Preparation and characterization of Fe2O3-CeO2-TiO2/γ-Al2O3 catalyst for degradation dye wastewater

In order to develop a catalyst with high activity for catalytic wet oxidation （CWO） process at room temperature and atmospheric pressure, Fe2O3-CeO2-TiO2/γ-Al2O3 catalyst was prepared by consecutive impregnation method and the prepared parameters were optimized. The structure of the catalyst was characterized by BET, XRF, SEM and XPS technologies, and the actual wastewater was used to investigate the catalytic activity of Fe2O3-CeO2-TiO2/γ-Al2O3 in CWO process. The experimental results showed that the prepared catalyst exhibited good catalytic activity when the doping amount of Ti was 1.0 wt% （the weight ratio of Ti to carriers）, and the middle product, Fe2O3-CeO2-TiO2/γ-Al2O3, was calcined in 450℃ for 2 h. The CWO experiment for treating actual dye wastewater indicated that the COD, color and TOC of actual wastewater were decreased by 62.23%, 50.12% and 41.26% in 3 h, respectively, and the ratio of BOD5/COD was increased from 0.19 to 0.30.     

O3/H2O2法降解甲基叔丁基醚（MTBE）的试验研究

采用自制鼓泡反应器对臭氧/双氧水(O3/H2O2)降解水中甲基叔丁基醚(MTBE)进行了试验研究,考察了进气(含O3)流量、H2O2 投加量、MTBE初始浓度、pH、温度等因素对MTBE降解的影响.结果表明,在MTBE初始浓度为10 mg·L-1,气体流量为0.5 L·min-1,温度293K, pH=6.5, H2O2 添加量为2.4mg·L1 条件下,反应30 min后, MTBE去除率可达75.5%, COD去除率为68.0%.降解得到的中间产物主要有叔丁基甲酯(TBF)、叔丁醇(TBA)、乙酸甲酯(MA)和丙酮(AC)等,据此探讨了O3/H2O2氧化MTBE的可能反应机理和降解途径.     

Removal of elemental mercury by photocatalytic oxidation over La2O3/Bi2O3 composite

La₂O₃/Bi₂O₃ photocatalysts were prepared by impregnation of Bi₂O₃ with an aqueous solution of lanthanum precursor followed by calcination at different temperatures. The composite materials were used for the first time for the photocatalytic removal of Hg⁰ from a simulated flue gas under UV light irradiation. The results showed that the sample containing 6 wt.% La₂O₃ and calcined at 500°C has the highest dispersion of the active sites, which was promoted by the strong interaction with the support (i.e., the formation of Bi-O-La species). Since they are fully accessible on the surface, the material also exhibits excellent optical properties while the heterojunction formed in La₂O₃/Bi₂O₃ promotes the separation and migration of photoelectron-hole pairs and thus Hg⁰ oxidation efficiency is enhanced. The effects of the various factors (e.g., the reaction temperature and composition of the simulated flue gas (i.e., O₂, NO, H₂O, and SO₂)) on the efficiency of the Hg⁰ photocatalytic oxidation were investigated. The results demonstrated that O₂ and SO₂ enhanced the efficiency of the reaction while the reaction temperature, NO, and H₂O had an inhibitory effect.     

O_3/H_2O_2催化氧化对苯二酚的影响因素及急性毒性变化

研究了O_3/H_2O_2催化氧化对苯二酚的去除效果及氧化过程中产物的急性毒性变化情况,并探讨了O_3/H_2O_2催化氧化对苯二酚的反应机理。结果表明:O_3/H_2O_2在中性条件下氧化对苯二酚反应中,通过H_2O_2和O_3分子联合作用(O_3投加量为210 mg/L、H_2O_2投加量为0.15%)可完全去除对苯二酚(浓度为150 mg/L)以及42%的TOC。以污染物在水环境中对发光细菌的抑光率为毒性指标,反应过程中的毒性作用先增大后减小。O_3/H_2O_2氧化是一种高效去除酚类化合物、降低急性毒性的方法,具有良好的应用前景。     

Pd/ZrO【sub】2【/sub】-Al【sub】2【/sub】O【sub】3【/sub】催化剂加氢脱硫性能的研究

采用等体积浸渍法制备了一系列不同Zr含量的ZrO2-Al2O3复合载体和Pd/ZrO2-Al2O3催化剂,利用连续流动微反装置考察了Pd/ZrO2-Al2O3催化剂的噻吩加氢脱硫(HDS)性能,并运用程序升温还原(TPR),程序升温脱附(H2-TPD,NH3-TPD)和N2物理吸附等技术对载体及催化剂进行了表征.结果表明:ZrO2-Al2O3复合载体中Zr含量对Pd基催化剂的HDS性能有较大影响,加入适量Zr可增大Pd/Al2O3催化剂的分散度及H2吸附量和酸量,减弱活性组分与载体的相互作用,使活性中心和噻吩吸附位增多以及活化能降低,从而有利于Pd基催化剂HDS反应活性的提高,w(Zr)为9%时Pd/ZrO2-Al2O3催化剂的活性最好.     

