亚甲基兰在AC和TiO2/AC上的吸附及催化臭氧氧化

研究了活性炭(AC)和负载二氧化钛的活性炭(TiO2/AC)对亚甲基兰的吸附特性及单独臭氧氧化,AC催化臭氧氧化和TiO2/AC催化臭氧氧化处理水中亚甲基兰的效果.结果表明:AC、TiO2/AC吸附亚甲基兰均较好地符合一级动力学模型及Langmuir方程,AC对亚甲基兰的吸附性能优于TiO2/AC;催化臭氧氧化的脱色速率比单独臭氧氧化略高,且对亚甲基兰吸附性能好的AC作催化剂时脱色效率更高.催化臭氧氧化比单独臭氧氧化对亚甲基兰的矿化率有明显的提高,TiO2/AC的催化活性优于AC.在催化臭氧氧化过程中,伴随着亚甲基兰的分解生成一系列中间产物并逐渐完全氧化.     

超声波改性强化Mn/AC催化臭氧化降解苯酚效能分析

为提高臭氧氧化降解含酚废水的效能,对载体活性炭进行超声改性,并利用浸渍沉淀法制备Mn/AC催化剂,通过BET、SEM、EDS、XRD表征分析超声处理对其结构的影响,同时用苯酚模拟废水考察超声改性对其去除效能的影响。结果表明,超声改性起到清灰造孔作用,载体孔道增多,比表面积和孔体积增高,强化了负载,Mn的负载量由2. 40%升至3. 85%并以MnO2形式存在,增大分散度;超声改性增强了催化剂的吸附及催化臭氧化能力,提高体系的吸附-催化臭氧氧化协同效应,Mn/U60-AC+O3体系在催化剂质量浓度为2 g/L、苯酚初始质量浓度为100 mg/L、温度为(25±1)℃、臭氧质量浓度为3 mg/L、气体通入流量为4 m L/min、pH=10、水体积为1 L的条件下反应24 min,苯酚的去除率高达99. 64%,比Mn/AC+O3体系提高了16%。     

木棉基活性炭纤维的结构与吸附性能

采用浸渍磷酸氢二铵及化学活化法制备了3种木棉基活性炭纤维,其中AK-1没有经过预氧化处理,AK-2先浸渍再经预氧化处理,AK-3先经预氧化处理再浸渍;表征了3种活性炭纤维的表面物理化学结构及吸附性能。结果表明:3种活性炭纤维的平均孔径均约为2nm;预氧化处理提高了纤维的比表面积和纤维表面的含氧基团含量。AK-1具有最大的苯酚吸附量为65.8mg/g;AK-3具有最大的亚甲基蓝吸附量为156.7mg/g;AK-2具有最大的比表面积为1518m2/g和最多的表面含氧基团,对苯酚和亚甲基蓝的吸附量均不高,说明表面含氧基团降低了纤维对苯酚和亚甲基蓝的吸附量。吸附动力学研究表明,木棉基活性炭纤维吸附苯酚和亚甲基蓝符合拟二级动力学方程。     

炭载体对Pt-C复合物非碱性条件下催化甘油氧化性能的影响

采用等量浸渍法制备了具有相似平均粒径的活性炭(AC)和碳纳米管(CNTs)负载的Pt催化剂,并比较研究了非碱性条件下两种催化剂催化甘油氧化反应的性能。结果表明,炭载体对Pt-C复合物催化甘油氧化反应的活性、选择性和稳定性有重要影响。相对于Pt/CNTs催化剂,Pt/AC催化剂中Pt 4f结合能较低,导致其表面氧的覆盖度相对较高,因而抑制了甘油的吸附,降低了甘油氧化反应的初始活性;Pt/AC催化剂会促进甘油醛进一步氧化成甘油酸以及C3产物的氧化断键;Pt/AC催化剂失活的主要原因是氧中毒和中间产物的吸附,而Pt/CNTs催化剂的失活主要是由于甘油酸的吸附堵塞Pt表面的活性位造成的。     

