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1.
Hexachlorobenzene (HCB) in the milligram range was co-heated with calcium oxide (CaO) powder in sealed glass ampoules at 340–400 °C. The heated samples were characterized and analyzed by Raman spectroscopy, elemental analysis, gas chromatography/mass spectrometry, ion chromatography, and thermal/optical carbon analysis. The degradation products of HCB were studied at different temperatures and heated times. The amorphous carbon was firstly quantitatively evaluated and was thought to be important fate of the C element of HCB. The yield of amorphous carbon in products increased with heating time, for samples treated for 8 h at 340, 380 °C and 400 °C, the value were 17.5%, 34.8% and 50.2%, respectively. After identification of the dechlorination products, the HCB degradation on CaO at 340–400 °C was supposed to through dechlorination/polymerization pathway, which is induced by electron transfer, generate chloride ions and form high-molecular weight intermediates with significant levels of both hydrogen and chlorine, and finally form amorphous carbon. Higher temperature was beneficial for the dechlorination/polymerization efficiency. The results are helpful for clarifying the reaction mechanism for thermal degradation of chlorinated aromatics in alkaline matrices.  相似文献   

2.
Ma X  Zheng M  Liu W  Qian Y  Zhao X  Zhang B 《Chemosphere》2005,60(6):796-801
Dechlorination of hexachlorobenzene (HCB) was achieved by a mixture of commercial CaO and alpha-Fe2O3 (CaO/alpha-Fe2O3) in closed systems at temperatures of 300 degrees C and 350 degrees C, which exhibited a synergic effect compared to CaO or alpha-Fe2O3 alone, and the dechlorination efficiency was dramatically enhanced. When CaO and alpha-Fe2O3 coexisted, HCB was dechlorinated by about 98% after 0.5 h reaction at 300 degrees C. All TeCB-, TrCB-, and DCB-isomers were detected, showing the presence of more than one dechlorination pathway. The pathway to form 1,2,4-TrCB must be a major pathway because the greatest amount of 1,2,4-TrCB was detected. There existed discrepancy of the material balance between the starting and dechlorinated materials. It implies that besides dechlorination other decomposition processes may be present. The mechanism of synergic effect of calcium and iron oxides was investigated.  相似文献   

3.
Matsunaga A  Yasuhara A 《Chemosphere》2005,59(10):1487-1496
Electrochemical reduction with electrochemically generated naphthalene radical anion in N,N-dimethylformamide was applied to the dechlorination of five representative POPs, namely HCB, lindane, DDT, PCP and aldrin. Rapid and complete dechlorination was possible for lindane and DDT to give nearly quantitative yields of benzene and 1,1-diphenylethane, respectively. HCB was reduced through complex reaction pathways to yield unknown products. Dechlorination of PCP and aldrin beyond dichlorinated compounds was difficult because of their very negative reduction potential. The reaction pathways for each dechlorination were proposed with the identification of intermediates.  相似文献   

4.
Synthesized lead–iron (Pb/Fe) bimetallic particles were applied to dechlorinate hexachlorobenzene (HCB) under various conditions (e.g. bimetal amount, initial pH value, reaction temperature, and reaction duration). The results showed that adding Pb onto Fe benefited the dechlorination of HCB and the bimetal with 1.4% Pb content performed best. The degradation rate decreased regularly as the initial pH value of the aqueous increased from 1.9 to 11.1 except for pH 7.0 where the fastest dechlorination rate emerged. The dechlorination could be enhanced by increasing the amount of Pb/Fe or the reaction temperature. The dechlorination ratio of HCB within 15 min increased from 24.3% to 81.3% when Pb/Fe amount increased from 0.1 g to 0.8 g. The dechlorination followed pseudo-first-order kinetics, and the dechlorination rate constants were 0.0027, 0.0064, 0.0157, and 0.0321 min?1 at 25, 50, 70, and 85 °C, respectively, and the activation energy (Ea) of the dechlorination by Pb/Fe was 37.86 kJ mol?1.  相似文献   

