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1.
以经预处理的烟气脱硫石膏为原料, 分别以氯化铜、 硫酸铜和硝酸铜为添加剂, 采用水热法制备了脱硫石膏晶须; 通过傅里叶变换红外光谱(FTIR)、 X射线光电子能谱(XPS)和X射线衍射(XRD)等对晶须进行了表征; 并探讨了不同阴离子及其作用下的Cu 2+在晶体结晶过程中的作用机理. 结果表明, Cu 2+存在条件下阴离子对脱硫石膏的溶解特性和晶须的结晶形貌均有显著影响, 且其作用强于Cu 2+, 并会影响Cu 2+在晶须表面的吸附状态. N O 3 - 可促进脱硫石膏的溶解, Cl -次之, 而S O 4 2 - 则阻碍了脱硫石膏的溶解. 在Cl -作用下, 晶须样品直径均匀, 长径比较大, 在S O 4 2 - 作用下晶须样品中颗粒状产物含量较多, 而在N O 3 - 作用下晶须样品粗化. 在不同阴离子作用下Cu 2+化学吸附的程度不同, 导致样品表面S O 4 2 - 的反对称伸缩振动吸收峰向低波数方向漂移并发生窄化; 并导致晶须表面氧元素电子结合能的减小幅度及Cu—O结合能的大小出现差异, 其在N O 3 - 作用下最大, S O 4 2 - 作用下次之, Cl -作用下最弱.  相似文献   

2.
以铁基离子液体(Fe-IL) /聚乙二醇二甲醚(NHD)为脱硫体系, 通过静态吸收反应装置研究了共溶体系吸收氧化H2S的动力学过程. 结果表明, 纯Fe-IL脱硫体系的动力学方程可表示为r=54.62exp(-11720/RT c H 2 S ·cFe(Ⅲ), Fe-IL/NHD吸收氧化H2S属于快速拟一级反应, 复配NHD后, 对Fe(Ⅲ)的反应级数随NHD复配比的增大而增大, 提高温度和NHD的复配比可强化传质过程, 提高脱硫过程的反应速率.  相似文献   

3.
利用水热法制备了一种可在纯水体系中连续“OFF-ON-OFF”荧光识别Fe 3+和H2P O 4 - 的B, N, S共掺杂的石墨烯量子点探针材料(BNS-GQDs), 并对其形貌和结构进行了表征, 结果表明, BNS-GQDs粒径分布均匀, 平均粒径为4 nm, 具有类似石墨烯的结构, 且成功掺杂了B, N, S原子. 光谱表征结果表明, 其在纯水体系中可以实现对Fe 3+的荧光猝灭识别; 同时, BNS-GQDs+Fe 3+体系能够专一性地荧光增强识别H2P O 4 - . 识别机理研究表明, BNS-GQDs可与Fe 3+通过静电作用形成配合物并向Fe 3+转移电子, 从而引起荧光猝灭; H2P O 4 - 可从上述配合物中置换出Fe 3+, 引起体系荧光恢复. BNS-GQDs识别Fe 3+和H2P O 4 - 具有较好的可逆性, 可应用于Hela细胞和实际水样中Fe 3+和H2P O 4 - 的检测.  相似文献   

4.
对反夹心体系[M(AIP)](C5H5)[M'(AIP)](M, M'=V, Cr, Mn; AIP=1-氨基-3-亚氨基-1-丙烯脱氢阴离子, C3N2 H 5 - )进行了理论研究. 结果表明, V-Cr体系存在五重态、 七重态和九重态的多稳态构型; Cr-Mn体系存在三重态、 五重态和七重态的多稳态构型. 在上述体系中, 金属原子的价态会随着异构体自旋态的不同而有所改变, V, Cr和Mn原子均可出现+1和+2价. 由于V-Cr和Cr-Mn体系一些双稳态构型间的自旋交叉能垒较低, 这使自旋交叉和价态互变过程变得可能. 解离能的研究结果表明, V-Cr体系解离能较大, 而Cr-Mn体系解离能略小, 两类体系均较稳定. [M(AIP)](C5H5)[M'(AIP)]存在自旋交叉和价态互变的可能性, 并具有较好的解离稳定性, 具有成为分子磁性材料的潜能.  相似文献   

