Effects of metal and acidic sites on the reaction by-products of butyl acetate oxidation over palladium-based catalysts

Catalytic oxidation is widely used in pollution control technology to remove volatile organic compounds. In this study, Pd/ZSM-5 catalysts with different Pd contents and acidic sites were prepared via the impregnation method. All the catalysts were characterized by means of N2 adsorption- desorption, X-ray fluorescence （XRF）, HE temperature programmed reduction （H2-TPR）, and NH3 temperature programmed desorption （NH3-TPD）. Their catalytic performance was investigated in the oxidation of butyl acetate experiments. The by-products of the reaction were collected in thermal desorption tubes and identified by gas chromatography/mass spectrometry. It was found that the increase of Pd content slightly changed the catalytic activity of butyl acetate oxidation according to the yield of CO2 achieved at 90%, but decreased the cracking by-products, whereas the enhancement of strong acidity over Pd-based catalysts enriched the by-product species. The butyl acetate oxidation process involves a series of reaction steps including protolysis, dehydrogenation, dehydration, cracking, and isomerization. Generally, butyl acetate was cracked to acetic acid and 2- methylpropene and the latter was an intermediate of the other by-products, and the oxidation routes of typical by-products were proposed. Trace amounts of 3-methylpentane, hexane, 2-methylpentane, pentane, and 2-methylbutane originated from iso4merization and protolysis reactions.     

SBR法处理低C/N污水的工程应用——以某基地污水处理站改造工程为例

低C/N污水的生化处理过程中,由于碳源不足,不能满足硝化和反硝化的要求,造成出水NH3-N超标。采用SBR工艺对某基地污水处理站厌氧处理后的低C/N污水进行改造,处理后出水COD去除率达到97%以上,NH3-N去除率达到93%以上。     

CdSe/ZnS量子点对稀有鮈鲫胚胎发育的影响及其氧化应激作用

本研究以稀有鮈鲫(Gobiocypris rarus)为对象,研究了不同浓度CdSe/ZnS量子点(QDs)暴露下,稀有鮈鲫胚胎发育过程中自主运动频率、内心率和体长的变化,以及利用体内超氧化物歧化酶(SOD)和丙二醛(MDA)作为毒性指标,反映CdSe/ZnS QDs暴露对稀有鮈鲫胚胎发育的氧化应激作用.结果显示:CdSe/ZnS QDs对稀有鮈鲫胚胎72 hpf(hours post fertilization)的半致死浓度(LC50)为319.629 nmol·L-1,96 hpf的半致畸浓度(EC50)为203.312 nmol·L-1.CdSe/ZnS QDs暴露不仅影响稀有鮈鲫胚胎死亡率、畸形率、自主运动频率、孵化时间和孵化率,而且使其内心率减缓、体长缩短,导致胚胎卵凝结,心包囊肿,出现脊椎弯曲等多种毒性现象.同时发现,CdSe/ZnS QDs暴露导致稀有鮈鲫体内MDA含量增加以及SOD活力的降低.这表明CdSe/ZnS QDs对稀有鮈鲫胚胎发育具有致畸、致死作用,而氧化应激可能是引起其胚胎致畸、致死的重要机制之一.     

EDTA优化纳米Pd/Fe对2,4-D的催化脱氯研究

采用EDTA优化纳米Pd/Fe催化脱氯水中2,4-二氯苯氧乙酸(2,4-D),并考察了EDTA投加浓度、pH、钯化率、温度等因素对2,4-D还原的影响.结果表明,EDTA的加入络合了纳米Pd/Fe在催化脱氯过程中生成的铁离子,抑制纳米Pd/Fe颗粒表面钝化层的形成,提高了体系的反应活性.适宜的EDTA浓度、低pH、高钯化率、低温等有利于2,4-D的还原脱氯.当EDTA浓度为25.0 mmol·L-1,纳米铁含量为1.0 g·L-1,初始pH=4.3、钯化率为0.5%,温度为25.0℃,搅拌速率为200 r·min~(-1)时,反应50 min,10.0 mg·L-1的2,4-D去除率及苯氧乙酸(PA)生成率均达到100%.     

