高铁酸钾强化铁锰氧化膜过滤去除水中有机物

前期研究发现铁锰氧化膜（MeO _x ）对水中氨氮、铁、锰等污染物具有较高的去除率，但对水中有机物（以COD_Mn计）的去除效果较差。为了提高MeO _x 对COD_Mn的去除率，本研究采用高铁酸钾强化MeO _x 的催化氧化过程，探究其对水中COD_Mn的有效去除及相关影响因素。实验结果表明：仅投加0.1mg/L的高铁酸钾强化MeO _x 过滤，对于进水中20mg/L的COD_Mn，去除率可达到约92.5%；滤速对其具有一定的影响，去除率随着滤速的提高呈下降的趋势，在6~10m/h出水滤速中的COD_Mn均能达到3.0mg/L以下，当滤速达到11m/h时去除率下降到81.65%；较低的pH（约6.51）具有一定的不利影响，COD_Mn的去除率随着pH的降低而逐渐下降；进水中NH₄⁺也会影响COD_Mn的去除，NH₄⁺浓度越高其去除率越低。扫描电子显微镜（SEM）结果显示，高铁酸碱强化过滤约60天后，可在MeO _x 的表面生成某种物质；由电子能谱（EDS）分析MeO _x 表面可知，约60天后C元素和O元素的比例明显增加，Mn元素和Fe元素的比例明显降低，但MeO _x 表面减少的部分铁锰物质并未影响COD_Mn的去除；由X射线光电子能谱（XPS）分析可知，Mn元素强化过滤前后对应的化合物主要为MnO、Mn₂O₃以及Mn₃O₄，对C、O元素分析后发现附着在MeO _x 表面的物质为(CH₂)₄O_n。     

Ti-Al复合载体载锰催化剂同时脱硝脱汞实验

采用溶胶-凝胶法制备了一系列TiO₂、TiO₂-Al₂O₃（TiAl）、MnO₂/TiO₂（MnTi）和MnO₂/TiO₂-Al₂O₃（MnTiAl）样品,在固定床实验装置上研究了MnTi和MnTiAl催化剂的脱硝、脱汞性能,并对相应的样品进行了BET、XRD、H₂-TPR、XPS表征分析。表征结果表明,Al₂O₃掺入TiO₂后能极大提高载体的比表面积,提升催化剂氧化还原性能,且有利于高价态锰离子（Mn³⁺和Mn⁴⁺）和化学吸附氧（O*）在催化剂表面富集。固定床实验结果表明,在反应温度范围内,MnTiAl催化剂脱硝、脱汞性能均优于MnTi催化剂,MnTiAl催化剂在200℃时脱硝、脱汞效率分别高达88.5%和96.1%。MnTiAl脱除烟气Hg⁰过程中,将Hg⁰氧化为Hg²⁺的同时,催化剂表面Mn³⁺、Mn⁴⁺和O*浓度均被消耗,同时烟气中的O₂能将催化剂表面较低价态的锰离子（Mn²⁺和Mn³⁺）重新氧化为高价态锰离子（Mn³⁺和Mn⁴⁺）,并且能补充催化剂表面的化学吸附氧（O*）,进而实现催化剂催化氧化Hg⁰过程。     

改性分子筛滤料制备及其同步去除水中氨氮和锰

为了改善分子筛的表面性质,在中试过滤系统中,向进水中持续投加高锰酸钾、氯化锰等物质对分子筛进行改性,并探究其制备条件以及改性完成后的去除效果。结果表明：在进水中持续投加约1.5 mg/L的氯化锰和1.1～1.2 mg/L的高锰酸钾（理论值的70%～80%）,在制备过程中分子筛表面会逐渐生成黑褐色的锰氧化物,待27 d后分子筛表面的锰氧化物完全覆盖,此时滤料制备完成,之后不再投加任何药剂。利用改性后的分子筛作为滤料,当进水中氨氮和锰的质量浓度为2 mg/L和1.5 mg/L时,去除率分别可达95.0%和93.3%。由扫描电子显微镜可知,改性后分子筛表面覆盖的锰氧化膜结构紧密、孔隙发达,比表面积明显增大;由能谱仪分析可知,改性后分子筛滤料的锰元素增加至4.16%,且氧元素的含量也由41.01%增加至46.15%,表明在分子筛表面已经成功负载锰氧化物。该锰氧化膜提高了分子筛表面的氧化性,可以对水中氨氮和锰等污染物起到催化氧化去除作用,从而将分子筛的反冲洗周期由原来的2 d提高至4 d。     