5.
采用介质阻挡放电等离子体法合成了氧原子掺杂的具有氮空穴的石墨相氮化碳催化剂(g-C3N4), 并对催化剂的结构和形貌进行了表征分析. 结果表明, 等离子体处理没有改变催化剂的形貌, 并同时将氮空穴和氧原子引入了g-C3N4的晶格. 在可见光条件下, 制备的共掺杂g-C3N4催化剂的铵离子产率高达5.9 mg·L -1·h -1· g cat - 1 , 分别是具有氮空穴的g-C3N4和纯g-C3N4的2.2倍和20倍, 同时还表现出优异的催化稳定性. 密度泛函理论计算结果显示, 与具有氮空穴的g-C3N4相比, 氧原子的引入能提高氮空穴对反应物氮气分子的活化能力, 提高光催化固氮性能.  相似文献   

6.
利用十二烷基苯磺酸钠(SDBS)为模板剂, 研究了SDBS的浓度、 Ca 2+和Si O 3 2 - 离子的浓度、 是否搅拌和反应时间等条件对水合硅酸钙(CSH)形貌特征和分散性能的影响, 并提出了不同CSH球壳形貌特征的形成机理. 结果显示, 溶液中Na2SiO3·9H2O浓度增大、 SDBS浓度增大及反应时间延长均会使CSH的结晶度变好, 聚合度增大, Q 2结构的相对含量增加, 其中Na2SiO3·9H2O和SDBS浓度是主要控制因素. SDBS在溶液中形成的球形胶束具有极强的模板作用, 能有效改变CSH的结晶生长方式; 通过调节SDBS浓度和钙硅比例, 并适当延长CSH的生长时间, 能够获得球壳完整、 分散性好且稳定性强的CSH.  相似文献   

7.
张剑辉  张宁  林昭  吴水平 《分析测试学报》2019,38(10):1171-1178
室内燃烧源排放颗粒物及其多环芳烃(PAHs)的粒径分布是定量评估室内人群呼吸暴露风险的重要参数之一。该研究在再悬浮箱内模拟燃香、燃蚊香、艾灸和吸烟等过程,采用MOUDI采样器采集和分析颗粒物中17种PAHs;同时,采用颗粒物计数器,在实际房间中模拟艾灸和吸烟过程,得到室内颗粒物数浓度的衰减曲线。结果表明,燃烧源烟雾颗粒的排放因子为3.68~22.46 mg/g,颗粒质量粒径呈单峰型,峰值为0.25~0.44μm;US EPA 16种优控PAHs的排放因子为10.52~91.30μg/g,艾绒燃烧排放PAHs的粒径峰值为0.44~1.0μm,略大于其它燃烧源;1μm颗粒中PAHs的BaP等效毒性当量(BaP_(TEQ))的贡献占比为85%~98%。来源特征比值的研究显示,艾灸、燃香和吸烟释放的PAHs均归属于生物质燃烧类别。实际室内监测显示,在艾绒和香烟燃烧后室内颗粒物数浓度快速上升,在燃尽时达到峰值,而后在4 h内呈指数规律衰减,且0.3μm的细颗粒衰减最快。  相似文献   

