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1.
氨法脱硫工艺S(IV)氧化动力学模型研究   总被引:1,自引:0,他引:1  
贾勇  柏家串  钟秦 《环境科学学报》2014,34(8):1954-1960
目前,有关氨法脱硫技术对S(IV)氧化的研究未考虑HSO-3及离子强度等因素的影响.因此,本文根据氨法脱硫反应机理建立实验装置对S(IV)氧化动力学进行了研究,考察了SO2-3浓度、SO2-4浓度、pH值、温度和氧化空气量对S(IV)氧化速率的影响.结果表明,S(IV)的氧化速率与SO2-3浓度呈-0.5级关系,与SO2-4浓度之间的关系为r(IV)=0.00121exp(-0.89CSO2-4);HSO-3较SO2-3更容易被氧化,保持较低pH值时对S(IV)的氧化有利;S(IV)的氧化速率随氧化空气量和温度的升高而增大,反应的表观活化能约为28.0 kJ·mol-1.利用数学模型对S(IV)氧化过程进行了数值模拟,结果表明,该模型能够较好地反映氨法脱硫S(IV)氧化过程.  相似文献   

2.
Experiments were conducted in a fixed-bed reactor containing a commercial V2O5/WO3/TiO2 catalyst to investigate mercury oxidation in the presence of HCl and O2. Mercury oxidation was improved significantly in the presence of HCl and O2, and the Hg0 oxidation efficiencies decreased slowly as the temperature increased from 200 to 400°C. Upon pretreatment with HCl and O2 at 350°C, the catalyst demonstrated higher catalytic activity for Hg0 oxidation. Notably, the effect of pretreatment with HCl alone was not obvious. For the catalyst treated with HCl and O2, better performance was observed with lower reaction temperatures. The results showed that both HCl and Hg0 were first adsorbed onto the catalyst and then reacted with O2 following its adsorption, which indicates that the oxidation of Hg0 over the commercial catalyst followed the Langmuir–Hinshelwood mechanism. Several characterization techniques, including Hg0 temperature-programmed desorption (Hg-TPD) and X-ray photoelectron spectroscopy (XPS), were employed in this work. Hg-TPD profiles showed that weakly adsorbed mercury species were converted to strongly bound species in the presence of HCl and O2. XPS patterns indicated that new chemisorbed oxygen species were formed by the adsorption of HCl, which consequently facilitated the oxidation of mercury.  相似文献   

3.
Experiments were conducted in a fixed-bed reactor that contained a commercial catalyst, V2O5–WO3/TiO2, to investigate mercury oxidation in the presence of NO and O2. Mercury oxidation was improved by NO, and the efficiency was increased by simultaneously adding NO and O2. With NO and O2 pretreatment at 350°C, the catalyst exhibited higher catalytic activity for Hg0 oxidation, whereas NO pretreatment did not exert a noticeable effect. Decreasing the reaction temperature boosted the performance of the catalyst treated with NO and O2. Although NO promoted Hg0 oxidation at the very beginning, excessive NO counteracted this effect. The results show that NO plays different roles in Hg0 oxidation; NO in the gaseous phase may directly react with the adsorbed Hg0, but excessive NO hinders Hg0 adsorption. The adsorbed NO was converted into active nitrogen species (e.g., NO2) with oxygen, which facilitated the adsorption and oxidation of Hg0. Hg0 was oxidized by NO mainly by the Eley–Rideal mechanism. The Hg0 temperature-programmed desorption experiment showed that weakly adsorbed mercury species were converted to strongly bound ones in the presence of NO and O2.  相似文献   

4.
A spectrophotometric study employing stopped-flow techniques was performed of the sulfite-induced autoxidation of Fe(II) in acidic aqueous solution (pH < 3.9). In the presence of an excess Fe(II), simultaneous autoxidation of Fe(II) and sulfite occurs, and completes the catalytic cycle for the Fe(III) catalyzed autoxidation of sulfite. In the presence of an excess sulfite, the rapid formation of Fe(III) is followed by a slower redox process during which Fe(II) and sulfate are produced. The sulfite-induced autoxidation of Fe(II) is independent of the Fe(II) concentration. The suggested mechanism involves the rate-determining formation of SO3, followed by the formation of SO5and the subsequent oxidation of Fe(II).  相似文献   

