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1.
以Pd和Fe为活性金属组分通过沉积沉淀法制备了负载型Pd-Fe/C双金属催化剂,针对氯酚类污染物进行催化还原脱氯和催化氧化的连续降解处理.通过ICP-MS、XRD和TEM对催化剂进行表征,证实0.5%Pd-0.5%Fe/C催化剂中活性金属组分Pd和Fe在载体表面分散性最好,催化剂比表面积达到718.8 m~2·g~(-1).在温和条件下,以水作为反应介质,研究了负载型Pd-Fe/C催化剂对4-氯苯酚(4-CP)和2,4-二氯苯酚(2,4-DCP)的连续降解过程和反应条件,以及催化剂的重复使用情况.考察了Pd和Fe的负载量及p H值对催化剂活性的影响,得到了最佳反应条件,以0.5%Pd-0.5%Fe/C为催化剂,20 min内完成4-CP和2,4-DCP的催化还原脱氯,产物都为苯酚;之后加酸调节pH=5,并加入H2O2继续进行催化氧化,苯酚被彻底降解为H_2O和CO_2,而且转化率在60 min内可以达到97.5%以上,从而实现4-CP和2,4-DCP的彻底降解.  相似文献   

2.
镍/铁和铜/铁双金属降解四氯乙烯的研究   总被引:13,自引:0,他引:13  
选用镍 /铁和铜 /铁双金属对四氯乙烯 (PCE)进行脱氯试验 .结果表明 ,双金属系统对四氯乙烯有明显的脱氯作用 ,且脱氯反应符合准一级反应动力学方程 ,双金属在降解PCE的过程中 ,无三氯乙烯 (TCE)、二氯乙烯 (DCE)和氯乙烯 (VC)等中间产物形成 ,与零价铁系统相比 ,双金属系统对PCE的降解速率有明显提高 ,尤其是Ni/Fe双金属 ,反应速率常数kSA从 0 1 2 89ml·m- 2 ·h- 1 提高到 0 3697ml·m- 2 ·h- 1 ,Cu/Fe双金属的反应速率常数kSA为 0 2 2 79ml·m- 2 ·h- 1 .无论是哪种反应介质 ,在制备过程中干燥与否对脱氯速率都有很大的影响  相似文献   

3.
二氧化钛催化下的氯代二苯并-对-二恶英光解反应   总被引:6,自引:0,他引:6  
本文利用中压汞灯作光源,研究了氯代二苯并-对-二恶英(CDDs,包括CDD,DCDD,PeCDD和OCDD)在二氧化钛催化下的光解反应,并讨论了二氧化钛浓度、pH值、反应温度以及取代氯原子数目等对反应速率的影响.结果表明,二氧化钛能有效地催化CDDs的光降解,在室温下,4h内DCDD,PeCDD,OCDD分别降解了87.2%,84.6%,91.2%,反应温度和二氧化钛浓度是控制该反应的主要因素.  相似文献   

4.
水溶液中氯代烷烃的催化还原脱氯研究   总被引:11,自引:1,他引:10  
研究了氯代甲烷系列和氯代乙烷系列的各种氯代烷烃在铁、铜二相金属体系中的还原脱氯反应,分析了氯代有机物结构性质对还原脱氯反应的影响和规律性,探讨了氯代烷烃在金属还原作用下的还原脱氯机理.  相似文献   

