离子液体吸收废印刷线路板热拆解过程中挥发性有机物——基于COSMO-RS模型

模拟废印刷线路板（WPCB）的热拆解过程,分析热拆解过程中的挥发性有机物（VOCs）组分;利用真实溶剂似导体屏蔽（COSMO-RS）模型对浓度较高的污染物进行量子力学模拟,研究离子液体（ILs）组成单元对目标污染物溶解度的影响差异,分析溶解过程中主导分子间作用力类型,确定优选吸收剂;测定不同溶剂进行溶解性,验证模型适用性.结果表明：①乙酸乙酯和环戊酮是浓度较高的VOCs组分,在240和250℃时浓度分别为43.1,153mg/m³和105,252mg/m³,质量百分比总和分别为76.3%和67.3%.②高表面屏蔽电荷密度分布峰、长烷基链阴阳离子和亲电基团的存在可提高乙酸乙酯和环戊酮在ILs中的溶解度.双三氟甲磺酰基亚胺盐（NTf₂^-）类ILs是一类优良吸收剂.静电力和范德华力对溶解过程起主导作用.③COSMO-RS模型可定性和半定量用于预测乙酸乙酯和环戊酮的溶解度.     

Advanced molecular-fingerprinting analysis of dissolved organic sulfur by electrospray ionization-Fourier transform ion cyclotron resonance mass spectrometry using optimal spray solvent

Molecular level characterization of dissolved organic sulfur (DOS) by electrospray ionization-Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICR MS) is necessary for further understanding of the role of DOS in the environment. Here, ESI spray solvent, a key parameter for ion production during ESI process, was investigated for its effect on the molecular characterization of DOS by ESI-FTICR MS. 100% MeOH as spray solvent was found for the first time to remarkably enhance the ionization efficiency of the majority of CHOS-molecules in NOM, which facilitated a total of 1473 CHOS-molecular formulas with one sulfur atom to be detected. The number of CHOS-molecular formulas obtained using 100%MeOH as spray solvent increased notably over 740 in comparison with those using 50% MeOH aqueous solution (731) or 50% ACN aqueous solution (653). Moreover, due to the enhancement of ionization efficiency of DOS during ESI processes, the tandem mass spectra of the NOM CHOS-molecules could be easily obtained using 100% MeOH as spray solvent, which were hardly obtained using 50% MeOH aqueous solution as spray solvent. The results of the tandem mass spectra suggested the first discovery of organosulfates or sulfonic acids in Suwannee River NOM sample. A simple method based on 100% MeOH as ESI spray solvent for advanced molecular characterization of DOS by ESI-FTICR MS was proposed and applied, and the results revealed more molecular information of DOS in sea DOM samples.     

环烷酸脱油工艺的实验研究

以锦州化工二厂生产的２＃环烷酸为原料，采用减压蒸馏──初馏分皂化萃取脱油工艺，可制得中性油含量分别低于１０％和５％的一级品环烷酸．该工艺具有流程简单、物料消耗少、产品收率高等优点．通过实验，初步探讨了蒸馏真空度、氢氧化钠浓度及用量、乙醇用量、萃取剂用量等工艺条件对脱油效果及产品质量的影响。     

Efficient dechlorination of chlorinated solvent pollutants under UV irradiation by using the synthesized TiO2 nano-sheets in aqueous phase

Titanium dioxide(TiO2), which is the widely used photo-catalyst, has been synthesized by simple hydrothermal solution containing tetrabutyl titanate and hydrofluoric acid. The synthesized product has been applied to photo-degradation in aqueous phase of chlorinated solvents, namely tetrachloroethene(PCE), trichloroethene(TCE) and 1,1,1-trichloroethane(TCA). The photo-degradation results revealed that the degradation of these harmful chemicals was better in UV/synthesized TiO2 system compared to UV/commercial P25 system and UV only system. The photo-catalytic efficiency of the synthesized TiO2 was 1.4, 1.8 and 3.0 folds higher compared to the commercial P25 for TCA, TCE and PCE degradation, respectively. Moreover, using nitrobenzene(NB) as a probe of hydroxyl radical(.OH), the degradation rate was better over UV/synthesized TiO2, suggesting the high concentration of.OH generated in UV/synthesized TiO2system. In addition,.OH concentration was confirmed by the strong peak displayed in EPR analysis over UV/synthesized TiO2system. The characterization result using XRD and TEM showed that the synthesized TiO2 was in anatase form and consisted of well-defined sheet-shaped structures having a rectangular outline with a thickness of 4 nm, side length of 50 nm and width of 33 nm and a surface 90.3 m2/g. XPS analysis revealed that ≡Ti-F bond was formed on the surface of the synthesized TiO2. The above results on both photocatalytic activity and the surface analysis demonstrated the good applicability of the synthesized TiO2 nano-sheets for the remediation of chlorinated solvent contaminated groundwater.     

不同溶剂和反应温度对污泥热液化制取生物质油性质影响研究

选取4种溶剂(水、乙醇、正己烷、水-乙醇共溶济)作为污泥热液化制取生物质油的溶剂,分析溶剂种类和反应温度对热液化效果和生物质油性质的影响.结果表明:相同温度下,生物质油产率随溶剂种类变化趋势为:乙醇水-乙醇共溶剂正己烷水,最高产率为54.82%(乙醇溶剂,240℃).污泥有机物转化率随溶剂种类变化趋势为:水-乙醇共溶剂乙醇水正己烷,最高有机物转化率为96.40%(水-乙醇共溶剂,330℃).污泥经热液化处理后,碳、氢、氮、硫元素在生物质油中富集,氧含量下降,热值36 MJ·kg-1(乙醇、240℃除外).不同溶剂油成分差别较大,采用水或正己烷,产物主要是脂肪酸类、烷烃及部分酰胺和腈类,采用乙醇或水-乙醇共溶剂,产物主要是酯类、烷烃类.生物质油沸点集中分布在250~500℃,添加乙醇溶剂可显著提高生物质油轻组分含量.     

