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1.
采用实验方法研究了低成本环境友好型添加剂抗坏血酸(AA)对Fe2+/H2O2体系氧化NO气体及其对体系内H2O2分解的影响,分析了AA对体系氧化NO能力及H2O2分解的影响机制。研究结果表明:AA通过加速Fe3+向Fe2+的转化而促进Fe2+/H2O2体系对NO的氧化。[AA]0:[Fe2+]0对体系氧化NO的能力及H2O2的分解具有重要影响。综合考虑NO氧化脱除量及H2O2消耗量,合理的[AA]0:[Fe2+]0为1/3~1/2。AA的分次添加方式可大幅度提升体系氧化NO气体的能力。研究结果可望为发展基于H2O2为氧化剂的烟气NO绿色氧化技术提供理论基础。  相似文献   

2.
Ta3N5 was synthesized by nitridation of Ta2O5 under NH3 flow at 700 °C. The catalyst was pure Ta3N5 according to X-ray diffraction (XRD), and was about 5 nm in size with a BET specific surface area 52.8 m2/g. When Ta3N5 was added to Fe3+/H2O2 solution (known as Fenton-like system), most Fe3+ were adsorbed on the Ta3N5 surface and could not react with H2O2 in the dark, which is different from the general Fenton reaction. Under visible light irradiation, adsorbed Fe3+ ions were reduced to Fe2+ rapidly and Fe2+ were reoxidized by H2O2 on the Ta3N5 surface, thus a fast Fe3+/Fe2+ cycling was established. Kinetics and ESR measurements supported this mechanism. The Ta3N5/Fe3+/H2O2 system could efficiently decompose H2O2 to generate hydroxyl radicals driven by visible light, which could accelerate significantly the degradation of organic molecules such as N,N-dimethylaniline (DMA), and 2,4-dichlorophenol (DCP). A mechanism was proposed for iron cycling on the basis of experimental results.  相似文献   

3.
H2O2 used in the photo-Fenton reaction with iron catalyst can accelerate the oxidation of Fe2+ to Fe3+ under UV irradiation and in the dark (in the so called dark Fenton process). It was proved that conversion of phenol under UV irradiation in the presence of H2O2 predominantly produces highly hydrophilic products and catechol, which can accelerate the rate of phenol decomposition. However, while H2O2 under UV irradiation could decompose phenol to highly hydrophilic products and dihydroxybenzenes in a very short time, complete mineralization proceeded rather slowly. When H2O2 is used for phenol decomposition in the presence of TiO2 and Fe–TiO2, decrease of OH radicals formed on the surface of TiO2 and Fe–TiO2 has been observed and photodecomposition of phenol is slowed down. In case of phenol decomposition under UV irradiation on Fe–C–TiO2 photocatalyst in the presence of H2O2, marked acceleration of the decomposition rate is observed due to the photo-Fenton reactions: Fe2+ is likely oxidized to Fe3+, which is then efficiently recycled to Fe2+ by the intermediate products formed during phenol decomposition, such as hydroquinone (HQ) and catechol.  相似文献   

4.
掌握Fe2+/H2O2体系O2的生成路径,可为避免H2O2无效分解,开发经济高效的Fe2+/H2O2体系利用技术指明方向。采用添加自由基捕获剂的方法,探究Fe2+/H2O2体系内各种自由基对O2生成速率的影响,进而确定O2的生成路径。结果表明:Fe2+/H2O2体系内不会产生大量O2-·,O2-·不是生成O2的主要反应物质;O2-·被全部捕获后,体系中仍产生大量O2-·,但此时无O2生成,证明生成O2的反应由·OH和HO2·两种自由基直接参与。分析认为反应·OH+HO2·-H2O+O2是体系内O2生成的主要路径。控制Fe2+/H2O2体系定向生成·OH,抑制HO2·的产生,是提高Fe2+/H2O2体系中H2O2利用率的有效手段。  相似文献   