5.
冯璞阳  李哲  者渝芸  黄杰  梁东丽 《环境科学》2016,37(8):3160-3168
硒在土壤中的环境化学行为及其生物有效性在很大程度受到吸附解吸作用的影响,土壤对硒的吸附解吸因为土壤理化性质的不同差异很大.本文采用批量吸附实验,选择土壤性质差异较大的我国18种农田土壤,探讨了土壤p H、无定形铁铝氧化物、有机质和机械组成等对SeO_4~(2-)吸附的影响.结果表明,18种土壤对SeO_4~(2-)的吸附均是一个先快后慢的过程,在24 h达到吸附平衡;二级动力学方程为描述SeO_4~(2-)吸附的最佳模型(R20.976),18种土壤对SeO_4~(2-)吸附大多符合Freundlich模型(R20.842);土壤对SeO_4~(2-)吸附量与p H值(P0.01)、碳酸盐含量(P0.05)呈显著负相关,而与无定型铁、铝含量(P0.01)及有机质含量(P0.05)呈正相关;18种土壤对SeO_4~(2-)吸附的固液分配系数(Kd值)均很低(0.99~18.18 L·kg~(-1));土壤SeO_4~(2-)解吸率均大于80%,表明吸附是可逆的;土壤吸附SeO_4~(2-)的低Kd值和高解吸率反映了硒酸盐易迁移淋溶的特性,这应当在区域环境硒的评价和调控中受到关注.  相似文献   

6.
Series of Cu-USY zeolite catalyst with different Cu loading content were synthesized through simple impregnation method. The obtained catalysts were subjected to selective catalytic reduction of NOx with NH3 (NH3-SCR) performance evaluation, structural/chemical characterizations such as X-ray diffraction (XRD), N2 adsorption/desorption, H2 temperature-programmed reduction (H2-TPR), NH3 temperature-programmed desorption (NH3-TPD) as well as detailed in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) experiments including CO adsorption, NH3 adsorption and NO+O2 in situ reactions. Results show that Cu-USY with proper Cu loading (in this work 5Cu-USY with 5 wt.% Cu) could be promising candidates with highly efficient NH3-SCR catalytic performance, relatively low byproduct formation and excellent hydrothermal stability, although its SO2 poisoning tolerability needs alleviation. Further characterizations reveal that such catalytic advantages can be attributed to both active cu species and surface acid centers evolution modulated by Cu loading. On one hand, Cu species in the super cages of zeolites increases with higher Cu content and being more conducive for NH3-SCR reactivity. On the other hand, higher Cu loading leads to depletion of Brønsted acid centers and simultaneous formation of abundant Lewis acid centers, which facilitates NH4NO3 reduction via NH3 adsorbed on Lewis acid centers, thus improving SCR reactivity. However, Cu over-introduction leads to formation of surface highly dispersed CuOx, causing unfavorable NH3 oxidation and inferior N2 selectivity.  相似文献   

7.
Despite the heterogeneous reaction of sulfur dioxide (SO2) on mineral dust particles significantly affects the atmospheric environment, the effect of acidic gases on the formation of sulfite and sulfate from this reaction is not particularly clear. In this work, using the in-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) technique, we employed a mineral dust particle model (CaCO3) combined with NO2 and acetic acid to investigate their effects on the heterogeneous reaction of SO2 on CaCO3 particles. It was found that water vapor can promote the formation of sulfite and simulated radiation can facilitate the oxidation of sulfite to sulfate. The addition of NO2 or acetic acid to the reaction system altered the production of sulfate and sulfite accordingly. There was a synergistic effect between NO2 and SO2 that promoted the oxidation of sulfite to sulfate, and a competitive effect between acetic acid and SO2 that inhibited the formation of sulfite. Moreover, light and water vapor can also affect the heterogeneous reaction of SO2 with the coexistence of multiple gases. These findings improve our understanding of the effects of organic and inorganic gases and environmental factors on the formation of sulfite and sulfate in heterogeneous reactions.  相似文献   

