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1.
The use of hydrogen peroxide (H2O2) for improved photocatalytic degradation of phenol in aqueous suspension of commercial TiO2 powders (Degussa P-25) was investigated. Photodegradation was compared using direct photolysis (UV alone), H2O2/UV, TiO2/UV, and H2O2/TiO2/UV processes in a batch reactor with high-pressure mercury lamp irradiation. The effects of operating parameters such as catalyst dosage, light intensity, pH of the solution, the initial phenol, and H2O2 concentrations on photodegradation process were examined. It was shown that photodegradation using H2O2/TiO2/UV process was much more effective than using either H2O2/UV or TiO2/UV process. The effect of the initial phenol concentration on TOC removal was also studied, demonstrating that more than 8 h was required to completely mineralize phenol into water and carbon dioxide. For all the four oxidation processes studied, photodegradation followed the first-order kinetics. The apparent rate constants with 400-W UV ranged from 5.0 × 10−4 min−1 by direct photolysis to 1.4 × 10−2 min−1 using H2O2/TiO2/UV process. The role of H2O2 on such enhanced photodegradation of phenol in aqueous solution was finally discussed.  相似文献   

2.
倪金雷  彭若帆  童少平  马淳安 《化工学报》2015,66(10):3950-3956
研究了不同物相TiO2对H2O2/O3氧化效能的影响,目标有机物为羟基自由基探针化合物乙酸。结果表明,在初始pH为7.0和10.0时,加入TiO2反而降低了H2O2/O3的氧化效率,其中锐钛矿TiO2比金红石TiO2的减弱作用更为明显。当初始pH为3.0时,金红石TiO2能显著提高H2O2/O3的氧化效率,但锐钛矿TiO2影响不明显。机理分析表明,H2O2浓度及其衰减速率与乙酸的去除效率有很大的相关性。在pH为7.0和10.0时,两种物相TiO2均能加快H2O2的分解,其中锐钛矿TiO2作用更为显著。此条件下HO2-能有效引发臭氧分解产生羟基自由基,故H2O2过快分解反而降低了乙酸的去除效果。在pH为3.0时,H2O2去质子化反应困难,故O3/H2O2氧化效率极低,H2O2浓度也几乎不变。加入TiO2能明显提高H2O2的分解速率,相比金红石TiO2,锐钛矿TiO2使H2O2在5 min内基本分解完毕,但其对H2O2/O3氧化效率几乎没有影响。饱和臭氧水分解速度的批处理实验也有相似的结果。由此可见,合适引发剂浓度可能是保证臭氧类高级氧化技术较高效率的关键,否则只会导致氧化剂的无效过快分解。利用氯化硝基四氮唑蓝法对比分析了酸性条件下H2O2/O3、锐钛矿TiO2/H2O2/O3和金红石TiO2/H2O2/O3体系产生超氧自由基(·O2-)的量,其大小顺序为:H2O2/O3< 金红石TiO2/H2O2/O3< 锐钛矿TiO2/H2O2/O3,这与前面结果吻合很好。  相似文献   

3.
研究了臭氧催化氧化降解煤化工高盐废水有机物的机理。实验采集了国内典型煤化工企业高盐废水,明确了水中盐离子的组成及含量;制备高盐性臭氧催化剂,研究了不同活性组分对臭氧催化氧化效率的影响,确定了最佳的臭氧催化剂;对臭氧催化剂开展表征分析,明确催化剂表观形貌、元素组成及负载情况;最后采用甲酸模拟水样,研究臭氧催化氧化作用方式、臭氧衰减率变化、羟基自由基(·OH)变化、H2O2变化及超氧自由基(·O2-)变化,明确臭氧催化氧化作用机理及反应历程。结果表明:煤化工高盐废水阳离子主要为钠离子,其次是钾离子、钙离子、镁离子;阴离子主要为氯离子、硫酸根,其次是硝酸根离子;通过研究不同活性组分对臭氧催化氧化效率确定最佳催化剂为SiO2/Al2O3-Fe2O3。对催化剂开展表征分析发现:催化剂载体为硅铝复合氧化物,铁作为活性组分均匀负载于载体上。臭氧催化氧化降解机理研究发现:臭氧催化氧化过程遵从羟基自由基作用机理,O3通过衰减产生羟基自由基,而催化剂的加入促进了·OH生成;反应过程中产生的H2O2量与·?OH有关,·?OH越多,H2O2产生量越多,但·O2-的产生与·OH没关系。  相似文献   