5.
Brahushi F  Dörfler U  Schroll R  Munch JC 《Chemosphere》2004,55(11):1477-1484
The reductive dechlorination and behaviour of 14C-hexachlorobenzene (HCB) was investigated in an arable soil. The activity of the native anaerobic microbial communities could be induced by saturating the soil with water. Under these conditions high rates of dechlorination were observed. After 20 weeks of incubation only 1% of the applied 14C-HCB could be detected in the fraction of extractable residues. Additional organic substances, like wheat straw and lucerne straw, however considerably delayed and reduced the dechlorination process in the soil. The decline of HCB was not only caused by dechlorination but also by the formation of non-extractable residues, whereby their amounts varied with time depending on the experimental conditions. Several dechlorination products were detected, indicating the following main HCB transformation pathway: HCB → PCB → 1,2,3,5-TeCB → 1,3,5-TCB → 1,3-DCB, with 1,3,5-TCB as main intermediate dechlorination product. The other TeCB-, TCB- and DCB-isomers were also detected in low amounts, showing the presence of more than one dechlorination pathway. Since the methane production rates were lowest when the dechlorination rates were highest, it can be assumed that methanogenic bacteria were not involved in the dechlorination process of HCB. The established 14C-mass balances show, that with increasing dechlorination and incubation times, the 14C-recoveries decreased.  相似文献   

6.
Su YF  Hsu CY  Shih YH 《Chemosphere》2012,88(11):1346-1352
The effect of several anions and cations normally co-present in soil and groundwater contamination sites on the degradation kinetics and removal efficiency of hexachlorobenzene (HCB) by nanoscale zero-valent iron (NZVI) particles was examined. The degradation kinetics was not influenced by the HCO(3)(-), Mg(2+), and Na(+) ions. It was enhanced in the presence of the Cl(-) and SO(4)(2-) ions due to their corrosion promotion. The NO(3)(-) competes with HCB so it inhibits the degradation reaction. The Fe(2+) ions would inhibit the degradation reaction due to passivation layer formed, while it was enhanced in the presence of Cu(2+) ions resulted from the reduced form of copper on NZVI surfaces. These observations lead to a better understanding of HCB dechlorination with NZVI particles and can facilitate the remediation design and prediction of treatment efficiency of HCB at remediation sites.  相似文献   

7.
2,2',4,4',5,5'-Hexachlorobiphenyl (HCB) was dechlorinated with potassium-sodium (K-Na) alloy under an inert gas atmosphere. Solvent effect was observed in the reaction. Dechlorination yields in benzene and cyclohexane were 99.9998%, and 99.99996%, respectively. The reaction was exothermic and proceeded at room temperature. In benzene, trace amounts of polychlorinated biphenyls (PCBs) as products by stepwise dechlorination and polychlorinated quarterphenyls as product of Wurtz-Fittig reaction were detected as reaction intermediate. Reaction products were biphenyl, cyclohexylbenzene, and dicyclohexyl. In cyclohexane, there were no products of Wurtz-Fittig reaction. Dechlorination at para-position preferred to that at ortho-position, judging from analysis of PCBs as intermediates of stepwise dechlorination.  相似文献   

8.
9.
Inhibition of PCDD/Fs formation from dioxin precursors by calcium oxide   总被引:1,自引:0,他引:1  
Liu W  Zheng M  Zhang B  Qian Y  Ma X  Liu W 《Chemosphere》2005,60(6):785-790
Research aimed at understanding the inhibition effect of CaO on polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) formation form dioxins precursors, such as chlorophenols (CPs) and chlorobenzenes (CBs). The results indicated that a clear dioxin inhibition effect occurred both in open and sealed system when CaO was used. In the open system, PCDDs were the main congeners and the inhibition efficiency was all over 99% in the experiments. In the experiments with CaO, less than 0.1% of the initial PCP was detected in the absorption tube and only about 1% of the initial PCP was examined as calcium pentachlorophenate in the reaction tube. In the sealed system, the inhibition efficiency was over 90% at temperature range between 280 and 450 degrees C when PCP was used as model precursor. When HCB and 2,3,4,5-T4CP replaced PCP, significant inhibition effect was also observed. As CaO has the advantageous properties of non-toxicity and non-volatile nature, it is our hope that the result will contribute to the development of a new technique to cope with the problem of dioxin pollution in MWIs.  相似文献   