8.
Due to the ever-tightening regulation on mercury emission in recent decades, there is an urgent need to develop novel materials for the removal of elemental mercury at coal-fired power plants. In this study, a series of MoS2 quantum dots (QDs)-based MoS2/HKUST-1 composite materials were prepared. It is found that MoS2 QDs were encapsulated by HKUST-1 and enhanced the crystallinity and specific surface area of HKUST-1. The MoS2/HKUST-1 showed excellent performance in catalytic oxidation of Hg0 as compared with pristine HKUST-1. It is found that surface layer of lattice oxygens is active and participates in Hg0 oxidation, while the consumption of surface oxygens then leads to the formation of oxygen vacancies on the surface. These vacancies are effective in the adsorption and dissociation of O2, which subsequently participates in the oxidation of Hg0. Moreover, the study on the influence of commonly seen gas components, such as SO2, NO, NH3 and H2O, etc., on Hg0 oxidation demonstrated that synergistic effects exist among these gas species. It is found that the presence of NO promotes the oxidation of Hg0 using oxygen as the oxidant.  相似文献   

9.
电流密度对BDD电极电化学矿化吲哚的影响与机制   总被引:1,自引:1,他引:1  
张佳维  王婷  郑彤  蒋欢  倪晋仁 《环境科学》2017,38(9):3755-3761
掺硼金刚石膜(BDD)电极电化学氧化法是去除难降解有机污染物的有效手段.与总有机碳(TOC)等的测定相比,气态中间产物的逸出量能够更直观有效地反映有机物的矿化程度与去除效果.本研究以吲哚为代表性污染物,通过对比不同电流密度(10、20和30 m A·cm-2)下BDD电极对吲哚的去除率与矿化率,结合降解过程中碳和氮形态的变化与守恒情况,分析吲哚的降解机制.结果表明,BDD电极对吲哚有良好的去除效果,电流密度为10、20、30 m A·cm-2时,吲哚达到100%去除的时间分别为8、5和4 h;TOC去除率、CO_2产生量均随电流密度的增加而增大,证明矿化率与电流密度成正相关;电解产生的CO_2气体与TOC、无机碳(TIC)构成了碳守恒体系.4~5 h时,体系TOC、TON和CO_2产生量均没有变化,表明电解产生的靛红具有较高的稳定性,此时为中间产物积累阶段;XPS表征进一步证实了中间产物靛红、苯醌等在电极表面的吸附,随着电解时间的延长,这些吸附的中间产物可进一步被降解.本研究从气态产物检测及碳氮形态分析与守恒的角度阐释吲哚矿化过程,对于辅助揭示有机物的电解过程有重要意义.  相似文献   

10.
以南方酸性黄棕壤为研究对象,采用根箱进行小白菜种植,研究了不同剂量的外源硒(0、0.25、1.00 mg·kg-1,以Se计)处理下,小白菜根际与非根际土壤Cd的含量变化;同时,通过Langmuir和Freundlich吸附模型进一步分析了经Se(0、0.25、1.00 mg·kg-1)预处理并经历过小白菜生长的根际与非根际土壤对Cd的吸附与解吸特性.结果表明,在Cd含量较低(0.50 mg·kg-1)的土壤中,低剂量的Se处理(0.25 mg·kg-1)根际土壤与非根际土壤的Cd含量均高于Se剂量为0、1.00 mg·kg-1的两个处理;在Cd含量较高(5.00 mg·kg-1)的土壤中,不同剂量的Se处理未能对土壤中Cd含量造成显著差异.通过吸附解吸试验及Langmuir和Freundlich两种吸附模型的模拟,发现根际土壤对Cd的吸附容量和吸附能力均小于非根际土壤,且根际土壤Cd的非专性吸附比率大于非根际土壤,表明小白菜的生长能够改变根际土壤对重金属Cd的吸附解吸特性,增加土壤中Cd的环境风险;然而,在本实验剂量范围内,外源Se预处理并未显著改变小白菜土壤Cd的吸附解吸特性,尚不足以证明Se通过影响小白菜根系分泌物等微域环境进而改变土壤重金属Cd的吸附解吸等环境化学行为.  相似文献   

