黄河河口地区生态供水效益分析

流域生态需水是指流域生态系统为维持一定程度的生态系统健康所需要一定质量的水量,以保证流域生态系统结构和生态功能等为目标,实现流域生态系统健康。流域生态需水量的研究对于社会经济的可持续发展具有重要的战略意义。论文针对南水北调西线一期工程的供水规划,在提出配水效益计算方法的基础上,针对不同的配水量,计算了黄河河口地区的生态需水量、生态效益以及供水对减少断流所带来的生态效益,并进行了方案比较分析。主要结论是:当来水量分别为55×10⁸、122.8×10⁸或240×10⁸m³时,产生的湿地综合生态效益则为34.85×10⁸、47.18×10⁸或54.72×10⁸元。     

甲基丙烯基醛和甲基乙烯基酮水相臭氧化反应

利用实验室模拟的方法研究了甲基丙烯基醛(MAC)和甲基乙烯基酮(MVK)在大气水相中的臭氧化反应,测定了250℃±0.1℃温度和1.0×10⁵Pa空气压力条件下生成过氧化物和二次羰基物的种类和产率.结果表明,MAC水相臭氧化生成2种羰基物(甲醛和丙酮醛)和2种过氧化物,即过氧化氢(H₂O₂)和羟甲基过氧化氢(HOCH₂OOH ,HMHP) ,它们的产率(%)分别为49.9±2.9、26.6±3.9、4.6±0.4和10.0±0.8;同MAC类似,MVK水相臭氧化也生成甲醛、丙酮醛、H₂O₂和HMHP ,它们的产率(%)分别为40.8±2.2、40.7±35、6.8±0.5和10.4±0.8.对MAC和MVK水相臭氧化反应机理进行了推测,解释了各产物的生成.     

Na_2SO_4-MgSO_4-(NH_4)_2SO_4-H_2O四元体系相图研究及其应用

根据不同温度下Na_2SO_4-MgSO_4-(NH_4)_2SO_4-H_2O四元体系相图的绘制,分析了该四元体系相图受温度影响的相图特征,设计了以硫酸铵为盐析剂加工分离白钠镁矾的最佳生产工艺。新工艺具有反应时间短,操作简单,可以生产得到氮镁复肥和无水硫酸钠等优点。此工艺对于克服白钠镁矾的加工分离困难,实现白钠镁矾资源的综合开发和利用具有重要的现实意义。     

黄骅港三期筒仓防煤体高温对策研究

黄骅港三期是单个容量3万吨共24座筒仓的超大型群仓储煤系统,储煤主要来自神华集团所属煤矿,少部分为外购协作煤,多属易自燃煤种。为更有效控制火灾隐患,通过工艺流程分析及危险因素提取,试运营期间数据分析等,研究了致使煤体高温的危险因素和对策。发现运输过程中出现因雨淋而产生润湿热,因粉尘积聚发热的危险;筒仓储煤曾出现数天内温度从10℃升高到45℃,筒仓内有毒有害气体可能超限的危险;输煤皮带可能跑偏引起摩擦生热的危险等。试运营期间针对性采取了喷洒抑尘剂,设置警报系统及检测装置,加强皮带机监控和管理等安全措施。     

Chemically modified silica gel with 1-{4-[(2-hydroxy-benzylidene)amino]phenyl}ethanone: Synthesis, characterization and application as an efficient and reusable solid phase extractant for selective removal of Zn(II) from mycorrhizal treated fly-ash samples

1-{4-[(2-hydroxy-benzylidene)amino]phenyl}ethanone functionalized silica gel was synthesized and used as a highly efficient, selective and reusable solid phase extractant for separation and preconcentration of trace amount of Zn(II) from environmental matrices. The adsorbent was characterized by fourier transform infrared spectroscopy (FT-IR), elemental analysis,¹³C CPMAS NMR spectroscopy, scanning electron microscopy (SEM), thermogravimetric analysis (TGA) and BET surface area analysis. The dependence of zinc extraction on various analytical parameters such as pH, type and amount of eluent, sample flow rate and interfering ions were investigated in detail. The material exhibited superior adsorption efficiency for Zn(II) with high metal loading capacity of 1.0 mmol/g under optimum conditions. After adsorption, the recovery (> 98%) of metal ions was accomplished using 1.0 mol/L HNO₃ as an eluent. The sorbent was also regenerated by microwave treatment in milder acidic environment (0.1 mol/L HNO₃). The lower detection limit and preconcentration factor of the present method were found out to be 0.04 μg/L and 312.5 respectively. The modified silica surface possessed excellent selectivity for the target analytes and the adsorption/desorption process remained effective for at least ten consecutive cycles. The optimized procedure was successfully implemented for the extraction of Zn(II) from mycorrhizal treated fly ash and pharmaceutical samples with reproducible results.     

