Experimental study of NO2 reduction in N2/Ar and O2/Ar mixtures by pulsed corona discharge

Non-thermal plasma technology has been regarded as a promising alternative technology for NOx removal. The understanding of NO2 reduction characteristics is extremely important since NO2 reduction could lower the total NO oxidation rate in the plasma atmosphere. In this study, NO2 reduction was experimentally investigated using a non-thermal plasma reactor driven by a pulsed power supply for different simulated gas compositions and operating parameters. The NO2 reduction was promoted by increasing the specific energy density （SED）, and the highest conversion rates were 33.7%, 42.1% and 25.7% for Ar, N2/Ar and O2/Ar, respectively. For a given SED, the NO2 conversion rate had the order N2/Ar 〉 Ar 〉 02/Ar. The highest energy yield of 3.31 g/kWh was obtained in N2/Ar plasma and decreased with increasing SED; the same trends were also found in the other two gas compositions. The conversion rate decreased with increasing initial NO2 concentration. Furthermore, the presence of N2 or O2 led to different reaction pathways for NO2 conversion due to the formation of different dominating reactive radicals.     

CuO(-CeO2)/Al2O3催化剂对萘催化氧化性能研究

采用浸渍法制备了CuO/Al2O3、CeO2/Al2O3和CuO-CeO2/Al2O3这3种催化剂,通过氮吸附、SEM、XRD等手段对催化剂的结构及组成进行了表征,利用固定床反应装置考察了活性组分、气体流量、催化反应温度对萘催化氧化性能的影响.结果表明,18%CeO2/Al2O3的萘催化活性较低,18%CuO/Al2O3和9%CuO-9%CeO2/Al2O3的活性较高,两者在300℃时对萘的去除率分别达到91%和89%;CuO-CeO2/Al2O3催化剂具有比CuO/Al2O3更好的低温活性;气流量的变化对两种催化剂性能的影响不大.     

新型铈钨钛复合氧化物催化还原脱硝机理

利用水热共沉淀法制备了铈钨钛复合氧化物催化剂,考察了H₂O₂络合修饰对其催化脱硝转化频率（TOF）的影响;并借助傅里叶原位红外光谱仪研究了H₂O₂络合修饰后铈钨钛复合氧化物的催化脱硝机理.结果表明：H₂O₂络合修饰可增强铈钨钛复合氧化物表面Brønsted酸位强度,提高其表面NH₃低温吸附和中低温NH₃-SCR脱硝性能,400℃时其NO_x催化脱除频率TOF高达0.658s^-1;NH₃和NO_x在H₂O₂络合修饰后铈钨钛复合氧化物表面存在竞争吸附,其表面催化脱硝反应主要为吸附态NH₃、NH₂和NH₄⁺与气态NO+O₂的反应,其低温NH₃-SCR反应机理遵循Eley-Rideal（E-R）机理.     

O3/H2O2降解水中扑灭通效能研究

利用拟一级降解速率常数表征O3/H2O2对扑灭通(Prometon)的氧化效能,探讨了n(H2O2)/n(O3)、pH值、水质和碳酸氢根离子对去除的影响,对有机氧化产物进行了气相和液相质谱分析,以离子色谱法测定了反应过程中产生的NO3-,在此基础上对扑灭通降解途径进行了研究.结果表明,扑灭通初始浓度2 mg.L-1,反应温度25℃,O3投量13 mg.L-1时,最佳反应条件为n(H2O2)/n(O3)=0.7,体系pH为7～8;扑灭通在自来水中的去除效果好于纯水;HCO3-浓度>50 mg.L-1时,对扑灭通的氧化有明显的抑制作用.液质和气质的分析结果表明扑灭通并未开环,氧化过程中扑灭通三嗪环支链上的2个异丙基首先被氧化脱去,离子色谱检测到的NO3-是三嗪环支链胺基氧化的产物.     

