Cu/Co掺杂多孔炭活化过硫酸盐降解水中硝基酚研究

以MOF-74为模板制备了Cu/Co双金属掺杂多孔炭催化剂。用X射线衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)、N₂物理吸附/脱附等对催化剂结构进行了表征。研究并阐释了Cu/Co双金属掺杂多孔炭催化剂活化过一硫酸盐(PMS)氧化降解4-硝基酚性能及机理。结果表明，在投加100 mg·L^-1催化剂、2 g·L^-1 PMS、初始pH为6时，15 min内硝基酚(60 mg·L^-1)去除率达98%以上。降解反应符合伪一级反应动力学模型。催化剂循环反应4次，降解率均高于90%。猝灭实验及电子顺磁共振分析表明自由基(·SO₄^-、·OH、·O₂^-)和非自由基(¹O₂)均参与了降解反应。在反应过程中，Co²⁺/Co³⁺和Cu+/Cu²⁺的氧化还原循环有效活化了PMS并促进活性氧化物种的生成，从而提升了催化剂...     

甲硫醚降解菌JLM-8的分离鉴定与降解条件优化

从制药厂的活性污泥中分离到一株能以唯一碳源和硫源降解甲硫醚的菌株JLM-8,经过生理生化测试与16S rDNA系统发育树分析鉴定为嗜麦芽寡养单胞菌(Stenotrophomonas maltophilia)。通过测定菌株的生长量、甲硫醚的降解率,利用响应面法优化最佳降解条件,并测定了该菌降解甲硫醚的动力学参数。结果表明:当接种量为25 mg·L^-1时,通过响应面法优化的最佳降解条件为温度31.3℃、pH 7.5,初始甲硫醚浓度50 mg·L^-1时最大预测降解率为98.2%,实验验证降解率为97.9%。菌株降解动力学参数最大比降解速率、半饱和系数、抑制系数分别为2.37 h^-1、143.55 mg·L^-1、51.35 mg·L^-1,临界抑制浓度为78.46 mg·L^-1。     

微波辅助二氧化氯氧化降解苯酚

采用微波辅助二氧化氯（MW/ClO₂）氧化降解苯酚模拟水溶液,研究了影响该系统氧化降解苯酚的各种因素和动力学。结果表明：在单独的微波辐照或者ClO₂氧化工艺和MW/ClO₂强化氧化系统中苯酚的降解均符合拟一级动力学关系,其中MW/ClO₂氧化系统速率常数增强因子可达到1.4,表明存在较明显的协同效应。在MW/ClO₂强化氧化系统降解苯酚初始体积质量浓度为100 mg·L^-1,pH值为5.0,微波功率200 W,二氧化氯初始浓度100 mg·L^-1相似文献   

食品污水中异养硝化-好氧反硝化菌Bacillus sp.JG441的筛选鉴定及其脱氮特性

高氨氮、高盐、含有机物的食品工业污水处理难度大、周期长，添加高效硝化菌株可以大幅提高污水处理效率。本研究通过高盐培养基，从腌渍食品厂排放污水中筛选出一株对复杂环境有较强耐受性的新型高效异养硝化-好氧反硝化菌株JG441，经鉴定为Bacillus sp.，对其脱氮条件、异养硝化、好氧反硝化、极端环境耐受和脱氮通路进行研究。结果表明，菌株JG441可以利用(NH₄)₂SO₄和KNO₃为氮源进行异养硝化和好氧反硝化；在NaCl浓度为30g·L^-1，苯酚浓度为400mg·L^-1时，24h NH₄⁺-N去除率可达99%，在NH₄⁺-N浓度为500mg·L^-1时，24h NH₄⁺-N去除率为57.4%。菌株JG441脱氮能力强，在高盐含氮和成分复杂的污水处理方面具有较好应用潜力。     

