Feasibility of honeycomb monolith supported sugar catalyst to produce biodiesel from palm fatty acid distillate (PFAD)

Carbon coated monolith was prepared by sucrose solution 65 wt.% via dip-coating method. Sulfonation of incomplete carbonized carbon coated monolith was carried out in order to synthesize solid acid catalyst. The textural structure characteristics of the solid acid catalyst demonstrated a low surface area and pore volume. Palm fatty acid distillate (PFAD), a by-product of palm oil refineries, was utilized as oil source in biodiesel production. The esterification reaction subjected to different reaction conditions was performed by using the sulfonated carbon coated monolith as heterogeneous catalyst. The sulfonation process had been performed by using vapour of concentrated H₂SO₄ that was much easier and efficient than liquid phase sulfonation. Total acidity value of carbon coated monolith was measured for unsulfonated sample (0.5 mmol/g) and sulfonated sample (4.2 mmol/g). The effect of methanol/oil ratio, catalyst amount and reaction time were examined. The maximum methyl ester content was 89% at the optimum condition, i.e. methanol/oil molar ratio (15:1), catalyst amount (2.5 wt.% with respect to PFAD), reaction time (240 min) and temperature 80 °C. The sugar catalyst supported on the honeycomb monolith showed comparable reactivity compared with the sugar catalyst powder. However, the catalyst reusability studies showed decrease in FFA% conversion from 95.3% to 68.8% after four cycles as well as the total acidity of catalyst dropped from the value 4.2 to 3.1 mmol/g during these cycles. This might be likely due to the leaching out of SO₃H group from the sulfonated carbon coated monolith surface. The leaching of active species reached a plateau state after fourth cycle.     

基于不同废污泥源的短程反硝化快速启动及稳定性

为探究不同废污泥源快速启动短程反硝化和实现稳定NO_2~--N积累的可行性,在3个完全相同的SBR反应器(S1、S2和S3)分别接种:实验室城市污水反硝化除磷系统排泥、城市污水厂剩余污泥及河涌底泥,比较其短程反硝化启动快慢和NO_2~--N积累特性,考察系统短程反硝化活性和NO_3~--N→NO_2~--N转化性能,并从微生物学角度分析反应器功能菌群特征.结果表明,在乙酸钠为唯一碳源、高碱度和适宜COD/NO_3~--N比进水条件下,3个SBR短程反硝化反应器在短时间内均能够成功启动,系统平均NO_3~--N→NO_2~--N转化率为S1 S2 S3(75. 92% 73. 36% 69. 90%).同时发现持续低温条件下S1和S2呈现不同程度的短程反硝化性能恶化趋势,但S3能够稳定维持良好NO_2~--N积累性能.微生物高通量测序表明,变形菌门和拟杆菌门居PD系统主导地位,3个短程反硝化反应器NO_2~--N积累关键功能菌属Thauera属丰度差异明显:S3 S1 S2(25. 09% 4. 71% 3. 60%),表明S3具备稳定高效的NO_2~--N积累性能,同时高丰度Thauera属可能是维持低温短程反硝化活性的重要原因.     

河岸过滤中氨氮的削减及其浓度对细菌与氨氧化微生物的影响

通过小试滤柱模拟河岸过滤,结合荧光定量PCR和高通量测序等手段研究了河岸过滤对氨氮的削减效能和进水氨氮浓度对细菌与氨氧化微生物的影响.结果表明,低浓度（0.2 mg·L^-1）氨氮未被削减,较高浓度（1.0 mg·L^-1和2.0 mg·L^-1）氨氮的削减率可达70%.进水处细菌丰度随氨氮浓度升高而增加,细菌群落组成随氨氮浓度升高发生规律性变化.出水处氨氧化古菌（Ammonia oxidizing archaea,AOA）丰度与氨氮浓度呈负相关,氨氧化细菌（Ammonia oxidizing bacteria,AOB）丰度与氨氮浓度无显著相关关系;进水处AOA-α多样性与氨氮浓度呈正相关,但AOB-α多样性与氨氮浓度呈负相关;进水处AOA群落组成受氨氮浓度影响,而进、出水处AOB群落组成均受氨氮浓度影响.可见,进水氨氮浓度会影响河岸过滤对氨氮的削减效能,还会影响细菌、氨氧化微生物的丰度及群落结构,AOB对氨氮浓度的变化比AOA更敏感.     