MnO2/Al2O3催化剂-微气泡臭氧体系催化降解喹啉及其机理

制备了纳米MnO₂,并以Al₂O₃为载体制备了掺杂型MnO₂/Al₂O₃颗粒催化剂.催化剂焙烧温度和时间分别为500℃和4 h、MnO₂质量分数为8%时,催化剂具有最高的臭氧催化氧化活性.SEM分析表明,纳米MnO₂均匀分布于Al₂O₃载体表面.MnO₂/Al₂O₃催化剂的比表面积（BET）为183.22 m²·g^-1,平均孔容为0.27 cm³·g^-1,平均孔径为4.87 nm.建立了MnO₂/Al₂O₃催化剂-微气泡臭氧催化反应体系,研究了该体系对喹啉的降解去除效果及其机理.臭氧微气泡的平均粒径为61.7 μm.微气泡臭氧投量为30 mg·L^-1时,反应60 min后喹啉去除率能达到95%以上;反应20 min后,MnO₂/Al₂O₃催化剂-微气泡臭氧体系对实际煤化工废水二级出水的TOC去除率可达到55%以上.以叔丁醇作为分子探针,证明了羟基自由基（·OH）氧化作用在臭氧微气泡催化氧化体系中对喹啉的降解起到主导作用.     

臭氧过氧化氢降解西马津试验研究

利用O3/H2O2体系降解内分泌干扰物类除草剂西玛津,对氧化产物进行了色谱分析,以评价该体系去除西玛津效能.西玛津浓度为2mg/L,过氧化氢与臭氧摩尔比为0.7,臭氧浓度为10.0mg/L,室温(26℃), pH值为7～8条件下,西玛津的去除率最高可达87.1%,说明O3/H2O2体系氧化西玛津的反应条件温和,易于工程应用;自来水本底西玛津的去除率较纯水中高约10%,达到86.9%;腐殖酸对西玛津的降解影响表现为低浓度促进高浓度抑制,碳酸氢根对西玛津降解的抑制作用较小;GC-MS检测到脱乙基西玛津的存在,通过对LC-MS谱图的分析也证明伴随西玛津的氧化,有脱乙基产物的生成;产物的IC检测结果表明存在脱氯反应过程,且有部分三嗪环被打开,说明臭氧过氧化氢系统氧化降解能力较强.     

青海湖区域背景点夏季大气NO2，SO2 和O3 浓度变化规律

利用ECOTECH 公司系列气体监测仪,对青海湖区域背景点夏季的大气污染物的变化规 律及其和气象因素之间的关系进行了分析。结果表明,夏季三种气体中NO₂ 浓度较低,平均值 为2.30×10^-9,其日内变化呈现单峰形式,日较差非常小;SO₂ 浓度较高,平均值达到20.82×10^-9, 波幅变化较大, 其日内变化表现的较不规则;O₃ 浓度夏季平均值高达57.63×10^-9,日变化呈现单 谷形态,早晨7:00-8:00 达到最低值;三种污染物均在凌晨或午夜达到高值。和气象因子的相关 分析表明,NO₂ 静风情况下浓度较低,主要污染源为西北及东北方向的公路及铁路机动车排放; SO₂ 主要来源于当地生物质燃烧排放,同时东南风向时其浓度增高;静风时O₃ 浓度最高,其受 风向影响较小。     

O3/H2O2氧化苯乙烯气体性能及机制

O3/H2O2体系能产生大量自由基,臭氧与自由基的耦合氧化作用能提高苯乙烯的氧化去除效率.采用O3/H2O2氧化高浓度苯乙烯有机废气,研究了臭氧投加量、停留时间、H2O2体积分数、循环液喷淋密度和O3/C8H8摩尔比对苯乙烯去除率的影响.结果表明,O3/H2O2气液两相氧化能高效净化苯乙烯有机废气,苯乙烯去除率可达85.7%.适宜运行条件:停留时间为20.6 s,H2O2体积分数为10%,喷淋密度为1.72 m3·(m2·h)-1,O3/C8H8摩尔比为0.46.采用GC-MS分析O3/H2O2气液两相高级氧化苯乙烯出口气样,研究结果表明苯甲醛(C6H5CHO)和苯甲酸(C6H5COOH)为O3/H2O2氧化苯乙烯的中间产物,并推测出苯乙烯的降解机制.     