Cu2(NO3)(OH)3催化过硫酸盐降解苯酚

基于过硫酸盐的高级氧化工艺在高浓度含酚废水处理中引起了越来越多的关注。我们研究了Cu₂（NO₃）（OH）₃和过硫酸盐对于废水中苯酚的降解效果和机理。结果表明,Cu₂（NO₃）（OH）₃-过硫酸盐体系在较广泛的pH条件下（pH值为5.0~10.0）对苯酚的降解效率均较高。溶液中的总有机碳（TOC）分析表明,在pH值为8.0,1 g·L^-1过硫酸盐和1 g·L^-1 Cu₂（NO₃）（OH）₃条件下,该体系可在4 h内将初始浓度为100 mg·L^-1的苯酚完全矿化而没有产生二次污染。猝灭剂实验和电子顺磁共振（EPR）分析进一步证实Cu₂（NO₃）（OH）₃-过硫酸盐体系中的主要氧化物种是O₂^·-、SO₄^·-和¹O₂。     

CuCe氧化物催化剂的制备及CWPO降解双酚A废水研究

为解决Fenton法存在活性组分流失及通常在pH 2～3条件下运行的局限性，采用柠檬酸络合法制备了CuCe氧化物催化剂，建立了双酚A非均相催化湿式过氧化氢氧化（CWPO）反应体系。考察了焙烧温度、Cu/Ce摩尔比、H₂O₂用量、双酚A初始浓度和pH对催化剂物化结构和CWPO性能的影响。并分析了可能的降解路径。结果表明：催化剂具有良好的高温稳定性和pH适应性，在pH 1.6～7.9范围内对双酚A都具有较高的降解性能，不需要调节pH。在焙烧温度450℃、Cu/Ce摩尔比1.0、催化剂用量1 g·L^-1、H₂O₂用量196 mmol·L^-1、BPA浓度152 mg·L^-1、pH 6.6、反应温度75℃、反应95 min后，BPA和TOC去除率分别为91.8%和84.5%,Cu²⁺析出浓度为19.3 mg·L^-1。推测了双酚A可能的降解路径。     

含苯酚有机废水微波联合二氧化氯催化氧化处理技术

含苯酚有机废水的污染性和危害性较大，微波催化氧化技术是处理含苯酚有机废水的一种非常有效的方法。因此，室内以Mn-x作为催化剂，以ClO₂作为氧化剂，辅助以微波加热，对模拟含苯酚有机废水进行了室内氧化处理实验，并对其工艺参数进行了优化。结果表明，对含苯酚浓度为100mg·L^-1的有机废水，微波联合ClO₂催化氧化处理技术的最佳工艺条件为：催化剂Mn-x的加量为2000mg·L^-1、Cl O2的浓度为200mg·L^-1、苯酚废水pH值为7、微波功率为75W、处理反应时间为7min，此时含苯酚有机废水的苯酚去除率可达95%以上，达到了良好的处理效果。另外，与其他5种不同处理工艺对比结果显示，微波联合ClO₂催化氧化处理技术对含苯酚有机废水的处理效果最好，微波和催化剂的联合诱导作用能够显著提高ClO₂氧化处理苯酚的效率。     

新型过碳酸盐降解水中苯酚的效能和机理研究

过碳酸盐是H₂O₂和Na₂CO₃的固体加合物，与H₂O₂相比有着相同的功能优势，但更容易储存和运输，因此近年来得到水处理界越来越广泛的关注。本文利用Fe²⁺活化过碳酸钠(SPC)降解水溶液中典型目标污染物苯酚，研究了降解效能、反应机理以及环境影响因素。结果表明，Fe(Ⅱ)/SPC体系对于苯酚有着良好的去除效果：在pH=5、SPC投加量为4 mmol/L、Fe(Ⅱ)投加量为1.5 mmol/L条件下，20 min就可将苯酚完全去除；通过自由基探针试验、自由基淬灭实验，确定了Fe(Ⅱ)/SPC体系存在·OH、O₂^·-、CO₃^·-和¹O₂，且·OH是Fe(Ⅱ)/SPC体系降解苯酚的主要活性物种，O₂^·-和CO₃^·-也部分参与...     