10.
BACKGROUND AND AIMS: Polychlorinated diphenyl ethers (PCDEs), which are among the members of persistent organic pollutants, and PCDEs have been determined in a number of environmental samples. The main possible sources are the technical production of chlorinated phenols and all processes of incomplete combustion. PCDEs were observed in the fly ash from a municipal waste incinerator (MWI). It was speculated that the condensation of chlorophenols with chlorobenzenes occurred via PCDEs to form polychlorinated dibenzofurans (PCDFs). Nevertheless, PCDEs formation from condensation of chlorophenols with chlorobenzenes has not been confirmed by experimental observation. The objective of this paper is to investigate the formation mechanism of PCDEs from the condensation of chlorophenols with chlorobenzenes. The results are expected to be helpful in understanding the formation of PCDEs and in controlling and abating PCDEs emissions from MWI. METHODS: The pyrolysis of pentachlorophenol (PCP) and/or polychlorobenzenes (PCBz) was carried out in a sealed glass tube. The reaction products were extracted and purified with K2CO3 solution. The samples were concentrated and then cleaned up on an alumina column. GC/MS was used for identification and quantification of reaction products. RESULTS AND DISCUSSION: The results showed that the pyrolysis of hexachlorobenzene (HCB) at 340 degrees C for 6 h led to the formation of decachlorodiphenyl ether (DCDE) (2.41 microg/mg) and octachlorodibenzo-p-dioxins (OCDD) (0.24 micropg/mg), while the pyrolysis of PCP yielded DCDE (13.08 microg/mg) and OCDD (180.13 microg/mg). In addition, the amount of DCDE formation from the pyrolysis of the mixture of PCP and HCB was 4.65 times higher than the total amount of DCDE formation from the pyrolysis of HCB and PCP, respectively. This indicated that PCP and HCB were prone to condensation and formation of DCDE. DCDE was the main congener of PCDEs from condensation of PCP with HCB at 340, 400 and 450 degrees C. A small amount of nonachlorodiphenyl ether (NCDE) was formed by dechlorination reaction at 450 degrees C. The condensation of PCP with 1,2,4,5-tetrachlorobenzene (Cl4Bz) formed 2,2',3,4,4',5,5',6-octachlorodiphenyl ether (OCDE). Small amounts of heptachlorodiphenyl ether (HpCDE) and hexachlorodiphenyl ether (HxCDE) were detected at 450 degrees C. Meanwhile, polychlorinated dibenzo-p-dioxins (PCDDs) and PCDFs were detected from the condensation of PCP and PCBz. CONCLUSIONS: Experimental studies clarified the behavior of the formation of PCDEs from condensation of polychlorophenols and PCBz. The condensation of polychlorophenols with PCBz formed PCDEs through elimination of HCl between polychlorophenols and PCBz molecules. Another pathway of PCDEs formation was elimination of H2O between two polychlorophenol molecules. In addition, dechlorination processes had caused the specific homologous pattern of PCDEs under higher temperatures.  相似文献   

11.
Jung B  Batchelor B 《Chemosphere》2007,68(7):1254-1261
This study examines the effect of iron-bearing phyllosilicates on dechlorination rates of chlorinated aliphatic hydrocarbons (CAHs) in iron-based degradative solidification/stabilization (DS/S-Fe(II)). Laboratory batch experiments were conducted to evaluate dechlorination rates of 1,1,1-trichloroethane (1,1,1-TCA) in a mixture solution of Fe(II), cement and three different iron-bearing phyllosilicates (biotite, vermiculite, and montmorillonite). A first-order rate model was generally used to describe the dechlorination kinetics and the rate constants were dependent on soil mineral type (biotite, vermiculite, and montmorillonite), Fe(II) dose, and the mass ratio of cement to soil mineral. The pseudo-first-order rate constant for montmorillonite was lower than that for biotite and vermiculite by factors of 11-27 when the mass ratio of cement to phyllosilicates was fixed at one. The presence of biotite and vermiculite increase and the presence of montmorillonite decrease the degradation rate that would be observed in their absence. The effect of cement/mineral ratio on rate constants with three different soil minerals indicates that biotite was more reactive than the other two phyllosilicates. This may be due to high accessible natural Fe(II) content in biotite. Montmorillonite appears to inhibit dechlorination by either inactivating Fe(II) by ion exchange or by physically blocking active sites on cement hydration products.  相似文献   

12.
The final disposal of ash from an incinerator is of special concern because of the possibility of its releasing toxic substances. Melting/vitrification has been regarded as a prospective technology of ash treatment. The object of this investigation was to evaluate the effect of silica (SiO2) addition on the immobilization of hazardous metals and the encapsulation of a glass network during the vitrification process. Four specimens with SiO2/fly ash mixing ratios of 0, 0.1, 0.2, and 0.3, respectively, were tested. The mobility of metals in slag was then estimated by a sequential extraction procedure. X-ray diffraction analysis indicates that SiO2 leads to the polymerization of silicates. The encapsulation of aluminum, calcium, and magnesium would not be observed unless adequate amount of SiO2 was added. It was also found that SiO2 addition enhances the formation of a compact and interconnected glass network structure and, thus, contributes to the chemical stability of metals in slag. After vitrification, the mobility of cadmium, copper, iron, chromium, nickel, lead, and zinc was significantly reduced. However, there is no significant correlation between the immobilization of these metals and the addition of SiO2.  相似文献   