5.
通过共沉淀法制备了Fe-Cu-柱撑黏土(Fe-Cu-PILC)催化剂,并以单氯酚、二氯酚、三氯酚作为模式化合物,研究了氯酚中氯原子取代数目、取代位置对其降解动力学的影响,并探讨了氯离子的存在对反应的影响,也基于费米分布函数对其降解动力学进行非线性拟合.结果显示,这种基于费米函数的半经验模型适用于模拟氯酚氧化降解动力学反应(R20.818).氯酚降解速率如下:3-氯酚(3-CP)3,5-二氯酚(3,5-DCP)2,3-二氯酚(2,3-DCP)3,4-二氯酚(3,4-DCP)2,5-二氯酚(2,5-DCP)4-氯酚(4-CP)2-氯酚(2-CP)2,4-二氯酚(2,4-DCP)2,4,6-三氯酚(2,4,6-TCP)2,6-二氯酚(2,6-DCP).氯酚降解过程明显受到苯环氯原子取代数目、取代位置的影响,且氯原子取代位置具有更重要的影响:氯原子取代数目相同时,间位氯越多,降解越快,邻、对位越多,降解越慢.这主要通过影响表观速率常数k和半衰期t*得以实现.3,5-DCP降解表观速率常数k高达18.17 h~(-1),半衰期为0.2 h,而2,6-DCP表观速率常数仅为0.64 h~(-1),半衰期为5.88 h.氯离子的存在对氯酚降解动力学过程产生不同程度的抑制作用,其中2,6-DCP、2,4,6-TCP的抑制作用最为明显,这主要是由于氯离子的存在延长了其半衰期(分别由5.88 h、4.29 h延长至9.00 h、5.99 h),而对3,4-DCP、3,5-DCP则几乎没有抑制作用.表明氯离子抑制邻位氯代程度高的氯酚降解而不抑制间位氯代程度高的氯酚降解.研究结果为深入揭示氯酚降解机理提供了理论基础,也为提高含酚废水降解速率提供了技术参考.  相似文献   

6.
通过把起相转移作用的聚乙二醇链固载在硅胶上(SiO2-PEG600),再将聚乙稀吡咯烷酮(PVP)络合双金属Pd-Cu(PVP-PdCl2-CuCl2)后负载其中,制成一种新型双负载双金属水相脱卤催化剂PVP-PdCl2-CuCl2/SiO2-PEG600。以甲酸钠为氢转移试制,在水相中催化有机卤化物脱卤,研究结果表明:反应温度为800℃,Pd∶Cu=2∶1(摩尔比),反应介质pH≈11.7左右时,该催化剂对芳香氯化物及α-氯代酮、酯具有良好的催化脱氯和重复使用性能。  相似文献   

7.
使用碱式共沉淀法成功制备Fe(Mn)OOH催化剂,并且证实Fe(Mn)OOH可以高效催化臭氧降解水中扑米酮(PMD)和溶解性有机物(DOMs).表征分析表明,Fe(Mn)OOH表现出α-FeOOH和MnFe_2O_4两相的特征晶相结构.在相同条件下,Fe(Mn)OOH催化臭氧体系比单独臭氧、MnFe_2O_4和FeOOH催化臭氧体系表现出更好的扑米酮降解效能.在20 min时,Fe(Mn)OOH催化臭氧体系可以降解去离子水中97.5%的扑米酮,并且在快速和慢速反应阶段的反应速率常数分别可达0.46044 min~(-1)和0.10723 min~(-1).结果还表明,初始扑米酮和臭氧浓度以及催化剂投量之间的配比关系可能对扑米酮的降解有重要影响.Fe(Mn)OOH催化体系遵循羟基自由基的反应机制,可能是通过促进臭氧快速分解产生大量的羟基自由基,进而提高了水中有机物的降解效能.此外,Fe(Mn)OOH还具有结构稳定,可重复利用性好的优势.  相似文献   

8.
以木质生物炭为载体制备了负载型硫化铁(FeS_x/BC),采用扫描电镜/能量色散X射线光谱(SEM/EDX)、X射线粉末衍射(XRD)和X射线光电子能谱(XPS)对其结构进行了表征分析.然后将其用于催化除草剂2,4-二氯苯氧乙酸(2,4-D)的类Fenton氧化降解,并与市售硫化亚铁(c-FeS)进行对比.结果表明,生物炭可以提高硫化铁分散性,炭载催化剂中的Fe主要以Fe_3S_4形式存在.与c-FeS相比,采用FeS_x/BC催化降解2,4-D的反应速率常数(k_(obs))提高了约20倍.降解反应速率随催化剂、H_2O_2用量增加而提高,但是随初始pH(2.0—9.0)上升而下降.机理研究表明,生物炭作为电子穿梭体有助于提高·OH的生成量,促进2,4-D降解中间产物转化、并使脱氯反应更完全.  相似文献   

