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, 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.     

向日葵秸秆生物炭强化Fe(Ⅲ)/S2O82-体系降解苯甲酸

二价铁离子活化过硫酸盐(PS)产生自由基可降解有机污染物,但体系中Fe(Ⅲ)/Fe(Ⅱ)循环速率较慢,成为制约降解效率的关键因素之一.为提高反应体系效率,制备向日葵秸秆生物炭(SFBC),以苯甲酸(BA)为目标污染物,探究SFBC强化Fe(Ⅲ)/S₂O^2-₈体系降解BA的效果.SFBC表征结果说明其具有孔隙结构,由无定形炭组成,表面有丰富的官能团及持久性自由基(PFRs).考察了反应条件(pH、PS浓度和SFBC投加量)对降解的影响,结果表明,SFBC/Fe(Ⅲ)/S₂O^2-₈体系对BA降解效率明显高于Fe(Ⅲ)/S₂O^2-₈及SFBC体系,在SFBC=2.0 g·L^-1、BA=10.0mg·L^-1、PS=2.0mmol·L^-1、Fe(Ⅲ)=1.0mmol·L^-1和pH=3.0条件下, 90 min时BA...     

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.     

水体系中EDTA-Fe(Ⅱ)/Ｋ２Ｓ２Ｏ８降解敌草隆的研究

对水体系中EDTA-Fe(Ⅱ)/K2S2O8降解敌草隆的方法进行了研究.在综合考虑经济性和降解率的前提下,提出了反应的最佳条件:K2S2O8初始浓度为2.0 mmol·L-1, Fe(Ⅱ)初始浓度为1.0 mmol·L-1, EDTA初始浓度为0.5 mmol·L-1,反应时间为300 min, pH=7.0,最终0.1 mmol·L-1,敌草隆降解率可达67.6%.同时,采用分子探针竞争实验鉴定了体系中产生的硫酸根自由基和羟基自由基,并采用LC/MS法鉴定了敌草隆的主要降解产物,从而探讨了敌草隆在EDTA-Fe(Ⅱ)/K2S2O8体系中可能的降解途径.     

FeⅡEDTA络合-Na2SO3还原吸收NO性能

为研究FeⅡEDTA络合-Na₂SO₃还原吸收NO性能,对制备参数〔pH、V(FeⅡEDTA)(FeⅡEDTA溶液用量)、初始c(FeⅡEDTA)、n(FeⅡ)∶n(EDTA)〕和操作条件〔温度、φ(O₂)、烟气流量、入口ρ(NO)〕及SO₃2-〔以c(Na₂SO₃)计〕进行了考察,并采用FT-IR(傅里叶红外光谱仪)和Raman(拉曼光谱仪)等表征手段对吸收体系进行表征.结果表明:①pH和初始c(FeⅡEDTA)对NO络合吸收量影响较显著,V(FeⅡEDTA)和n(FeⅡ)∶n(EDTA)次之.在pH为3～9的范围内,NO络合吸收量先增加后降低,pH为7时达到最大(0.502 mol/mol);初始c(FeⅡEDTA)由0.005 mol/L增至0.025 mol/L,NO络合吸收量随之增加了0.198 mol/mol.②温度和φ (O₂)的升高不利于NO吸收,当温度由30 ℃升至60 ℃、φ (O₂)从0%增至6%,NO络合吸收量却分别降低了71.69%、63.3%;此外,烟气流量和入口ρ (NO)的增加对NO络合吸收量也无显著影响.③SO₃2-的存在显著提高了FeⅡEDTA高效络合NO吸收时间.结合试验结果确定最佳反应条件:pH为7、V(FeⅡEDTA)为550 mL、初始c(FeⅡEDTA)为0.020 mol/L、n(FeⅡ)∶n(EDTA)为1∶1.0、温度为30 ℃、烟气流量为900 mL/min、无氧、c(Na₂SO₃)为0.20 mol/L,此时,NO络合吸收量为1.099 mol/mol,NO最大脱除率达到96.98%.研究显示,溶液中n(FeⅡEDTA)∶n(NO)对络合吸收NO起到主导作用,同时SO₃2-对FeⅡEDTA(NO)还原作用是促进NO吸收的重要机制.      