13.
BACKGROUND, AIMS AND SCOPE: It is well known that the fly ash from filters of municipal waste incinerators (MWI-FA) shows dehalogenation properties after heating it to 240-450 degrees C. However, this property is not general, and fly ash samples do not possess dehalogenation ability at all in many cases. Fly ash has a very variable composition, and the state of the fly ash matter therefore plays the decisive role. In the present paper, the function of important components responsible for the dehalogenation activity of MWI-FA is analysed and compared with the model fly ash. METHODS: With the aim of accounting for the dehalogenation activity of MWI-FA, the following studies of hexachlorobenzene (HCB) dechlorination were performed: The role of copper in dehalogenation experiments was evaluated for five types of metallic copper. The gasification of carbon in MWI-FA was studied in the 250-350 degrees C temperature range. Five different kinds of carbon were used, combined with conventional Cu(o) and activated nanosize copper powder. The dechlorination experiments were also carried out with Cu(II) compounds such as CuO, Cu(OH)2, CuCl2 and CuSO4. The results were discussed from the standpoint of thermodynamics of potential reactions. Based on these results, the model of fly ash was proposed, containing silica gel, metallic copper and carbon. The dechlorination ability of MWI-FA and the model fly ash are compared under oxygen-deficient atmosphere. CONCLUSIONS: The results show that, under given experimental conditions, copper acts in the dechlorination as a stoichiometric agent rather than as a catalyst. The increased surface activity of copper enhances its dechlorination activity. It was found further that the presence of copper leads to a decrease in the temperature of carbon gasification. The cyclic valence change from Cu(o) to Cu+ or Cu2+ is a prerequisite for the dehalogenation to take place. RECOMMENDATION AND OUTLOOK: Thermodynamic analysis of the dechlorination effect, as well as the comparison of dechlorination pathways on MWI-FA and model fly ash, can provide a deeper understanding of the studied reaction.  相似文献   

14.
以颗粒活性炭(AC)和钛酸丁酯为原料,采用微波辐射法制备TiO2/AC复合光催化剂,并对制备的催化剂进行了表征;采用该催化剂对六氯苯进行光催化降解,确定了六氯苯降解的最佳工艺条件,并就几种外加试剂对TiO2/AC光催化降解六氯苯的强化作用进行了探讨。结果表明,制备的催化剂中TiO2均匀分布在活性炭表面、呈单一的锐钛矿晶型,晶粒生长完善。该催化剂催化降解六氯苯的最佳工艺条件为:pH值为5、TiO2负载量为18.2%、TiO2/AC投加量为0.4 g/L、反应时间为60 min。在此条件下,六氯苯降解效率达90.3%。添加适量的H2O2、AgNO3、K2S2O8、KIO4和KMnO4均能提高TiO2/活性炭对六氯苯的光催化降解效率。5种外加试剂的适宜添加量分别为0.3%、1.0、1.0、0.1和0.1 mmol/L,对TiO2/AC光催化效率的强化作用大小顺序为:H2O2〉AgNO3〉K2S2O8〉KMnO4〉KIO4。  相似文献   

15.
Chen IM  Chang FC  Wang YS 《Chemosphere》2001,45(2):223-229
To understand the dechlorination ability of chlorobenzenes (CBs) and polychlorinated biphenyls (PCBs) by untamed microorganisms under anaerobic condition and to correlate gas chromatographic properties with the occurrence of reductive dechlorination, introduction of CBs and PCBs in the culture medium inoculated with microorganisms from sludge and sediment, respectively, were performed. Three kinds of culture media preparing from sludge, river water and a synthetic medium were used in the experiments. HCB was degraded to 1,3,5-trichlorobenzene (1,3,5-TCB) and 1,3-dichlorobenzene (1,3-DCB) in both sludge medium and synthetic medium with inoculated microorganisms. Three PCB congeners including 2,3,4-, 3,4,5- and 2,3,4,5-CBp (chlorinated biphenyl) were not found to be dechlorinated in the river water medium with inoculation culture but to be dechlorinated in the synthetic medium. MNDO methodology was used to compute theoretical dechlorination reaction heats and GC-ECD techniques were used to estimate chromatographic data of CB and PCB congeners. Both CB and PCB congeners showed that dechlorination by untamed microorganisms under anaerobic mixed cultures were more likely to occur when larger amounts of energy were released and greater deltaln RRT value between the parent congener and the daughter product was observed. Deltaln RRT provided a more precise information on the singularity of PCBs ortho-dechlorination in an aspect of thermodynamic favorable rule.  相似文献   

