电子垃圾焚烧排放的二噁英对周围大气环境的影响

为了研究电子垃圾焚烧产生的二噁英对周围环境的影响,同时在E1和E2采样点分别采集9个大气样品.E1周围分布大量的电子垃圾焚烧点,E2则位于E1南9 km处,周围无其他明显的二噁英排放源.所采样品用同位素稀释法进行分析测定,结果表明,E1和E2大气样品中二噁英的平均质量浓度分别为127.37、22.37 pg/m3,平均毒性当量浓度分别为8.777、1.305 pg I-TEQ/m3.八氯代二苯并呋喃(OCDF)、八氯代二苯并二噁英(OCDD)、七氯代二苯并呋喃(1,2,3,4,6,7,8-HpCDF)和七氯代二苯并二噁英(1,2,3,4,6,7,8-HpCDD)对2,3,7,8位氯代的二噁英的总浓度贡献较大,而五氯代二苯并呋喃(2,3,4,7,8-PeCDF)则对总毒性当量浓度贡献最大,其贡献率超过40%.在E1和E2两个采样点,二噁英在气相中的比例均随着氯原子取代数的增加而降低.两采样点相似的二噁英分布模式和气固分配,说明E2大气中二噁英主要来自于E1电子垃圾焚烧产生的二噁英.     

钒基催化剂降解实际烟气中的二噁英研究

为开发高效降解实际烟气中二噁英的新型催化剂,在钒基催化剂中加入Mn和Cu,研究200℃时不同催化剂对二噁英的降解效率,并添加臭氧辅助催化,分析二噁英不同氯代同系物的降解规律。结果表明:催化剂中添加MnO_x或同时添加MnO_x和CuO_x时,催化剂降解效率明显提升;催化剂中仅添加CuO_x则会导致二噁英的大量生成;反应气氛中添加臭氧,能提升催化剂对二噁英的降解效率,特别是VO_x-CuO_x/TiO_2,二噁英由生成转变为降解。分析二噁英同系物的脱除效率发现,催化剂对二噁英的吸附效率随着氯代数增加而增加,降解效率随氯代数增加而降低。     

基于添加尿素的铁矿烧结过程二噁英减排技术研究

铁矿烧结过程是二噁英排放的主要污染源之一。研究了铁矿烧结过程中添加尿素对烧结烟气二噁英减排的影响。结果表明,烧结料层中混匀加入0.020%、0.035%、0.050%(质量分数)的固态尿素后,二噁英的排放质量浓度分别为0.20、0.12、0.20ng TEQ/m3,与未加尿素时的二噁英排放质量浓度(0.50ng TEQ/m3)相比均有大幅度降低。尿素混匀加入对二噁英的减排效果优于定点加入,固态尿素对二噁英的减排效果优于液态尿素。最后阐述了尿素对烧结过程二噁英的减排机制。     

Fe~(3+)和Cu~(2+)对饮用水氯消毒副产物三卤甲烷形成的影响

为了研究水中存在Br-的情况下,Fe3+和Cu2+对三卤甲烷(THMs)的生成及CHCl3、CHBr Cl2、CHBr2Cl、CHBr34种消毒副产物相对分布的影响,以腐殖酸模拟氯消毒过程中的前体物进行实验。结果表明,在p H为6、7和9 3种条件下,Fe3+抑制了THMs的生成,p H=6时只有CHCl3生成量随着Fe3+浓度的增加逐渐减少,其余3种消毒副产物均在增加,p H=7时4种消毒副产物浓度均减小并在Fe3+浓度为2 mg/L时生成量最低,p H=9时的生成趋势与p H=6时类似。Cu2+能促进THMs的生成,在p H为6、7和9时,当加入0.5 mg/L Cu2+时,THMs总量分别增加了16.7%、22.6%和2.5%,随着p H增加,THMs总量增加。在3种p H环境中,Cu2+对THMs生成的影响大于Fe3+,在偏酸性环境中,Fe3+影响THMs生成,产生的致癌风险高,当金属离子浓度为2.5 mg/L时,致癌风险相差最高为15%,在中性和偏碱性环境中,Cu2+影响THMs生成,产生的致癌风险高。     