Palladium-phosphinous acid complexes catalyzed Suzuki cross-coupling reaction of heteroaryl bromides with phenylboronic acid in water/alcoholic solvents

Highly active, air-stable and water-soluble palladium-phosphinous acid complexes have been applied to Suzuki cross-coupling reaction of heteroaryl bromides under mild conditions in water/alcoholic solvents. Suzuki cross-coupling reaction of heteroaryl bromides with phenylboronic acid occurred efficiently using palladium phosphinous acid complexes (POPd) and phase transfer catalyst (tetrabutylammonium bromide and polyethylene glycol) in water/ethanol mixture, water/propanol mixture and neat water respectively, the corresponding yields of cross-coupling heteroaryl-aryls were satisfied. The tert-butyl substituted ligand di-tert-butylphosphino in combination with POPd was found to be more active than the same family derived catalysts dipalladium complexes POPd1 and POPd2, and other two kinds of Pd-catalysts Pd(PPh₃)₄ and Pd₂(dba)₃. The mechanism of Suzuki cross-coupling reaction between heteroaryl bromides and phenylboronic acid in water was proposed with respect to the key role of phase transfer catalyst on the transmetallation step. Compared with other solid phase transfer catalysts, TBAB was tested as the ideal one. The alkalinity of base and the molar proportion between POPd and TBAB were investigated in water and alcoholic solvents. Notably, in the presence of TBAB adding alcoholic solvents into water enhanced the yields of target products. However in terms of the liquid phase transfer catalyst of PEGs, mixing water into PEGs could slightly decrease the yields with respect to the water free PEGs bulk phase, which was probably due to the homogenous liquid conditions in pure PEGs and weak interactions between PEGs and heteroaryl bromide molecules in water depending on their molecular chain lengths.     

模拟酸雨下铅锌冶炼废渣重金属的静态释放特征

以株洲某铅锌冶炼废水中和渣为研究对象,开展不同初始pH值（3.0,4.5,5.6和7.0）模拟酸雨静态浸出实验,研究22d浸泡过程中废渣Cd、Cu、Pb和Zn等重金属的动态释放规律及其化学形态变化和矿物相变特征.结果表明,废渣具有较强的酸缓冲潜力,浸出液pH值稳定在6.20~6.66.Cu和Pb在浸泡初期释放较快,Cd和Zn释放相对较慢.浸出液Cd浓度随浸出时间增加而上升,Zn浓度呈波动变化,Cu和Pb浓度变幅较小.提高雨水酸度促进废渣中重金属的释放,浸出液Cd、Cu、Pb和Zn浓度范围分别为1.38~8.70,0~0.02,1.21~2.26和27.2~135mg/L,其中Cd、Pb和Zn浓度分别超过我国《铅、锌工业污染物排放标准》（GB 25466-2010）限值的26.6~173倍、1.42~3.52倍和17.1~89.0倍..重金属BCR顺序提取表明,浸出液中较高Cd和Zn浓度与其赋存高活性态比例一致,且酸雨促使残渣态Cd和Pb向活性态转化.XRD分析显示,pH=3.0酸雨处理22d后原废渣中Cd和Zn的赋存矿物相消失,PbSO₄谱峰增强,表明废渣重金属的释放受其赋存矿物相及次生矿物形成的影响.重金属释放率呈现出Cd （2.50%~15.8%）> Zn （0.41%~2.13%）> Pb （0.06%~0.10%）> Cu （0.0003%~0.11%）的趋势.自然堆存酸雨作用下废渣中Cd、Pb和Zn具有较大环境风险,需加强降雨淋滤污染防治管控.     