4.
Although some studies concerning the effect of pH and ozone dosage on TiO2 photocatalysis (O2/TiO2/UV) have already been published, no complete investigation and explanation of the effects of both parameters on photocatalytic ozonation (O3/TiO2/UV) have been carried out. Aqueous solutions of neonicotinoid insecticides (thiacloprid and imidacloprid) were chosen as a degradation medium, since they exhibit a high threat for aquatic systems and it is of great importance to find an effective method for their elimination from the environment. In preliminary stability tests, thiacloprid showed higher photo- and chemical stability compared to imidacloprid, therefore its degradation was studied in detail. To assess the suitability of various treatments for degradation and mineralization of thiacloprid in water at different pH values and ozone dosages, we applied ozonation (O3) and three different photochemical advanced oxidation processes, namely ozonation, coupled with UV radiation (O3/UV), O3/TiO2/UV and O2/TiO2/UV. Light source emitting mainly in UVA range was applied in all three processes. The photocatalytic ozonation (O3/TiO2/UV) was found to be the most efficient process irrespective of pH. The synergistic effect of ozone and TiO2 photocatalysis was noticed at acidic and neutral pH, but the synergism was lost at basic pH, probably due to faster self-decompositon of ozone under alkaline conditions. At acidic pH, also the oxidation of chloride anions to chlorate(V) was noticed in O3/TiO2/UV and in O3/UV processes. By plotting the disappearance rate constants of thiacloprid degradation in O3/TiO2/UV and O3/UV systems as a function of the flow rate of ozone, the synergistic effect of ozone was undoubtedly proven. The slope of the linear fit in case of O3/TiO2/UV process was considerably steeper than in case of O3/UV, which would not happen in absence of synergistic effect. The linearity in O3/TiO2/UV system was lost only at very high flow rates of ozone.  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.
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   

7.
张华  张子鹏  张澜澜  张晓飞  刘译阳 《化工进展》2020,39(12):5299-5308
研究者在苯胺模拟废水高级氧化处理方面开展了很多研究,但针对炼化企业苯胺装置废水含盐高、色度高、COD降解难等问题尚未开展工程应用。为解决苯胺生产废水的实际问题,本研究开展了TiO2/UV-H2O2氧化降解苯胺废水(1~2m3/h)的现场试验研究。考察了苯胺废水在单独TiO2/UV、单独H2O2氧化及TiO2/UV-H2O2协同作用下的处理效果,提出了苯胺废水的最佳处理工艺方案,并进行了成本核算。结果表明,单独TiO2/UV和单独H2O2氧化对苯胺废水的脱色率和COD去除率偏低,而TiO2/UV-H2O2协同作用时苯胺废水脱色率和COD去除率可达95%以上。协同氧化体系中,H2O2的氧化降解作用显著,H2O2投加量1%~2%;酸性条件利于苯胺废水的降解,特别是pH=3.8~4.2时;TiO2/UV和H2O2协同作用一段时间后,停止UV而凭借残余H2O2可以将体系中的中间产物继续降解直至矿化成CO2。TiO2/UV- H2O2协同处理炼化企业苯胺生产废水,出水COD≤60mg/L,色度≤20倍,单位能耗约18.44kW·h/m3,明显低于文献报道值,具有显著的技术性与经济性。  相似文献   

8.
The Electro-Fenton (EF) process is one of the promising advanced oxidation processes (AOPs) for environmental remediation. The H2O2 yield of EF process largely determines its performance on organic pollutants degradation. Conventional Pd-catalytic EF process generates H2O2 via the combination reaction of anodic O2 and cathodic H2. However, the relatively expensive catalyst limits its application. Herein, a hybrid Pd/activated carbon (Pd/AC)-stainless steel mesh (SS) cathode (PACSS) was proposed, which enables more efficient H2O2 generation. It utilizes AC, the support of Pd catalyst, as part of cathode for H2O2 generation via 2-electron anodic O2 reduction, and SS serve as a current distributor. Moreover, H2O2 could be catalytically decomposed upon AC to generate highly reactive ·OH, which avoids the use of Fe2+. Compared with conventional Pd catalyst, H2O2 concentration obtained by PACSS cathode is 248.2% higher, the O2 utilization efficiency was also increased from 3.2% to 10.8%. Within 50 min, 26.3%, 72.5%, and 94.0% H2O2 was decomposed by Pd, AC, and Pd/AC. Fluorescence detection results implied that Pd/AC is effective upon H2O2 activation for OH generation. Finally, iron-free EF process enabled by PACSS cathode was examined to be effective for reactive blue 19 (RB19) degradation. After continuous running for 10 cycles (500 min), the PACSS cathode was still stable for H2O2 generation, H2O2 activation, and RB19 degradation, showing its potential application for organic pollutants degradation without increase in the running cost.  相似文献   

