2017—2019年中国337个城市及重点区域臭氧污染状况分析

分析了2017—2019年中国337城市O_3污染特征,结果表明:2017—2019年全国O_3第20～70百分位浓度逐年增幅相对稳定,第80～95百分位浓度逐年上升速率最快,平均每年升高5.5μg/m~3。全国O_3超标以轻度污染为主,主要集中在5—9月,占全年O_3超标天数的85.3%;"2+26"城市、汾渭平原交界、长三角、苏皖鲁豫交界O_3超标天数占全国63.9%,"2+26"城市O_3污染最为严重,平均每城市超标71 d。2017—2019年O_3单因子超标分别损失全国空气质量优良天数比例为4.5个百分点、4.9个百分点和7.4个百分点,2019年9月O_3单因子超标天数比例为18.8个百分点,单月使全年优良天数减少1.2个百分点。天津、河北、山东、北京、河南、山西、江苏的O_3污染相对较重,天津市发生O_3污染的关键温度为26～34℃,风速为2.0～2.5 m/s,相对湿度为40%～80%,降水明显减少和温度偏高是导致2019年O_3浓度升高的重要气象因素。     

Biological conversion pathways of sulfate reduction ammonium oxidation in anammox consortia

• The SRAO phenomena tended to occur only under certain conditions. • High amount of biomass and non-anaerobic condition is requirement for SRAO. • Anammox bacteria cannot oxidize ammonium with sulfate as electron acceptor. • AOB and AnAOB are mainly responsible for ammonium conversion. • Heterotrophic sulfate reduction mainly contributed to sulfate conversion. For over two decades, sulfate reduction with ammonium oxidation (SRAO) had been reported from laboratory experiments. SRAO was considered an autotrophic process mediated by anammox bacteria, in which ammonium as electron donor was oxidized by the electron acceptor sulfate. This process had been attributed to observed transformations of nitrogenous and sulfurous compounds in natural environments. Results obtained differed largely for the conversion mole ratios (ammonium/sulfate), and even the intermediate and final products of sulfate reduction. Thus, the hypothesis of biological conversion pathways of ammonium and sulfate in anammox consortia is implausible. In this study, continuous reactor experiments (with working volume of 3.8L) and batch tests were conducted under normal anaerobic (0.2≤DO<0.5 mg/L) / strict anaerobic (DO<0.2 mg/L) conditions with different biomass proportions to verify the SRAO phenomena and identify possible pathways behind substrate conversion. Key findings were that SRAO occurred only in cases of high amounts of inoculant biomass under normal anaerobic condition, while absent under strict anaerobic conditions for same anammox consortia. Mass balance and stoichiometry were checked based on experimental results and the thermodynamics proposed by previous studies were critically discussed. Thus anammox bacteria do not possess the ability to oxidize ammonium with sulfate as electron acceptor and the assumed SRAO could, in fact, be a combination of aerobic ammonium oxidation, anammox and heterotrophic sulfate reduction processes.     

硬质聚氨酯泡沫和组合聚醚中消耗臭氧层物质的便携式GC-MS测定方法

建立了便携式顶空/气相色谱-质谱法测定硬质聚氨酯泡沫和组合聚醚中一氟三氯甲烷（CFC-11）、二氟二氯甲烷（CFC-12）、二氟一氯甲烷（HCFC-22）及一氟二氯乙烷（HCFC-141b）的定性分析方法，系统考察了色谱柱、顶空体系、顶空温度和顶空时间对测定结果的影响。结果表明，DB-WAX色谱柱对目标物质的分离效果最好，顶空温度为50℃、顶空时间为10 min条件下，目标物质的检测灵敏度最高。在优化条件下，硬质聚氨酯泡沫取样体积为1 cm³时，4种目标物的方法检出限为0.6~0.8 μg；组合聚醚取样量为10 mg时，4种目标物的方法检出限为0.5~0.6 μg。该方法具有较高的灵敏度，定性准确，适用于实际样品的现场快速定性分析。     

Effect of pyrolysis and oxidation characteristics on lauric acid and stearic acid dust explosion hazards