11.
Time-resolved single-particle measurements were conducted during Chinese New Year in Nanning, China. Firework displays resulted in a burst of SO_2, coarse mode, and accumulation mode(100–500 nm) particles. Through single particle mass spectrometry analysis, five different types of particles(fireworks-metal, ash, dust, organic carbon-sulfate(OC-sulfate), biomass burning) with different size distributions were identified as primary emissions from firework displays. The fireworks-related particles accounted for more than70% of the total analyzed particles during severe firework detonations. The formation of secondary particulate sulfate and nitrate during firework events was investigated on single particle level. An increase of sulfite peak(80SO_3~-) followed by an increase of sulfate peaks(97HSO_4~-+ 96SO_4~-) in the mass spectra during firework displays indicated the aqueous uptake and oxidation of SO_2 on particles. High concentration of gaseous SO_2, high relative humidity and high particle loading likely promoted SO_2 oxidation. Secondary nitrate formed through gas-phase oxidation of NO_2 to nitric acid, followed by the condensation into particles as ammonium nitrate. This study shows that under worm, humid conditions, both primary and secondary aerosols contribute to the particulate air pollution during firework displays.  相似文献   

12.
The stronger coordination ability of mercury ions with organic ligands than the metal ions in metal organic framework (MOFs) provides an accessible way to separate mercury ions from solution using specific MOFs. In this study, a Co-based MOF (ZIF-67, Co(mIM)2) was synthesized. It did not introduce specific functional groups, such as -SH and -NH2, into its structure through complicated steps. It separate Hg2+ from wastewater with a new strategy, which utilized the stronger coordination ability of Hg2+ with the nitrogen atom on the imidazole ring of the organic ligand than the Co2+ ions. Hg2+ replaced Co2+ nodes from ZIF-67 and formed a more stable precipitate with mIM. The experimental results showed that this new strategy was efficient. ZIF-67 exhibited Hg2+ adsorption capacity of 1740 mg/g, much higher than the known MOFs sorbents. mIMs is the reaction center and ZIF-67 can improve its utilization. The sample color faded from purple to white due to the loss of cobalt ion. It is a great feature of ZIF-67 that allows users to judge whether the sorbent is deactivated intuitively. ZIF-67 can be sustainable recycled by adding organic ligands to the solution after treatment due to its simple synthesis method at room temperature. It's a high-efficient and sustainable sorbent for Hg2+ separation from wastewater.  相似文献   

13.
Two kinds of activated carbons modified by Na+ impregnation after pre-treatments involving oxidation by nitric acid or acidification by hydrochloric acid (denoted as AC/N-Na and AC/HCl-Na, respectively), were used as adsorbents to remove NH4+-N. The surface features of samples were investigated by BET, SEM, XRD and FT-IR. The adsorption experiments were conducted in equilibrium and kinetic conditions. Influencing factors such as initial solution pH and initial concentration were investigated. A possible mechanism was proposed. Results showed that optimal NH4+-N removal efficiency was achieved at a neutral pH condition for the modified ACs. The Langmuir isotherm adsorption equation provided a better fit than other models for the equilibrium study. The adsorption kinetics followed both the pseudo second-order kinetics model and intra-particle kinetic model. Chemical surface analysis indicated that Na+ ions form ionic bonds with available surface functional groups created by pre-treatment, especially oxidation by nitric acid, thus increasing the removal efficiency of the modified ACs for NH4+-N. Na+-impregnated ACs had a higher removal capability in removing NH4+-N than unmodified AC, possibly resulting from higher numbers of surface functional groups and better intra-particle diffusion. The good fit of Langmuir isotherm adsorption to the data indicated the presence of monolayer NH4+-N adsorption on the active homogenous sites within the adsorbents. The applicability of pseudo second-order and intra-particle kinetic models revealed the complex nature of the adsorption mechanism. The intra-particle diffusion model revealed that the adsorption process consisted not only of surface adsorption but also intra-particle diffusion.  相似文献   

