重庆市VOCs浓度特征和关键活性组分

2015年8月22日至9月26日利用在线GC-MS/FID和离线Canister-GCMS/FID采样并分析了重庆城区7个监测点位的96种VOCs,结果表明,城区总挥发性有机化合物平均体积分数为42.43×10-9,且空间分布特征为"中心城区高,周边低"。重庆本地高乙烷、高乙烯和高乙炔浓度呈区域污染现象,且城市监测点位主要受交通源、工业排放和溶剂挥发的影响,缙云山站则主要以生物源排放为主。重庆市城区气团的OH自由基反应速率平均值为8.86×10-12cm3/(mol·s),最大反应增量活性平均值为4.08 mol/mol,与乙烯相当,说明本地大气化学反应活性较强。重庆城区对OH自由基损耗速率贡献最大的组分是烯/炔烃(35%),对臭氧生成潜势贡献最大的组分是芳香烃(39%)。乙醛、乙烯和甲苯等物质是VOCs的关键活性组分。     

Inter-comparisons of VOC oxidation mechanisms based on box model: A focus on OH reactivity

Volatile organic compounds (VOCs) oxidation processes play a very important role in atmospheric chemistry, and the chemical reactions are expressed in various manners in chemical mechanisms. To gain an improved understanding of VOCs evolution during oxidation processes and evaluate the discrepancies of VOCs oxidation schemes among different mechanisms, we used the total VOC reactivity as a diagnostic and evaluated tool to explore the differences for six widely used chemical mechanisms. We compared the total VOC reactivity evolution under high-NO_x conditions for several sets of precursors, including n-pentane, toluene, ethene, isoprene and a mixture of 57 Photochemical Assessment Monitoring Stations (PAMS) species in a 0-D photochemical box model. Inter-comparison of total VOC reactivity of individual precursor simulations showed discrepancies to different extent of the oxidation schemes among the studied mechanisms, which are mainly attributed to the different lumping approaches for organic species. The PAMS simulation showed smaller discrepancy than individual precursor cases in terms of total VOC reactivity. SAPRC07 and RACM2 performances are found to better match the MCM for simulation of total VOC reactivity. Evidences suggest that the performance in simulating secondary organic products, OH concentrations and NO_x concentrations are related to the OH reactivity discrepancies among various chemical mechanisms. Information in this study can be used in selection of chemical mechanisms to better model OH reactivity in different environments. The results in this study also provide directions to further improve the ability in modelling total VOC reactivity with the chemical mechanisms.     

湿式烟气脱硫中石灰石反应活性

在分析选自国内不同地区天然石灰石化学组成的基础上,对具有不同CaCO₃含量的石灰石进行了孔结构表征,并采用硫酸滴定法和气液吸收法,考察了石灰石的脱硫反应活性.结果表明,石灰石的比表面都在1.8m²/g左右.投加硫酸溶液到石灰石浆液后,浆液pH迅速下降到最低值,随后回升.随着石灰石CaCO₃含量提高或粒径减小,pH回升速率增大.石灰石CaCO₃含量愈高或粒径愈小,气液吸收反应器出口检测到SO₂之前所经历的反应时间愈长,出口SO₂浓度上升愈快.硫酸滴定法与气液吸收法测得的石灰石反应活性具有相同的规律.与颗粒比表面相比,CaCO₃含量对脱硫反应活性的影响更大.当粒径较大时(<300～360目),粒径对石灰石脱硫反应活性的影响较大,反之较小.     

成都市春季O3污染特征及关键前体物识别

2018年4月在成都市区开展了臭氧（O₃）以及挥发性有机物（VOCs）等污染物的在线监测,搜集了成都市国控站点数据,对O₃污染特征进行分析,利用增量反应活性（RIR）的方法识别了O₃生成的关键前体物.结果表明,成都市2016~2018年的4月的O₃污染程度逐年加重,O₃日变化呈现单峰态;当温度大于20℃,风速处于1~1.5 m·s^-1,相对湿度小于65%时,O₃超标率在4月会高于80%;2018年4月,O₃超标天的NO_x日均浓度是非超标天的2.3倍,VOCs日均浓度是非超标天的2倍;人为源VOCs、CO、天然源VOCs和NO_x这4大类前体物在臭氧超标天对O₃的RIR值依次为2.4、0.87、0.06和-2.6,说明O₃处于VOCs控制区;从VOCs物种来看,间/对-二甲苯、乙烯、反-2-丁烯、丙烯、邻-二甲苯、甲苯、丙酮、异戊二烯、异戊烷和正丁烷等为O₃生成的关键活性VOCs物种.     