The effect of pyrolysis and oxidation characteristics on the explosion sensitivity and severity parameters, including the minimum ignition energy MIE, minimum ignition temperature MIT, minimum explosion concentration MEC, maximum explosion pressure P_max, maximum rate of pressure rise (dP/dt)_max and deflagration index K_st, of lauric acid and stearic acid dust clouds was experimentally investigated. A synchronous thermal analyser was used to test the particle thermal characteristics. The functional test apparatuses including the 1.2 L Hartmann-tube apparatus, modified Godbert-Greenwald furnace, and 20 L explosion apparatus were used to test the explosion parameters. The results indicated that the rapid and slow weight loss processes of lauric acid dust followed a one-dimensional diffusion model (D1 model) and a 1.5 order chemical reaction model (F1.5 model), respectively. In addition, the rapid and slow weight loss processes of stearic acid followed a 1.5 order chemical reaction model (F1.5 model) and a three-dimensional diffusion model (D3 model), respectively, and the corresponding average apparent activation energy E and pre-exponential factor A were larger than those of lauric acid. The stearic acid dust explosion had higher values of MIE and MIT, which were mainly dependent on the higher pyrolysis and oxidation temperatures and the larger apparent activation energy E determining the slower rate of chemical bond breakage during pyrolysis and oxidation. In contrast, the lauric acid dust explosion had a higher MEC related to a smaller pre-exponential factor A with a lower amount of released reaction heat and a lower heat release rate during pyrolysis and oxidation. Additionally, due to the competition regime of the higher oxidation reaction heat release and greater consumption of oxygen during explosion, the explosion pressure P_m of the stearic acid dust was larger in low concentration ranges and decayed to an even smaller pressure than with lauric acid when the concentration exceeded 500 g/m³. The rate of explosion pressure rise (dP/dt)_m of the stearic acid dust was always larger in the experimental concentration range. The stearic acid dust explosion possessed a higher P_max, (dP/dt)_max and K_st mainly because of a larger pre-exponential factor A related to more active sites participating in the pyrolysis and oxidation reaction. Consequently, the active chemical reaction occurred more violently, and the temperature and overpressure rose faster, indicating a higher explosion hazard class for stearic acid dust.     

钙钛矿型催化剂催化湿式氧化处理煤气化废水纳滤浓缩液

采用溶胶-凝胶法制备了Mn掺杂钙钛矿型催化剂LaFexMn1-xO3，并以其为催化剂催化湿式双氧水氧化处理煤气化废水纳滤浓缩液。采用XRD，SEM，FTIR技术对催化剂进行了表征。表征结果显示：制备的催化剂均具有标准的钙钛矿型结构，其中，LaFe0.9Mn0.1O3的结构稳定，比表面积大。实验结果表明：制备的催化剂中LaFe0.9Mn0.1O3的催化活性最高，且稳定性好，连续使用5次后催化活性未见明显减弱；在H2O2投加量3.0 g/L、n（H2O2）∶n（LaFe0.9Mn0.1O3）=12∶1、反应温度160 ℃、反应压力1 MPa、浓缩液pH 3、反应时间60 min的最优条件下，COD、UV254和TOC的去除率分别达到80.9%、95.2%和68.0%，BOD5/COD由0.02提升至0.40，可生化性大幅提高。     

微波强化CWPO工艺CuO_x-CeO_2/GAC催化剂的制备及其对二甲亚砜的降解

以颗粒活性炭(GAC)为载体、铜为活性组分、铈为助剂组分、草酸钠为沉淀剂,采用浸渍焙烧法制得CuO_x-CeO_2/GAC催化剂。以H_2O_2为氧化剂,微波强化催化湿式过氧化氢氧化(CWPO)处理二甲亚砜(DMSO)初始质量浓度为1 000 mg/L的废水,处理3 min后DMSO去除率达93.8%。催化剂第7次使用时DMSO去除率仍保持在75%以上。初始废水pH在3~9范围内,DMSO去除率均在85%以上。助剂Ce的加入提高了催化剂表面活性组分的分散性和稳定性,使催化剂的活性稳定性和使用寿命显著提高。     