5.
Fe2+/H2O2体系内各种自由基在氧化NO中的作用   总被引:1,自引:0,他引:1       下载免费PDF全文
Fe2+/H2O2体系可分解产生多种氧化性自由基, 主要包括O2-·、·OH和HO2·。本文实验研究了O2-·、·OH及HO2·在Fe2+/H2O2体系氧化NO气体过程中的作用。结果表明:在本实验条件下, O2-·对NO气体的氧化作用不明显;·OH及HO2·是该体系氧化NO气体的主要活性物质, 其中·OH的氧化作用更大。加快自由基的生成速率可以增强Fe2+/H2O2体系对NO气体的氧化能力, 但O2的生成速率同时加快。只有少量·OH及HO2·参与NO的氧化, ·OH与HO2·之间的快速反应是Fe2+/H2O2体系氧化NO过程中H2O2利用率低的主要原因。  相似文献   

6.
以亚甲基蓝(MB)作为目标污染物,实验研究了Fe2+/H2O2体系降解MB的活性物质,明确了主要反应条件对MB降解的影响特性。结果表明:HO2?没有直接降解MB的能力;Fe2+/H2O2体系对MB的降解能力主要来自于?OH;Fe2+/H2O2体系降解MB可分为快速反应阶段和匀速反应阶段。快速反应阶段的MB降解率随温度升高而下降。体系对MB降解能力随H2O2初始浓度增加呈现先升高后减弱的趋势,本实验条件下,最佳H2O2初始浓度为5 mmol·L-1。体系对MB降解能力随Fe2+初始浓度的增加而单调增加。MB降解速率随MB初始浓度的增加而增加,但MB降解率随其初始浓度呈现先增大后减小的趋势。保证?OH生成速率及其有效利用是提高体系氧化能力及H2O2利用率的关键。  相似文献   

7.
周伟  赵海谦  高继慧  吴少华 《化工学报》2016,67(10):4413-4421
Fe2+的再生直接决定Fenton体系产生的能力。选取羟胺、对苯二酚、对苯醌、亚硫酸钠4种典型添加剂,通过分析不同改性Fenton体系中Fe2+浓度、H2O2浓度、氧化还原电极电位(ORP),揭示了Fe2+再生机制的差异,并进一步分析了不同添加剂与体系中H2O2及·OH的反应情况。结果表明:NH2OH能快速使Fe2+再生,但伴随其消耗,Fe2+浓度不断降低。对苯二酚、对苯醌具有相似效果,两者均可大大强化Fe2+的再生。与NH2OH不同,两者在体系中可迅速建立醌循环,持续还原Fe3+,且以两种物质或其组合均可建立循环。与上述机理均不同,Na2SO3会先与·OH及H2O2反应,因而不能有效还原Fe3+。实验还发现添加剂均存在与·OH的反应,其中Na2SO3还会消耗H2O2。  相似文献   

8.
Degradation of pesticides in water using solar advanced oxidation processes   总被引:2,自引:0,他引:2  
Alachlor, atrazine and diuron dissolved in water at 50, 25 and 30 mg/L, respectively were photodegraded by Fe2+/H2O2, Fe3+/H2O2, TiO2 and TiO2/Na2S2O8 treatments driven by solar energy at pilot-plant scale using a compound parabolic collector (CPC) photoreactor. All the advanced oxidation processes (AOPs) employed mainly compared the TOC mineralisation rate to evaluate treatment effectiveness. Parent compound disappearance, anion release and oxidant consumption are discussed as a function of treatment time. The use of Fe2+ or Fe3+ showed no influence on the reaction rate under illumination and the reaction using 10 or 55 mg/L of iron was quite similar. TiO2/Na2S2O8 showed a quicker reaction rate than TiO2 and a similar rate compared to photo-Fenton. The main difference found was between TiO2/Na2S2O8 and photo-Fenton, detected during atrazine degradation, where pesticide transformation into cyanuric acid was confirmed only for TiO2/Na2S2O8.  相似文献   

