethene (TCE) and toluene (TOL) were added as representative VOCs of interest to a flow that contained Ar as a carrier gas in addition to O2 and steam. The O2 was necessary to ensure that undesirable byproducts were not formed in the process. Microwave power applied at 500-600 W was found to be sufficient to achieve the destruction of the test compounds, down to the detection limits of the gas chromatograph that was used in the analysis. Samples of the postmicrowave gases were collected on sorbent tubes for the analysis of dioxins and other byproducts. No hazardous byproducts were detected when sufficient O2 was added to the flow. The destruction efficiency at a fixed microwave power improved with the addition of steam to the flow that passed through the torch.     

真菌降解挥发性有机化合物的研究进展

挥发性有机化合物(VOCs)是一类重要的大气污染物,生物降解法是近年来兴起的VOCs治理技术,它具有费用低、净化效率高、无二次污染等特点。目前,有关生物降解污染物的研究大部分都以细菌作为优势微生物,而对于真菌的研究起步相对较晚。真菌具有耐干燥、耐弱酸等特性,使得其在处理疏水性VOCs上具有明显优势。分析了真菌的降解特征及优势,总结了已分离到的可降解VOCs的真菌及其善于降解的污染物,重点探讨了影响真菌生物反应器VOCs降解性能的主要因素和相关动力学研究,并对今后真菌降解VOCs的研究方向进行了展望。     

车内空气中挥发性有机物的研究

采用热脱附-气相色谱/质谱联用法对4辆处于静止状态下的车辆内部空气中挥发性有机物（VOCs）进行了研究,共定性检出了48种有机物,其中C6～C9之间的组分较多;并对VOCs的总浓度进行了定量,1#～4#车分别为1846、2289、1104和3146 μg/m^3;其中BTEX占VOCs总量的20%～30%;车内VOCs浓度与温度及车辆使用年限密切相关.