炭载体对Pt-C复合物非碱性条件下催化甘油氧化性能的影响

采用等量浸渍法制备了具有相似平均粒径的活性炭（AC）和碳纳米管（CNTs）负载的Pt催化剂,并比较研究了非碱性条件下两种催化剂催化甘油氧化反应的性能。结果表明,炭载体对Pt-C复合物催化甘油氧化反应的活性、选择性和稳定性有重要影响。相对于Pt/CNTs催化剂,Pt/AC催化剂中Pt 4f结合能较低,导致其表面氧的覆盖度相对较高,因而抑制了甘油的吸附,降低了甘油氧化反应的初始活性;Pt/AC催化剂会促进甘油醛进一步氧化成甘油酸以及C₃产物的氧化断键;Pt/AC催化剂失活的主要原因是氧中毒和中间产物的吸附,而Pt/CNTs催化剂的失活主要是由于甘油酸的吸附堵塞Pt表面的活性位造成的。     

B2O3·TiO2/Ti催化剂对水中腐殖酸吸附行为研究

TiO2光电催化氧化有机物的反应被认为是表面反应,有机物在TiO2表面的吸附是其降解的先决条件,因此系统研究有机物在TiO2表面的吸附行为,可以为进一步的光电催化降解提供实验依据.现采用阳极氧化法在基体钛表面原位合成B2O3·TiO2/Ti催化剂为吸附剂,系统地研究了腐殖酸在膜催化剂上的吸附行为,探讨了温度、溶液pH值、腐殖酸初始浓度、外加偏压等因素对吸附的影响,结果表明:低温、酸性条件下有利于腐殖酸在膜催化剂上吸附,吸附量随初始浓度、外加偏压的增加而增大,B2O3·TiO2/Ti催化剂吸附腐殖酸的等温线数据可用Freundlich等温吸附方程描述,吸附过程遵循Lagergren二级吸附动力学模型.     

RuO_2/ZrO_2-CeO_2催化湿式氧化降解乙酸机理研究

采用不同方法制备了不同的载Ru催化剂,对催化剂表面吸附氧、Ru的分散度和晶粒大小进行了表征,测试了不同催化剂催化湿式氧化降解乙酸的活性。结果表明,不同催化剂的活性高低与其表面吸附氧含量大小排序一致。当反应温度为140℃、压力为3 MPa,Ru/ZrO_2-Ce O_2催化氧化降解乙酸,反应120 min后乙酸溶液中COD(约5 g/L)的去除率达到了99%。相比传统沉淀法,加热回流法将催化剂Ru的分散度提高了33%,COD去除率提高了54%。自由基的激发机理可能为,通过表面的-O~(2-)-Ce~(4+)-O~(2-)-Ru~(4+)-键将电子传递给催化剂表面的吸附氧,最后与水中的H~+结合形成自由基HO_2~·,完成自由基的引发过程。     

湿式催化氧化法处理含酚清洗废水的研究

针对化工集装罐清洗废水中含酚废水浓度大的特点,采用湿式催化氧化法进行了较深入的研究。对硝酸铜-AC制备CuO/AC催化剂过程中的浸渍液浓度、焙烧温度、焙烧时间等影响因素进行探讨;用该催化剂催化氧化降解模拟苯酚废水,对反应温度、氧化剂投加量、催化剂投加量、反应时间等工艺参数进行优化,确定最佳反应条件并进行了应用研究。研究结果表明,硝酸铜-AC制备CuO/AC催化剂的最佳条件为:硝酸铜质量分数为3%,浸渍温度为30℃,浸渍时间为6 h,焙烧温度为300℃,焙烧时间为3 h。湿式催化氧化法处理苯酚废水的最佳工艺条件为:反应温度为170℃,反应时间为1 h,催化剂投加质量浓度为2 g/L,氧化剂H2O2按m(H2O2)∶m(COD)=3投加,含酚清洗废水的COD去除率达到95%以上,处理效果显著。     