9.
在浸没式循环撞击流反应器中,以氨水为沉淀剂,用七水合硫酸亚铁和六水合三氯化铁为原料,采用共沉淀法制备了纳米四氧化三铁粒子。考察了搅拌转速、亚铁与三价铁物质的量比、反应温度和溶液pH对所得纳米四氧化三铁的分散性和粒径的影响。采用傅里叶红外光谱仪、透射电镜、X射线衍射仪等对制得的纳米粒子的结构和性能进行了表征。结果表明:用撞击流反应器制备纳米四氧化三铁粒子的最佳工艺条件:亚铁与三价铁物质的量比为1 ∶1,反应温度为40 ℃,搅拌转速为1 600 r/min,以氨水作沉淀剂,最佳pH控制在11.0左右。在上述条件下,可以制备出分散性好、纯度高、平均粒径为10 nm的四氧化三铁粒子。  相似文献   

10.
A lost of culturability of bacteria Escherichia coli K12 was observed after exposition to a solar simulator (UV–vis) in a laboratory batch photoreactor. The bacterial inactivation reactions have been carried out using titanium dioxide (TiO2) P25 Degussa and FeCl3 as catalysts. At the starting of the treatment, the suspensions were at their “natural” pH. An increase in the efficiency in the water disinfection was obtained when some advanced oxidation processes such as UV–vis/TiO2, UV–vis/TiO2/H2O2, UV–vis/Fe3+/H2O2, UV–vis/H2O2 were applied. The presence of H2O2 accelerates the rate of disinfection via TiO2. The addition of Fe3+ (0.3 mg/l) to photocatalytic system decreases the time required for total disinfection (<1 CFU/ml), for TiO2 concentrations ranging between 0.05 and 0.5 g/l. At TiO2 concentrations higher than 0.5 g/l the addition of Fe3+ does not significantly increase the disinfection rate. The systems: Fenton (H2O2/Fe3+/dark), H2O2/dark, H2O2/TiO2/dark showed low disinfection rate. The effective disinfection time (EDT24) was reached after 60 and 30 min of illumination for the Fe3+ and TiO2 photoassisted systems, respectively. EDT24 was not reached for the system in the absence of catalyst (UV–vis). The effect on the bacterial inactivation of different mixture of chemical substance added to natural water was studied.  相似文献   

11.
Phenol hydroxylation using Fe-MCM-41 catalysts   总被引:5,自引:0,他引:5  
Highly ordered iron-containing mesoporous material, Fe-MCM-41, with 0.5–4 Fe/Si mol% loading was prepared and characterization was performed using XRD, SEM/TEM, EDS, N2-sorption, and FT-IR and UV–vis spectroscopies. Fe-MCM-41 exhibited high catalytic activity in phenol hydroxylation using H2O2 as oxidant, giving phenol conversion of ca. 60% at 50 °C [phenol:H2O2 = 1:1, water solvent]. Effects of Fe contents in Fe-MCM-41 and catalyst concentration, temperature, solvent used, phenol/H2O2 mole ratios and H2O2 feeding method, and catalyst calcination temperature on conversion profiles were examined. Catalyst recycling was performed to investigate the extent of potential metal leaching. Comparisons in performance were also made using nano-sized Fe2O3 particles and Fe-salt impregnated MCM-41 as catalyst. Catechol to hydroquinone in product ratio was close to 2:1 in accordance with a free radical reaction scheme involving Fe2+/Fe3+ redox pair and the larger amount of Fe species always achieved the given phenol conversion at a shorter reaction time. As the calcination temperature increases from 400 to 800 °C increasing amount of Fe species came out from the MCM-41 framework. Both tetrahedral Fe and extra-framework Fe species were found catalytically active, but high dispersion of Fe species achieved in Fe-MCM-41 was an advantage.  相似文献   