碳酸盐岩对Fe2+生物氧化及铁矿物合成的影响

利用从高硫煤矸石堆场浸出液中培养驯化获得的氧化亚铁硫杆菌（Acidithiobacillus ferrooxidans,A.f）,通过静态实验,探讨添加不同量的碳酸盐岩对酸性硫酸盐体系中Fe²⁺生物氧化速率及次生铁矿物合成的影响.结果表明：添加10 g和30 g碳酸盐岩不会对体系中pH、氧化还原电位（ORP）和Fe²⁺生物氧化速率产生明显影响,但总铁（TFe）的去除率可从37%分别提高到55%和62%,矿物生成量也从8.17 g·L^-1分别增加到12.03 g·L^-1和13.69 g·L^-1;同时,体系中合成的次生铁矿物相与不加碳酸盐岩时无明显变化,主要为黄铁矾和施氏矿物的混合物.随着碳酸盐岩添加量增至50、70和90 g时,体系pH快速上升,Fe²⁺生物氧化速率受到抑制,并产生大量结晶程度较好的硫酸钙,形成的铁矿物主要为纤铁矿或针铁矿.而适量的碳酸盐岩添加可使体系中产生Ca²⁺和Mg²⁺,从而影响次生铁矿物的合成.因此,在以碳酸盐岩为反应介质的酸性矿山废水处理工艺设计中,可通过添加A.f菌并控制碳酸盐岩投加量,强化系统中Fe²⁺生物氧化及次生矿物的合成,从而进一步提高反应系统对TFe的去除效果.     

挺水植物对城市河流中典型污水印记药物的去除

以AZM（阿奇霉素）、STZ（磺胺噻唑）、IBU（布洛芬）、DCF（双氯芬酸）、PRC（扑热息痛）、ATL（阿替洛尔）、CLF（氯贝酸）、CBM（卡马西平）和CAF（咖啡因）共9种WWMPs（wastewater-marking pharmaceuticals,污水印记药物）为目标物,采用HPLC-MS/MS检测方法,通过室内河流模拟系统,研究3种挺水植物组合（旱伞草+灯芯草、菖蒲+灯芯草、旱伞草+菖蒲）的人工生态系统在不同介质（水相、泥相、水生植物）中WWMPs的变化特性及对常规污染物（如COD_Cr、NH₃-N、TP、TN）的去除效果,并运用物料衡算等手段计算目标物的实际去除率.结果表明:3种挺水植物组合的人工生态系统对4种常规污染物的去除效果较为明显,COD_Cr、NH₃-N、TP、TN去除率范围分别为39.7%~47.8%、88.2%~99.4%、39.1%~58.1%和49.1%~58.5%;与无植物系统相比,挺水植物组合的人工生态系统对水相中药物有明显的去除效果,尤其是对CBM、IBU和DCF,最大去除率均在54.0%以上;旱伞草+菖蒲组合的人工生态系统对水相中CAF、CBM、CLF、DCF、IBU和STZ的去除效果较好,去除率为51.6%~87.7%;3种挺水植物组合的人工生态系统对泥相中WWMPs的去除效果大小依次为菖蒲+灯芯草>旱伞草+菖蒲>旱伞草+灯芯草;不同挺水植物组合的人工生态系统对WWMPs的富集特性不同,9种WWMPs吸收效果大小依次为CBM > CLF > CAF > IBU > DCF > ATL > PRC > AZM > STZ;3种挺水植物组合的人工生态系统对WWMPs的实际总去除率大小依次为菖蒲+灯芯草>旱伞草+菖蒲>旱伞草+灯芯草.研究显示,挺水植物组合的人工生态系统可以有效地去除城市河流中WWMPs及常规污染物,能作为净化水质、改善城市河流水环境的一种有效手段.      

TiO2复合催化剂弱光催化降解模拟海水中苯酚及其催化活性的影响

为了获得适用于海水中有机污染物光降解催化剂,分别选用纳米SiO_2粒子和氧化石墨烯GO为载体,利用吸附相反应技术并结合热处理过程制备了基于TiO_2的复合催化剂,研究了弱光(光强小于1mW·cm~(-3))激发下复合催化剂光催化降解模拟海水中苯酚.结果表明,吸附相反应技术结合焙烧得到的La~(3+)掺杂TiO_2-SiO_2,表面亲水性较强和对苯酚吸附能力较弱,难以克服盐离子的干扰并有效降解模拟海水中高浓度苯酚.而吸附相反应技术结合醇溶剂热还原处理后,La~(3+)掺杂TiO_2-SiO_2催化剂表面亲水性显著减弱,但该催化剂在模拟海水中不能形成稳定的悬浮体系.吸附相反应技术得到的TiO_2-GO和La~(3+)掺杂TiO_2-GO中,TiO_2粒子粒径小于10nm且均匀负载于GO的表面.醇溶剂热还原处理可使TiO_2形成晶型结构,从而提高其催化活性,同时还能将GO表面的含氧基团还原,降低催化剂表面亲水性.从而提升催化剂对苯酚的吸附能力和对盐离子的抗干扰能力.另外,还原GO与小粒径TiO_2粒子紧密结合,使光生电子能很快转移至还原GO表面,增大光生电荷分离率,进一步提升催化剂的光降解性能.