Mn2+催化臭氧氧化活性污泥强化溶胞

研究了不同浓度活性炭、活性焦和Mn²⁺催化作用下臭氧氧化污泥碳源释放情况,发现Mn²⁺为较佳催化剂。本文进一步对比考察了不同Mn²⁺投加量对催化臭氧化污泥溶胞释放有机物的影响以及反应前后污泥特性的差异,探究了Mn²⁺催化臭氧化促进溶胞作用的机理。结果表明,在臭氧氧化污泥时添加Mn²⁺能促进污泥碳源的释放,其中当Mn²⁺投加量为1.5mmol/L时,污泥碳源的释放效果较佳,溶解性化学需氧量的变化值（ΔSCOD）质量浓度为76mg/L,约为单独臭氧氧化（O₃组）的4倍;污泥絮体胞外聚合物溶解性蛋白和腐殖质含量较原泥（空白组）和O₃组相比均有显著增加,分别为2倍和2.3倍,证实了Mn²⁺催化氧化促进了活性污泥胞内有机物的溶出。进一步的机理探究得出,O₃+Mn²⁺组·OH产量为O₃组的1.15～1.74倍,说明Mn²⁺催化氧化促进了反应过程中活性自由基尤其是·OH的生成。Mn²⁺催化臭氧氧化活性污泥在强化污泥破胞的同时,对污泥的理化性质影响较小,基本与单独臭氧氧化维持在同一水平,后续将其应用于基于臭氧旁路处理的污泥原位减量连续工艺有较大的可行性和实际意义。     

KMnO4、UV/H2O2预氧化对微污染水中消毒副产物生成势影响研究

采用高锰酸钾（KMn O₄）、紫外/过氧化氢（UV/H₂O₂）两种预氧化方式,通过改变氧化剂的投加量对三卤甲烷（THMs）、卤乙腈（HANs）生成势去除效果进行研究。结果表明两种预氧化方式均能很好的削减生成势,其中 UV/H₂O₂预氧化效果较佳。在 KMn O₄预氧化过程中,KMn O₄投加量为 5 mg/L 时,THMs、HANs 生成势去除率分别为82.7%、80.2%;在 UV/H₂O₂预氧化过程中,紫外光强 12 W,H₂O₂投加量为 5 mg/L 时,THMs、HANs 生成势减少幅度较大,生成势去除率分别增长到 83.1%、83.7%。当两种预氧化方式的氧化剂投加量均大于 5 mg/L 时,两种物质生成势去除率增长缓慢并趋于平缓。     

Fenton氧化降解水中磺胺甲恶唑的研究

以 COD 为评价指标,考察了 Fenton氧化法对水中磺胺甲噁唑（SMX）去除效果。通过探讨 H₂O₂投加量、Fe²⁺投加量以及溶液初始 pH 对 COD 去除的影响,确定了 Fenton 去除 SMX 的优化工艺条件为：pH=3,H₂O₂投加量为 10mmol/L,Fe²⁺投加量为 1.0 mmol/L,在该条件下,COD 去除率可达 71.8%。与经典动力学相比,伪动力学模型能很好拟合 SMX 的去除过程,其中伪二级动力学模型的相关系数为 0.999 9。此外,根据 GC/MS 分析结果,推测了 SMX 可能的降解途径。     

浓盐水深度处理及零排放资源回收

摘要针对反渗透浓盐水中的高COD_Cr、高盐特点,提出深度处理及排放资源回收方案为化学软化-高级氧化-超滤-树脂软化-高压反渗透-纳滤分盐-电渗析浓缩-双极膜电渗析酸碱再生。重点考察了化学软化、高级氧化、树脂软化以及电渗析和双极膜电渗析满足处理要求时的最佳操作参数。结果表明,化学软化最优加药量为理论值的1.2倍,使Ca²⁺、Mg²⁺质量浓度分别降低为3.29、2.04 mg/L,满足树脂软化硬度进水要求;高级氧化对比了O₃催化氧化、Fenton氧化、O₃/H₂O₂复合氧化的效果,其中O₃/H₂O₂复合氧化效果最优,反应1.0 h,COD_Cr去除率为66.41%,出水COD_Cr质量浓度<100 mg/L,满足树脂软化及后续膜系统进水要求;SO₄^2-的存在会降低树脂软化硬度去除效率,...     