固定化微藻流化床反应器去除低碳污水中氨氮的潜力

以固定化微藻颗粒为原料,通过搭建流化床反应器强化微藻对氨氮（NH₄⁺-N）的去除,设计了藻种、污水上升流速、光周期和光照强度四组单一变量实验,系统地研究了不同条件下微藻去除NH₄⁺-N的能力.结果表明,当以固定化斜生栅藻为原料、污水上升流速为6.8m/h、光周期为8：16h和光照强度为4800Lux时,NH₄⁺-N去除效果最优（96.7%）.在最优操作条件下,探究了COD为200mg/L时微藻去除NH₄⁺-N的潜力,结果表明,当NH₄⁺-N初始浓度不高于50mg/L时,NH₄⁺-N去除率高于95%.本实验建立了一套半连续微藻流化床实验方法,该方法显著减弱了微藻在生物同化过程中对有机碳源的依赖性,为低COD条件下微藻生物脱氮工艺的设计提供了技术参考和理论基础.     

模拟土壤淋洗废液中重金属的选择性去除与淋洗液的回收研究

土壤淋洗废液中污染物的选择性去除是实现淋洗液回收的关键.本文以硫化钠（Na₂S）、乙基黄原酸钾（PEX）、二甲基二硫代氨基甲酸钠（DTC）作为重金属沉淀剂处理电子垃圾污染土壤模拟淋洗废液,在筛选出Na₂S作为理想重金属沉淀剂的基础上,研究初始pH值、反应温度、沉淀剂浓度等因素对Na₂S分离络合态重金属的影响,并通过软件模拟和产物表征等方式推测反应机理.结果表明：Na₂S对柠檬酸络合态重金属的分离顺序依次为Cu、Pb、Cd,符合硫化物溶度积原则;反应温度、初始pH值对Na₂S处理络合态重金属无显著影响,重金属去除率均保持在90%以上,柠檬酸的回收率约为95%;Visual MINTEQ模拟结果显示,S^2-投加前液相中重金属主要以H₂CA^-、HCA^2-和CA^3-结合形式存在,S^2-投加后液相中重金属则以HS^-和S^2-结合形式存在;扫描电镜及能谱（SEM-EDS）表明,S^2-与金属阳离子按物质的量比1：1生成硫化物沉淀物,沉淀主要呈团聚、成簇和圆片状存在;X射线衍射（XRD）分析结果表明,沉淀产物中存在CuS、CdS、PbS和CuPbS₂.本研究结果可为化学沉淀法处理重金属污染土壤淋洗废液提供技术参考.     

色氨酸对生物成因铁硫酸盐次生矿物形成的影响

采用氧化亚铁硫杆菌催化合成铁硫酸盐次生矿物,研究不同L-色氨酸添加浓度对矿物合成体系pH、氧化还原电位（ORP）、Fe²⁺氧化率、总Fe沉淀率,以及次生矿物产量、化学组成及矿物相的影响.结果表明,随着体系色氨酸浓度的增加,pH降低幅度越小,ORP上升越不明显.色氨酸对铁硫酸盐次生矿物合成的影响依赖于其浓度,当色氨酸浓度低于1.67 g·L^-1时,色氨酸对铁硫酸盐次生矿物的形成起促进作用,表现为总Fe沉淀率及矿物产量随着色氨酸浓度升高而增加.而当色氨酸浓度升高至6.67 g·L^-1时,Fe²⁺氧化率、总Fe沉淀率和矿物产量远低于对照组,表明高浓度色氨酸会抑制铁硫酸盐次生矿物的形成.次生矿物内Fe/S比介于施氏矿物和黄钾铁矾的理论值之间,表明不同合成体系所得次生矿物均为黄钾铁矾和施氏矿物的混合物.矿物学特征分析表明,随着色氨酸浓度的升高,矿物的合成表现为黄钾铁矾向施氏矿物转移.     

雨水管道沉积物中典型无机氮的干期粒径分布

以南京江北新区分流制雨水管道沉积物为研究对象,考察不同粒径沉积物中铵态氮（NH₃-N）和硝态氮（NO₃^--N）干期分布特征,分析其随干期长度的变化关系,并探讨沉积物理化性质及微生物菌群结构对NH₃-N和NO₃^--N干期分布的影响.结果表明：粒径≤0.075mm的沉积物中NH₃-N占比最高（交通区30.8%,商业区36.7%）;交通区粒径≤0.075mm的沉积物中NO₃^--N占比最高（33.0%）,而商业区粒径0.075~0.15mm沉积物中NO₃^--N占比最高（34.4%）;干期长度与交通区0.075~0.15mm粒径段的沉积物中NO₃^--N含量及商业区粒径≥0.3mm的沉积物中NH₃-N含量之间的相关性均最显著;雨水管道沉积物中NH₃-N和NO₃^--N的干期分布与O-H和N-H等官能团、表面极性和亲水性、微观形貌等有一定关联;交通区雨水管道沉积物中Gemmobacter等反硝化优势菌种（相对丰度总和为20.15%）对NO₃^--N干期分布影响更显著.     