聚氨酯泡沫固定化Alcaligenes sp.DN25去除苯酚的研究

载体材料是构建固定化体系的基础,其中孔结构直接影响固定化的生物量及降解结果,开展了制备不同孔径聚氨酯泡沫材料并考察其固定化产碱杆菌DN25降解苯酚的研究。结果表明,孔隙结构的聚氨酯泡沫材料在孔径均值为150 μm时所固定的生物量达到最大值（0.0253±0.0010） g,固定化细胞能在48 h内完全降解1160 mg·L^-1苯酚,而游离细胞则完全受到抑制,并且发现载体材料PUF在降解前12 h内吸附苯酚的平衡吸附率为56.1%。进一步研究固定化细胞在初始pH6.0~9.0,NaCl浓度0~4.0%条件下降解900 mg·L^-1苯酚的情况,固定化细胞对苯酚的去除率受pH、NaCl浓度的影响不显著。并且,固定化细胞重复使用11个批次对500 mg·L^-1苯酚的去除率仍能保持100%,反映了PUF-固定化细胞体系对苯酚处理浓度和系统稳定性两方面的强化作用。     

LTNE条件下界面对流传热系数对部分填充多孔介质通道传热特性的影响

在多孔介质区考虑局部非热平衡,采用Brinkman-extended Darcy模型结合应力跳跃条件对部分填充多孔介质通道内流体传热特性进行分析。获得了各区域温度分布及Nusselt数解析解,并分析了各参数对温度及Nusselt数的影响。结果表明：界面对流传热系数H_s较小时,界面应力跳跃系数β和Darcy数Da的增加会减小流固两相间温差。而在高H_s下,Da减小也会减小两相温差。在Da、H_s和固流两相热导率之比K较大且空心率S（自由流体区高度与通道高度之比）和Biot数Bi较小时,流固两相间会在接近多孔介质区中部出现最大温差,而该最大温差会随着S增加和Da及H_s的减小向界面区移动。对于不同K与Bi,Nusselt数Nu与S的关系曲线存在不同的类型,与模型A（界面处多孔介质固相和流相根据各自温度梯度和热导率划分总热流）不同的是,采用模型C（界面处固相热流分配与自由流体区流相的热交换相关）所获得的Nu曲线类型与H_s有关。在K较小时,β对Nu的影响大于H_s对Nu的影响;而在K较大时,H_s对Nu的影响要远大于β对Nu的影响,且H_s增加会明显提高通道内的Nu。     

新型嗜热耐碱脂肪酶的纯化表征及应用

将来源于解脂嗜热互营杆菌（Thermosyntropha lipolytica）的脂肪酶（TlLipA）基因tll1导入大肠杆菌BL21（DE3）中表达，通过热处理和镍柱亲和层析获得纯酶，并对其酶学性质进行研究。十二烷基硫酸钠-聚丙烯酰胺凝胶电泳（SDS-PAGE）显示TlLipA分子量为53×10³，其最适反应温度为65℃，最适反应pH为8.0。在55~65℃范围内酶活较高且比较稳定；在pH^{7.0~11.0于室温保存1 h后，残留相对酶活仍达80%以上。1 mmol/L 金属离子Zn2+、Fe3+和试剂SDS，0.05%（质量分数）Tween 80，对酶活力具有强烈的抑制作用，残留相对酶活皆低于15%；1 mmol/L Mg2+、Mn2+对酶活力表现出轻微的激活作用。由底物专一性实验可得，该酶对辛酸对硝基苯酯（C8）和癸酸对硝基苯酯（C10）偏好明显。以棕榈酸对硝基苯酯（p-NPP）为底物，该酶动力学参数K_m值为0.23 mmol/L，V_max为33.50 mmol/(L·min)，k_cat为22.83 _S-1。以重组脂肪酶为催化剂在无溶剂体系中制备生物柴油，含水率20%，酶加量200 U/g油，醇油比为4∶1的条件下，在55℃催化大豆油反应48 h，收率可达91.75%。}     

Purification and characterization of novel thermo-alkaline lipase and its application