14.
The acid snow/rain model [describedin Part I, Kitada et al., Atmospheric Environment27A, 1061–1076, 1993] was applied to investigate transport/transformation/deposition of acidic species in association with snow-precipitating cloud over the Japan Sea in winter. The model results showed: (1) The snow-precipitating clouds generated by relatively weak convective motions tend to trap aerosols of sulfate and nitrate and soluble gases such as SO2 and HNO3 below cloud levels, thus keeping their concentrations at higher levels than those for no-cloud situations. The mechanisms involved are: transfer of gas- and aerosol-phase species to cloud-phase through absorption and nucleation scavenging, then their transfer from cloud to snow through riming, and subsequent release from sublimating snow back to gas- and aerosol-phases below cloud base. (2) In-cloud oxidation enhanced the overall conversion of SO2 to SO42− by some 25% with respect to no-cloud situation after 12 h. Furthermore, contributions to the oxidation were 77.4%, 21.1% and 1.5% for S(IV)H2O2, S(IV)O2 with catalysts of Fe3+ + Mn2+ and S(IV)O3 reactions, respectively. (3) The sulfate wet deposited by precipitating snow for 12 h was due mostly to in-cloud scavenging and in-cloud oxidation, i.e. 66% by nucleation scavenging and the remaining by in-cloud oxidation of S(IV), while the contribution of below-cloud scavenging was negligible. (4) The adsorption process of HNO3 onto the surface of falling snow was found to account for major below-cloud scavenging of snow, and thus in contrast to SO42−, the below-cloud scavenging contributed very significantly to the nitrate wet deposition. Throughout the stimulation, below-cloud scavenging was responsible for 75% of the snow-NO3 formation. Therefore, taking account of this process in acid snow models is important.  相似文献   

15.
Fly ash is a potential alternative to activated carbon for mercury adsorption. The effects of physicochemical properties on the mercury adsorption performance of three fly ash samples were investigated. X-ray fluorescence spectroscopy, X-ray photoelectron spectroscopy, and other methods were used to characterize the samples. Results indicate that mercury adsorption on fly ash is primarily physisorption and chemisorption. High specific surface areas and small pore diameters are beneficial to efficient mercury removal. Incompletely burned carbon is also an important factor for the improvement of mercury removal efficiency, in particular. The C-M bond, which is formed by the reaction of C and Ti, Si and other elements, may improve mercury oxidation. The samples modified with CuBr2 , CuCl 2 and FeCl3 showed excellent performance for Hg removal, because the chlorine in metal chlorides acts as an oxidant that promotes the conversion of elemental mercury (Hg0) into its oxidized form (Hg2+). Cu2+ and Fe3+ can also promote Hg 0 oxidation as catalysts. HCl and O2 promote the adsorption of Hg by modified fly ash, whereas SO2 inhibits the Hg adsorption because of competitive adsorption for active sites. Fly ash samples modified with CuBr2 , CuCl2 and FeCl3 are therefore promising materials for controlling mercury emissions.  相似文献   

16.
In this study, the mercury adsorption characteristics of HBr-modified fly ash in an entrained-flow reactor were investigated through thermal decomposition methods. The results show that the mercury adsorption performance of the HBr-modified fly ash was enhanced significantly. The mercury species adsorbed by unmodified fly ash were HgCl2, HgS and HgO. The mercury adsorbed by HBr-modified fly ash, in the entrained-flow reactor, existed in two forms, HgBr2 and HgO, and the HBr was the dominant factor promoting oxidation of elemental mercury in the entrained-flow reactor. In the current study, the concentration of HgBr2 and HgO in ash from the fine ash vessel was 4.6 times greater than for ash from the coarse ash vessel. The fine ash had better mercury adsorption performance than coarse ash, which is most likely due to the higher specific surface area and longer residence time.  相似文献   