9.
液相中MnO2催化臭氧化降解磺基水杨酸   总被引:1,自引:2,他引:1  
研究了β-MnO2,γ-MnO2和MnSO4产生的胶状MnO2在液相中催化臭氧化降解磺基水杨酸的催化性能。结果表明,液相中MnO2催化臭氧化降解磺基水杨酸的活性与体系的pH值有关,而与其物相无关.在本实验条件下,三种MnO2在pH=1.0时均显示了较好的催化臭氧化活性,而在pH=6.8和8.0时却无活性。实验结果还表明,催化剂催化分解臭氧活性的高低与其催化臭氧化降解有机物的活性并无直接关系。  相似文献   

10.
零价铁还原脱氯污染土壤中PCBs的实验研究   总被引:1,自引:0,他引:1  
利用零价铁或铁的双金属对模拟污染土中多氯联苯(PCBs)在常温常压下的还原脱氯情况进行实验研究.采用高效离子色谱分析样本,结果表明:零价铁或者镍(Ni)铁双金属对土壤中浓度为5 mg·g-1的PCBs有一定的脱氯效果;当PCBs浓度降低为1 mg·g-1时只有钯(Pd)含量为0.05%的钯铁处理具有显著的脱氯效果;升高土壤温度到45℃,或者简单加入醋酸、活性炭、石墨以及硫粉等处理均不能有效提高脱氯效果;先添加硫粉和水培养,使土壤氧化还原电位降低后,添加含铜(Cu)为2%的铜铁及含钴(Co)为1%的钴铁双金属对土壤中的PCBs有明显的脱氯效果.  相似文献   

11.
农田重金属污染原位钝化修复研究进展   总被引:52,自引:0,他引:52  
污染土壤重金属原位钝化修复是通过向土壤中施加一些活性钝化修复材料,通过溶解沉淀、离子交换吸附、氧化还原、有机络合等反应来改变重金属在土壤中的赋存状态,降低土壤中重金属的有效浓度、迁移性和生物有效性。这种方法成本较低、操作简单、见效快且适合大面积推广,在重金属污染土壤修复中有着不可替代的作用。尤其对主要由污水灌溉、大气沉降等造成的农田土壤面源污染,一些具有吸附固定土壤中重金属离子特性的天然物质和工业副产品都可运用在实地的钝化修复中,且不同类型的钝化修复剂对重金属污染土壤的钝化修复效果各不相同。采用实验室评价和实地应用评价,一方面可以评估钝化修复材料对污染土壤中重金属离子的固定效率;另一方面可以评估钝化修复材料对土壤理化性状、养分状况和生物活性的影响。对重金属污染土壤原位钝化修复中不同来源的钝化剂进行了分类,目前广泛使用的钝化修复剂主要包括硅钙物质、含磷材料、有机物料、黏土矿物、金属及金属氧化物、生物碳及新型材料等,概述了它们各自对重金属污染土壤的钝化修复效果。从研究方法、评价指标、环境影响因子、钝化机制以及环境风险评价等方面分析了该领域的研究现状以及存在的主要问题,今后应重点关注钝化修复剂对土壤-作物系统的潜在环境风险以及钝化材料修复效果的田间长期稳定性评价。  相似文献   

12.
Wet air oxidation (WAO) and catalytic wet air oxidation (CWAO) are efficient processes to degrade organic pollutants in water. In this paper, we especially reviewed the WAO and CWAO processes for phenolic compounds degradation. It provides a comprehensive introduction to the CWAO processes that could be beneficial to the scientists entering this field of research. The influence of different reaction parameters, such as temperature, oxygen pressure, pH, stirring speed are analyzed in detail; Homogenous catalysts and heterogeneous catalysts including carbon materials, transitional metal oxides and noble metals are extensively discussed, among which Cu based catalysts and Ru catalysts were shown to be the most active. Three different kinds of the reactor implemented for the CWAO (autoclave, packed bed and membrane reactors) are illustrated and compared. To enhance the degradation efficiency and reduce the cost of the CWAO process, biological degradation can be combined to develop an integrated technology.
  相似文献   

