非均相催化臭氧化降解水中苯酚动力学

在常温常压下对MgO催化臭氧化降解苯酚的动力学进行了详细研究,考察了MgO加量、臭氧投加量、pH值、苯酚初始浓度和反应温度对催化臭氧化降解苯酚废水的反应速率常数k的影响,分析了多相催化臭氧化的反应活化能,构建了反应动力模型。结果表明,臭氧对苯酚的催化降解遵循表观拟一级反应动力学,且反应速率常数k随着MgO加量(20~80 mg·L-1)的增加而增大,在MgO加量为40 mg·L-1时达到0.185 7 min-1;随着臭氧加量(0.54~5.5 mg·min-1)的增加,k从0.030 49 min-1增大到0.217 77 min-1;随着溶液初始pH(1.7~10.15)的升高,k从0.087 75 min-1增加到0.205 49 min-1;随着初始苯酚浓度(50~400 mg·L-1)的增加,k从0.253 68 min-1降低到0.036 82 min-1;随着反应温度(10~50 ℃)的增加,k从0.120 62 min-1增加到0.466 46 min-1。证明了催化臭氧化降解苯酚的表观反应速率常数分别与催化剂加量、臭氧加量、pH和反应温度成正相关,与苯酚初始浓度则成负相关。反应活化能较低(Ea＝2.616 7×104 J·mol-1),并且动力学模型计算数值与实际数据吻合良好(平均相对误差为8.9%)。     

活性炭纤维的氧化处理研究

采用静态保干器法测定了活性炭纤维对乙醇、丙酮、N-甲基吡咯烷酮的吸附量.研究了酸氧化处理对活性炭纤维吸附性能的影响,并用电位滴定法确定了活性炭纤维氧化前后表面含氧官能团的变化.结果表明,活性炭纤维对3种吸附质的吸附量均随时间延长而增加,但饱和吸附量及达到饱和吸附的时间因吸附质的不同而不同.氧化处理后,活性炭纤维表面含氧官能团发生变化,对乙醇的吸附量增加18%,而对N-甲基吡咯烷酮的吸附量提高了300%.     

TiO2负载型活性炭电催化氧化苯酚性能研究

以活性炭为载体,采用溶胶凝胶法制备TiO2负载型活性炭,采用电子显微镜(SEM)和X射线衍射(XRD)仪对催化剂进行表征,TiO2负载型活性炭晶体结构牢固,为锐钛矿.在苯酚质量浓度为600mg/L、30 000 mg/L Na2SO4为支持电解质、恒流泵、电流密度30 A/m2、流速0.6 L/h的条件下对模拟废水进行连续处理,研究TiO2负载型活性炭对COD、平均电流效率和电耗的影响.结果表明,填料为TiO2负载型活性炭比填料为活性炭的最终出水COD去除率提高6.45百分点,平均电流效率提高10百分点,电耗下降7.20 kW· h/kg,说明TiO2负载型活性炭有较高的电流利用率且催化活性较高.进一步说明,在一定的浓度范围内,TiO2负载型活性炭能更有效降解苯酚废水.     

活性炭纤维吸附废水中对硝基苯酚及其脱附研究

采用新型高效吸附剂——活性炭纤维吸附废水中对硝基苯酚，对其吸附和脱附影响因素进行了较详细的研究，确定了最佳工艺参数，并对动态吸附一脱附进行了稳定性实验。在最佳的吸附条件下，装填4g活性炭纤维可处理含对硝基苯酚1000mg/L的废水1400mL，出水对硝基苯酚浓度〈2mg／L，达到国家综合污水一级排放标准，活性炭纤维有效吸附量可达349．87mg／g。在最佳脱附条件下，脱附率〉99％，并可从高浓度脱附液中回收对硝基苯酚。稳定性实验表明，吸附-脱附性能稳定，采用活性炭纤维吸附处理对硝基苯酚废水是一种行之有效的处理方法。     

活性炭纤维的氧化处理研究

采用静态保干器法测定了活性炭纤维对乙醇、丙酮、N-甲基吡咯烷酮的吸附量。研究了酸氧化处理对活性炭纤维吸附性能的影响,并用电位滴定法确定了活性炭纤维氧化前后表面含氧官能团的变化。结果表明,活性炭纤维对3种吸附质的吸附量均随时间延长而增加,但饱和吸附量及达到饱和吸附的时间因吸附质的不同而不同。氧化处理后,活性炭纤维表面含氧官能团发生变化,对乙醇的吸附量增加18%,而对N-甲基吡咯烷酮的吸附量提高了300%。     

活性炭表面酸性含氧官能团对吸附甲醛的影响

利用Bothem滴定法测定了化学浸渍处理的活性炭表面酸性含氧官能团浓度,研究表面酸性含氧官能团对甲醛吸附的效应。结果表明,HNO3浸渍处理能有效增大活性炭表面的羧基、酚羟基和内酯基浓度;H2O2浸渍处理主要增大了活性炭表面的酚羟基浓度;随着NaOH浓度的增大,活性炭表面的酚羟基、内酯基和羰基浓度大致呈先增大后减小的趋势,这是由于NaOH的化学清洗作用和酸碱中和反应所致;HNO3浸渍处理的活性炭表面的酸性含氧官能团浓度显著超过NaOH、H2O2浸渍处理的活性炭,而30%(质量分数)NaOH浸渍处理的活性炭和30%(体积分数)H2O2浸渍处理的活性炭吸附甲醛的饱和时间比HNO3浸渍处理的活性炭吸附甲醛最大饱和时间分别多4.0、1.5 h,说明酚羟基能够显著影响活性炭吸附甲醛的效果。     