Fe2O3/AC催化剂的低温选择性催化还原脱硝性能

以活性焦(AC)为载体、Fe2O3为活性组分,采用等体积浸渍法制备Fe2O3/AC催化剂,研究了Fe含量对Fe2O3/AC催化剂低温脱硝性能的影响. 结果表明,当Fe负载量为6wt%时能获得比其它负载量更佳的NOx转化率,尤其在240℃时NOx转化率达93.9%,当分别有120?10?6(vol) SO2和3.5vol H2O存在时,脱硝率分别稳定在约86%和74%;催化剂孔径≤4 nm,随Fe负载量增加,孔径呈增大趋势;催化剂较稳定;Fe主要以γ-Fe2O3分散在催化剂表面,负载适量Fe2O3使表面吸附氧Oβ和Fe3+增多,为催化剂提供更多活性位,提高了Fe2O3/AC催化剂的低温选择性催化还原脱硝活性.     

V2O5/AC催化剂吸附NH3及其选择性还原脱硝活性

在不同活性焦(Activated Coke, AC)载体上以等体积浸渍法负载V2O5,制备出一系列V2O5/AC催化剂. 通过NH3暂态响应实验和NH3穿透时间实验考察了在200℃下V2O5/AC的表面积、灰分、表面官能团和V2O5对NH3的吸附量及NO的选择性催化还原活性的影响. 结果表明,对于载体未经硝酸处理的催化剂,NH3的吸附位主要是V2O5(参与脱硝反应的NH3的吸附量与催化剂上V2O5负载量的比值为1:5),活性焦及其中的灰分对NH3的吸附量很小;硝酸处理在活性焦表面引入的含氧和含氮酸性官能团对参与脱硝反应的NH3的吸附量是V2O5上吸附量的1.3倍,这些官能团不影响V2O5对NH3的吸附;活性焦上吸附的NH3的脱硝活性很低,但可迁移至V2O5上参与脱硝.     

Behavior of Cu–Ce/AC catalyst–sorbent in dry oxidation of phenol

An activated carbon-supported copper and cerium catalyst–sorbent (Cu–Ce/AC) is studied for phenol adsorption from a water phase and catalytic oxidation of the adsorbed phenol under dry conditions. The Cu–Ce/AC has high phenol adsorption capacities and high phenol oxidation activities. The phenol saturation adsorption capacity of the fresh Cu–Ce/AC is about 209 mg/g. With increasing adsorption–oxidation cycles (repeat uses), the phenol adsorption capacity decreases consecutively to a stable value of about 78 mg/g when the oxidation is carried out at 250 °C for 2 h, which is better than that of other types of AC-based materials. The initial oxidation temperature for phenol is about 160 °C, which is 150 °C lower than the ignition temperature of the AC. The main oxidation products are CO₂ and H₂O with a small amount of desorbed phenol. The decrease in phenol adsorption capacity after the oxidation is caused by the formation of phenol polymeric residues, which block the micro-pore and perhaps cover the active sites.     

基于AC/SnO2-Sb粒子电极的苯酚电催化氧化

采用热分解法,以活性炭(AC)颗粒为基体,利用Sn-Sb固溶特性制备具有催化活性的AC/SnO₂-Sb粒子电极,并通过N₂吸附法、扫描电镜(SEM)、X射线衍射(XRD)及电化学测试对其微孔结构、微观形貌、物相组成和电催化活性进行表征.结果表明,SnO₂-Sb活性组分减少了AC介孔但未破坏高孔隙结构,且以固溶体形式广泛分布于AC孔道表面,不仅增强了AC孔隙内部降解有机物的活性,还增加了电催化活性位点,有助于提升催生羟基自由基的能力;同时只有AC/SnO₂-Sb粒子电极的循环伏安曲线(CV)在1.10V存在明显的苯酚氧化峰,说明SnO₂-Sb固溶体在电催化氧化的作用下,可直接参与苯酚的催化降解.以模拟苯酚废水考察粒子电极的电催化活性以及稳定性,结果表明,在电流密度12.0mA/cm² 和反应时间3h条件下,AC/SnO₂-Sb粒子电极的COD和苯酚去除率分别为78.43%和79.52%,均高于AC粒子电极的去除率.此外,AC/SnO₂-Sb在30天连续水处理中表现出较好的电化学稳定性.     