氧化铁催化甲烷脱硝的实验研究

文章使用固定床反应器在350℃~850℃范围内对氧化铁催化甲烷脱硝进行了实验研究。研究结果发现在有2%氧气存在条件下,氧化铁催化甲烷脱硝的效果最高只有20%,而且在350℃~750℃范围的氧化铁催化甲烷脱硝反应机理与850℃时的脱硝反应机理并不相同。在高温的850℃~950℃范围无氧气条件下,NOx转化率随着温度升高而单调增加,随CH4/NO摩尔比的增加而升高,氧化铁催化甲烷脱硝的最佳效果可以达到将近100%。通过进一步分析发现高温850℃~950℃无氧气条件下的脱硝反应机理是在催化剂表面进行了氧化还原反应,即首先发生了CH4与Fe2O3的气固反应,将Fe2O3还原为Fe3O4,而后Fe3O4再与NO反应将其还原为N2。     

基于新型陶粒催化剂的H_2O_2/O_3多相催化氧化体系降解刚果红的研究

用自制陶粒催化剂与臭氧(O_3)、双氧水(H_2O_2)构建多相催化氧化体系降解水中的刚果红。采用电镜扫描、能谱分析与红外光谱等表征了陶粒催化剂,考察了反应时间、O_3浓度、H_2O_2投加量等因素下多相催化氧化体系对刚果红色度和COD去除率。结果表明:自制的陶粒催化剂表面较为粗糙,比表面积较大,反应后的陶粒催化剂表面较为平滑,比表面积较反应前减少;自制陶粒催化剂对H_2O_2催化能力差,但对O_3、H_2O_2/O_3具有较好的催化效果。当O_3浓度在1.2~3.8 mg/L时,陶粒/H_2O_2/O_3体系较O_3、H_2O_2/O_3对刚果红(100 mg/L)的脱色率分别平均提高了11.72%、15.32%,COD去除率分别提高了16.37%、24.29%,将陶粒引入O_3、H_2O_2/O_3体系中可减少O_3和H_2O_2的用量,提高体系的氧化性能,降低运行成本。     

纳米TiO_2包覆微米Cr_2O_3粒子的制备及表征研究

目的研究室温条件下纳米TiO_2包覆微米Cr_2O_3粒子的物相、显微组织及其光催化活性。方法采用钛酸丁酯为原料,通过酸催化的胶溶-沉淀法制备纳米TiO_2包覆微米Cr_2O_3复合粒子,利用SEM,XPS,XRD,Raman及紫外-可见漫反射光谱等手段对复合粒子进行表征。结果 XPS分析表明,微米Cr_2O_3粒子的表面存在C,O,Ti,Sn,Cr等元素。场发射扫描电镜观察表明,粒径大小为10~15 nm左右的TiO_2颗粒包覆在Cr_2O_3微粒表面,从而形成纳米/微米复合结构。Raman光谱结果显示,空载实验获得的TiO_2颗粒样品呈现锐钛矿型。UV-Vis光谱分析表明,负载Cr_2O_3微粒后使半导体的吸收峰值明显红移,在370,460,600 nm处出现了3个吸收峰,最大吸收波长达到750 nm左右。结论锐钛矿相TiO_2成功包覆在微米Cr_2O_3粒子表面,扩展了复合半导体的光响应范围,有望实现可见光催化活性。     

Comparison of degradation reactions of Acid Yellow 61 in both oxidation processes of H2O2/UV and O3

ＩｎｔｒｏｄｕｃｔｉｏｎＣｏｌｏｒｓｕｂｓｔａｎｃｅｓｉｎｄｙｅｉｎｇｅｆｆｌｕｅｎｔｓｎｏｒｍａｌｌｙｃａｕｓｅｃｅｒｔａｉｎｄｉｆｆｉｃｕｌｔｉｅｓｉｎｔｒａｄｉｔｉｏｎａｌｂｉｏｌｏｇｉｃａｌｔｒｅａｔｍｅｎｔｐｒｏｃｅｓｓｅｓｄｕｅｔｏｔｈｅｄｙｅｍｏｌｅｃｕｌｅｓａｒｅｈｉｇｈｌｙｓｔｒｕｃｔｕｒｅｄｐｏｌｙｍｅｒｓａｎｄｔｈｅｉｒｔｏｘｉｃｉｔｙ (Ｈａｍｚａ ,1980 ;Ｇｉｎｏｃｃｈｉｎｉｏ ,1984 ;ＭａＫａｙ ,1980 ) .Ｉｔｉｓｎｅｃｅｓｓａｒｙｔｏｉｍｐｒｏｖｅｔｈｅｔｒｅａｔｍｅｎｔｅ…     