孔结构和表面化学性质对活性炭吸附性能的影响

测定了室温下3种活性炭(GAC-C、GAC-P和GAC-T)对CO2、CH4和N2的吸附性能,并对颗粒活性炭孔结构和表面化学性质进行了表征,探讨了孔结构和表面化学性质对活性炭吸附性能的影响。结果表明:由于吸附机理、孔结构、表面含氧官能团和分子极性的差异,CO2、CH4和N2在活性炭上的饱和吸附量和吸附常数的关系为CO2>CH4>N2;CH4和N2的饱和吸附量主要受活性炭微孔孔容的影响,N2和CO2饱和吸附量的差异分别是由0.572～2.0 nm的微孔和0.4～6 nm的孔引起的;CH4吸附常数主要受较大中孔和大孔影响,N2吸附常数与微孔密切相关,大孔对CO2的吸附常数影响最大。     

木棉基活性炭纤维吸附性能的研究

采用浸渍(NH₄)₂HPO₄化学活化法650℃时制备得到3种新型木棉基活性炭纤维,即只浸渍不预氧化方法处理的AK1(activated kapok),先浸渍后预氧化的AK-2和先预氧化后浸渍的AK-3。利用制备得到的活性炭纤维处理苯酚和亚甲基蓝的模拟废水,AK-2具有苯酚最大吸附量(137.00 mg/g),AK-1具有亚甲基蓝最大吸附量(274.11 mg/g)。吸附苯酚时,在静态平衡实验中,更符合Freundlich吸附等温线;在动力学实验中,更符合准一级反应。吸附亚甲基蓝时,在静态平衡实验中,AK-1更符合Langmuir模型,AK-2 、AK-3更符合Freundlich吸附等温线;在动力学实验中,更符合准二级反应。     

微波诱导活性炭纤维催化氧化实现污泥减量的研究

采用SBR装置,对应用微波诱导活性炭纤维催化氧化实现污泥减量进行了研究。结果表明,在微波功率为800W,微波辐照时间为50s,每克SS加入0.19g活性炭纤维条件下,微波诱导活性炭纤维催化氧化污泥的分解率明显高于单独微波消解处理。将微波诱导处理后的污泥返回到处理系统中,随着被微波诱导处理的污泥占反应器内污泥的比例(污泥处理比例)的增大,污泥表观产率系数随之减小,污泥减量也越明显;污泥处理比例为5%(体积分数,下同)、10%、15%时,与对照系统相比,处理系统污泥减量分别为24.3%、43.6%、62.2%;随着污泥处理比例的增大,处理系统出水溶解性COD(SCOD)呈升高趋势,但系统仍能保持其生物处理能力,SCOD去除率在85%以上。处理系统和对照系统的氨氮降解速率常数及污泥耗氧速率相差不大,处理系统的硝化能力及污泥活性基本没有受到微波诱导催化氧化作用的影响。     

Ozonation of aniline promoted by activated carbon

The removal of aniline from aqueous solutions by simultaneous use of ozone and activated carbon was investigated at different solution pH. For comparative purposes, single ozonation and adsorption on activated carbon were carried out in the same experimental set-up. In order to evaluate the role of the activated carbon surface chemistry during ozonation, a commercial activated carbon, Norit GAC 1240 PLUS, was submitted to oxidation in the liquid phase with HNO(3). The texture and surface chemistry of the activated carbon samples were characterized. During ozonation, complete conversion of aniline was achieved after approximately 20 min, regardless of the presence of activated carbon. In all cases, several by-products were formed during ozonation. Nitrobenzene, o- and p-aminophenol were the primary aromatic oxidation by-products identified. In terms of TOC removal, best results were achieved by the simultaneous use of ozone and activated carbon. Though there is a strong contribution of adsorption, a considerable synergetic effect between ozone and activated carbon is observed. In general, activated carbon promotes the reaction of ozonation enhancing the efficiency of this treatment process. The basic activated carbon presented greater activity in this process leading to higher mineralization rates.     