In order to excavate thermo-alkaline lipases from bacterial living in extreme conditions, we try to express new gene from Thermosyntropha lipolytica DSM 11003, an anaerobic, thermophilic, alkali-tolerant bacterium which grows in alkaline hot springs Lake Bogoria in Kenya and explore its application in biodiesel production. The lipase gene (tll1) of 1434 bp were ligated at the Nco I / EcoR I sites of the expression vectors pET28a to yield the construct of pET28a-TLL1. The strain harboring pET28a-TLL1 was cultivated for expression at 25℃, the specific activity of 1.99 U/mg protein were detected in disrupted cells. The recombinant lipase TlLipA was purified by a simple two-step procedure involving heat treatment and Ni-chelating affinity chromatography. The subunit of purified TlLipA showed a molecular mass of 53×10³ on 12% sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS-PAGE). The purified TlLipA exhibited optimal activity at 65℃ and pH 8.0 and it was stable from 55℃ to 65℃. The enzyme remained above 80% of its original activity at pH ranging from 7.0 to 11.0 and at room temperature for 1 h. The activity of TlLipA was little unaffected by Co²⁺, K⁺, Na⁺, and Ni²⁺, and a little activated by Mg²⁺ and Mn²⁺, ^{but were significantly inhibited by Zn2+, Fe3+, and SDS, and Tween 80 under the assay conditions. The purified recombinant TlLipA had a specific activity of 22.11 U/mg protein using p-nitrophenyl palmitate (p-NPP) as substrate. Determined by Sigma-Plot of reaction rate on p-NPP, the K_m was 0.23 mmol/L, the V_max was 33.50 mmol/(L·min), and the k_cat was 22.83 s-1. The enzyme was also active towards p-NPP, p-nitrophenyl laurate (p-NPL), p-nitrophenyl myristate (p-NPM) and p-nitrophenyl caproate (p-NPC), moreover TlLipA exhibited a strong preference for p-nitrophenol decanoate (p-NPD) and p-nitrophenyl octoate (p-NPO). Using recombinant lipase as a catalyst to prepare biodiesel in a solvent-free system, with a water content of 20%, an enzyme dosage of 200 U/g oil, and an alcohol-to-oil ratio of 4∶1, catalyzed soybean oil reaction at 55℃ for 48 h, the yield can reach 91.75%.}     

刺芹侧耳多功能过氧化物酶的纯化与鉴定

A versatile peroxidase (VP-Peco60-7) was generated and purified from the liquid culture of Pleurotus eryngii. The purification procedure included ammonium sulfate precipitation, ion exchange chromatography, and gel chromatography. The molecular weight and isoelectric point (pI) of VP-Peco60-7 were determined to be approximately 40 kDa and 4.1, respectively. By N-terminal sequence determination and peptide mapping analysis, VP-Peco60-7 was found to be similar to the versatile peroxidase isoenzyme VPL1, which was previously isolated from liquid cultures of the same species. However, the molecular weight and pI of VP-Peco60-7 were different from those of versatile peroxidases of liquid cultures, implying that the VP-Peco60-7 in this study is of a novel type. With 2,2′-azino-bis-(3-ethylbenzothiazoline-6-sulphonic acid) (ABTS) as a substrate, the maximal enzyme activity was obtained at 50 °C and pH 3.0. The catalysis of ABTS by VP-Peco60-7 was expressed by the Michaelis-Menten equation. At 50 °C and pH 3.0, the maxi-mum velocity (Vmax) was 188.68 U•mg1 and the michaelis constant (Km) was 203.09 mmol•L1.     