无定形氧化铁-胡敏酸复合胶体对Cu2+的吸附特征

采用Cu2 选择电极研究了不同pH值条件下胡敏酸(HA)、无定形Fe2O3、HA-Fe2O3复合胶体对Cu2 的等温吸附规律.结果表明,随着pH值的升高,3种胶体饱和吸附量和吸附平衡常数均增大,有利于吸附的进行.HA和无定形Fe2O3等温吸附Cu2 的4种拟合方程中,Langmuir方程整体拟合效果最佳,其次为对数方程和Freundlich方程,Linear方程较差.HA-Fe2O3复合胶体等温吸附Cu2 的4种拟合方程均达到显著相关.在相同pH值条件下,无定形Fe2O3对Cu2 吸附量最小,复合胶体次之,HA胶体最大;而且,无定形Fe2O3和复合胶体的饱和吸附量之和小于HA胶体.     

光Fenton反应的Ce-Fe/Al2O3催化剂制备及性能表征

采用等量浸渍法制备具有相同铁负载量的Fe/Al2O3和Ce-Fe/Al2O3催化剂,以解决光Fenton反应过程中催化剂溶出的问题并提高反应过程的pH值.通过X射线衍射(XRD)、扫描电镜(SEM)、氢程序升温还原(H2-TPR)及紫外-可见漫反射(UV-Vis DRS)等手段分别表征催化剂的物相结构、表面形貌、还原性能及光吸收特性,利用媒介黄的光Fenton脱色反应来考察催化剂的活性和稳定性.结果表明,铈掺杂使活性组分Fe2O3分散均匀,有效防止Fe2O3颗粒的长大,增加催化剂对光的吸收,增强催化剂的储氧能力,提高了催化剂的催化活性,降低铁的溶出.该催化剂在pH3.0～6.0条件下,60min内可将100mg/L媒介黄完全脱色,在pH6.0连续使用10次,其催化能力保持稳定.     

Catalytic oxidation of gas-phase elemental mercury by nano-Fe2O3

Heterogeneous oxidation of gas-phase Hg0 by nano-Fe2O3 was investigated on a fixed bed reactor, and the e ects of oxygen concentration, bed temperature, water vapour concentration and particle size have been discussed. The results showed that Hg0 could be oxidized by active oxygen atom on the surface of nano-Fe2O3 as well as lattice oxygen in nano-Fe2O3. Among the factors that a ect Hg0 oxidation by nano-Fe2O3, bed temperature plays an important role. More than 40% of total mercury was oxidized at 300°C, however, the test temperature at 400°C could cause sintering of nano-catalyst, which led to a lower e ciency of Hg0 oxidation. The increase of oxygen concentration could promote mercury oxidation and led to higher Hg0 oxidation e ciency. No obvious mercury oxidation was detected in the pure N2 atmosphere, which indicates that oxygen is required in the gas stream for mercury oxidation. The presence of water vapour showed di erent e ects on mercury oxidation depending on its concentration. The lower content of water vapour could promote mercury oxidation, while the higher content of water vapour inhibits mercury oxidation.     

Photocatalytic performance of TiO2 catalysts modified by H3PW12O40, ZrO2 and CeO2

The binary composite photo-catalysts CeO2/TiO2, ZrO2/TiO2 and the ternary composite photo-catalysts H3PW12O40-CeO2/TiO2,H2PW12O40-ZrO2/TiO2 were prepared by sol-gel method. The catalysts were characterized by thermogravimetric-differential thermal analysis (TG-DTA), scanning electron microscopy (SEM) and X-ray diffraction (XRD). The photocatalyfic elimination of methanol was used as model reaction to evaluate the photocatalytic activity of the composite catalysts under ultraviolet light irradiation. The effects of doped content, activation temperature, time, initial concentration of methanol and gas flow rate on the catalytic activity were investigated. The results showed that after doping a certain amount of CeO2 and ZrO2, crystaniTation process of TiO2 was restrained, particles of catalysts are smaller and more uniform. Doping ZrO2 not only significantly improved the catalytic activity, but also increased thermal stability. Doping H3PW12O40 also enhanced the catalytic activity. The catalytic activities of binary and ternary composite photocatalysts were significantly higher than tin-doped TiO2. The dynamics law of photocatalytic reaction over the binary CeO2/TiO2 and ZrO2/TiO2 catalysts has been studied. The activation energy 15.627 and 15.631 kJ/mol and pre-exponential factors 0.5176 and 0.9899 s-1 over each corresponding catalyst were obtained. This reaction accords to the first order dynamics law.     