16.
BACKGROUND: The spent waste of aliphatic chlorinated solvents has caused severe deterioration of groundwater quality. Trichloromethane (TCM), which shows health and toxicological effects on human beings, was selected as a model compound to be dechlorinated through a redox system. METHODS: The Fe0-based system including Fe0/H2O, Fe0/UV, Fe0/H2O2, and Fe0/UV/H2O2 was explored to evaluate its performance in dechlorinating TCM. H2O2 was dosed at later reaction time points to initiate Fenton or photo-Fenton reactions. The first two systems demonstrate the reductive dechlorination of TCM by Fe0-released electrons, while the latter two show dechlorination of TCM by both electron reduction and hydroxyl radical oxidation. The system parameters of TCM remaining, Cl- buildup, Fe2+ accumulation, H2O2 residue, and ORP were measured to describe different redox characteristics of TCM dechlorination. The Cl- buildup was used as a way to describe the degree of TCM dechlorination in an open reaction system. RESULTS: Reductive dechlorination efficiencies of TCM were 5% and 6% for the systems of Fe0/H2O and Fe0/UV, respectively. In contrast, the Fe/H2O2 and Fe0/UV/H2O2 systems were capable of dechlorinating TCM reductively and oxidatively by 14% and 15%, respectively. The presence of UV light was found to retard the dissolution of Fe2+, but it enhanced the rate of chloride buildup, based on the comparison of Fe0/H2O and Fe0/UV systems. In addition, WV irradiation plays only a minor role in the Fe0/UV/H2O2 system, in view of TCM dechlorination. Application of small amount of H2O2 results in the increase of Fe2+ accumulation rate in the Fe0/H2O2 system. CONCLUSIONS: TCM was dechlorinated mostly through post Fenton oxidation; reductive reaction represents a less efficient way to dechlorinate TCM. The efficiencies of overall TCM dechlorination for the two systems of Fe0/H2O2 and Fe0/UV/ H2O2 are comparable to each other, and this implies that the presence of UV irradiation imposes no significant enhancement. RECOMMENDATIONS AND OUTLOOKS: It is highly recommended to initiate effective redox dechlorination of TCM with the system of Fe0/H2O2, where the H2O2 in excess is applied at a later reaction time point.  相似文献   

17.
Ghauch A  Tuqan A 《Chemosphere》2008,73(5):751-759
Modified zero valent iron (MZVI) was used to study the transformation of a chlorothalonil (CLT) solution and the variation of the observed degradation rate of the reduction reactions. This was carried out when transition metals e.g. Pd, Cu and Co plated on the surface of micrometric iron particles (< 150 microm) were used as reducing catalytic agents for pesticide removal. Reactions were undertaken under both oxic and anoxic conditions in the presence and the absence of a phosphate buffer solution (PBS). Results of batch studies in nitrogen sparged solutions revealed that incomplete slow dechlorination merely occurred with zero valent iron (ZVI), however, complete rapid dechlorination reactions took place with MZVI especially Fe/Pd. Dechlorination was depicted by studying UV absorbance and MS spectra of CLT and all corresponding by-products. Typical blue shifts (deltalambda = 4-6 nm/chlorine atom) were observed at the same time as chlorine cluster isotopes disappeared. After the plating process, metal loading was controlled by analyzing the remaining metal in the solution by atomic absorption spectroscopy. Experiments showed that CLT degradation mechanism is faster in nitrogen sparged solutions in the absence of PBS. Time needed for complete removal of 2.08 +/- 0.19 microM CLT solution was about 2 h when experiments were conducted with ZVI (t1/2 = 15.0 min) and about 10 min when the reaction was carried out under the same conditions with Fe/Pd 1% (t1/2 = 1.0 min). Degradation rates for all bimetallic systems were determined showing that Pd is the more exciting catalytic transition metal followed by Cu and Co. Furthermore, MZVI method showed obvious advantage to traditional CLT treatment methods.  相似文献   