8.
将一维粒子(碳纳米管, CNTs; 碳纳米纤维, CF)加入聚乙烯醇(PVA)水溶液中, 考察碳粒子表面含氧官能团含量(羟值)、 长径比、 温度及PVA本体溶液浓度等对复合体系流变行为的影响. 结果显示, 复合溶液的黏度(η)随CNTs用量(φCNTs)先增大后降低, 然后继续增大, 呈“N”形变化趋势, 出现两个拐点(φ1φ2). 在φ1附近, CNTs主要起物理交联点作用, 体系η增加; 在φ2附近, CNTs对PVA分子间氢键作用破坏最为严重, 体系η低于纯PVA溶液, 表明不同羟值CNTs仅改变其用量即可使PVA水溶液增黏或降黏. 随着羟值增大, CNTs与PVA大分子间相互作用加强, φ1φ2减小, φ2对应的η下降, 降黏效果显著. CNTs的加入使PVA水合数下降, 羟值大的CNTs可与PVA上更多的羟基形成氢键作用, 水合数更低. 随着φCNTs增大, 复合体系黏流活化能增大. CNTs对不同质量分数PVA水溶液的η具有类似的调控作用, 但调控幅度有差异. 相同羟值、 不同长径比的CNTs对PVA水溶液的黏度调控均呈“N”形变化, 长径比小的CNTs复合体系, φ1φ2较大. 长径比相近但直径较大的CF复合体系表现出更低的φ1φ2.  相似文献   

9.
非常规离子是指伴随离子液体(ILs)不断创制而出现的离子, 其最大特点是具有可设计性. 当ILs处于无限稀释状态时, 最为重要的传递性质是单个离子的无限稀释摩尔电导率(λB), 其能反映离子的溶剂化作用, 是联系不同传递性质的重要纽带. 建立了基团贡献法预测咪唑类阳离子和季铵类阳离子的无限稀释摩尔电导率模型(λB-GCM), 获得了咪唑中心离子[Im]、 烷基铵[N]、 甲基[—CH3]、 亚甲基[—CH2—]、 环氢[ring-H]、 醚基 [—O—]和羟基[—OH]等基团对无限稀释摩尔电导率的贡献值. 建立的λB-GCM不仅能反映不同基团对无限稀释摩尔电导率的影响, 还能体现温度对无限稀释摩尔电导率的影响. 研究结果表明, GCM预测的lnλB含有超过70%的数据点的绝对相对偏差小于2%, 绝对相对偏差超过5%的数据点不足1%, 总的平均绝对相对偏差为1.57%, 说明采用基团贡献法预测非常规阳离子无限稀释摩尔电导率是一种简单可靠的方法.  相似文献   

10.
利用失重法、 电化学阻抗谱法、 环境扫描电镜观测和接触角测试等研究了3-丁基-5,5-二甲基海因咪唑季铵盐(BDMHI)对HCl溶液中Q235钢的缓蚀性能和其在Q235钢表面的吸附行为. 结果显示, 缓蚀效率随BDMHI浓度的增加而增加, 随温度的升高而降低, 最高缓蚀效率为91.62%; 在25~35 ℃温度范围内, BDMHI质量浓度为1.0 g/L时, 缓蚀效率达80%以上. 测定了BDMHI在Q235钢表面吸附的吸附吉布斯自由能(ΔGads0)和吸附热(ΔHads0). 结果表明, BDMHI在Q235钢表面的吸附为放热反应, 符合Langmuir等温式, 是包含物理吸附和化学吸附的混合吸附. 运用量子化学方法探究了BDMHI的缓蚀机理.  相似文献   

11.
A sedimentary record of the 16 polycyclic aromatic hydrocarbon (PAH) pollutants from Dongping Lake, north China, is presented in this study. The influence of regional energy structure changes for 2–6-ring PAHs was investigated, in order to assess their sources and the impact of socioeconomic developments on the observed changes in concentration over time. The concentration of the ΣPAH16 ranged from 77.6 to 628.0 ng/g. Prior to the 1970s, the relatively low concentration of ΣPAH16 and the average presence of 44.4% 2,3-ring PAHs indicated that pyrogenic combustion from grass, wood, and coal was the main source of PAHs. The rapid increase in the concentration of 2,3-ring PAHs between the 1970s and 2006 was attributed to the growth of the urban population and the coal consumption, following the implementation of the Reform and Open Policy in 1978. The source apportionment, which was assessed using a positive matrix factorization model, revealed that coal combustion was the most important regional source of PAHs pollution (>51.0%). The PAHs were mainly transported to the site from the surrounding regions by atmospheric deposition rather than direct discharge.  相似文献   