臭氧氧化—湿式钙法吸收工艺对烟气的同时脱硫脱硝

采用臭氧氧化—湿式钙法吸收工艺对模拟烟气进行同时脱硫脱硝处理。O₃于150 ℃下具有较高的热稳定性,可将NO氧化为高价态氮氧化物,且NO氧化率随n（O₃）∶n（NO）的增大而逐渐提高。烟气中SO₂和H₂O的存在对NO氧化率的影响不大。O₃对SO₂的氧化率较低,约为5%。3%（w）石灰石浆液对SO₂的吸收率接近100%,NO_x吸收率随n（O₃）∶n（NO）的增大而逐渐提高,当n（O₃）∶n（NO）为1.6时NO_x吸收率可达约65%。SO₂能促进吸收液对NO_x的脱除。石灰石浆液中加入0.2%（w）的（NH₄）₂SO₃或Na₂SO₃后NO_x吸收率可达约85%或82%,且吸收率随添加剂加入量的增加而提高,添加（NH₄）₂SO₃的NO_x吸收率略高于添加Na₂SO₃。     

三维电极电Fenton氧化法处理染料废水

采用三维电极电Fenton氧化法处理实际染料废水,探究了染料废水处理效果的影响因素。实验结果表明：以钌铱镀层钛电极为阳极、不锈钢板为阴极、粉末活性炭为颗粒电极,在粉末活性炭投加量为2.0 g/L、电流密度为0.5 mA/mm²、极板间距为3 cm、pH为2.0、硫酸亚铁投加量为0.50 g/L的最优工艺条件下,反应2 h后COD、TOC、氨氮、色度的去除率达到最大,分别为62.80%、41.15%、42.48%和95.00%;粉末活性炭作为颗粒电极可使染料废水COD去除率提高18个百分点;重复使用10次的处理效果与第2次基本持平。     

衡阳市区和衡山背景站臭氧浓度变化规律的对比分析

选取衡阳市区和衡山背景站臭氧自动监测数据,分析两地的臭氧污染特征。对空气质量的优良率情况、臭氧作为首要污染物的变化情况、臭氧浓度的日变化特征、典型时段的浓度变化特征、臭氧浓度的月际变化特征和臭氧与PM_(2.5)的关联情况等进行了分析。结果表明,多云及阴雨天气时,衡阳市区的臭氧浓度日变化幅度大于衡山背景站。夏季,衡阳市区和衡山背景站的臭氧浓度的日变化特征规律差异较大,臭氧浓度分布比较分散,前者为典型的单峰形,后者则波动平缓。冬季,日变化幅度不大,但衡阳市区的臭氧浓度明显低于衡山背景站。衡山背景站和衡阳市区的臭氧基本同步变化,但日均值高于衡阳市区。     

北京市城区挥发性有机物污染特征及其对臭氧影响分析

对2020年4月—2021年3月北京市建成区挥发性有机物（VOCs）的化学特征、污染来源及其对臭氧（O₃）污染的影响进行了研究。结果显示：O₃日最大8 h滑动平均值在臭氧季（4—9月）均值为134 μg/m³，是非臭氧季（10月至次年3月）均值（59.6 μg/m³）的2.2倍。臭氧季VOCs体积浓度均值为14.3×10^-9，明显低于非臭氧季（21.1×10^-9），可能与光化学反应速率和VOCs来源的季节性差异有关。臭氧生成潜势（OFP）贡献率排名前10位的物种在臭氧季和非臭氧季相似，均包括间/对-二甲苯、甲苯、乙烯、邻二甲苯、异戊烷、正丁烷、丙烯、反式-2-丁烯和1，2，4-三甲基苯，但排名有所差异，燃煤源特征明显的乙烯等物种在非臭氧季上升明显，与溶剂使用、油气挥发相关的间/对二甲苯、甲苯、异戊烷和正丁烷等物种在臭氧季上升明显。甲苯/苯的值和异戊烷/正戊烷的值在臭氧季明显高于非臭氧季，反映出机动车排放和油气挥发等在臭氧季影响突出，非臭氧季是燃煤影响显著。基于正交矩阵因子分解模型（PMF），臭氧季解析出机动车尾气排放（40.9%）、溶剂使用（20%）、油气挥发（16.4%）、工业排放（17.6%）和植物排放（5.1%）等5种污染源；非臭氧季解析出机动车尾气（38.9%）、燃烧源（26.3%）、工业排放（17.8%）和溶剂使用（17%）等4种污染源。