12.
The catalytic behavior of the Fe3+/Fe2+ system in the electro-Fenton degradation of the antimicrobial drug chlorophene has been studied considering four undivided electrolytic cells, where a Pt or boron-doped diamond (BDD) anode and a carbon felt or O2-diffusion cathode have been used. Chlorophene electrolyses have been carried out at pH 3.0 under current control, with 0.05 M Na2SO4 as supporting electrolyte and Fe3+ as catalyst. In these processes the drug is oxidized with hydroxyl radical (OH) formed both at the anode from water oxidation and in the medium from electrochemically generated Fenton's reagent (Fe2+ + H2O2, both of them generated at the cathode). The catalytic behavior of the Fe3+/Fe2+ system mainly depends on the cathode tested. In the cells with an O2-diffusion cathode, H2O2 is largely accumulated and the Fe3+ content remains practically unchanged. Under these conditions, the chlorophene decay is enhanced by increasing the initial Fe3+ concentration, because this leads to a higher quantity of Fe2+ regenerated at the cathode and, subsequently, to a greater OH production from Fenton's reaction. In contrast, when the carbon felt cathode is used, H2O2 is electrogenerated in small extent, whereas Fe2+ is largely accumulated because the regeneration of this ion from Fe3+ reduction at the cathode is much faster than its oxidation to Fe3+ at the anode. In this case, an Fe3+ concentration as low as 0.2 mM is required to obtain the maximum OH generation rate, yielding the quickest chlorophene removal. Chlorophene is poorly mineralized in the Pt/O2 diffusion cell because the final Fe3+–oxalate complexes are difficult to oxidize with OH. These complexes are completely destroyed using a BDD anode at high current thanks to the great amount of OH generated on its surface. Total mineralization is also achieved in the Pt/carbon felt and BDD/carbon felt cells with 0.2 mM Fe3+, because oxalic acid and its Fe2+ complexes are directly oxidized with OH in the medium. Comparing the four cells, the highest oxidizing power regarding total mineralization is attained for the BDD/carbon felt cell at high current due to the simultaneous destruction of oxalic acid at the BDD surface and in the bulk solution.  相似文献   

13.
Oxidative reactions of phenol and chlorobenzene with electrogenerated Fenton's reagent, Fe2+ + H2O2, were investigated. The electrogeneration of H2O2 and the regeneration of Fe2+ were performed at a graphite cathode. Results are compared for conventional vs. electrogenerated Fenton's reagent. It was found that the conversion of chlorobenzene was substantially greater by the electrochemical method than the conventional system. The rates of H2O2 generation were dependent on solution pH; electrogeneration was favored at low pH, while the opposite was the case for the hydroxylation of the organics. The hydroxylation products of phenol with electrogenerated Fenton's reagent included hydroquinone, catechol and resorcinol. For chlorobenzene, a hydroxylated product (p-chlorophenol) and a dehalogenated product (phenol) were obtained. The rates of phenol and chlorobenzene hydroxylation were dependent on pH, and concentrations of F2+ and H2O2. Results indicated that the electrochemical system provided an efficient way to regenerate Fe2+  相似文献   

14.
This work shows that aqueous solutions of clofibric acid (2-(4-chlorophenoxy)-2-methylpropionic acid), the bioactive metabolite of various lipid-regulating drugs, up to saturation at pH 3.0 are efficiently and completely degraded by electrochemical advanced oxidation processes such as electro-Fenton and photoelectro-Fenton with Fe2+ and UVA light as catalysts using an undivided electrolytic cell with a boron-doped diamond (BDD) anode and an O2-diffusion cathode able to electrogenerate H2O2. This is feasible in these environmentally friendly methods by the production of oxidant hydroxyl radical at the BDD surface from water oxidation and in the medium from Fenton's reaction between Fe2+ and electrogenerated H2O2. The degradation process is accelerated in photoelectro-Fenton by additional photolysis of Fe3+ complexes under UVA irradiation. Comparative treatments by anodic oxidation with electrogenerated H2O2, but without Fe2+, yield much slower decontamination. Chloride ion is released and totally oxidized to chlorine at the BDD surface in all treatments. The decay kinetics of clofibric acid always follows a pseudo-first-order reaction. 4-Chlorophenol, 4-chlorocatechol, hydroquinone, p-benzoquinone and 2-hydroxyisobutyric, tartronic, maleic, fumaric, formic and oxalic acids, are detected as intermediates. The ultimate product is oxalic acid, which is slowly but progressively oxidized on BDD in anodic oxidation. In electro-Fenton this acid forms Fe3+–oxalato complexes that can also be totally destroyed at the BDD anode, whereas in photoelectro-Fenton the mineralization rate of these complexes is enhanced by its parallel photodecarboxylation with UVA light.  相似文献   

