Pd/Fe催化脱氯水中PCE的动力学研究

以GC-MS为分析方法,采用Pd／Fe双金属对水溶液中四氯乙烯（PCE）进行了催化还原脱氯处理,考察了PCE初始浓度、钯含量、Pd／Fe用量和溶液初始pH值等各因素对脱氯效果影响及还原动力学规律。结果表明,Pd／Fe双金属对PCE有较好的还原脱氯效率,反应遵循准一级反应动力学规律,以反应物PCE浓度为参照的反应速率常数K变化范围为0．019min^-1～0．16min^-1,对应的PCE半衰期从6min到36min,揭示反应有可能是在过量的Pd／Fe双金属表面进行。当PCE溶液初始浓度为1mmol／L,投加1．2g钯含量为0．03％的Pd／Fe双金属,在25℃下反应60min,PCE的脱氯率达到95％以上。增大钯含量和Pd／Fe用量可有效提高脱氯率,在初始pH值为弱酸性条件下有利于还原脱氯反应进行。     

Electroreductive dechlorination of chlorophenols with Pd catalyst supported on solid electrode

Electroreductive dechlorination of chlorophenols with Pd catalyst supported on solidelectrode was studied. As solid electrodes, carbon cloth (CC), carbon felt (CF) and titanium mesh were used, and palladium was plated on solid electrodes by either electrolytic or electroless method. On each electrode with Pd, chlorophenols were qualitatively dechlorinated to phenol, while they were entirely intact on electrodes without Pd. Moreover, neither base electrode nor plating method significantly affected the activity of Pd as far as it was sufficiently loaded on the electrode. Based on the results in the experiments using one electrode repeatedly, Pd catalyst proved to possess a satisfactory duarability under the present condition. It was suggested that the reactive species responsinble for the dechlorination of chlorophenols could be formed during preliminary electrolysis. Thus, (Pd)_x-H resulting from the adsorption of electrogenerated hydrogen on metallic Pd might be assumed most probable.     

多氯联苯的生物降解研究

PCBs的氧化反应是通过加氧酶的作用,分子氧在PCBs的无氯环或带较少氯原子环的2,3位发生反应,形成顺二氢醇混合物PCBs的完全降解需要不同系列微生物的协同作用,这些微生物可以利用不同的PCBs降解产物。另外氯原子的位置和数量也影响着微生物氧化攻击的效率。UNTERMAN等假设出A.eutrophus sp.,P. putida和Corynebacterium sp.对于PCBs的氧化机制。Alcalegenes eutrophus和P.putida sp.等微生物是对多氯联苯2,3-位的亲核攻击发生作用。对于Corynebacteriun降解混合物的反应则是对污染物3,4位的亲核攻击。     

Coupled anaerobic/aerobic biodegradation of 2,4,6 trichlorophenol

Degradation of 2, 4, 6-trichlorophenol(TCP) with co-immobilizing anaerobic granular sludge and isolated aerobic bacterial species was studied in coupled anaerobic/aerobic integrated reactors. The synergism of aerobes and anaerobes within co-immobilized granule might facilitate degrading the TCP and exchange of anaerobic metabolites 4-CP, which promoted system organic removal efficiency and recovered from organic shock-loads more quickly. The bionmass specific activities experiment further confirmed that strict anaerobes be not affected over the crsurse of this experiment by the presence of an oxic environment, aerobic activity predominated in the outer co-immobilized grange layers,while the interior was characterized by anaerobic activity. The co-immobilized granule could thus enable both aerobic and anaerobic microbes function in the same reactor and thereby integrate the oxidative and reductive catabolism.     

负载型纳米Pd/Fe对氯代烃脱氯机理研究

采用实验室制备的负载型纳米Pd/Fe对几种常见的挥发性氯代烃:四氯乙烯(ICE)、三氯乙烯(TCE)、1,1-二氯乙烯(1,1-DCE)、氯乙烯(VC)和林丹(γ-HCH)进行了还原脱氯研究.负载型纳米Pd/Fe对PCE、TCE、1,1-DCE、VC和γ-HCH的还原脱氯符合准一级反应动力学方程,其反应速率常数分别为2.79 h-1、2.35 h-1、1.12 h-1、2.14 h-1和4.02 h-1.氯代烃降解过程中几乎没有中间产物生成,终产物主要为C2 H6和C2 H4,如对TCE进行降解时,生成的C2H6和C2 H4分别占总碳质量比的70%和10%.采用暴露在空气中24 h的负载型纳米Pd/Fe对PCE进行脱氯,8次循环后仍能对PCE快速完全降解,表明负载型纳米Pd/Fe的稳定性能良好.以γ-HCH为目标污染物对负载型纳米Pd/Fe的反应持久性进行了研究,200 h后负载型纳米Pd/Fe的反应性没有明显降低,表明负载型纳米Pd/Fe反应持久性能良好.温度对负载型纳米Pd/Fe的脱氯反应影响较大,测得各氯代烃脱氯反应的活化能均高于29 kJ·mol-1.对PCE、TCE进行了脱氯动力学模拟,模拟结果与试验数据基本吻合,表明负载型纳米Pd/Fe对氯代烃的脱氯,是连串、平行及多步骤反应的结合.     

Enhanced dechlorination of 2,4-dichlorophenol by recoverable Ni/Fe–Fe3O4 nanocomposites

Ni/Fe-Fe_3O_4 nanocomposites were synthesized for dechlorination of 2,4-dichlorophenol(2,4-DCP). The effects of the Ni content in Ni/Fe-Fe_3O_4 nanocomposites, solution pH, and common dissolved ions on the dechlorination efficiency were investigated, in addition to the reusability of the nanocomposites. The results showed that increasing content of Ni in Ni/Fe–Fe_3O_4 nanocomposites, from 1 to 5 wt.%, greatly increased the dechlorination efficiency; the Ni/Fe–Fe_3O_4 nanocomposites had much higher dechlorination efficiency than bare Ni/Fe nanoparticles. Ni content of 5 wt.% and initial p H below 6.0 was found to be the optimal conditions for the catalytic dechlorination of 2,4-DCP. Both 2,4-DCP and the intermediate product 2-chlorophenol(2-CP) were completely removed, and the concentration of the final product phenol was close to the theoretical phenol production from complete dechlorination of 20 mg/L of 2,4-DCP, after 3 hr reaction at initial p H value of 6.0,3 g/L Ni/Fe-Fe_3O_4 , 5 wt.% Ni content in the composite, and temperature of 22℃. 2,4-DCP dechlorination was enhanced by Cl-and inhibited by NO3-and SO_4~(2-). The nanocomposites were easily separated from the solution by an applied magnetic field. When the catalyst was reused, the removal efficiency of 2,4-DCP was almost 100% for the first seven uses, and gradually decreased to 75% in cycles 8–10. Therefore, the Ni/Fe–Fe_3O_4 nanocomposites can be considered as a potentially effective tool for remediation of pollution by 2,4-DCP.