再生铝制造企业飞灰中二噁英污染特征

连续8d采集中国某大型再生铝制造企业的飞灰样品,通过高分辨气相色谱/高分辨质谱联用仪对其中的二噁英污染特征开展了研究。结果表明:飞灰样品中二噁英质量浓度为58.64~261.14μg/kg,平均为103.93μg/kg,其中1,2,3,4,6,7,8-七氯代二苯并呋喃(1,2,3,4,6,7,8-HpCDF)、八氯代二苯并呋喃(OCDF)和八氯代二苯并二噁英(OCDD)是飞灰中最主要的单体,分别占二噁英浓度的19.54%(质量分数,下同)、15.57%和14.62%;二噁英毒性当量浓度为4.21~14.77μg TEQ/kg,平均为7.10μg TEQ/kg,其中2,3,4,7,8-五氯代二苯并呋喃(2,3,4,7,8-PeCDF)对飞灰中二噁英毒性当量浓度贡献最大,平均贡献率为50.15%;二噁英毒性当量浓度均未超过《危险废物鉴别标准毒性物质含量鉴别》(GB 5085.6—2007)规定限值,因此可以判定该企业的飞灰不属于具有二噁英毒性的危险废物。     

垃圾焚烧厂周围环境空气中二噁英浓度分布及其健康风险评估

2015年11月至2016年1月在浙江嘉兴、江西南昌和江苏淮安的3个垃圾焚烧厂(MSWI)周围进行了环境空气中二噁英(PCDD/Fs)的浓度测定,并对其组成特征进行了分析,同时采用VLIER-HUMAAN模型评估其对人体的健康风险。结果表明,浙江嘉兴的MSWI周围环境空气中PCDD/Fs质量浓度为1.876~6.032 pg/m3,江西南昌为1.365~4.745 pg/m3,江苏淮安为1.526~1.777 pg/m3。1,2,3,4,6,7,8-七氯代二苯并二噁英(1,2,3,4,6,7,8-Hp CDD)、八氯代二苯并二噁英(OCDD)、1,2,3,4,6,7,8-七氯代二苯并呋喃(1,2,3,4,6,7,8-Hp CDF)和八氯代二苯并呋喃(OCDF)是3个MSWI周围环境空气中主要的PCDD/Fs单体。健康风险评估结果表明,在3个MSWI周围的居民均处于较为安全的状态,但儿童的PCDD/Fs呼吸日暴露量约是成人的11倍。     

水热条件下碳酰肼分解二噁英的研究

研究了保温温度为245、260℃水热条件下使用碳酰肼分解垃圾焚烧飞灰中二噁英的分解效果.结果表明,在高温水热条件下使用碳酰肼作为添加剂有利于二噁英的分解;在245、260℃下保温1 h,二噁英的分解率分别达到80%和90%以上,但二噁英毒性当量因2,3,7,8-TCDD的再生成减小很少,甚至增大;同时,在水热条件下,垃圾焚烧飞灰中的重金属取得了良好的稳定效果.     

固定化斜生栅藻净化畜禽废水中氨氮和磷的影响因素

为探讨Cu2+、p H和流速对固定化斜生栅藻去除畜禽废水中NH+4-N、TP效果的影响,在实验室条件下模拟实际污水处理过程,并采用正交实验方案对结果进行分析。结果表明低质量浓度Cu2+(0~0.05 mg/L)改善藻的净化效果,高质量浓度Cu2+(0.50~5.00 mg/L)抑制藻的净化效果;在p H较高的条件下(p H=9),固定化斜生栅藻的净化效果明显提高;流速对结果没有明显影响。通过正交实验,得出固定化斜生栅藻去除畜禽废水中NH+4-N、TP的优化条件如下:Cu2+质量浓度为0.05 mg/L,p H为9,流速为0.3 m/s。此时NH+4-N去除率为96.11%,TP去除率为97.53%。     

含硫化合物对氯苯和二噁英的抑制作用

为有效控制废物焚烧过程中氯代有机污染物的排放,利用管式炉及某实际医疗废物焚烧炉研究了含硫添加剂对氯苯和二噁英的抑制,并分析了抑制剂对氯化反应的影响。结果表明,硫代硫酸钠是非常有效的抑制剂,对氯化反应的抑制率达90%;在实际焚烧炉应用上,单质硫对五氯苯、六氯苯和二噁英均存在抑制能力。     