12.
袁继委  王金成  徐威力  徐方曦  卢宪波 《色谱》2020,38(11):1308-1315
多环芳烃和酞酸酯是国际公认的优控污染物,因此准确快速地测定水中多环芳烃和酞酸酯非常重要。凝固漂浮有机液滴-分散液液微萃取(DLLME-SFO)是一种简便、快速、环境友好、灵敏度高的样品前处理技术。采用DLLME-SFO同时测定地表水中多环芳烃和酞酸酯的分析方法鲜有报道。该文采用凝固漂浮有机液滴-分散液液微萃取富集技术,结合高效液相色谱紫外/荧光法,建立了同时测定地表水中16种多环芳烃和6种酞酸酯的分析方法。考察优化了影响萃取效率的主要因素,包括萃取剂的种类和用量、分散剂的种类和用量、萃取时间和离子强度等。优化后的萃取实验条件为:5.0 mL水样,10 μL十二醇为萃取溶剂,500 μL甲醇为分散溶剂,涡旋振荡时间2 min,氯化钠用量0.2 g。目标化合物经多环芳烃专用色谱柱(SUPELCOSILTM LC-PAH,150 mm×4.6 mm,5 μm)结合乙腈-水梯度洗脱分离,16种多环芳烃除苊烯外采用荧光检测,苊烯和6种酞酸酯采用紫外检测,外标法定量。结果表明,22种目标化合物的基质加标回收率为60.2%~113.5%,相对标准偏差为1.9%~14.3%;多环芳烃和酞酸酯的检出限分别为0.002~0.07 μg/L和0.2~2.2 μg/L;多环芳烃和酞酸酯的定量限分别为0.006~0.23 μg/L和0.8~7.4 μg/L。该方法简便、快速,环境友好,灵敏度高,可用于地表水中多环芳烃和酞酸酯的快速分析检测。  相似文献   

13.
优化了土壤中16种优控多环芳烃( PAHs)的分析方法,建立了一套完备的质量控制体系,解决了PAHs分析中常见的技术难点,如苯并(a)芘(BaP)回收率低,基质复杂的样品净化效果不理想,萘(Nap)和菲(Phe)挥发损失和环境本底影响等.样品经加速溶剂提取(ASE),固相萃取(SPE)净化,逐级减压浓缩,气相色谱质谱( GC - MS)测定,并以氘代苯并a芘(BaP - d12)作回收率指示物.实验比较了3种正相SPE吸附剂的效果,发现弗罗里硅土对BaP存在明显的降解现象,BaP的定量应使用同位素稀释法,以降低其分析不确定度;氧化铝对PAHs的吸附性过强,不利于样品净化;硅胶最为理想.PAHs的仪器检出限为0.26~5.7 pg,方法检出限为0.067 ~0.97 ng/g(干重),土壤基质加标回收率为71%~ 122%,相对标准偏差为1.6%~8.3%.将该法用于7个电子废物焚烧区域农田土壤样品的测定,PAHs含量在28~ 283 ng/g(干重)之间,样品中BaP-d12的回收率为90%~124%,各项质控指标符合检测要求.  相似文献   