9.
高文强  焦纬洲  刘有智 《化工学报》2020,71(3):1045-1052
提出一种超重力环境下甲苯合成苯甲酸的新方法,对比不同臭氧化工艺合成苯甲酸的收率,研究了反应溶剂、臭氧气相浓度、过氧化氢与甲苯的摩尔比、超重力因子、液体流量对苯甲酸收率的影响规律。研究结果表明:RPB (rotating packed bed)-O3/H2O2较其他工艺具有更高的反应性能;得到优化的工艺条件是反应溶剂为乙腈、臭氧气相浓度为80 mg·L-1、过氧化氢与甲苯的摩尔比为0.15、超重力因子为40、液体流量为120 L·h-1,在优化的工艺条件下得到苯甲酸收率为45%。通过电子顺磁共振仪 (EPR)对反应过程中产生的活性自由基进行表征,结果表明,O3/H2O2体系中存在·OH。另外,用气相色谱-质谱联用仪(GC-MS)分析了中间产物,结果表明反应过程中生成的中间产物包括苯甲醇和苯甲醛。基于ERP实验和GC-MS表征结果,探索臭氧/双氧水氧化甲苯合成苯甲酸可能的反应历程。  相似文献   

10.
Benzene (B) and two representative chlorobenzenes (1,4-dichlorobenzene (DCB) and 1,2,3-trichlorobenzene (TCB)) were oxidized by means of UV irradiation alone, ozone alone, and the combinations UV/H2O2 and O3/H2O2. In the single photolytic process, the influence on the photodegradation of the pH, temperature, and type of radiation source used was established. A kinetic study was performed by evaluating the first-order rate constants and the quantum yields. The effect of the additional presence of hydrogen peroxide was pointed out in the combined process UV/H2O2,with the determination of the specific contribution of the radical pathway to the overall photodegradation system. In the oxidation by ozone based systems (ozone alone and the combination O3/H2O2), the rate constants at 20°C for the reaction of each compound with ozone and hydroxyl radicals were determined.  相似文献   

11.
The photodegradation of phenol was investigated in the presence of TiO2 (anatase) as photocatalyst in near-UV-irradiated aqueous unbuffered suspensions. The distribution of degradation products and a reduction in total organic carbon are reported, focusing on the influence of charge-trapping species (O2, Ag+ and H2O2). In the presence of dissolved O2, the degradation proceeds predominantly via OH, where hydroxylated aromatics were detected: catechol, hydroquinone and 1,2,4-trihydroxybenzene; in the presence of Ag+, the direct hole oxidation dominates, with p-benzoquinone as the only identified transient product; in the presence of H2O2, both OH and direct oxidation by positive holes contribute to the degradation of phenol. Besides the identified compounds, the formation of presumed ring-opening products occurs simultaneously. In contrast with the general view, it is pointed out that the appearance of aliphatic products in the early stage of the oxidation process is not unambiguous proof of the participation of direct hole oxidation in the degradation mechanism.  相似文献   

12.
以256 m2烧结机O3氧化烧结烟气中NO过程为研究对象,采用CFD数值模拟方法考察了含O3喷射气体与烧结烟气流动及NO低温氧化特性。通过与76步复杂反应机理的对比验证了11步简化机理的适用性,分析了反应温度、O3/NO摩尔比以及O3分布特性对NO氧化效率和不同价态NO x 转化率的影响规律。通过对简单结构反应器的模拟结果表明:NO3稳定性较差,烟道内主要氧化产物为NO2与N2O5;随反应温度升高,NO氧化效率基本保持不变,NO2转化率提高且提升速率逐渐增大而N2O5呈相反规律;随O3/NO摩尔比增大,NO氧化效率提高但提升速率逐渐减小,NO2转化率先增大后在摩尔比高于1.25时开始减小,而各工况均产生N2O5且生成量逐渐增大,其原因为射流核心区可提供高O3/NO摩尔比条件;通过优化O3分布器结构改善O3与烟气接触与混合条件,O3与NO摩尔比为1.0、停留时间为0.87 s时NO氧化率可提高约12.8%,摩尔比为2.0、停留时间为1.73 s时N2O5转化率可提高约15.6%。  相似文献   