流化床垃圾焚烧炉产生的有毒二噁英同类物分布研究

测定了流化床垃圾焚烧炉焚烧产生的飞灰、烟尘和烟气中的2，3，7，8位氯取代二噁英同类物的含量及其毒性当量。结果表明，产生的二噁英主要存在于飞灰中，烟气中的含量很少。飞灰中二噁英总浓度和毒性当量分别为8.44ng／g和0．80ng／g，经过布袋除尘器后的烟尘和烟气中二噁英的浓度之和与毒性当量之和分别为0．34ng／m^3和0．02ng／m^3，而布袋除尘器前的烟尘和烟气中二噁英的浓度之和与毒性当量之和分别为40．78ng／m^3和3．0ng／m^3。飞灰和烟尘中2，3，7，8位氯取代二噁英同类物的分布相似，但是与烟气中2，3，7，8位氯取代二噁英同类物的分布差别较大。通过了解有毒二噁英同类物的分布，可以进一步优化流化床垃圾焚烧炉的焚烧条件，降低二噁英的排放量，减少垃圾焚烧对环境的污染。     

Formation and emission status of PCDDs/PCDFs in municipal solid waste incinerators in Korea

This study was carried out to examine the formation and the emission status of polychlorinated dibenzo-p-dioxins/polychlorinated dibenzofurans (PCDDs/PCDFs) in the flue gases of commercial-scale municipal solid waste (MSW) incinerators, and thus to provide the engineering data for the reduction of PCDDs/PCDFs emitted from MSW incinerators. The formation concentrations of the PCDDs/PCDFs generated at the outlet of waste heat boilers (WHB) were in the range of 1.18-29.61 ng-TEQ/N m3 (average 5.75 ng-TEQ/N m3), while the emission concentrations at the stacks were in the range of 0.026-4.548 ng-TEQ/N m3 (average 0.924 ng-TEQ/N m3). Two major 2,3,7,8-substituted congeners were 2,3,4,7,8-PeCDF and 2,3,4,6,7,8-HxCDF, and their concentrations were up to 50% and 64% of total TEQ values at the outlet of WHB and the stack, respectively. From the results of multi-regression analysis, the formation concentration of PCDDs/PCDFs could be predicted as follows with the correlation factor of r2 = 0.962: PCDDs/PCDFs (ng-TEQ/N m3) = 3.036 (Cl) + 0.094 (T1) - 0.472 (Combustibles) + 0.059 (CO) - 0.039 (THC) - 3.366 (H) + 22.157, where T1 (degrees C) is the temperature at the outlet of the WHB. Cl, Combustibles and H are given as percentages and the others are in parts per million.     

Combined PCDD/F destruction and particulate control in a baghouse: experience with a catalytic filter system at a medical waste incineration plant

Phoenix Services, Inc., owns and operates the Baltimore Regional Medical Waste Incinerator in Baltimore, MD. New regulations for dioxins and furans imposed a limit that was considerably below historical emission levels. To determine a method to comply with the new dioxin/furan regulations, Phoenix Services performed trials with powdered activated carbon (PAC). Although the results with carbon were acceptable, Phoenix Services decided to replace their woven fiberglass filter bags with catalytic filters that simultaneously destroy dioxins and furans and collect particulate matter (PM). The catalytic filter system offered several advantages to Phoenix Services, including destruction of dioxins and furans instead of adsorption on carbon. The catalytic filters also offered a passive solution that did not require new carbon injection equipment. In January 2000, a campaign to measure dioxins/furans and PM was undertaken. The measurements allowed the catalytic filter system to be evaluated. Some of the key findings of this investigation are The dioxin/furan emission was less than 0.1 ng toxicity equivalents (TEQ)/Nm3 at 11% O2. This concentration is approximately 2 orders of magnitude less than historical averages and it is well below the new regulatory limits, for both existing and new sources of this type; the amount of dioxin/furans destroyed by the catalytic filters was approximately 1.73 ng TEQ/Nm3 at 11% O2; and the particulate emission was 12-17 times less than the regulatory limit.     