Fe2O3纳米棒的制备及其H2S气敏性能研究

为快速检测H2S泄漏,以一步水热法制备的Fe2O3纳米棒为基础,制备了H2S气体传感器。研究表明,该传感器在300℃工作温度下对10μmol/mol的H2S的灵敏度为2左右,响应时间为12s左右,恢复时间约4s。而且该传感器具有优异的稳定性和选择性,对CH4、CO等多种气体响应较差,适合用于长时间快速检测H2S气体的泄漏。     

O3、O3/H2O2、O3/H2O2/UV工艺降解炸药工业废水中RDX的试验研究

为了研究高级氧化技术对含黑索今(RDX)的炸药工业废水的处理效果,本文采用O3、O3/H2O2、O3/H2O2/UV 3种氧化工艺分别对废水中的RDX进行了降解试验,并对比分析了3种工艺的处理效果和机制。结果表明:O3/H2O2、O3/H2O2/UV工艺对RDX的去除率明显优于O3工艺;提高体系的pH值将有利于RDX的降解;随着RDX初始浓度的增加,RDX的去除率呈现下降趋势;投加H2O2和UV照射可提高臭氧的利用率,且O3/H2O2/UV工艺催化臭氧分解的能力比O3/H2O2工艺强。     

4-CP在零价铁/H2O2系中的降解研究

文章对4-氯酚在非均相零价铁/H2O2体系中的降解进行了实验研究.结果表明,4-氯酚能在低pH零价铁/H2O2体系中迅速降解.pH对降解具有重要影响,当pH大于5,4-CP降解效果<10%.同时在低pH(pH3)环境下考察了铁粉和H2O2投加量的影响,在最佳条件下对溶液中亚铁离子的形成和过氧化氢的分解进行了进一步的实验研究.最后在对中间产物分析的基础上提出了4-CP降解路径假设.     

O3/H2O2降解Atrazine效能研究

利用O3/H2O2降解莠去津,对氧化产物进行了色谱分析,以评价该体系降解莠去津效能.莠去津初始浓度2 mg/L,7.5mg/L的O3单独氧化去除率为27.2%;相同O3投量下,H2O2/O3摩尔比0.75时,5 min莠去津的去除率最高可达96.5%,表明H2O2/O3体系对莠去津的去除效果良好,降解速度快.以离子色谱对产物的离子进行分析,莠去津浓度下降的同时,硝酸根和氯离子浓度增高.GC-MS检测的产物和对LC-MS谱图的分析表明,有机产物中存在脱乙基、脱异丙基和脱氯莠去津,说明H2O2/O3并不能彻底氧化莠去津,因此工程中作为主要去除单元或突发性污染事件的应急手段可能还需要与活性炭等单元联用.     

Cu2+/Na2S2O8体系中自由基的研究

利用自由基与乙醇和叔丁醇之间反应速率差异,研究在不同条件下Cu2+/Na2S2O8体系中产生自由基的状况.实验研究表明:Na2S2O8体系会产生·OH和SO-4由于Cu2+的催化作用,使用Cu2+Na2S2O8体系比单独使用Na2S2O8能产生更多的自由基·OH和SO-4.研究还发现:pH值降低能促进Na2S2O8分解产生自由基,但是会抑制SO-4转化为·OH;温度升高,Na2S2O8分解产生的·OH和SO-4均增加.     

铈掺杂Ru/Al2O3催化臭氧氧化降解邻苯二甲酸二甲酯

考察了铈(Ce)的掺杂对Ru/Al2O3催化臭氧氧化邻苯二甲酸二甲酯(DMP)溶液过程的影响.结果表明,Ce的掺杂可以显著提高臭氧氧化的效果,反应100min后,TOC的去除率可以由原催化剂的61.3%提高到75.1%,而单独臭氧氧化仅有14.0%.在实验范围内,Ru和Ce同时浸渍催化效果较好,且活性组分的溶出最少,Ce的最佳掺杂量为1.0%.通过催化剂吸附试验、单独臭氧氧化试验、Ce的均相催化试验及Ru-Se/Al2O3催化剂的非均相催化实验,证明Ru-Ce/Al2O3催化剂对DMP溶液臭氧氧化体系TOC的去除率达到50%,这是基于Ru-Ce/A12O3催化剂的非均相催化作用.