13.
高级氧化技术是一种新型、绿色的水处理工艺,通过各种强化技术更快、更多地产生具有强氧化性的羟基自由基,使其与废水中的有机物发生链式反应,从而将废水中的有机物快速高效降解为无害的无机盐。采用两种典型的高级氧化技术:电芬顿和臭氧,一体化处理船舶生活污水,研究结果表明:在电流密度20 mA/cm2,芬顿试剂n(H2O2):n(Fe2+)=3:1,C(Fe2+)为0.01 mol/L,氧气速率2 L/min,臭氧投加量6 g/L时,电芬顿-臭氧一体化装置能有效降解船舶生活污水中的污染物,当处理时间为120 min时,对COD去除率可达86.4%。  相似文献   

14.
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   

15.
Ethanol steam reforming was studied over Ni/Al2O3 catalysts. The effect of support (- and γ-Al2O3), metal loading and a comparison between conventional H2 reduction with an activation method employing a CH4/O2 mixture was investigated. The properties of catalysts were studied by N2 physisorption, X-ray diffraction (XRD) and temperature programmed reduction (TPR). After activity tests, the catalysts were analyzed by scanning electron microscopy (SEM) and thermogravimetric analysis (TG/DTA). Ni supported on γ-Al2O3 was more active for H2 production than the catalyst supported on -Al2O3. Metal loading did not affect the catalytic performance. The alternative activation method with CH4/O2 mixture affected differently the activity and stability of the Ni/γ-Al2O3 and the Ni/-Al2O3 catalyst. This activation method increased significantly the stability of Ni/-Al2O3 compared to H2 reduction. SEM and TG/DTA analysis indicate the formation of filamentous carbon during the CH4/O2 activation step, which is associated with the increasing catalyst activity and stability. The effect of temperature on the type of carbon formed was investigated; indicating that filamentous coke increased activity while encapsulating coke promoted deactivation. A discussion about carbon formation and the influence on the activity is presented.  相似文献   

16.
梁文俊  郭书清  武红梅  李坚  何洪 《化工学报》2017,68(7):2755-2762
采用自制线管式介质阻挡放电反应器,针对非热等离子体协同Mn-Ce/La/γ-Al2O3催化剂对低浓度甲苯的去除开展研究。研究中制备了Mn/γ-Al2O3、Mn-Ce/γ-Al2O3、Mn-La/γ-Al2O3催化剂,从甲苯去除率、产物O3生成、COx选择性及其他副产物生成情况考察比较了空管放电、协同催化剂放电时催化降解甲苯性能,并对催化剂进行了BET、SEM、H2-TPR和ICP-OES表征研究。结果表明:稀土助剂的加入有助于提高甲苯去除率及降低程度,且La催化性能优于Ce.,当外加电压22 kV、气量6 L·min-1、甲苯初始浓度600 mg·m-3时,Mn-La/γ-Al2O3催化剂对甲苯去除率达到72.74%。H2-TPR结果表明,稀土助剂的加入提高了催化剂低温活性及储氧能力,添加La的效果优于Ce。催化剂有助于抑制副产物O3生成,提高CO2和COx选择性。  相似文献   

17.
邵圣娟  焦纬洲  刘有智 《化工进展》2020,39(12):4798-4811
臭氧高级氧化技术因其绿色高效、适用性广、操作简便等优势,成为当前水处理领域前沿技术之一,但臭氧在传统反应器内普遍存在吸收效果差,臭氧利用率低等缺陷。旋转填料床(RPB)利用高速旋转的填料产生超重力场,将液体剪切破碎为细小的液膜、液丝或液滴,其较高的相界面积、不断更新的界面以及内部流体的强制湍动,加快了臭氧的传质与分解,该技术对于传质受限的臭氧高级氧化过程的强化有着突出的优势。本文简述了超重力强化臭氧氧化过程的原理,介绍了RPB与O3、O3/H2O2、O3/Fenton、O3/PS(过硫酸盐)、催化臭氧氧化等高级氧化法耦合应用处理有机废水的研究现状,并对超重力技术的优势及技术突破进行了述评,总结了超重力应用臭氧高级氧化技术的潜在经济效益和环境效益,提出功能化填料及大型RPB的开发需求,以期为超重力技术在废水处理领域的拓展应用提供理论基础和技术参考。  相似文献   