rGO-Fe3O4活化过硫酸盐处理酸性红73

采用共沉淀法制备了还原石墨烯纳米片和磁铁矿复合材料（rGO-Fe₃O₄）。利用X射线衍射（XRD）、X射线光电子能谱（XPS）和透射电镜（TEM）对其进行了表征。以酸性红73（AR73）为目标物,研究了rGO-Fe₃O₄活化过硫酸盐（PS）处理酸性红73的效能,考察了催化剂投加量、PS浓度、溶液初始pH以及反应温度的影响。结果表明,室温下催化剂投加量为1.0 g/L、PS的浓度为1.0 g/L及初始pH为6.9时,10 min内50 mg/L酸性红73的脱色率达到100%。淬灭实验结果表明rGO-Fe₃O₄/PS反应体系同时存在SO₄^-?、?OH和单线态氧¹O₂,其中¹O₂的氧化反应起主导作用。复合材料rGO-Fe₃O₄不但活性高,而且便于分离,应用前景良好。     

回流固定床臭氧催化氧化煤化工反渗透浓水

设计了一种具有回流的固定床臭氧催化氧化反应装置，对浸渍法制得的α-Fe₂O₃/γ-Al₂O₃催化剂的性能进行了表征，并利用其在回流固定床反应装置中对煤化工反渗透浓水的臭氧催化氧化性能进行了研究。结果表明：α-Fe₂O₃/γ-Al₂O₃的比表面积、平均孔径、总孔容和活性组分α-Fe₂O₃含量分别为161.74m²/g、10nm、0.4533cm³/g和8.73%。反渗透浓水COD去除率随催化剂装填高度、臭氧投加浓度和过氧化氢投加量的增加而均呈现为先增加、后降低的变化趋势，回流可显著地提高废水COD去除率，适宜的催化剂装填高度、臭氧投加浓度、过氧化氢投加量和回流比分别为350mm、300mg/L、150mg/L和50%，臭氧催化氧化反渗透浓水的COD去除率达74.33%。煤化工反渗透浓水中大部分溶解性有机物和腐殖酸类物质均被臭氧催化氧化分解。     

锰氧化物制备及其对锰和氨氮的去除研究

为制备具有优良吸附性能的材料,采用高锰酸钾氧化(分别在酸性条件和中性条件下进行)和空气自然氧化水中2价锰,制备了3种锰氧化物(ORIG-MnO_x、Na₂CO₃-MnO_x、O2-MnO_x),对其结构进行了表征,并探究了对水中NH₄⁺-N和Mn²⁺污染的去除特性及影响因素。结果表明,所制备的ORIG-MnO_x与Na₂CO₃-MnO_x为结晶度较低的ε-MnO₂,但二者形貌和精细结构存在明显差异,O₂-MnO_x为结晶度较高的黑锰矿(Mn₃O₄);ORIG-MnO_x、Na₂CO₃-MnO_x具有比O₂-MnO_x更好的除Mn²⁺、除NH₄⁺-N性能,且Na₂CO₃-MnO_x吸附性能最佳,其NH₄⁺-N和Mn²⁺去除过程符合Langmuir吸附等温线模型和准2级反应动力学模型。可为以锰氧化物为基础的NH₄⁺-N和锰的去除工艺提供理论和技术支撑。     

铁强化电解锰阳极液体系中氧化锰矿烟气脱硫和锰浸出工艺

结合电解锰生产工艺,以氧化锰矿为原料,以电解锰生产过程产生的电解阳极液废水配置烟气脱硫浆液,在其中添加FeSO₄强化电解锰阳极液体系下氧化锰矿烟气脱硫及浸锰能力,探讨铁强化氧化锰矿烟气脱硫和浸锰的工艺条件对烟气SO₂脱除和锰浸出的影响机制。研究发现FeSO₄的加入,通过FeSO₄与MnO₂之间的氧化还原反应以及产物三价铁离子和二价锰离子的协同催化作用,可同时提高锰矿烟气脱硫效率和锰的浸出率。锰矿粒径越小,脱硫及浸锰效率越高。温度升高,氧化锰矿浆液烟气脱硫率逐渐下降,浸锰率则先升高后下降,并在60℃时达到最大。浆液液固比和烟气流量的增大均会导致烟气脱硫率的下降,但会提高氧化锰矿浸锰率。进口SO₂浓度过高会导致脱硫率下降,但更有利于浸锰。采用5级逆流吸收对7%的烟气进行铁离子强化氧化锰浆脱硫,得到最终SO₂出口浓度293μL/L,溶液Mn²⁺浓度为44.72g/L,满足电解要求。铁强化电解锰阳极液体系有效回收利用了电解锰生产废水,不仅集脱硫浸锰工艺为一体,且可实现脱硫和浸锰效率的同时提升,为电解锰行业的清洁生产和资源综合利用提供理论依据和技术参考。     