Ozonation of activated carbon and its effects on the adsorption of VOCs exemplified by methylethylketone and benzene

Ozonation can modify the surface property of an activated carbon such as specific surface area, pore volume, and functional group. Results indicate that ozonation can increase the specific surface area of an activated carbon from 783+/-51 to 851+/-25 m2/g due in part to increasing micropores (those below 15 A). However, there is no change in macropore and mesopore upon ozonation. The amount of oxygen functional group (OFG) increases from 197+/-4 to 240+/-4 microeq/g, mostly in hydroxyl and carboxyl groups upon ozone treatment. These oxygen-containing functional groups are stable in the temperature range 30-250 degrees C, but begin to decompose when temperature increases beyond 300 and 350 degrees C. When the temperature reaches 1200 degrees C, all OFGs virtually disappear. The effect of ozone treatment on the adsorption of volatile organic carbon (VOC) was exemplified by methylethylketone (MEK) and benzene. The adsorption density of MEK and benzene by ozone treated activated carbon (AC(O3)) are greater than that by the untreated (AC), with MEK being more adsorbable than benzene. Results of factorial analysis indicate that physical characteristics, namely, micropore, BET surface area, pore diameter (PD), micropore volume (MV) play an important role on benzene and MEK adsorption.     

CO2高温活化活性炭材料对苯酚的吸附行为研究

以CO2为活化气体,在高温条件下对国产椰壳活性炭进行活化。研究了活化前后的活性炭在不同温度和pH等条件下对水溶液中苯酚的吸附行为。结果表明,活性炭经活化后,微孔体积和中孔体积增加,吸附容量明显提高;苯酚在活性炭上的吸附符合Freundlich吸附等温方程和准二级反应动力学方程;在一定范围内降低温度有利于吸附的进行;在pH为2～8时,吸附效果较好;在pH9时,吸附效率明显降低。     

Comparison on surface properties and desulfurization of MnO2 and pyrolusite blended activated carbon by steam activation

In this study, MnO₂ and pyrolusite were used as the catalysts to prepare modified activated carbon, that is, AC-Mn and AC-P, respectively, from coals by blending method and steam activation. The Brunauer–Emmett–Teller (BET) results indicated that the AC-P had higher surface areas and micropore volumes than the AC-Mn with the same blending ratio. The relative contents of basic functional groups (i.e., C = O, π-π*) on AC-P were slightly lower than those on AC-Mn, while both contained the same main metal species, namely, MnO. The desulfurization results showed that with 3 wt% of blending ratio, AC-Mn3 and AC-P3 had higher sulfur capacities at 220 and 205 mg/g, respectively, which were much higher than for the blank one (149.6 mg/g). Moreover, the AC-P had relatively higher sulfur capacity than the AC-Mn with the same contents of Mn, which might be attributed to the existence of other metals in pyrolusite. After the desulfurization process, MnO were gradually transferred into MnSO₄, and the relative contents of basic functional groups decreased evidently for both AC-Mn3 and AC-P3. The results demonstrated that pyrolusite could be one good alternative to MnO₂ to prepare modified activated carbon for desulfurization.

Implications: MnO₂ and pyrolusite were used as the additives to prepare modified activated carbon from coals by a blending method and by steam activation, that is, AC-Mn and AC-P, respectively. The AC-P had higher surface areas and micropore volumes than the AC-Mn with the same blending ratio. The AC-Mn and AC-P had higher sulfur capacities than a blank one. Moreover, the AC-P had relatively higher sulfur capacity than the AC-Mn with the same contents of Mn. The results demonstrated that pyrolusite could be one good alternative to MnO₂ to prepare modified activated carbon for desulfurizatio.     

Multi-component behavior of fixed-bed adsorption of dioxins by activated carbon fiber

The multi-component behavior of fixed-bed adsorption of dioxins (DXNs) was examined through detailed analyses of the concentration profiles of isomers in fixed-bed activated carbon fiber (ACF). Regularities in both adsorption rates and strengths were clarified. (1) The rate of transfer in the adsorption of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCCDs/DFs) tends to increase with decreasing number of chlorine substituents. Axial dispersion also tends to increase with a decreasing number of chlorine substituents under our experimental conditions. (2) Homologues with the same number of chlorine substituents in PCDDs/DFs have similar adsorption strengths. The adsorption strength of PCDD/DF isomers is probably greater than that of co-planar polychlorinated biphenyls (co-PCB) isomers when the number of chlorine substituents is identical. (3) The adsorption strength of isomers depends on their molecular structure. In PCDDs/DFs the toxic isomers, all of which have vicinal chlorine substituents at the 2, 3, 7 and 8 positions, are relatively strong. It is clear, especially in TeCDDs, that isomers with vicinal chlorine substituents are stronger than isomers without. In co-PCBs, isomers without chlorine substituents at ortho positions are stronger than those with, and (4) A close analogy exists between the adsorption strength order for ACF and the elution order in gas chromatography (GC).     

腐殖酸、细颗粒泥沙对粉末活性炭吸附苯酚特性影响的研究

通过一系列实验,探讨了粉末活性炭吸附水中苯酚时,腐殖酸(HA)浓度和细颗粒泥沙用量对苯酚吸附量和去除率的影响.实验结果表明:在中性条件下,随着HA浓度的增加,粉末活性炭对苯酚的吸附量减少;在不同质量细颗粒泥沙的影响下,苯酚的去除率基本不变;在未加HA时,粉末活性炭对苯酚的吸附行为用Langmuir吸附等温式拟合效果最好,对苯酚的最大吸附量为150.60 mg/g,而在有HA存在时,粉末活性炭对苯酚的吸附行为用Freundlich吸附等温式拟合效果最好,对苯酚的最大吸附量为28.49 mg/g.