The study of biological activity of transformation products of diclofenac and its interaction with chlorogenic acid

In the present work we compared the biological activity of DCF, 4′-OHDCF and 5-OHDCF as molecules of most biodegradation pathways of DCF and selected transformation products (2-hydroxyphenylacetic acid; 2,5-dihydroxyphenylacetic acid and 2,6-dichloroaniline) which are produced during AOPs, such as ozonation and UV/H₂O₂. We also examined the interaction of DCF with chlorogenic acid (CGA). CGA is commonly used in human diet and entering the environment along with waste mainly from the processing and brewing of coffee and it can be toxic for microorganisms included in activated sludge. In the present experiment the evaluation of following parameters was performed: E. coli K-12 cells viability, growth inhibition of E. coli K-12 culture, LC₅₀ and mortality of Chironomus aprilinus, genotoxicity, sodA promoter induction and ROS generation. In addition the reactivity of E. coli SM recA:luxCDABE biosensor strain in wastewater matrices was measured. The results showed the influence of DCF, 4′-OHDCF and 5-OHDCF on E. coli K-12 cells viability and bacteria growth, comparable to AOPs by-products. The highest toxicity was observed for selected, tested AOPs by-products, in comparison to the DCF, 4′-OHDCF and 5-OHDCF. Genotoxicity assay indicated that 2,6-dichloroaniline (AOPs by-product) had the highest toxic effect. The oxidative stress assays revealed that the highest level of ROS generation and sodA promoter induction were obtained for DCF, 4′-OHDCF and 5-OHDCF, compared to other tested compounds. We have also found that there is an interaction between chlorogenic acid and DCF, which resulted in increased toxicity of the mixture of the both compounds to E. coli K-12, comparable to parent chemicals. The strongest response of E. coli SM biosensor strain with recA:luxCDABE genetic construct in filtered treated wastewaters, comparable to control sample was noticed. It indicates, that E. coli SM recA:luxCDABE biosensor strains is a good tool for bacteria monitoring in wastewater environment. Due to toxicity and biological activity of tested DCF transformation products, there is a need to use additional wastewater treatment systems for wastewater contaminated with pharmaceutical residues.     

石灰对生物炭和腐殖酸阻控水稻Cd吸收的效应

采用田间试验,研究了石灰-生物炭和石灰-腐殖酸两种联合修复剂及其不同施用量对酸性土壤中稻米Cd含量、产量和品质的影响,并对不同处理修复效果进行综合评估.结果表明,两种联合修复剂能显著降低稻米Cd含量17.39%~45.96%,降低土壤有效Cd含量18.29%~29.88%,.生物炭、腐殖酸施用量分别为5000,6000kg/hm²时,稻米Cd的降低效果最佳.石灰-生物炭处理中,降低稻米Cd含量的主要因子为土壤pH和土壤有效Cd含量（P<0.05）,而石灰-腐殖酸处理则为土壤有机质含量与土壤有效Cd含量（P<0.05）.施加修复剂后稻米产量可达6637~7890kg/hm²,直链淀粉含量达到19.47%~27.26%;当腐殖酸施用量为7500kg/hm²时可使稻米产量提高10.97%,而石灰-生物炭处理对稻米产量无显著影响;采用层次分析法确定了稻米Cd含量、稻米产量、稻米品质和修复费用在修复效应评估中所占权重为0.608、0.150、0.102、0.140,综合评估结果显示土壤-水稻系统Cd阻控效应的联合修复技术为：在施用1200kg/hm²石灰的基础上同时施加6000kg/hm²腐殖酸.     

氧基氯化铁非均相活化过一硫酸盐降解金橙Ⅱ

采用部分热分解法制备了氧基氯化铁（FeOCl）,用于活化过一硫酸盐（PMS）降解难降解偶氮染料金橙Ⅱ（AO7）.利用X射线光电子能谱分析（XPS）、扫描电镜（SEM）和X射线衍射光谱（XRD）对其进行了表征;通过实验评估FeOCl/PMS体系对AO7的降解效果并分析了影响AO7去除率的各种因素.结果表明：FeOCl活化PMS降解AO7效果良好,矿化率达44%.在中性条件下,当FeOCl投加量50mg/L、PMS浓度1.0mmol/L、AO7浓度0.05mmol/L时,AO7可在30min内完全降解.随PMS投加量、FeOCl投加量、Cl^-浓度和反应初始pH值的增大,AO7的脱色效果提高.FeOCl还具有良好的重复利用性.此外,通过自由基淬灭实验、EPR测试和XPS分析了反应的主要活性物种和反应机理：由PMS活化产生的SO₄^-·和·OH对污染物进行降解,其中主要活性物种为SO₄^-·.