UV/oxone降解水中甲氧苄啶的效能及模型评价

研究采用UV、oxone、UV/oxone共3种工艺降解甲氧苄啶（TMP）的效果及动力学。采用响应面曲线法研究含有HCO₃ ^-、Cl^-、NO₃ ^-和pH四因素、三水平的水体条件下UV/oxone对TMP的降解效果及模型，并选用4种实际水源水体为水质背景来评价模型预测值与实际降解值的差别，最后比较了3种工艺的同等降解率条件下的降解效能。结果发现UV和oxone单独降解TMP时仅降解了5.5%和62.0%，而UV/oxone可达到93.2%，且降解过程符合拟一级反应动力学，动力学常数为0.1768min^-1。采用相对速率法可得到?SO₄ ^–与TMP的反应速率常数为2.07×10⁸L/(mol·s)。通过响应面曲线法得到UV/oxone降解TMP的回归方程式，对应的p值小于0.0001，拟合缺失项P不显著（0.9726>0.05），校正决定系数R ²=0.82＞0.8，说明该模型可信度高，采用实际水体进行模型验证后发现实际降解值基本符合模型预测值。降解率一定的条件下UV/oxone耗时最短，是一种高效、快速、可行的降解工艺。     

利用电解锰渣制备As(Ⅲ)吸附材料及其性能研究

通过对工业废弃物电解锰渣(electrolytic manganese residues, EMRs)进行改性制备As(Ⅲ)吸附材料（改性EMRs），探究了NaOH用量、超声及微波对其表面结构及吸附性能的影响。结果表明：该工业废渣在固液比M(EMRs)∶V(NaOH, aq) = 1∶10(C _NaOH，aq = 2.0 mol·L^-1)条件下，经超声反应（200 W）2 h脱除大部分Si、S、Ca后，再微波（700 W）反应5 min以使Fe、Mn等活性吸附基团在其表面沉积，最后经105℃烘干制得改性EMRs。SEM结果表明，EMRs改性后表面形成片层纳米结构，对砷具有良好的吸附性能，可将初始As(Ⅲ)浓度为50 mg·L^-1废水出水中砷降至0.042 mg·L^-1，符合国家地表水环境质量标准Ⅰ类水质量要求(GB 3838—2002)；同时，经3% NaOH溶液再生处理后可继续使用。XPS结果表明，改性EMRs吸附砷性能与其表面Fe₃O₄、FeOOH、MnO₂等对As(Ⅲ)具有吸附作用或氧化作用的活性物种的增多密切相关。     

Influence of nitrogen concentration on operation of a novel bio-electrochemical-granular sludge reactor

The performance of nitrogen removal and electricity generation of a novel bio-electrochemical-granular sludge reactor at different influent nitrogen concentration was investigated. The impact mechanism of granular sludge, key enzyme activity, extracellular polymer composition and microbial community distribution were systematically studied. The results showed that COD, NO₃^--N, NO₂^--N and dissolved methane were efficiently removed in stages Ⅰ, Ⅱ, Ⅲ and Ⅳ (Influent NO₃^--N and NO₂^--N concentrations were 60 and 20 mg·L^-1, 100 and 40 mg·L^-1, 140 and 60 mg·L^-1, 180 and 80 mg·L^-1, respectively). The removal efficiency of COD was the highest in stage Ⅳ, and it was above 96%. The effluent concentration of NO₃^--N was the most stable at stage Ⅱ, and the removal efficiency was over 99%. The NO₂^--N removal efficiency was above 99% in each stage. In stage Ⅳ, the maximum power density and output voltage was 471.2 mV·m^-3 and 608.1 mV at the fourth compartment, respectively. The polysaccharide and protein content of LB-EPS was the highest in stage Ⅱ of the fifth compartment, 13.7 mg·g^-1 and 14.7 mg·g^-1, respectively. Coenzyme F₄₂₀ activity was the lowest in the first compartment. The protease activity of the sludge was increased due to the increase of influent nitrogen concentration. From stage Ⅰ to stage Ⅳ, the relative abundance of Protebaoteria was decreased, while the relative abundance of Chloroflexi, Firmicutes and Planctomycetes were increased. Although Thauera with denitrification effect was decreased by 8.64% in the first compartment, the nitrogen removal was still well in the reactor. The relative abundance of Methanothrix was increased to 12.3% in the fourth compartment, indicating that Methanothrix could co-exist with other bacteria in the reactor.     