掺杂聚乙烯醇的壳聚糖小球对铜离子-腐殖酸的单一和连续吸附行为

以三聚磷酸钠作为离子交联剂,合成了一种掺杂聚乙烯醇的壳聚糖小球,采用SEM和FTIR表征了小球的表面性能及官能团分布情况,进一步研究了这种小球对腐殖酸和铜离子的单独吸附行为、连续吸附行为及两者共存状态下的吸附行为,并通过XPS能谱分析了吸附过程的机理.结果表明:在单独吸附过程中,壳聚糖小球与腐殖酸和铜的作用方式主要是通过静电引力和络合作用;在连续吸附过程中,先吸附了腐殖酸的小球,后续对铜离子的吸附效果变弱;而先吸附了铜离子的小球,后续对腐殖酸的吸附能力变强,说明这种小球在吸附过程中可以被连续使用.而在腐殖酸和铜离子共存的吸附实验中发现,壳聚糖小球除了会吸附溶液中的铜离子和腐殖酸外,还导致它们的聚集沉降.     

Temperature Effect on Migration of Zn and Cd Through Natural Clay

To investigate the effect of temperature on effective diffusion coefficients and retardation factors for Zn and Cd, combined diffusion and sequential extraction analyses were conducted at 15 ^˚C and 55 ^˚C. The effective diffusion coefficients of the metals increased up to ten times according to the increased temperature. On the other hand, the effect of temperature on the retardation factor depended on the retention mechanisms of the metals. The distribution coefficient for Zn, which was mainly partitioned in the carbonate phase, increased up to two times with the increase in temperature. On the other hand, the distribution coefficient for Cd, which was mainly partitioned in the exchangeable phase, was hardly affected by the temperature change. Results of combined diffusion and sequential extraction analysis showed that the effect of temperature on the heavy metals’ (Zn and Cd) migration through the compacted natural clay was influenced by the combined effects of the diffusion coefficient and the retardation factor. Additionally, we could also observe the change in retention mechanism for the metals with the change in pore water concentration.     

改良倒置A2/O工艺设计

在目前广泛采用的AO、A2O、倒置A2O等工艺的基础上,为提高脱氮除磷效率,提出改良倒置A2O工艺。并对其工艺的特点、设计和脱氮除磷效率进行了详细的研究和分析。     

Dissipation,residues, and risk assessment of imidacloprid in Zizania latifolia and purple sweet potato under field conditions using LC-MS/MS

A shortened version of Quick, Easy, Cheap, Effective, Rugged, and Safe method (QuEChERS) for determining the dissipation and residue of imidacloprid present in Zizania latifolia and purple sweet potato was established by using liquid chromatography-tandem mass spectrometry (LC-MS/MS). The average recoveries of imidacloprid in the two crops ranged from 82.12 to 113.79%, with relative standard deviation (RSD) of <7.32%. The dissipation dynamics of imidacloprid in Z. latifolia plants and purple sweet potato plants followed first-order kinetics, with half-lives of 3.2–5.5?days in each of sampling locations. The terminal imidacloprid residues in Z. latifolia and purple sweet potato at each of location were <0.005–0.120?mg kg^?1. According to the risk assessment results, both the acute dietary risk quotient and chronic dietary risk quotient values were <1, indicating that imidacloprid is unlikely to pose health risks to humans with normal recommended use. The present study may serve as a valuable reference for the safe and reasonable use of imidacloprid in Z. latifolia and purple sweet potato fields.     

以膨润土为辅助添加剂固化/稳定化污泥的试验研究

针对传统以水泥固化污泥,带来的水泥用量大与固化体的浸出液pH过高等问题,提出了以膨润土为添加剂辅助水泥固化/稳定化污泥的思路.通过开展无侧限抗压强度试验、毒性浸出试验,测量掺入膨润土后污泥固化体的强度、重金属浸出率、浸出液COD及pH值,研究该固化/稳定化方法的效果.结果表明,膨润土的掺入极大地提高了固化体的抗压强度,将掺入量为0.4(相对污泥的质量比)的水泥一半用膨润土替代时,固化体的强度提高了6左右.体积安定性也能够满足要求.随膨润土掺入量增加,固化体中锌、铅的浸出率与浸出液的pH值呈现不断减小的趋势,锌与铅的浸出率分别由6.9%下降至0.25%,9.6%下降至5%,pH值由12.3下降至12.1.在强碱条件下及烘干或风干条件下,铜会随着有机物的分解而析出,从而增加铜的浸出率,而膨润土的加入能弥补水泥造成的强碱环境及风干或烘干过程对固化污泥中铜的稳定产生的不利影响.