Dioxins and their fingerprint in size-classified fly ash fractions from municipal solid waste incinerators in China--mechanical grate and fluidized bed units

The distribution of polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs), in brief dioxins, has seldom been addressed systematically in fly ash from municipal solid waste incinerators (MSWIs). This study shows the amount and fingerprint of PCDD/Fs in fly ash from four different Chinese MSWIs, that is, three mechanical grate units and one circulating fluidized bed unit. In these fly ash samples, dioxins-related parameters (international toxic equivalent quantity, total amount of PCDD/Fs, individual isomer classes, and 17 toxic 2,3,7,8-substituted congeners) all tend to increase with decreasing particle size for mechanical grate incinerators, yet only for the finest fraction for fluidized bed units. Moreover, the fluidized bed incinerator seems superior to grate incineration in controlling dioxins, yet a comparison is hampered by internal differences in the sample, for example, the fluidized bed fly ash has much lower carbon and chlorine contents. In addition, the presence of sulfur from mixing coal as supplemental fuel to the MSW may poison the catalytic steps in dioxins formation and thus suppress the formation of dioxins. With more residual carbon and chlorine in the fly ash, it is easier to form dioxins during cooling. Nevertheless, there is no apparent relation between Fe, Cu, and Zn contents and that of dioxins in fly ash.     

Catalytic performance of Ag/Al2O3-C2H5OH-Cu/Al2O3 system for the removal of NOx from diesel engine exhaust

The selective catalytic reduction (SCR) of NOx by C(2)H(5)OH was studied in excess oxygen over Ag/Al(2)O(3) catalysts with different Ag loadings at lab conditions. The 4% Ag/Al(2)O(3) has the highest activity for the C(2)H(5)OH-SCR of NOx with a drawback of simultaneously producing CO and unburned THC in effluent gases. An oxidation catalyst 10% Cu/Al(2)O(3) was directly placed after the Ag/Al(2)O(3) to remove CO and unburned THC. Washcoated honeycomb catalysts were prepared based on the 4% Ag/Al(2)O(3) and 10% Cu/Al(2)O(3) powders and tested for the C(2)H(5)OH-SCR of NOx on a diesel engine at the practical operating conditions. Compared with the Ag/Al(2)O(3) powder, the Ag/Al(2)O(3) washcoated honeycomb catalyst (SCR catalyst) has a similar activity for NOx reduction by C(2)H(5)OH and the drawback of increasing the CO and unburned THC emissions. Using the SCR+Oxi composite catalyst with the optimization of C(2)H(5)OH addition, the diesel engine completely meets EURO III emission standards.     

Formation of dioxins from combustion of polyvinylidene chloride in a well-controlled incinerator

Polyvinylidene chloride (PVDC; polymer of 1,1-dichloroethylene) was combusted with paper in a well-controlled, small-scale incinerator at an average grate temperature of 700 °C, and then dioxins (PCDDs, PCDFs, and coplanar-PCBs) formed in the exhaust gases were analyzed by gas chromatography/mass spectrometry. PVDC lowered the combustion temperature due to its less flammable character. The amount of total dioxins (PCDDs + PCDFs + coplanar-PCBs) formed in the exhaust gas was 58.0 ng/g of a combustion sample and its toxicity equivalency quantity (TEQ) value was 0.64 ng-TEQ/g. The amount of PCDDs formed in the sample ranged from 2.33 ng/g (Cl₈-isomer) to 0.048 ng/g (Cl₁-isomer). The lower the number of chloride, the less production of PCDDs. On the other hand, there was no relation between the number of chloride and PCDF formation. The amount of PCDFs formed in the sample ranged from 8.02 ng/g (Cl₂-isomer) to 4.46 ng/g (Cl₈-isomer). A polyvinylchloride (PVC) sample produced 207 ng/g of total dioxins and a PVDC sample produced 57.4 ng/g of total dioxins when they were combusted under the same conditions. An approximately equal composition of dioxin isomers was formed from PVDC and PVC samples. Paper was found to contribute to PCDF formation when it was combusted with plastics.     