TiO2改性银铝催化剂选择性丙烯还原NOx硫失活机制研究

采用溶胶凝胶法制备4%Ag/Al2O3、4%Ag/10%TiO2-Al2O3催化剂.利用N2物理吸附、氮氧化物/二氧化硫程序升温脱附(NOx/SO2-TPD)以及普通/原位漫反射傅里叶变换红外光谱(FT-IR/DRIFTs)对催化剂进行表征,并探讨催化剂在含硫气氛前后选择性还原NOx活性的变化及中毒机理.结果表明在4%Ag/Al2O3催化剂中掺杂10%TiO2能提高催化剂的中低温活性以及在400℃下抗SO2中毒的能力.TiO2引入后可促进甲酸盐物种的形成从而有利于低温反应的进行;SO2与NO在同一活性位上出现的竞争吸附以及活性组分Ag的硫酸化是4%Ag/Al2O3催化剂失活的重要原因;TiO2的加入能促进NO在催化剂表面的吸附并能减弱其对SO2的吸附,同时能有效抑制活性组分Ag的硫酸化,从而提高催化剂的抗硫性.     

O3/TiO2催化氧化工艺对饮用水中AOC的影响

以陶粒、硅胶和沸石为载体,分别负载二氧化钛（TiO₂）进行臭氧催化氧化去除硝基苯的实验,并对饮用水中生物可同化有机碳（AOC）所代表的小分子有机物(酮、醛、醇和羧酸类物质)的生成情况进行了研究.发现臭氧催化氧化比单纯的臭氧氧化能更彻底地将部分大分子有机物氧化成小分子中间产物,陶粒、硅胶和沸石负载TiO₂ 3种催化剂分别将AOC从大约300　μg·L^-1增加到 674.1　μg·L^-1、847.2　μg·L^-1和882.1　μg·L^-1,并且分别使AOC/TOC从原水的4.68%升高到30.5%、33.21%和46.04%,大大地提高了水中有机物的可生物降解性.如果增加臭氧投量,催化氧化可使小分子有机物部分被氧化,致使水样AOC又略有回降.在这一过程中,AOC-NOX所代表的羧酸类物质急剧增加,达到总AOC的90％以上,取代AOC-P17成为了AOC的主体组成部分.     

Co/Al2O3催化剂上CH4的CO2重整反应研究

通过研究不同Ｃｏ负载量的Ｃｏ／Ａｌ２Ｏ３催化剂对ＣＨ４的ＣＯ２重整剂合成气活性的影响,发现Ｃｏ负载量为１３％（Ｗｔ）的Ｃｏ／Ａｌ２Ｏ３活性最好,考察了反应温度,空速,还原温度等对催化剂活性和产物中ＣＯ／Ｈ２比例的影响,结果表明反应温度升高,ＣＨ４的ＣＯ２的转化率均增加,但随空速的增加而降低,还原温度在４００℃时催化剂显示出活性最好,产物中ＣＯ／Ｈ２的比例,随反应条件不同而略有增减。     

Effects of Ce on catalytic combustion of methane over Pd-Pt/Al2O3 catalyst

Activity and stability of 1%Pd-0.2%Pt/Al₂O₃ and 1%Pd-0.2%Pt/0.6%Ce/Al₂O₃ catalysts prepared by impregnation method for catalytic combustion of methane in air were investigated. The catalysts before and after reaction were characterized by BET, CO chemisorption, XRD and XPS techniques. Results showed that the presence of Ce significantly increased the activity and thermal stability of the Pd-Pt/Al₂O₃ catalyst towards methane combustion, which could be attributed to more highly-dispersed active PdO particles over the Pd-Pt/Ce/Al₂O₃ catalyst surface as well as the retarded sintering of PdO and the maintained oxidized state of surface Pd during the combustion process in the presence of Ce.     