Synthesis of recyclable catalyst-sorbent Fe/CMK-3 for dry oxidation of phenol

The magnetic mesoporous material Fe/CMK-3 acting as a catalyst-sorbent was synthesized by using ordered mesoporous carbon CMK-3 as the supporter, Fe(NO₃)₃ as the iron source, and glycol as the reducing agent. The samples synthesized were characterized by powder X-ray diffraction (XRD), N₂ adsorption-desorption, scanning electron microscope (SEM) and transmission electron microscopy (TEM). The results show that the prepared Fe/CMK-3 preserved the ordered mesoporous structure of CMK-3, and magnetic species was mainly Fe₃O₄, which was dispersed inside channels of CMK-3 as nanoparticles with the diameter of around 10 nm. The adsorption and catalytic dry oxidation efficiency of the prepared Fe/CMK-3 were determined. The results also show that Fe/CMK-3 had good adsorption performance of phenol in aqueous solution and could be easily separated from water and recycled due to its ferromagnetic nature. Iron oxides supported on CMK-3 were excellent catalysts for dry oxidation of phenol. After 15 adsorption-catalytic oxidation cycles, the phenol adsorption capacity of Fe/CMK-3 only decreased a little, suggesting the good practicality. Combined thermogravimetry and mass spectrum (TG-MS) instrument was used to investigate the catalytic oxidation of phenol on Fe/CMK-3 and the ignition characteristics of the catalyst-sorbent. The supported Fe₃O₄ was found to be not only the magnetic component but also the active catalyst for the oxidation of phenol. The adsorbed phenol could be oxidized into CO₂ and H₂O at 220 °C at which no obvious phenol desorption or CMK-3 ignition occurred.     

Simultaneous adsorption of phenol and Cu2+ from aqueous solution by activated carbon/chitosan composite

A multifunction adsorbent was synthesized by incorporating AC into CTS, and the ratio of AC to CTS was 1/1. The resultant was called activated carbon (AC)/chitosan (CTS) composite. The simultaneous adsorption of phenol and Cu²⁺ from aqueous solution onto AC/CTS composite was investigated by a batch procedure. The adsorption processes for both Cu²⁺ and phenol obeyed the pseudo second-order kinetic model. Phenol was prone to be adsorbed more quickly as compared with Cu²⁺ when they coexisted in solution. The adsorption behavior of both phenol and Cu²⁺ followed the Langmuir isotherm. The maximum adsorption capacities of phenol and Cu²⁺ were 34.19 mg/g and 74.35 mg/g at 293 K, respectively. No obvious competitive adsorption existed between phenol and Cu²⁺.     