13.
Manganese oxides (MnOx) have been demonstrated to be effective materials to activate Oxone (i.e., PMS) to degrade various contaminants. However, the contribution of direct oxidation by MnOx to the total contaminant degradation under acidic conditions was often neglected in the published work, which has resulted in different and even conflicting interpretations of the reaction mechanisms. Here, the role of MnOx (as both oxidants and catalysts) in the activation of Oxone was briefly discussed. The findings offered new insights into the reaction mechanisms in PMS-MnOx and provided a more accurate approach to examine contaminant degradation for water/wastewater treatment.  相似文献   

14.
A five-step sequential extraction technique was used to determine the chemical association of heavy metals (Pb, Zn, Cu and Cd), with major sedimentary phases (exchangeable, surface oxide and carbonate, Fe and Mn oxides, organic and residual metal ions), in samples from floodplain and recent flood sediments of the River Aire, West Yorkshire. Analysis indicates that metals Pb and Zn are primarily associated with the Fe and Mn oxides, Cu with the organic fraction and Cd with exchangeable and surface oxide and carbonate metal ions. Knowledge of the chemical speciation of heavy metals in river sediment, despite the procedure's inherent limitations, facilitates an understanding of their bioavailability, storage and remobilisation in floodplain and river channel environments.  相似文献   

15.
This investigation discloses a greener reaction to prepare pyrrole derivatives. Metal-free catalysts are greener alternatives to existing metal catalysts in synthetic organic chemistry. Indeed, transition metals are often costly and toxic. They may be found as traces in health reaction products such as pharmaceuticals. Alternatively small organic molecules termed “organocatalysts” allow the synthesis of valuable products without traces of toxic metals. Here, we show for the first time the use of vitamin B1 as new organocatalyst for the Paal–Knorr pyrrole synthesis under ambient conditions. Reaction conditions were optimized for the reaction of hexane-2,5-dione with 4-methoxyaniline. Ethanol was the most effective solvent. The conversion was quantitative using vitamin B1, by comparison with a low yield of 30?% without catalysis. The best conditions were performed in ethanol with 5?mol % of vitamin B1 during 1?h. This reaction was tested using various aromatic amines. To conclude the use of vitamin B1 for the Paal–Knorr pyrrole, cyclocondensation has mild reaction conditions, is simple to perform, and gives moderate to excellent yields. It is therefore a promising reaction for the preparation of various pyrrole derivatives.  相似文献   

16.
土壤中有机污染物-重金属复合污染的交互作用   总被引:5,自引:0,他引:5  
有机污染物-重金属复合污染是一种普遍存在的环境污染形式,对其进行研究具有重要的理论意义和实践价值。本文主要讨论了有机污染物和重金属在土壤中的吸附过程、化学作用过程以及生物学过程等的交互作用方式及其机理。  相似文献   

17.
• Superior catalytic activity observed for o-chlorophenol oxidation on Co2MgAlO. • The reducibility, oxygen species and basicity influenced catalytic activity. • The organic by-products were generated in o-chlorophenol catalytic oxidation. A cobalt-based hydrotalcite-like compound was prepared using a constant-pH coprecipitation method. Cobalt-transition metal oxides (Co2XAlO, X= Co, Mg, Ca and Ni) were investigated for the deep catalytic oxidation of o-chlorophenol as a typical heteroatom contaminant containing chlorine atoms. The partial substitution of Co by Mg, Ca or Ni in the mixed oxide can promote the catalytic oxidation of o-chlorophenol. The Co2MgAlO catalyst presented the best catalytic activity, and could maintain 90% o-chlorophenol conversion at 167.1°C, compared only 27% conversion for the Co3AlO catalyst. The results demonstrated that the high activity could be attributed to its increased low-temperature reducibility, rich active oxygen species and excellent oxygen mobility. In the existence of acid and base sites, catalysts with strong basicity also showed preferred activity. The organic by-products generated during the o-chlorophenol catalytic oxidation over Co2MgAlO catalyst included carbon tetrachloride, trichloroethylene, 2,4-dichlorophenol, and 2,6-dichloro-p-benzoquinon, et al. This work provides a facile method for the preparation of Co-based composite oxide catalysts, which represent promising candidates for typical chlorinated and oxygenated volatile organic compounds.  相似文献   