O3/H2O2降解水中致嗅物质2-MIB的效能与机理

采用O3/H2O2工艺对水中致嗅物质二甲基异莰醇(2-methylisoborneol,2-MIB)的去除效能与机理进行了研究,探讨了H2O2与O2的投加方式、摩尔比以及溶液pH值和水质等因素对2-MIB降解的影响,并通过Gc-MS对2-MIB的氧化降解中间产物进行了分析.实验结果显示,H202能明显促进O3对水中2-MIB的氧化降解.单独臭氧氧化2Omin时2-MIB的降解率为38.7%;在同样体系中加入适量的H202后2.MIB的降解率最大能提高到89.2%,H202与O3最佳投加摩尔比为0.6左右.低浓度(0.5 mg·L-1)腐殖酸对O3/H2O2体系2.MIB的降解速率有比较明显的促进作用,高浓度的腐殖酸则会产生较明显的抑制作用;自由基捕获剂叔丁醇对O3/H2O2体系中2-MIB氧化降解具有明显的抑制作用.鉴定出2-MIB的氧化降解产物有4-羟基-1,7,7-三甲基双环[2,2,1]庚烷-2-酮、1,7,7-三甲基双环[2,2,1]庚烷-2,4-二酮、1,7,7-三甲基双环[2,2,1]庚烷-2-酮等,并对2-MIB氧化机制和降解的可能途径进行了推导.     

Ce-Mn/Al2O3-H2O2催化氧化皮革废水的研究

以浸渍法制备了Ce-Mn/Al_2O_3催化剂,研究该催化剂在H_2O_2非均相类Fenton体系中对皮革废水污染物的催化降解性能.在单因素试验的基础上,以COD去除率为响应值,采用Box-Behnken响应曲面法考察了催化剂投加量、H_2O_2投加量、初始pH、反应时间等4个因素之间的单独作用及交互作用,实验数据用Design-Expert 8.0.6软件进行处理,得到二次响应曲面模型.结果表明,4个独立变量对响应值的影响顺序如下:初始pHH_2O_2投加量催化剂投加量反应时间,数学模型拟合度高(R_(adj)~2=0.9349),利用该模型预测的最大COD去除率为78.86%,最佳反应条件为:催化剂投加量56.63 g·L~(-1),H_2O_2投加量315.15 mg·L~(-1),初始pH3.51,反应时间2 h,经实验验证COD去除率为80.94%,与模型预测值偏差2.08%.     

Pd/CZ/Al2O3催化剂的制备、表征与三效催化性能

以共浸渍法制得的氧化铝负载铈锆固溶体为载体,并浸渍贵金属Pd得到了Pd/CZ/Al₂O₃催化剂.实验结果表明,该催化剂在老化前后都表现出良好的三效催化活性,新鲜样品Pd/CZ/Al₂O₃活性与Pd/CZ相当,老化后样品前者优于后者.结合XRD,BET,TPR等表征手段,讨论了Pd/CZ/Al₂O₃的催化活性特别是高温老化后活性与其组成结构之间的内在关系,揭示了其老化后仍具有较高活性的主要原因在于保持了Pd与CZ/Al₂O₃复合载体之间的强相互作用(SMSI).     

粉煤灰负载Fe2O3脱除气态单质汞的试验研究

在固定床反应器中研究了利用燃煤电厂固废粉煤灰(FA)负载Fe2O3所制备的Fe2O3/FA催化剂对气态Hg0的脱除情况,发现Fe2O3/FA具有较高的脱除Hg0的能力.同时,考察了Fe2O3负载量、温度、空速、Hg0浓度、烟气成分等对Fe2O3/FA脱除Hg0的影响.结果表明,Fe2O3/FA对Hg0的脱除能力随Fe2O3负载量(1%~10%)的增加和温度(120~200℃)的升高而增强;Fe2O3/FA在较低的空速和Hg0浓度条件下表现出了更高的脱除Hg0的活性;HCl和O2促进了Fe2O3/FA对Hg0的脱除,而SO2和H2O抑制了Fe2O3/FA对Hg0的脱除.逐级化学提取实验结果证实,Fe2O3将Hg0氧化为Hg2+的化合物并吸附在FA上,这是Fe2O3/FA具有较高的脱除Hg0能力的原因.     