15.
Field disinfection of water in a large solar compound parabolic collector (CPC) photoreactor (35–70 l) was conducted at 35 °C by different photocatalytic processes: sunlight/TiO2, sunlight/TiO2/Fe3+, sunlight/Fe3+/H2O2 and compared to the control experiment of direct sunlight alone. Experiments were carried out using a CPC and natural water spiked with E. coli K 12. Under these conditions, total disinfection by bare sunlight irradiation was not reached after 5 h of treatment; and bacterial recovery was observed during the subsequent 24 h in the dark.

The addition of TiO2, TiO2/Fe3+ or Fe3+/H2O2 to the water accelerates the bactericidal action of sunlight, leading to total disinfection by solar-photocatalysis. No bacterial regrowth was observed during 24 h after stopping sunlight exposure. For some samples, the decrease of bacteria continues in the dark. A “residual disinfection effect” was observed for these samples before reaching the total inactivation. The effective disinfection time (EDT24), defined as the treatment time required to prevent any bacterial regrowth during the subsequent 24 h in the dark, after stopping the phototreatment, was reached in the presence but not in the absence of different photocatalytic systems. EDT24 was 2 h 30 min, 2 h and 1 h 30 min for sunlight/TiO2, sunlight/TiO2/Fe3+ and sunlight/Fe3+/H2O2 systems, respectively. The post irradiation events observed when the phototreated water is poured into an optimal growth medium are also discussed.  相似文献   


16.
Metal ions including Fe3+, Ca2+, Mg2+, Ni2+, Co2+ and Cu2+ are commonly found in the leaching solution of laterite-nickel ores, and the pre-removal of Fe3+ is extremely important for the recovery of nickel and cobalt. Di(2-ethylhexyl)phosphate acid (D2EHPA) showed high extraction rate and selectivity of Fe3+ over other metal ions. The acidity of the aqueous solution is crucial to the extraction of Fe3+, and the stoichiometry ratio between Fe3+ and the extractant is 0.86:1.54. The enthalpy for the extraction of Fe3+ using D2EHPA was 19.50 kJ/mol. The extraction of Fe3+ was ≥99% under the optimized conditions after a three-stage solvent extraction process. The iron stripping effects of different reagents showed an order of H2C2O4>NH4HCO3>HCl>NaCl>NaHCO3>Na2SO3. The stripping of Fe was ≥99% under the optimized conditions using H2C2O4 as a stripping reagent.  相似文献   

17.
Decolorization of reactive brilliant red X-3B was studied by using an Fe–Ce oxide hydrate as the heterogeneous catalyst in the presence of H2O2 and UV. The decolorization rate was in the order of UV–Fe–Ce–H2O2 > UV–Fe3+–H2O2 > UV–H2O2 > UV–Fe–Ce ≥ Fe–Ce–H2O2 > Fe–Ce. Under the conditions of 34 mg l−1 H2O2, 0.500 g l−1 Fe–Ce, 36 W UV and pH 3.0, 100 mg l−1 X-3B could be decolorized at efficiency of more than 99% within 30 min. The maximum dissolved Fe during the reaction was 1 mg l−1. From the fact that the decolorization rate of the UV–Fe–Ce–H2O2 system was significantly higher than that of the UV–Fe3+–H2O2 system at Fe3+ = 1 mg l−1, it is clear that the Fe–Ce functioned mainly as an efficient heterogeneous catalyst. UV–vis, its second derivative spectra, and ion chromatography (IC) were employed to investigate the degradation pathway. Fast degradation after adsorption of X-3B is the dominant mechanism in the heterogeneous catalytic oxidation system. The first degradation step is the breaking down of azo and CN bonds, resulting in the formation of the aniline- and phenol-like compounds. Then, the breaking down of the triazine structure occurred together with the transformation of naphthalene rings to multi-substituted benzene, and the cutting off of sulphonic groups from the naphthalene rings. The last step includes further decomposition of the aniline structure and partial mineralization of X-3B.  相似文献   