The role of metals in dioxin formation from combustion of newspapers and polyvinyl chloride in an incinerator

Newspapers impregnated with NaCl mixed with various chloride metals (CuCl2, MgCl2, MnCl2, FeCl3, NiCl2, and CoCl2) and electric wire coated with polyvinyl chloride (PVC) were combusted in a well-controlled incinerator. Exhaust gas samples collected at the outlet of the incinerator were analyzed for dioxins (PCDDs, PCDFs, and coplanar PCBs) by gas chromatography/mass spectrometry. The amount of total dioxins formed from newspaper samples ranged from 34.2 ng/g (with NaCl+CoCl2) to 67.0 ng/g (with NaCl+CuCl2). PCDFs composed 88-94% of the total dioxins formed in the exhaust gases. The highest levels of PCDF isomers obtained were Cl3-CDF from the sample with NaCl+CuCl2 (14.8 ng/g), Cl2-CDF from the sample with NaCl+MgCl2 (12.3 ng/g), and Cl(1)-CDF from samples with NaCl+MnCl2 (12.6 ng/g), with NaCl+FeCl3 (11.8 ng/g), and with NaCl+NiCl2 (13.3 ng/g), and with NaCl+CoCl2 (8.62 ng/g). The total of Cl4-8-CDDs comprised 76-88% of the total Cl1-8-CDDs. In particular, Cl7-CDDs had the highest levels except for the sample with NaCl+NiCl2. Total dioxins formed from samples of electric wire coated with PVC and PVC alone were 38.3 ng/g and 112 ng/g, respectively, suggesting that the presence of copper reduced dioxin formation.     

The promoter effect and a rate expression of the catalytic incineration of (CH3)2S2 over an improved CuO-MoO3/gamma-Al2O3 catalyst

The CuO-MoO3/gamma-Al2O3 catalyst, confirmed previously as having good activity in the catalytic incineration of (CH3)2S2, was employed as the principal catalyst in this study. With the aim of improving catalyst activity and resistance to deactivation by sulfur compounds, a promoter was added either before adding the precursors of Cu and Mo or together with Cu and Mo onto the gamma-Al2O3. Promoters included transition metals and elements from groups IA-VIIA in the chemical periodic table. Experimental results reveal Cr2O3 as the most effective promoter, with an optimal composition of 5 wt.% Cu, 6 wt.% Mo and 4 wt.% Cr (designated as Cu(5)-Mo(6)-Cr(4)/gamma-Al2O3). Knowing that higher acidity can improve activity, we further investigated the effect of acid treatment on the performance of the Cu(5)-Mo(6)-Cr(4)/gamma-Al2O3 catalyst. Experimental results indicate the H2SO4-treated catalyst (Cu(5)-Mo(6)-Cr(4)/sulfated-gamma-Al2O3) has a better activity and durability. A study for finding an appropriate rate expression for the catalytic incineration of (CH3)2S2 by Cu(5)-Mo(6)-Cr(4)/sulfated-gamma-Al2O3 was carried out in a differential reactor. The results show that the Mars-Van Krevelen model is applicable to this destructive oxidation reaction. Results additionally reveal that competitive adsorption of CH4 reduces conversion of (CH3)2S2.     

Atmospheric deposition of polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans, and dioxin-like polychlorinated biphenyls in the Kanto Region, Japan