炭化活化条件对Cu/AC表面Cu价态及其催化降解苯酚的影响

采用前体浸渍法研制了生物质基载铜活性炭催化剂（Cu/AC）,利用N₂-吸附脱附、X射线光电子能谱等技术对Cu/AC性质进行了表征,在固定床反应器中研究了不同炭化活化条件所得Cu/AC催化湿式氧化降解苯酚性能。结果表明：Cu/AC表面Cu物种以Cu²⁺和（Cu⁺+Cu⁰）共存。随着制备Cu/AC炭化温度的升高,炭化过程中产生更多的挥发分,促进Cu²⁺还原为Cu⁺和Cu⁰,（Cu⁺+Cu⁰）含量增大,Cu/AC降解苯酚催化活性逐渐升高;随着炭化时间延长,（Cu⁺+Cu⁰）含量下降,Cu₂O、CuO较好地并入载体使晶格氧含量增加,催化活性先升高后下降;随着活化温度升高和活化时间延长,Cu/AC比表面积达到1096.1m²/g并有大量微孔生成,大量含氧官能团分解将炭化过程中还原生成的（Cu⁺+Cu⁰）氧化为Cu²⁺,晶格氧含量增加,催化活性随着活化温度的升高而升高,随着活化时间的延长先升高后下降。催化湿式氧化降解苯酚过程中,Cu/AC具有良好的稳定性和低的Cu离子浸出浓度。Cu/AC的最优制备条件为炭化温度800℃,炭化时间2h,活化温度880℃,活化时间为2h,所得Cu/AC在反应8.5h时实现98.5%的苯酚转化率和91.1%的COD转化率。     

改性活性炭负载高分子季铵盐的杀菌性能

引言活性炭比表面积大、吸附性能好,广泛应用在空气污染防治和工业废水处理中,如大型通风系统的过滤器、肾透析病房的水处理系统[1-2]。然而,活性炭表面易繁殖细菌,使其本身也成了微生物的污染源,从而影响净化空气或水的效果[3]。目前,对抗菌炭材料的研究越来越受到关注,多数工作者     

Treating High COD Dyeing Wastewater via a Regenerative Sorption-Oxidation Process Using a Nano-Pored Activated Carbon

Nowadays, the structural complexity of dyes used in the textile industry and the widely adopted water-saving strategy in the dyeing processes often fail plants’ biological wastewater treatment units due to chemical oxygen demand (COD) overload. To alleviate this problems, this study investigated a regenerable adsorption–oxidation process to treat dyeing wastewater with COD around 10,000 mg/dm³ using a highly nano-pored activated carbon (AC) as a COD adsorbent, followed by its regeneration using hydrogen peroxide as an oxidizing reagent. In addition to studying AC’s COD adsorption and oxidation performance, its operational treatment conditions in terms of temperature and pH were assessed. The results firstly demonstrated that about 50–60% of the COD was consistently adsorbed during the repeated adsorption operation before reaching AC’s maximum adsorption capacity (q_max) of 0.165 g-COD/g-AC. The optimal pH and temperature during adsorption were 4.7 and 25 °C, respectively. Secondly, AC regeneration was accomplished by using an initial peroxide concentration of 2.5% (by wt %) and EDTA-Fe of 2.12 mmole/dm³. The reuse of the regenerated ACs was doable. Surprisingly, after the first AC regeneration, the COD adsorption capacity of the regenerated AC even increased by ~7% with respect to the virgin AC. Thirdly, the results of a five-consecutive adsorption–regeneration operation showed that a total of 0.3625 g COD was removed by the 5 g AC used, which was equivalent to an adsorption capacity (q) of 0.0725 (= 0.3625/5) g-COD/g-AC during each adsorption stage. Based on the obtained results, a regenerable COD adsorption–oxidation process using a nano-pored AC to treat the high-textile-COD wastewater looks promising. Thus, a conceptual treatment unit was proposed, and its potential benefits and limitations were addressed.     

新生态水合二氧化锰对水中酚类化合物的吸附和氧化

试验研究了新生态水合二氧化锰对水中苯酚，4－氯酚以及2，6－二氯酚的去除，结果表明水合二氧化锰对水中苯酚及氯酚均有一定的去除效果，试验中从酚的去除情况及还原性Mn^2 的生成量判断出水合二氧化锰的吸附和氧化作用程度，同时，从水合二氧化锰对水中三种酚的吸附及氧化去除结果的比较，分析出氯取代对酚在水合二氧化锰表面吸附氧化能力的影响，结果表明了氯的取代使得酚易于被二氧化锰吸附而不易于被氧化。