18.
李家飞  徐凯  张永明  潘莉莎 《硅酸盐通报》2021,40(11):3762-3768
具有复杂分子结构的三苯甲烷类染料孔雀石绿是一种典型的较难降解染料,是工业废水处理的难点之一。本文根据Goldschmidt半径容差规则法,设计了用于孔雀石绿降解的ABO3型SrFe(1-x)CoxO3催化剂,并选择出活性较高的SrFe0.6Co0.4O3催化剂。通过XRD、SEM、BET吸附及XPS分析表明:该催化剂是纯净钙钛矿结构,颗粒形貌为无规则堆叠的“蜂窝”片状;吸附等温线没有明显的回滞环,说明没有“墨水瓶”类孔结构;XPS谱中,B位离子同时存在Fe2+/Fe3+和Co2+/Co3+ 4种价态离子,且反应前后,4种离子的分布比例有较大变化。根据实验结果,推测该催化反应机理为:催化剂B位Co3+与溶解氧形成活性氧[O2]+和Co2+;活性氧[O2]+完成氧化反应后其正电荷转移到B位Fe2+上形成Fe3+,Fe3+的正电荷可再转移到Co2+形成Co3+,完成催化过程的电荷转移与循环。  相似文献   

19.
采用二(2-乙基己基)磷酸酯(P204)-磺化煤油萃取体系从高硫酸氰化尾渣矿浆电解液中富集铁离子,重点研究了P204浓度、相比(O/A)、振荡时间、振荡频率及温度等对Fe3+萃取率的影响及其萃取过程。研究表明,在P204体积分数为25%、电解液pH为1.5、温度25℃、O/A=1∶1、振荡时间10 min、振荡频率180r/min的条件下,电解液中Fe3+的单级萃取率可达97.73%以上,饱和萃取容量可达到21.57g/L。Fe3+在有机相中的萃取富集主要归因于其与P204分子结构中羟基的阳离子交换反应以及磷酰基的配位反应,形成的配合物为FeSO4A(HA)3与FeA3(HA)3。在草酸1mol/L、O/A=1∶1、振荡时间10min、振荡频率190r/min的条件下,负载有机相中Fe3+的单级反萃率可达82.64%以上,反萃液中铁主要以[Fe(C2O4)3<...  相似文献   

20.
Catalytic wet oxidation of H2S to sulfur on Fe/MgO catalyst   总被引:1,自引:0,他引:1  
The room temperature wet catalytic oxidation was conducted in a batch reactor with Fe/MgO catalyst. Fe/MgO catalyst was prepared by the dissolution–precipitation method. XRD and temperature-programmed reductions (TPR) indicate that Fe oxide in the Fe/MgO is finely dispersed in the MgO support. The high H2S removal capacities of Fe/MgO can be explained by the finely dispersed iron oxide MgO. The H2S removal capacities of Fe/MgO are dependent on oxygen partial pressure (1.0 g H2S/gcat in air and 2.6 g H2S/gcat in oxygen). The valence state analysis of Fe/MgO catalyst suggests that the H2S oxidation on Fe/MgO can occur by a redox couple reaction, reducing Fe3+ into Fe2+ by H2S and oxidizing Fe2+ to Fe3+ by O2.  相似文献   

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