Effects of atamp-charging coke making on strength and high temperature thermal properties of coke

The stamp-charging coke making process has some advantages of improving the operation environment, decreasing fugitive emission, higher gas collection efficiency as well as less environmental pollution. This article describes the different structure strength and high temperature thermal properties of 4 different types of coke manufactured using a conventional coking process and the stamp-charging coke making process. The 4 kinds of cokes were prepared from the mixture of five feed coals blended by the petrography blending method. The results showed that the structure strength indices of coke prepared using the stamp-charging coke method increase sharply. In contrast with conventional coking process, the stamp-charging process improved the coke strength after reaction but had little impact on the coke reactivity index.     

脱硫灰中杂质对石灰石脱硫活性的影响

研究脱硫灰中杂质对石灰石脱硫活性的影响具有重要意义,采用烟气湿法脱硫用石灰石粉反应速率的测定方法,使用瑞士万通902智能电位滴定仪,分析了SiO2、Al2O3、Fe2O3、CaSO3与MgO等脱硫灰中5种杂质对石灰石脱硫活性的影响.结果表明,在实验浓度范围内,SiO2、Al2O3、CaSO3的加入在一定程度上促进了石灰石的溶解,而MgO、Fe2O3的加入在一定程度上抑制了石灰石的溶解.将脱硫灰与石灰石掺合作脱硫剂时,要综合考虑这5种杂质对石灰石溶出的影响,选择适宜的脱硫灰和石灰石掺合比.     

Regioselective oxidation of tetracycline by permanganate through alternating susceptible moiety and increasing electron donating ability

Permanganate has attracted much attention in wide range of chemistry and particularly in degradation of environmental pollutants.However,few studies have discussed the feature of regioselective reactivity of permanganate with specific moiety of the target compound.Herein,we studied the reaction between permanganate and tetracycline that is an emerging micropollutant with different species containing several electron-rich groups.The second-order rate constants increased from 6.0 to 9.0 and could ...     

杭州市城区挥发性有机物污染特征及反应活性

使用Summa罐在杭州市城区朝晖站点离线采样,利用GCMS分析122种挥发性有机物(VOCs).通过2018年5月至2019年4月连续1a的观测,结果发现,观测期间大气VOCs平均体积分数为(59.4±23.6)×10^-9,浓度高值出现在12月而低值出现在2月,含氧有机物(OVOC),尤其是醛酮类化合物是占比最高的组分,在夏季尤甚.朝晖站点VOCs浓度没有明显的周末效应,但节假日的VOCs浓度有明显下降.其大气VOCs浓度与空气质量指数(AQI)值呈现正相关性,首要污染物为PM_2.5时观测到的VOCs浓度最高.运用·OH消耗速率(L^·OH)和臭氧生成潜势(OFP)做大气反应活性评估,观测期间L^·OH均值为7.5 s^-1,OFP均值为152.1×10^-9,醛酮类化合物、芳烃和烯烃是活性最高的组分,该站点整体大气活性水平与2-甲基戊烷相当.观测期间甲苯/苯(T/B)均值为1.95,说明杭州市城区受到较明显的机动车排放影响.使用正定矩阵因子分析法(PMF)解析出...     

某石化企业三类成品油装载环节的有机污染物排放特征、环境影响及控制措施

石化行业的成品油装载环节是有机污染物的重点排放源,包括挥发性有机物(VOCs)和甲烷等。对我国某石化企业的汽油、航煤和柴油三类成品油在装载过程中外排的尾气进行了监测,并采用·OH损失速率和最大增量反应活性法,重点分析了装载过程中VOCs和甲烷的排放特征、大气反应活性及环境影响,并提出相关控制措施。结果表明,成品油装载环节外排的VOCs以烷烃为主。每吨成品油在装载过程中排放的VOCs强度达到2.2~36.4 g,其中汽油排放强度最高。丁烷、戊烷和己烷等C₄~C₆烃是主要烷烃组分;丙酮是含量最高含氧物质;丁烯、异戊二烯和戊烯是最主要的烯烃组分。这类VOCs具有较高大气光化学反应活性和臭氧生成潜势(OFP),大气活性与二甲苯活性相当。VOCs的OFP(即每克VOCs可产生的O₃质量)达到1.4~2.7 g·g⁻¹。航煤装载环节外排VOCs的反应活性与臭氧潜势高于汽油和柴油。装载环节外排VOCs的反应活性及臭氧生成潜势主要源于烷烃和烯烃组分,异戊烷、C₄~C₅烯烃和甲苯等是需优先控制的高活性物质。本研究可为石化企业从源头开展VOCs等有机污染物的精准管控提供参考。     

稳定化FeS纳米颗粒原位修复地下水中Cr(Ⅵ)的可行性

FeS纳米材料易团聚易氧化的特点,极大地限制了其工程应用.为此,选用羧甲基纤维素钠(CMC)、淀粉(ST)、瓜尔胶(GG)和海藻酸钠(SA)作为高聚物稳定剂,制得CMC-FeS、ST-FeS、GG-FeS和SA-FeS纳米材料,综合考察了4种改性FeS材料的稳定性、迁移能力及其对Cr(Ⅵ)的反应活性.结果 表明,4种高...