Controllable synthesis of novel nanoporous manganese oxide catalysts for the direct synthesis of imines from alcohols and amines

A novel template-free oxalate route was applied to synthesize different mesoporous manganese oxides (amorphous manganese oxide (AMO), Mn₅O₈, Mn₃O₄, MnO₂) in the narrow temperature range from 350℃ to 400℃ by controlling the calcination conditions, which were employed as the efficient catalysts for the oxidative coupling of alcohols with amines to imines. The chemical and structural properties of the manganese oxides were characterized by the methods of thermogravimetry analysis and heat flow (TG-DSC), X-ray diffraction (XRD), nitrogen sorption, scanning electron microscope (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), H₂ temperature-programmed reduction (H₂-TPR), and inductively coupled plasma optical emission spectrometry (ICP-OES) techniques. The structures of different manganese oxides were confirmed by characterization. The M-350 (AMO) presented the maximum surface area, amorphous nature, the lowest reduction temperature, the higher (Mn³⁺ + Mn⁴⁺)/Mn²⁺ ratio, and the higher adsorbed oxygen species compared to other samples. Among the catalysts, M-350 showed the best catalytic performance using air as an oxidant, and the conversion of benzyl alcohol (BA) and the selectivity of N-benzylideneaniline (NBA) reached as high as 100% and 97.1% respectively at the lower reaction temperature (80℃) for 1 h. M-350 had also the highest TOF value (0.0100 mmol·mg^-1·h^-1) compared to the other manganese oxide catalysts. The catalyst was reusable and gave 95.8% conversion after 5 reuse tests, the XRD pattern of the reactivated M-350 did not show any obvious change. Lattice oxygen mobility and (Mn³⁺ + Mn⁴⁺)/Mn²⁺ ratio were found to play the important roles in the catalytic activity of aerobic reactions.     

电解锰渣基沸石对锰离子的吸附性能研究

电解锰渣是电解锰行业露天堆存的大宗固体废弃物,在堆存过程中将产生毒性污染物锰离子。为有效利用电解锰渣的同时消除锰离子对环境的危害,以电解锰渣为原料采用微波碱熔活化法制备沸石,并用于吸附锰离子。考察了溶液初始锰离子质量浓度、溶液pH、吸附温度和吸附时间等因素对锰离子吸附效果的影响。结果表明:在溶液初始锰离子质量浓度为500 mg/L、溶液pH为6、吸附时间为2 h、吸附温度为50 ℃条件下,电解锰渣基沸石对锰离子具有较好的吸附能力,最大吸附量高达79.18 mg/g。探究了电解锰渣基沸石对锰离子的吸附行为。结果表明,锰离子在沸石表面的吸附符合准二级动力学模型,Langmuir等温吸附模型比Freundlich模型更适合于描述电解锰渣基沸石去除锰离子的等温吸附过程。电解锰渣基沸石循环使用性能良好,在重金属废水处理方面具有潜在的应用前景。     

温度对生物净化滤柱中氨氮、铁、锰去除效果的影响

温度是生物净化滤柱运行的一个重要参数，采用生物净化滤柱处理模拟含氨氮、铁、锰地下水，考察水温从约25℃降到约6℃过程中氨氮、铁、锰的去除效果。结果表明，出水氨氮、总铁、锰的浓度分别低于0.15mg/L、0.1mg/L、0.05mg/L，均低于国家标准。出水总铁、锰均未受到水温下降的影响，但是出水氨氮浓度逐渐从约0.02mg/L升高到约0.12mg/L。进一步分析发现，铁主要在滤层的0~0.4m段去除，去除效果没有受到水温变化的影响。氨氮、锰主要在滤层的0~0.8m段去除，其沿程浓度均随水温降低而明显升高。氨氮、锰的生物去除符合一级动力学反应，水温为24.6℃、15.3℃、6.7℃时，两者的动力学常数k分别为0.154min^-1、0.186min^-1，0.143min^-1、0.175min^-1，0.103min^-1、0.163min^-1；半反应时间t_1/2分别为4.51min、3.72min，4.83min、3.96min，6.72min、4.24min。随着试验水温的降低，氨氮、锰的去除效果明显受到影响。     