14.
Two freshwater sediments certified reference materials (CRMs) for 16 polycyclic aromatic hydrocarbons (PAHs) have been developed by the Institute for Environmental Reference Materials (IERM) of Ministry of Environmental Protection (MEP) in China. The methodology for preparing the CRMs of PAHs in sediments is described in this paper. The collected natural sediment samples were air-dried, ground, homogenised, packed, sterilised and tested on stability and homogeneity. Homogeneity results showed that the between-unit variation was confirmed to be below 4.5% for each compound. Stability was assessed after storage of samples for 16 months at temperature less than 30°C and in shade. The certification of the natural sediment matrix CRMs for PAHs was based on the agreement of results using different analytical techniques including gas chromatography/mass spectrometry (GC/MS) and reversed-phase liquid chromatography (LC) by no less than eight collaborating laboratories including IERM. Results of the homogeneity showed that the calculated ubb′ was 0.9–2.5% for environmental river standard-4 (ERS-4) and 9–2.3% for environmental lake standard-1 (ELS-1), whereas stability results of total 16 PAHs indicated that the calculated urel,lts was 4.2% for ERS-4 and 2.2% for ELS-1. Certified values of 16 PAHs in ERS-4 varied from 8.5 to 167 μg/kg and ranged from 0.036 to 2.8 mg/kg in ELS-1.The good comparability, together with the independent confirmation of the assigned mass fraction by using different methods, confirmed that the CRMs are suitable for the method validation and quality control in soil or sediments analysis.  相似文献   

15.
建立了快速溶剂萃取(ASE)-气相色谱-串联质谱(GC-MS/MS)分析海洋沉积物中16种多环芳烃(PAHs)的分析方法。样品由正己烷-丙酮(1∶1,v/v)溶液萃取,经无水硫酸钠脱水、氮吹浓缩后,采用硅胶固相萃取小柱进行净化,然后经HP-5MS色谱柱(30 m×0.25 mm×0.25 μm)分离,在电子轰击电离源下以多反应监测(MRM)模式进行检测,内标法定量。分析结果表明,16种PAHs在0.01~1.00 mg/L范围内线性关系良好,相关系数(R)大于0.997;目标物的加标回收率为75.8%~97.8%;日内与日间精密度(RSD)均小于10%。当取样量为20.0 g时,16种PAHs的方法检出限为0.048~0.234 μg/kg。该法快速、准确、稳定,能够满足海洋沉积物中痕量PAHs的测定。  相似文献   

16.
Increased attention has been given to the fate of pollutants such as polycyclic aromatic hydrocarbons (PAHs) introduced to the wastewater treatment plants.Dissolved and adsorbed PAHs were detected in the centralized wastewater treatment plant of a chemical industry zone in Zhejiang Province,China.The most abundant PAHs were the low molecular weight PAHs (e.g.,Acy,Ace,Flu and Phe),accounting for more than 80% of the total 16 PAHs in each treatment stage.Phase partitioning suggested that the removal of PAHs in every treatment stage was influenced greater by the sorption of particles or microorganisms.The removal efficiencies of individual PAHs ranged between 4% and 87% in the primary sedimentation stage,between 1% and 42% in anaerobic hydrolysis stage,between <1% and 70% in aerobic bio-process stage,between 1.5% and 80% in high-density clarifier stage,and between 44% and 97% in the whole treatment process.Mass balance calculations in primary stage showed significant losses for low molecular weight PAHs and relatively good agreements for high molecular weight PAHs as well as in anaerobic hydrolysis,high-density clarifier stage and sludge stream for most PAHs.Great gains of 60%-150% were obtained for high molecular weight PAHs in aerobic bio-process stage due to biosorption and bioaccumulation.Our investigations found that PAHs entering the wastewater treatment plant (WWTP) could be derived from the dyeing chemical processes as the byproducts,and the contribution supported by the largest dyeing chemical group was up to 48%.  相似文献   

17.
建立农用土壤中16种多环芳烃的改进QuEChERS快速提取净化方法及气相色谱-质谱检测方法,并通过对西安市周边农用土壤样品的分析,调查土壤中多环芳烃的污染情况.土壤样品用KOH饱和的甲醇碱化处理后,用丙酮-正已烷(1+1)为提取溶剂,涡旋混匀后超声提取,提取液按改进QuEChERS方法加入无水MgSO4、硅胶及正丙基乙二胺(PSA)进行净化,检测时选用DB -5 MS(30m×0.25 mm×0.25 μm)色谱柱分离,EI电离源及离子监测模式检测,16种多环芳烃的测定低限0.7~3.2μg/kg,加标回收率79.8% ~ 109.6%,相对标准偏差均低于9.4%.检测的农用土壤样品中均检出有不同程度的多环芳烃残留,约16.7%的土壤样品为轻度污染.  相似文献   