纳米Fe3O4/CeO2-H2O2非均相类Fenton体系对3,4-二氯三氟甲苯的降解

以浸渍法制备的新型纳米Fe3O4/Ce O2为催化剂,3,4-二氯三氟甲苯(3,4-DCBTE)为目标污染物,在Fe3O4/Ce O2-H2O2非均相类Fenton体系中对目标污染物的降解进行研究,考察催化剂的催化效果和温度、p H、H2O2投加量等因素对催化剂催化效果的影响.结果表明,以纳米Fe3O4/Ce O2作为催化剂的非均相类Fenton体系对3,4-二氯三氟甲苯的处理效果极佳;随着温度的升高,纳米Fe3O4/Ce O2的催化效果不断提高;在偏酸性环境中,p H越低催化效果越好,p H=2时反应去除效率可达96.67%;随着H2O2投加量的增加,3,4-二氯三氟甲苯的降解效率先提高后降低,投加量为15 mg·L-1时去除效果最好可达99.47%;随着催化剂投加量的增加,同样出现了处理效果先升高后降低的现象,投加量为0.5 g·L-1时催化效果最好可达99.64%.在以纳米Fe3O4/Ce O2为催化剂的非均相类Fenton体系中,3,4-二氯三氟甲苯的降解符合一级反应动力学,反应所需活化能较低只需30.26 k J·mol-1.     

Au/γ-Al2O3催化剂的制备及其对气相三苯系污染物的催化消除

采用沉积一沉淀法制备了负载型Au/γ-Al2O3,催化剂,对模拟污染气体的三苯系(苯,甲苯,二甲苯)蒸气进行催化消除反应,探讨了金含量、活化条件对催化剂活性的影响.结果表明,负载型Au/γ-Al2O3催化剂用量为0.50g、反应气流速为20 mL·min-1时,295℃下可完全催化消除浓度为7.57 g·m-3的苯;在252℃下可完全催化消除浓度为7.49 g·m-3的甲苯;在235 ℃下能完全催化消除浓度为3.07 g·m-3的二甲苯.苯、甲苯和二甲苯最后都完全矿化为CO2和H2O,没有生成新的有机物.对催化反应进行了动力学研究,上述催化反应都是准一级反应.测定得到苯、甲苯和二甲苯催化反应的总包反应表观活化能分别为118.47 kj·mol-1、101.43 kJ·mol-1和85.18 kJ·mol-1.     

MnO2@Fe3O4/石墨烯复合材料对水中Pb(Ⅱ)的吸附

以氧化石墨烯（GO）为原料制备MnO₂@Fe₃O₄/石墨烯（RGO）,考察吸附过程中MnO₂@Fe₃O₄/RGO投加量、溶液pH值、初始浓度和吸附时间等因素对Pb（Ⅱ）的去除率和吸附量的影响,并运用BET比表面积测试法计算MnO₂@Fe₃O₄/RGO的比表面积和平均孔径,采用扫描电子显微镜（SEM）,振动样品磁强计（VSM）,X射线衍射（XRD）和X射线光电子能谱（XPS）等对样品进行表征.结果表明：MnO₂@Fe₃O₄/RGO的比表面积为89.164m²/g,孔容为0.284cm³/g;随着pH值在2~10范围内增加,复合材料对Pb（Ⅱ）的去除率先增大后减小,pH=6时达到最大值.通过4种等温吸附模型（Langmuir、Freundlich、Temkin、D-R模型）和4种吸附动力学模型（伪一级动力学、伪二级动力学、Elovich、颗粒内扩散模型）拟合发现,MnO₂@Fe₃O₄/RGO对Pb（Ⅱ）吸附符合伪二级动力学模型.吸附等温线更符合Langmiur模型,属于典型的单分子层吸附,以化学吸附为主,最大吸附量为265.3mg/g.     