18.
蛋白土具有良好的应用前景,但是其自然白度较低制约了其开发应用。蛋白土硫酸铵煅烧法可去除其中的显色金属氧化物,提高蛋白土的白度,同时提取其中Al2O3。本文采用热重-差示扫描量热(TG-DSC)、同步热分析与红外质谱(TG-FTIR-MS)联用系统,结合X射线衍射对煅烧过程的固相及气相产物进行了表征分析,明析了其化学过程。结果表明,蛋白土中的Al2O3和Fe2O3在200~350℃时反应生成(NH43(Al,Fe)(SO43,同时逸出NH3和H2O;350~450℃时,进一步反应转化为NH4(Al,Fe)(SO42,同时逸出NH3、H2O、SO2和O2;450~550℃时,NH4(Al,Fe)(SO42分解生成(Al,Fe)2(SO43,同时逸出NH3、H2O、SO2和O2;550~750℃时(Al,Fe)2(SO43分解生成Al2O3和Fe2O3,同时逸出SO2和O2。采用Kissinger微分法与Ozawa积分法分别计算出4个阶段表观活化能后取二者平均值,分别为101.74kJ/mol、104.52kJ/mol、201.40kJ/mol、232.51kJ/mol,并获得对应4个热化学反应阶段的频率因子、反应级数和动力学方程。  相似文献   

19.
The use of hybrid advanced oxidation processes(AOPs) for the removal of pollutants from industrial effluents has been extensively studied in recent literature. The aim of this study is to compare the performance of the photo,Fenton, photo-Fenton and ozone–photo–Fenton processes in terms of color removal and chemical oxygen demand(COD) removal of distillery industrial effluent together with the associated electrical energy per order. It was observed from the experimental results that the O_3/UV/Fe~(2 +)/H_2O_2 process yielded a 100% color and95.50% COD removals with electrical energy per order of 0.015 k W·h·m~(-3) compared to all other combinations of the AOPs. The effects of various operating parameters such as H_2O_2 and Fe~(2+) concentration, effluent pH, COD concentration and UV power on the removal of color, COD and electrical energy per order for the ozone–photo–Fenton process was critically studied and reported. The color and COD removals were analyzed using a UV/Vis spectrometer and closed reflux method.  相似文献   

20.
A series of La(Co, Mn, Fe)1−x(Cu, Pd)xO3 perovskites having high specific surface areas and nanosized crystal domains was prepared by reactive grinding. The solids were characterized by N2 adsorption, X-ray diffraction (XRD), scanning electron microscopy (SEM), temperature programmed desorption (TPD) of O2, NO + O2, C3H6, in the absence or presence of 5% H2O, Fourier transform infrared (FTIR) spectroscopy, as well as activity tests towards NO reduction by propene under the conditions of 3000 ppm NO, 3000 ppm C3H6, 1% O2, 0 or 10% H2O, and 50,000 h−1 space velocity. The objective was to investigate the influence of H2O addition on catalytic behavior. A good performance (100% NO conversion, 77% N2 yield, and 90% C3H6 conversion) was achieved at 600 °C over LaFe0.8Cu0.2O3 under a dry feed stream. With the exposure of LaFe0.8Cu0.2O3 to a humid atmosphere containing 10% water vapor, the catalytic activity was slightly decreased yielding 91% NO conversion, 51% N2 yield, and 86% C3H6 conversion. A competitive adsorption between H2O vapor with O2 and NO molecules at anion vacancies over LaFe0.8Cu0.2O3 was found by means of TPD studies here. A deactivation mechanism was therefore proposed involving the occupation of available active sites by water vapor, resulting in an inhibition of catalytic activity in C3H6 + NO + O2 reaction. This H2O deactivation was also verified to be strictly reversible by removing steam from the feed.  相似文献   

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