The atmospheric bulk (dry and wet) deposition of dioxins was investigated at four locations (Tokyo, Yokohama, Tsukuba, and Tanzawa) in the Kanto region (in Japan) over one year using a stainless-steel pot. Annual average polychlorinated dibenzo-p-dioxins/polychlorinated dibenzofurans (PCDD/PCDF) deposition fluxes were estimated to be from 450 to 1300 ng/m2/yr, and the annual average TEQ fluxes from 5.7 to 17 ng-TEQ/m2/yr at the four locations. The PCDD/PCDF deposition flux was higher in winter than in summer. The deposition flux could be related to ambient temperature, particularly for less chlorinated PCDDs/PCDFs, while the deposition flux is not necessarily related to the amount of precipitation. The PCDD/PCDF deposition flux increased as the particle deposition flux increased, for the winter samples. Based on the ratio of the PCDD/PCDF deposition fluxes to the particle deposition fluxes, the contribution of the reentrainment of soil particles to the TEQ of PCDD/PCDF deposition was considered to be negligible in this region. Based on the air concentrations monitored near our deposition sampling points by the municipalities, the ratio of the annual deposition flux to the annual average air concentration was roughly estimated to be 0.082 cm/s. The range of deposition flux in the Kanto region was estimated to be from 1.5 to 31 (median: 9.8) ng-TEQ/m2/yr based on the range of air concentration data measured by the municipalities. The total annual deposition flux in the entire Kanto region was estimated to range from 50 to 900 g-TEQ/yr (median 320 g-TEQ/yr). This estimated flux was of the same order as the sum of estimated emissions from municipal solid waste incinerators and industrial waste incinerators in the Kanto region. The contributions of dioxin-like PCBs in Yokohama, Tsukuba, and Tanzawa depositions were less than 10% of the total TEQ; however, in Tokyo it was almost equal to or more than 50%.     

Destruction of PCDD/Fs by SCR from flue gases of municipal waste incinerator and metal smelting plant

Partitioning of PCDD/F congeners between vapor/solid phases and removal and destruction efficiencies achieved with selective catalytic reduction (SCR) system for PCDD/Fs at an existing municipal waste incinerator (MWI) and metal smelting plant (MSP) in Taiwan are evaluated via stack sampling and analysis. The MWI investigated is equipped with electrostatic precipitators (EP, operating temperature: 230 degrees C), wet scrubbers (WS, operating temperature: 70 degrees C) and SCR (operating temperature: 220 degrees C) as major air pollution control devices (APCDs). PCDD/F concentration measured at stack gas of the MWI investigated is 0.728 ng-TEQ/Nm(3). The removal efficiency of WS+SCR system for PCDD/Fs reaches 93% in the MWI investigated. The MSP investigated is equipped with EP (operating temperature: 240 degrees C) and SCR (operating temperature: 290 degrees C) as APCDs. The flue gas sampling results also indicate that PCDD/F concentration treated with SCR is 1.35 ng-TEQ/Nm(3). The SCR system adopted in MSP can remove 52.3% PCDD/Fs from flue gases (SCR operating temperature: 290 degrees C, Gas flow rate: 660 kN m(3)/h). In addition, the distributions of PCDD/F congeners observed in the flue gases of the MWI and MSP investigated are significantly different. This study also indicates that the PCDD/F congeners measured in the flue gases of those two facilities are mostly distributed in vapor phase prior to the SCR system and shift to solid phase (vapor-phase PCDD/Fs are effectively decomposed) after being treated with catalyst. Besides, the results also indicate that with SCR highly chlorinated PCDD/F congeners can be transformed to lowly chlorinated PCDD/F congeners probably by dechlorination, while the removal efficiencies of vapor-phase PCDD/Fs increase with increasing chlorination.     

Use of regenerated ferric oxide for CO destruction and suppressing dioxin formation in flue gas in a pilot-scale incinerator

Catalytic destruction of chlorinated compounds is one of the key methods in reducing pollutant emissions. For the purpose of utilizing waste materials, a catalyst was regenerated from ferric ion sludge, obtained from the addition of iron salts to precipitate heavy metals. The sludge was dewatered, heated (800 degrees C for 4 h), and ground into smaller particles. The regenerated ferric oxide particles were then used as the oxidation catalyst to destroy CO formation during the combustion of three chlorinated solvents and to suppress dioxin formation in flue gas in a real waste solvent. In the presence of catalyst, the combustion efficiency (ratio of CO(2) to the sum of CO(2) and CO) for chlorobenzene was more than 98% at 850 degrees C in a pilot-scale incinerator. The destruction and removal efficiencies of chlorobenzene, 2,4-dichlorophenol and trichlorofluoroethane were more than three nines. In the absence of catalysts, the flue gas emission from a real waste could not meet the regulatory dioxin standard of 0.1 ng-TEQ/Nm(3) even with the powdered activated carbon injection. The use of catalyst at either 100 or 300 g/h, however, was able to meet the emission standard.