水体系中Fe(II)/S2O82--S2O3 2-降解敌草隆的研究

在初始pH 值为7.0 的水体系中,通过正交实验确定了Fe(II)/S2O82--S2O32-降解敌草隆的最佳操作条件:Na2S2O8 浓度2.0mmol/L, Fe(II)浓度1.0mmol/L,Na2S2O3 浓度0.5mmol/L,反应时间120min.在此条件下0.1mmol/L 敌草隆降解率达到91.3%.利用乙醇和叔丁醇作为分子探针,采用分子探针法的竞争实验鉴定了体系中产生的SO₄^-· 和 ·OH     

Photocatalytic degradation of perfluorooctanoic acid with β-Ga2O3 in anoxic aqueous solution

Perfluorooctanoic acid (PFOA) is a new-found hazardous persistent organic pollutant, and it is resistant to decomposition by hydroxyl radical (HO·) due to its stable chemical structure and the high electronegativity of fluorine. Photocatalytic reduction of PFOA with β-Ga₂O₃ in anoxic aqueous solution was investigated for the first time, and the results showed that the photoinduced electron (e_cb^-) coming from the β-Ga₂O₃ conduction band was the major degradation substance for PFOA, and shorter-chain perfluorinated carboxylic acids (PFCAs, C_nF_2n+1COOH, 1 ≤ n ≤ 6) were the dominant products. Furthermore, the concentration of F^- was measured by the IC technique and defluorination efficiency was calculated. After 3 hr, the photocatalytic degradation efficiency was 98.8% and defluorination efficiency was 31.6% in the presence of thiosulfate and bubbling N₂. The degradation reaction followed first-order kinetics (k = 0.0239 min^-1, t_1/2 = 0.48 hr). PFCAs (C_nF_2n+1COOH, 1 ≤ n ≤ 7) were detected and measured by LC-MS and LC-MS/MS methods. It was deduced that the probable photocatalytic degradation mechanism involves e_cb^- attacking the carboxyl of C_nF_2n+1COOH, resulting in decarboxylation and the generation of C_nF_2n+1·. The produced C_nF_2n+1· reacted with H2O, forming C_nF_2n+1OH, then C_nF_2n+1OH underwent HF loss and hydrolysis to form C_nF_2n+1COOH.     

三水铝石(γ-Al(OH)3)和α-Al2O3表面酸碱性质与磷酸根吸附研究

采用批量实验法,对2种不同晶体结构铝氧化物(γ-Al(OH)3和α-Al2O3)表面上磷酸根的吸附进行了比较研究.吸附等温线实验在pH=4和pH=6的KNO3溶液(0.0l mol·L-1)中进行,并使用Langmuir等温方程进行定量描述.由吸附等温线可以发现,α-Al2O3表现出更大的吸附容量和吸附密度.且在pH 3.5～4.0范围内,表面对磷酸根的吸附达到最大值.为了更好的理解表面性质对磷酸根吸附的影响,使用X射线衍射、N2吸附比表面积分析、电镜观察和表面酸碱滴定技术对表面结构和性质进行了表征.结合表面信息和吸附结果可以发现,单位质量吸附剂上的吸附量大小与比表面积有关,而吸附密度与铝氧化合物表面对磷酸根的吸附反应活性有关.     

Zn(Ⅱ)在δ-MnO2和γ-MnOOH两种矿物上吸附的初始溶质浓度效应

研究了在Zn(Ⅱ)总量一定的情况下,不同的初始溶质浓度和吸附动力学过程对吸附等温线及吸附不可逆性的影响.将总量一定的吸附质Zn(Ⅱ),分批次(1次,3次,15次)加入到2种不同的吸附剂体系(δ-MnO2和γ-MnOOH)中,得到吸附等温线.实验结果表明,对于Zn(Ⅱ)-δ-MnO2吸附可逆体系,吸附-解吸等温线及可逆性随着Zn(Ⅱ)加入批次的增加未见明显变化;而对于Zn(Ⅱ)-γ-MnOOH吸附不可逆体系,吸附等温线随着Zn(Ⅱ)加入批次的增加显著升高,吸附量变大,吸附不可逆性降低.这主要是由于在两种矿物上的微观吸附状态不同所导致的,而这种差异是受吸附动力学过程影响的,这是传统吸附热力学所不能解释的,但是符合亚稳平衡态吸附(MEA)理论的预测.