有机-水混合溶剂中氯离子对C—H键的电氧化腈化性能

有机电化学合成中大部分有机反应底物不溶于水,往往需要添加适量的有机溶剂形成有机-水混合溶剂。氯离子作为无机媒质在有机电化学合成中应用广泛,但氯离子往往溶解于水相中。而溶剂是电化学合成中的一个重要影响因素,因此很有必要对氯离子在有机-水混合溶剂中的电化学性能进行系统研究。采用循环伏安法(CV)、线性扫描法(LSV)、计时电量法研究了氯离子在有机-水混合溶剂中的动力学参数,考察了阳极材料、扫描速率、混合溶液中水的含量、有机溶剂的种类等对氯离子电化学氧化性能的影响。并以氯离子为媒质,在无隔膜电解槽中,通过间接电化学活化对甲氧基甲苯(p-MeOBT)甲基上的C—H键原位生成醛,并进一步转化为相应的腈类化合物。以p-MeOBT为反应底物,在乙腈-水混合溶液(体积比7∶3)中,恒电流电解(CCE) 12 h,60℃下,目标产物对甲氧基苯甲腈(p-MeOBCN)的收率达80%。通过对反应过程中各中间物种的监测,提出了可能的C—H键间接电腈化腈化反应机理。     

有机-水混合溶剂中氯离子对C—H键的电氧化腈化性能

有机电化学合成中大部分有机反应底物不溶于水,往往需要添加适量的有机溶剂形成有机-水混合溶剂。氯离子作为无机媒质在有机电化学合成中应用广泛,但氯离子往往溶解于水相中。而溶剂是电化学合成中的一个重要影响因素,因此很有必要对氯离子在有机-水混合溶剂中的电化学性能进行系统研究。采用循环伏安法(CV)、线性扫描法(LSV)、计时电量法研究了氯离子在有机-水混合溶剂中的动力学参数,考察了阳极材料、扫描速率、混合溶液中水的含量、有机溶剂的种类等对氯离子电化学氧化性能的影响。并以氯离子为媒质,在无隔膜电解槽中,通过间接电化学活化对甲氧基甲苯(p-MeOBT)甲基上的C—H键原位生成醛,并进一步转化为相应的腈类化合物。以p-MeOBT为反应底物,在乙腈-水混合溶液(体积比7∶3)中,恒电流电解(CCE) 12 h,60℃下,目标产物对甲氧基苯甲腈(p-MeOBCN)的收率达80%。通过对反应过程中各中间物种的监测,提出了可能的C—H键间接电腈化腈化反应机理。     

Biosorption of mercury and lead by aqueous Streptomyces VITSVK9 sp. isolated from marine sediments from the bay of Bengal,India

Toxic heavy metals are increasingly accumulating in the environment worldwide and are considered to be life threatening contaminants. The biosorption of mercury and lead by marine actinomycetes isolated from marine sediment collected from the Bay of Bengal coast of Puducherry, India, was evaluated. The maximum tolerance concentration (MTC) of Streptomyces sp. was determined by a well diffusion method and a broth dilution method. The effects of the initial metal ion concentration, the pH and the biomass dosage on the biosorption of mercury and lead ions were investigated. The MTC of the isolate to metals was 200 mg·L^-1 for mercury and 1800 mg·L^-1 for lead. At neutral pH, the isolate had a maximum biosorption of metal ions of 200 mg·L^-1 and 150 mg·L^-1 for mercury and lead respectively. Fourier transform infrared (FTIR) absorption spectra showed the chemical interactions between the functional groups in the biomass such as hydroxyl (-OH), amine (-NH₂), carboxyl (-COOH) and the metal ions. The isolate was further characterized by molecular taxonomy and identified as a member of the genus Streptomyces. Based on the phenotypic and phylogenetic analysis, the strain was classified as a new species of the genus Streptomyces and designated as Streptomyces VITSVK9 sp. (HM137310). A blast search of the 16S rDNA sequence of the strain showed the most similarity (95%) with Streptomyces sp. A515 Ydz-FQ (EU384279). Based on the results, it can be concluded that this marine Streptomyces could be used as a biosorbent for the removal of heavy metal ions from aqueous environments.