17.
水合电子(e-aq)是已知活性最强的还原物种之一.基于SO_3~(2-)受紫外光激发活化会释放e-aq的性质,提出了SO_3~(2-)/UV高级还原体系,用于降解稳定污染物.以7种卤乙酸为目标物,从卤素取代种类、卤代程度、实际水质本底影响等角度,考察了该体系对毒性卤代有机物(HOCs)的降解及脱卤效能,并探讨了相关机理.结果表明:HOCs的降解至少有直接光解和e-aq还原两条途径.卤素取代种类与卤化程度决定了HOCs的直接光解特性,其速率随氯、溴、碘取代顺序及卤化程度的增加而加快.SO_3~(2-)/UV体系显著提高了HOCs的降解及脱卤效率;对于直接光解慢的HOCs,其降解与脱卤主要由e-aq还原引起.SO_3~(2-)/UV体系在两种地表水质本底下仍具有较高的脱卤效能.  相似文献   

18.
The elemental mercury removal abilities of three different zeolites (NaA, NaX, HZSM-5) impregnated with iron (III) chloride were studied on alab-scale fixed-bed reactor. X-ray diffraction, nitrogen adsorption porosimetry, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and temperature programmed desorption (TPD) analy-ses were used to investigate the physicochemical properties. Results indicated that the pore structure and active chloride species on the surface of the samples are the key factors for physisorption and oxidation of Hg0, respectively. Relatively high surface area and micropore volume are beneficial to efficient mercury adsorption. The active Cl species generated on the surface of the samples were effective oxidants able to convert elemental mercury (Hg0) into oxidized mercury (Hg2+). The crystallization of NaCl due to the ion exchange effect during the impregnation of NaA and NaX reduced the number of active Cl species on the surface, and restricted the physisorption of Hg0. Therefore, the Hg0 removal efficiencies of the samples were inhibited. The TPD analysis revealed that the species of mercury on the surface of FeCl3-HZSM-5 was mainly in the form of mercuric chloride(HgCl2), while on FeCl3-NaX and FeCl3-NaA it was mainly mercuri coxide(HgO).  相似文献   

19.
The elemental mercury removal abilities of three different zeolites (NaA, NaX, HZSM-5) impregnated with iron(III) chloride were studied on a lab-scale fixed-bed reactor. X-ray diffraction, nitrogen adsorption porosimetry, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and temperature programmed desorption (TPD) analyses were used to investigate the physicochemical properties. Results indicated that the pore structure and active chloride species on the surface of the samples are the key factors for physisorption and oxidation of Hg0, respectively. Relatively high surface area and micropore volume are beneficial to efficient mercury adsorption. The active Cl species generated on the surface of the samples were effective oxidants able to convert elemental mercury (Hg0) into oxidized mercury (Hg2 +). The crystallization of NaCl due to the ion exchange effect during the impregnation of NaA and NaX reduced the number of active Cl species on the surface, and restricted the physisorption of Hg0. Therefore, the Hg0 removal efficiencies of the samples were inhibited. The TPD analysis revealed that the species of mercury on the surface of FeCl3–HZSM-5 was mainly in the form of mercuric chloride (HgCl2), while on FeCl3–NaX and FeCl3–NaA it was mainly mercuric oxide (HgO).  相似文献   

20.
以稻草秸秆为原料,分别通过水热炭化和热解炭化制备生物质炭(分别记为RS-HC和RS-BC),并采用不同的洗涤剂(蒸馏水、乙醇、四氢呋喃)对水热炭进行洗涤,分别记为RS-HC1、RS-HC2和RS-HC3.探究了吸附时间、Cd2+初始浓度和溶液pH值对4种生物质炭吸附性能的影响.结果表明:4种生物质炭对Cd2+的吸附均符合准二级动力学方程,表明吸附过程主要受化学吸附速率控制;RS-HC对不同浓度下Cd2+的吸附符合Langmuir等温吸附模型,但对于RS-BC,Langmuir方程和Freundlich方程的拟合效果都比较好(R2>0.93),说明水热炭对Cd2+的吸附多为单分子层吸附,而Cd2+在热解炭上的吸附则是多分子层吸附和单分子层吸附共同作用的结果;4种生物质炭的平衡吸附容量排序为:RS-BC > RS-HC3 > RS-HC2 > RS-HC1,RS-HC3和RS-HC2的平衡吸附量分别是RS-HC1的3.32和1.7倍;随着pH(3~8)的增加,生物质炭对Cd2+的吸附量逐渐增加,在pH=4时,RS-BC的吸附量是RS-HC3的5.57倍.  相似文献   

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