18.
建立了热熔胶中16种多环芳烃( PAHs)的多次溶剂萃取-气相色谱/串联质谱测定方法。详细研究了样品的萃取条件、净化条件和气相色谱/串联质谱测定条件,并与气相色谱-质谱法进行了对比。样品以10 mL正己烷为萃取溶剂,于60℃超声萃取20 min,萃取液依次经冷冻后离心、二甲基亚砜萃取2次、正己烷反萃取2次进行净化,得到的净化液以气相色谱/串联质谱法多反应监测( MRM)模式进行检测。本方法的线性相关系数( R2)均大于0.9969,检出限为1.0~10μg/kg,精密度小于6.3%,16种PAHs的加标回收率为80.4%~117.6%。考察了串联质谱检测的基质效应,发现基质效应不明显。本方法检出限优于气相色谱-质谱法(23~94μg/kg),并能增加定性和定量分析的准确性。本方法灵敏、准确可靠,满足热熔胶中PAHs测试要求。  相似文献   

19.
烟气中多环芳烃吸附脱除的研究   总被引:7,自引:0,他引:7  
针对热电厂烟气中排放的多环芳烃(PAHs)污染物,在实验室规模上研究了六种吸附剂对烟气中典型的PAHs, 如萘(Nap)、芴(Flu)、菲(Phe)的吸附脱除行为。考察了吸附剂结构特征与Nap,Flu,Phe高温脱除的相关性,并对煤质活性炭(AC-1)在160 ℃~200 ℃下的吸附等温线进行了研究。结果表明,吸附剂对PAHs的吸附能力与其结构参数中BET表面积和微孔体积具有紧密相关性,而与中孔体积没有明显关系;活性炭表现出很好的脱除烟气中PAHs的作用;吸附剂对PAHs的吸附能力随着PAHs的质量分数增大而增大,随吸附温度的增加而减小;随着PAHs的碳原子数和芳环数增加,其在吸附剂上的吸附能力也增强。  相似文献   

20.
Airborne particulate matter contains numerous organic species, including several polycyclic aromatic hydrocarbons (PAHs) that are known or suspected carcinogens. Existing methods for measuring airborne PAHs are complex and costly, primarily because they are designed to collect both gas-phase and particle-phase PAH constituents. Here, we report an assay for measuring particle-bound PAHs in archived filters from the network of U.S. monitoring stations for particles less than 2.5 microm in diameter (PM2.5), without the need for deploying specialized samplers. PAHs are extracted from Teflon filters with dichloromethane, concentrated, and measured at trace levels using gas chromatography-mass spectrometry. Although PAHs with 3-6 aromatic rings can be assayed, results are only unambiguously accurate for compounds with 5- or 6-rings, due to variable vaporization losses of the more volatile 3- and 4-ring compounds during sampling and/or storage. The method was evaluated for sensitivity, recovery, precision, and agreement of paired air samples, using PM2.5 samplers locally in Chapel Hill, NC. Additionally, three sets of archived samples were analyzed from a study of PM2.5 in the Czech Republic. Levels of some 4-ring and all 5- and 6-ring PAHs in both the local and Czech samples were consistent with published results from investigations employing PAH-specific air samplers. This work strongly suggests that assessment of particle-bound 5- and 6-ring PAHs from archived PM2.5 filters is quantitatively robust. The assay may also be useful for selected 4-ring compounds, notably chrysene and benzo(a)anthracene, if PM2.5 filters are stored under refrigeration.  相似文献   

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