18.
柳葛贤  吕功煊 《环境化学》2007,26(5):626-629
研究了过渡金属硝酸盐及Al2O3为载体担载催化剂在罗丹明B臭氧氧化过程中的催化作用,考察了温度、pH值以及催化剂浓度等因素对反应的影响.结果表明,过渡金属离子可显著地提高罗丹明B的脱色速率,而担载型过渡金属氧化物催化剂活性较低.较低的pH值和反应温度有利于罗丹明B的催化臭氧化.罗丹明B溶液经过催化臭氧氧化后COD去除率可提高24%.  相似文献   

19.

The energy crisis and environmental pollution have recently fostered research on efficient methods such as environmental catalysis to produce biofuel and to clean water. Environmental catalysis refers to green catalysts used to breakdown pollutants or produce chemicals without generating undesirable by-products. For example, catalysts derived from waste or inexpensive materials are promising for the circular economy. Here we review environmental photocatalysis, biocatalysis, and electrocatalysis, with focus on catalyst synthesis, structure, and applications. Common catalysts include biomass-derived materials, metal–organic frameworks, non-noble metals nanoparticles, nanocomposites and enzymes. Structure characterization is done by Brunauer–Emmett–Teller isotherm, thermogravimetry, X-ray diffraction and photoelectron spectroscopy. We found that water pollutants can be degraded with an efficiency ranging from 71.7 to 100%, notably by heterogeneous Fenton catalysis. Photocatalysis produced dihydrogen (H2) with generation rate higher than 100 μmol h−1. Dihydrogen yields ranged from 27 to 88% by methane cracking. Biodiesel production reached 48.6 to 99%.

  相似文献   

20.
长春市土壤微生物生化作用与重金属化学形态关系研究   总被引:2,自引:0,他引:2  
研究了长春市土壤微生物的生化作用强度(氨化作用强度、固氮作用强度,纤维素分解强度和土壤基础呼吸)与重金属(Pb、Cd、Cu、Zn和Ni)化学形态的关系。通过科学采样和实验室测试分析了不同功能区土壤中,重金属含量和化学形态与微生物生化作用强度,并使用相关分析、偏相关分析多种数据统计方法进行数据处理。结果表明:各功能区因土地利用方式的差别和土壤中重金属的各种化学形态对土壤微生物生化作用强度有不同的影响。其中氨化作用与交换态Cd、Zn和Ni含量呈显著正相关;固氮作用与土壤重金属各化学形态相关性均不显著;呼吸作用与铁锰氧化物结合态Pd和交换态Cu呈显著正相关;纤维素分解作用强度与交换态Pd含量呈显著负相关。在土壤理化性质等相关变量受控时,重金属化学形态对微生物生化作用强度的影响有较明显的变化。其中与无控制变量相比,在控制变量作用下,纤维素分解作用强度受交换态Pd影响上升了0.0314,表现为交换态Pd抑制纤维素分解作用强度。呼吸作用与交换态Pd的相关系数在无控制因素情况下为-0.1425,在有控制因素情况下为-0.3230,表明交换态Pd促进呼吸作用强度。而有机结合态Ni表现为抑制固氮作用。因此可利用交换态Pd与纤维素分解作用强度、呼吸作用强度的相互关系,有机结合态Ni与固氮作用的相互关系等相结合来评价城市土壤重金属污染状况。文章为评价长春城市土壤重金属污染提供了微生物学指标的理论依据。  相似文献   

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