土壤和沉积物中的聚合有机质对多环芳烃分布和提取的影响

为了研究土壤和沉积物中凝聚型有机碳(碳黑、干酪根)的含量及其对多环芳烃(PAHs)分布和提取的影响,分别用三氟醋酸(TFA)和在375℃下通氧燃烧的方法从珠江三角洲2个污染土壤和5个河口沉积物样品中提取酸非水解有机碳(NHC)和碳黑(BC);用索氏抽提法和不同溶剂的加速溶剂萃取法(包括连续加速萃取法ASESum和标准溶剂萃取法ASESTD)抽提土壤和沉积物中的多环芳烃,并在不同温度梯度(25℃到150℃)下用水为溶剂加速溶剂萃取其水溶态.结果表明,1)NHC是珠江三角洲土壤和沉积物中总有机碳的重要组成部分,NHC碳明显高于BC碳,NHC和BC分别占土壤和沉积物中有机碳的25.6%￣73.8%和4.64%￣17.3%.2)3种有机溶剂(丙酮、甲苯1、甲苯2)连续抽提的PAHs含量是索氏抽提的2.11倍;5种ASE方法(丙酮、甲苯1、甲苯2、ASESum、ASESTD)提取的PAHs含量与NHC含量存在明显的相关性,而且比PAHs含量与BC或无定型有机碳(AOC)含量的相关性更明显.3)在不同温度梯度下水溶态PAHs浓度符合Van’tHoff方程.研究说明除了BC外,非水解有机碳对土壤和沉积物中PAHs的分布和提取具有重要影响.     

ASE-气相色谱法测定油田区土壤中多种石油烃

采用气相色谱法测定油田区土壤中C_(10)～C_(40)的石油烃,通过优化加速溶剂萃取的条件,使方法在62 mg/L～3 100 mg/L范围内线性良好,方法检出限为4.8 mg/kg。用该方法测定石油区短期、中期、长期油井污染土壤样品,5次测定结果的RSD为1.3%～5.2%,加标回收率为84.8%～98.5%,有证标准样品测定结果在可信区间内。     

Pressurized liquid extraction of six tetracyclines from agricultural soils

Veterinary antibiotics used in agriculture can be introduced into the environment through land application of animal manure, accumulating in soils and groundwaters and posing a significant risk to human health and animal well-being. As the analysis of tetracyclines in soil is challenging due to their strong interaction with soil minerals and organic carbon, the objective of this study was to develop a reliable and reproducible method for quantitative analysis of chlortetracycline and oxytetracycline, and their respective metabolites in soils. A method based on pressurized liquid extraction (PLE) with in-cell clean-up was developed for the extraction of chlortetracycline and oxytetracycline and four likely metabolites from a set of four soils. Optimized conditions included a cell size of 22?mL, soil loading of 5?g, pH of 8.0, methanol:water ratio of 3:1, 50?°C, and two cycles. Soil extracts were analysed by high-performance liquid chromatography (HPLC) coupled with ion trap mass spectrometry (MS). Recoveries of seven tetracyclines from soil ranged from 41% to 110%. The limits of detection for tetracyclines were 0.08–0.3 µg g^?1 soil, and intra- and inter-day variation ranged from 0.12–0.34%. The proposed PLE method is suitable for quantification of tetracyclines in agricultural soils at typical concentrations expected in contaminated environments.     

加速溶剂同时萃取和净化-气相色谱-三重四极杆串联质谱测定土壤和沉积物中8种多溴联苯醚

建立了土壤和沉积物中8种多溴联苯醚(PBDEs,BDE-28、BDE-47、BDE-99、BDE-100、BDE-153、BDE-154、BDE-183和BDE-209)加速溶剂同时萃取和净化-气相色谱-三重四极杆串联质谱(ASE-GC-MS-MS)的分析方法。通过优化加速溶剂萃取与弗罗里硅土在线净化和串联质谱多反应监测模式的条件,较好地去除基质干扰,并提高了三重四极杆串联质谱定性的准确性及定量的灵敏性。该方法采用改进的色谱柱能同时分析包括高溴代联苯醚BDE-209在内的8种PBDEs,其浓度范围为1～100 ng/mL(BDE-209为10～1 000 ng/mL),线性良好,线性回归系数均大于0.997。方法检出限为0.004～0.1 ng/g,方法回收率为75%～110%,方法精密度为2.4%～15.6%。适于批量处理土壤和沉积物中含有多组分痕量PBDEs的样品。     

煤气脱硫废料综合利用新工艺

针对煤气脱硫废料（简称废料）的成分（硫、碳、萘及少量其他有机物）,提出了一种处理废料的新工艺,先用乙酸乙酯提取废料中的萘和少量其他有机物,再用复合溶剂B加热溶解废料,热过滤得碳粉,最后将溶液冷却结晶分离出硫。实验结果表明：在乙酸乙酯与废料的质量比（R1）为3.75,提取温度为60℃,提取时间为4h的条件下,萘回收率为98%,纯度大于等于70%,在复合溶剂B与提取剩余物的质量比（R2）为2.69,过滤温度为100℃的条件下,硫回收率接近100%,纯度大于等于99%,碳回收率和纯度为100%。