Preparation and evaluation of α-Al2O3 supported lithium ion sieve membranes for Li+ extraction

Spinel lithium manganese oxide ion-sieves have been considered the most promising adsorbents to extract Li⁺ from brines and sea water. Here, we report a lithium ion-sieve which was successfully loaded onto tubular α-Al₂O₃ ceramic substrates by dipping crystallization and post-calcination method. The lithium manganese oxide Li₄Mn₅O₁₂ was first synthesized onto tubular α-Al₂O₃ ceramic substrates as the ion-sieve precursor (i.e. L-AA), and the corresponding lithium ion-sieve (i.e. H-AA) was obtained after acid pickling. The chemical and morphological properties of the ion-sieve were confirmed by X-ray diffraction (XRD) and scanning electron microscopy (SEM). Both L-AA and H-AA showed characteristic peaks of α-Al₂O₃ and cubic phase Li₄Mn₅O₁₂, and the peaks representing cubic phase could still exist after pickling. The lithium manganese oxide Li₄Mn₅O₁₂ could be uniformly loaded not only on the surface of α-Al₂O₃ substrates but also inside the pores. Moreover, we found that the equilibrium adsorption capacity of H-AA was 22.9 mg·g^-1. After 12 h adsorption, the adsorption balance was reached. After 5 cycles of adsorption, the adsorption capacity of H-AA was 60.88% of the initial adsorption capacity. The process of H-AA adsorption for Li⁺ correlated with pseudo-second order kinetic model and Langmuir model. Adsorption thermodynamic parameters regarding enthalpy (ΔH), Gibbs free energy (ΔG) and entropy (ΔS) were calculated. For the dynamic adsorption- desorption process of H-AA, the H-AA exhibited excellent adsorption performance to Li⁺ with the Li⁺ dynamic adsorption capacity of 9.74 mg·g^-1 and the Mn²⁺ dissolution loss rate of 0.99%. After 3 dynamic adsorption-desorption cycles, 80% of the initial dynamic adsorption capacity was still kept.     

Enhanced Mn2+ solidification and NH4+-N removal from electrolytic manganese metal residue via surfactants

Electrolytic manganese metal residue (EMMR) harmless treatment has always lacked a low-cost and quick processing technology. In this study, surfactants, namely tetradecyl trimethylammonium chloride (TTC), sodium dodecyl benzene sulfonate (SDBS), sodium lignin sulfonate (SLS), and octadecyl trimethylammonium chloride (OTC), were used in the solidification of Mn²⁺ and removal of NH₄⁺-N from EMMR. The Mn²⁺ and NH₄⁺-N concentrations under different reaction conditions, Mn²⁺ solidification and NH₄⁺-N removal mechanisms, and leaching behavior were studied. The results revealed that the surfactants could enhance the Mn²⁺ solidification and NH₄⁺-N removal from EMMR, and the order of enhancement was as follows: TTC > SDBS > OTC > SLS. The NH₄⁺-N and Mn²⁺ concentrations were 12.3 and 0.05 mg·L^-1 with the use of 60.0 mg·kg^-1 TTC under optimum conditions (solid–liquid ratio of 1.5:1, EMMR to BRM mass ratio of 100:8, temperature of 20 ℃, and reaction duration of 12 h), which met the integrated wastewater discharge standard (GB8978-1996). Mn²⁺ was mainly solidified as Mn(OH)₂, MnOOH and MnSiO₃, and NH₄⁺-N in EMMR was mostly removed in the form of ammonia. The results of this study could provide a new idea for cost-effective EMMR harmless treatment.     

Carbon black oxidation in the presence of Al2O3, CeO2, and Mn oxide catalysts: An EPR study

Carbon black oxidation in the presence of CeO₂, Al₂O₃ and manganese oxide catalysts has been studied in tight contact conditions. In the presence of manganese based catalysts, the temperature gain is about 275 °C compared to the non-catalysed carbon black oxidation. The contribution of the manganese species to enhance the reactivity of carbon black oxidation has been evaluated by EPR technique. For Mn/Ce + CB mixtures the Mn²⁺ content considerably increases consequently to tight milled treatment indicating the reduction of some manganese species with higher oxidation states into Mn²⁺ ions. This phenomenon can be considered as the first step in the carbon black oxidation mechanism in the presence of Mn/Ce catalysts.