18.
This study was conducted to examine the synthesis and application of novel nano-size calcium/iron-based composite material as an immobilizing and separation treatment of the heavy metals in fly ash from municipal solid waste incineration. After grinding with nano-Fe/Ca/CaO and with nano-Fe/Ca/CaO/[PO4], approximately 30 wt% and 25 wt% of magnetic fraction fly ash were separated. The highest amount of entrapped heavy metals was found in the lowest weight of the magnetically separated fly ash fraction (i.e., 91% in 25% of treated fly ash). Heavy metals in the magnetic or nonmagnetic fly ash fractions were about 98% and 100% immobilized, respectively. Additionally, scanning electron microscopy combined with energy-dispersive X-ray spectrometry (SEM-EDS) observations indicate that the main fraction of enclosed/bound materials on treated fly ash includes Ca/PO4-associated crystalline complexes. After nano-Fe/Ca/CaO/[PO4] treatment, the heavy metal concentrations in the fly ash leachate were much lower than the Japan standard regulatory limit for hazardous waste landfills. These results appear to be extremely promising. The addition of a nano-Fe/Ca/CaO/PO4 mixture with simple grinding technique is potentially applicable for the remediation and volume reduction of fly ash contaminated by heavy metals.

Implications: After grinding with nano-Fe/Ca/CaO and nano-Fe/Ca/CaO/[PO4], approximately 30 wt% and 25 wt% of magnetic fraction fly ash were separated. The highest amount of entrapped heavy metals was found in the lowest weight of the magnetically separated fly ash fraction (i.e., 91% in 25% of treated fly ash), whereas heavy metals either in the magnetic or nonmagnetic fly ash fractions were about 98% and 100% immobilized. These results appear to be very promising, and the addition of nano-Fe/Ca/CaO/PO4 mixture with simple grinding technique may be considered potentially applicable for the remediation and volume reduction of contaminated fly ash by heavy metals.  相似文献   

19.
In this study, the effects of the basicity on the pouring point of the municipal solid waste incinerator fly ash-sewage sludge ash mixture is investigated. Four kinds of sewage sludge ash, which were collected from several primary and secondary sewage treatment plants and were produced by different processes and sludge conditioning alternatives, were used as modifiers. The results indicate that the pouring point of the mixture increased with increasing basicity, within the range of 0.65-1.90. The pouring point is affected by the contents of the mixtures (CaO, SiO2, Al2O3, and the flux). It is suggested that an increase in the CaO content tends to raise the pouring point, whereas an increase in the SiO2 and/or the Al2O3 contents cause as adverse reaction. The prediction equation, obtained by multilinear regression (significant level is 0.05), is as follows: pouring temperature = 1189.6 + 4.19 CaO - 0.96 SiO2 - 4.33 Al2O3 (R2 = 0.91). In general, the pouring point decreased when the basicity was < 1. The pouring point apparently increased when the basicity was > 1.2. The regression squares for the different basicities were between 0.84 and 0.91. From these relationships, we note that a basicity index of 5 gave the best R2 (0.91). From the results of this study, it can be concluded that the modification of the basicity of the fly ash by the addition of sewage sludge ash to lower the pouring point is feasible and leads to a more energy-efficient melting process. In addition, these synthetic slags have a good pozzolanic reactive activity.  相似文献   

20.
Zhang F  Chen J  Zhang H  Ni Y  Liang X 《Chemosphere》2007,68(9):1716-1722
Dechlorination of octachlorodibenzo-p-dioxin (OCDD) was carried out in ethanol-water (v/v=1:1) solution of NaOH in the presence of Pd/C catalysts with the use of H(2). The substrate was dechlorinated with Pd/C under mild conditions (atmospheric pressure and <100 degrees C) to give a chlorine-free product, dibenzo-p-dioxin (DD), in high yields. After reaction of 3h at 50 degrees C, 95.9% OCDD was degraded to low dechlorinated congeners and the yield of DD was 77.4%. We have also studied the dechlorination selectivity of chlorine atoms on the different substituted positions and postulated the dechlorination pathway of OCDD. For OCDD, the 2-position has higher reactivity than 1-position, but the difference is very small. From the distribution statistics of the intermediates during the reaction, we postulate that the steric effect plays an important role during the reaction and affect the dechlorination pathway of OCDD.  相似文献   

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