Steady-state kinetics and osillation phenomena for complete oxidation of benzene over Pt/Al2O3 catalyst

The steady-state kinetics for complete oxidation of benzene over Pt/Al₂O₃ has been investigated by the external recycling reactor. The kinetics equation was described by the L-H model of adsorption of benzene and oxygen with the inhibition of carbon dioxide. The parameters of the kinetics model were estimated by the method of orthogonal design. The heats of adsorption of benzene, oxygen and carbon dioxide were determined by the method of gas-adsorption chromatography. The details of oscillations of complete oxidation of benzene were investigated.     

Treatment of phenol wastewater by microwave-induced ClO2-CuOx/Al2O3 catalytic oxidation process

The catalyst of CuOx/Al2O3 was prepared by the dipping-sedimentation method using γ-Al2O3 as a carrier. CuO and Cu2O were loaded on the surface of γ-Al2O3, characterized by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). In the presence of CuOx/Al2O3, the microwave-induced chlorine dioxide (ClO2) catalytic oxidation process was conducted for the treatment of synthetic wastewater containing 100 mg/L phenol. The relationships between removal percentage and initial ClO2 concentration, catalyst dosage, microwave power, contact time, initial phenol concentration and pH were investigated and the results showed that microwave-induced ClO2-CuOx/Al2O3 process could effectively degrade contaminants in a short reaction time with a low oxidant dosage, extensive pH range. Under a given condition (ClO2 concentration 80 mg/L, microwave power 50 W, contact time 5 min, catalyst dosage 50 g/L, pH 9), phenol removal percentage approached 92.24%, corresponding to 79.13% of CODCr removal. The removal of phenol by microwave-induced ClO2-CuOx/Al2O3 catalytic oxidation process was a complicated non-homogeneous solid/water reaction, which fitted pseudo-first-order by kinetics. Compared with traditional ClO2 oxidation, ClO2 catalytic oxidation and microwave-induced ClO2 oxidation, microwave-induced ClO2 catalytic oxidation system could significantly enhance the degradation efficiency. It provides an effective technology for the removal of phenol wastewater.     

La-腐殖酸/Al_2O_3凝胶复合物的制备及其氟吸附性能

以腐殖酸钠为原料,采用凝胶聚合法制备La-腐殖酸/Al2O3凝胶复合物(标记为LHAGC).用N2吸附-脱附试验,XRD,SEM,IR表征吸附剂的结构和形貌,并通过静态吸附试验探讨了LHAGC对水中F-的吸附性能以及吸附饱和LHAGC的再生方法.试验结果表明,LHAGC对F-等温吸附数据与Langmuir吸附等温方程拟合较好,最大吸附容量为219.30 mg·g-1,吸附过程符合准2级动力学方程,液膜扩散和颗粒内扩散过程控制着吸附速率;在p H值为5~11时,F-吸附率较高;当水中Cl-、NO-3、SO2-4、HCO-3或PO3-4以F-质量浓度的15倍存在时,F-吸附率仍能达到94%以上,LHAGC表现出较强的抗干扰能力.将F-吸附饱和的LHAGC用浓度为10-1mol·L-1的Na OH溶液进行脱氟,再用Al Cl3溶液将脱氟后LHAGC表面中和至p H值为5时所获得的再生吸附剂,再生率可达96.08%,由此表明LHAGC的潜在应用前景.     

Advanced treatment of oil recovery wastewater from polymer flooding by UV/H2O2/O3 and fine filtration

In order to purify oil recovery wastewater from polymer flooding （ORWPF） in tertiary oil recovery in oil fields, advanced treatment of UV/H2O2/O3 and fine filtration were investigated. The experimental results showed that polyacrylamide and oil remaining in ORWPF after the conventional treatment process could be effectively removed by UV/H2O2/O3 process. Fine filtration gave a high performance in eliminating suspended solids. The treated ORWPF can meet the quality requirement of the wastewater-bearing polymer injection in oilfield and be safely re-injected into oil reservoirs for oil recovery.