Formic acid as an alternative reducing agent for the catalytic nitrate reduction in aqueous media

Formic acid was used for the nitrate reduction as a reductant in the presence of Pd:Cu/γ-alumina catalysts. The surface characteristics of the bimetallic catalyst synthesized by wet impregnation were investigated by SEM, TEM-EDS. The metals were not distributed homogeneously on the surface of catalyst, although the total contents of both metals in particles agreed well with the theoretical values. Formic acid decomposition on the catalyst surface, its influence on solution pH and nitrate removal efficacy was investigated. The best removal of nitrate (50 ppm) was obtained under the condition of 0.75 g/L catalyst with Pd:Cu ratio (4:1) and two fold excess of formic acid. Formic acid decay patterns resembled those of nitrate removal, showing a linear relationship between kf (formic acid decay) and k (nitrate removal). Negligible amount of ammonia was detected, and no nitrite was detected, possibly due to buffering effect of bicarbonate that is in situ produced by the decomposition of formic acid, and due to the sustained release of H2 gas.     

新型磁性聚谷氨酸吸附剂对水中Pb2+的吸附去除

德岛大学安澤幹人首次利用γ-PGA在Fe3O4磁性纳米颗粒上进行涂层,制得了γ-聚谷氨酸-Fe3O4磁性纳米颗粒（PG-M）.本实验利用透射电镜以及扫描电镜对PG-M吸附剂的形貌进行了分析,发现PG-M与未涂层的Fe3 O4具有相似的形状以及大小,均为不规则的层状结构,且晶粒直径在120～320 nm之间;实验中针对性地对水溶液中Pb2＋进行了吸附探讨.在振荡实验中,通过主要参数的变化（pH值、吸附时间、竞争离子浓度、腐殖酸浓度）,得到如下结果：吸附最佳pH值为7.0;吸附量随着吸附时间的延长而增长,吸附平衡时间为45 min;Na＋对PG-M去除Pb2＋没有很强的干扰性,而Ca2＋则显示出一定的干扰作用;腐殖酸对吸附效果的影响是复杂的,表现为先增强吸附效果,随后降低吸附效果;最佳条件时Pb2＋的最大吸附量为93.3 mg/g.PG-M对Pb2＋的吸附均能较好地符合Freundlich和Langmuir等温吸附模型,其中Langmuir方程能更好地描述PG-M的吸附特征,说明PG-M在水溶液中对金属离子的吸附为单分子层吸附.PG-M吸附符合准二级动力学模型（r2〉0.99）.不同浓度的HCl和HNO3溶液的再生实验发现,0.1 mol/L的HCl溶液作为吸附再生液,可取得较好的再生效果.表明PG-M是可再生的,具有较好的经济性和可持续性.     

Mn/γ-Al2O3催化剂的制备及头孢合成废水的催化臭氧氧化法深度处理

对Mn/γ-Al₂O₃催化剂的制备条件及头孢合成废水的催化臭氧氧化法深度处理工艺条件进行了优化。实验结果表明：以Mn（NO₃）₂溶液为浸渍液,Mn/γ-Al₂O₃催化剂的最优制备条件为浸渍液浓度0.10 mol/L、浸渍时间9 h、焙烧温度400 ℃、焙烧时间2 h;在反应时间为30 min、废水pH为9.0、臭氧通量为4.6 mg/min、催化剂加入量为5 g/L的条件下,当进水COD、BOD₅、ρ（氨氮）和色度分别为220~250 mg/L,8~10 mg/L,10~12 mg/L和60~70倍时,出水COD、BOD₅、ρ（氨氮）和色度的平均去除率分别为53%,30%,33%和93%,出水水质满足GB 21904—2008《化学合成类制药工业水污染物排放标准》的要求。     

Bioremediation of chlorinated pesticide–contaminated soil using anaerobic sludges and surfactant addition

Methanogenic granular sludge and wastewater fermented sludge were used as inocula for batch tests of anaerobic bioremediation of chlorinated pesticide contaminated soil. Results obtained for both types of biomass were similar: 80 to over 90% of γ -hexachlorocyclohexane (γ-HCH), 1,1,1-trichloro-2,2-bis-(4-methoxyphenyl)ethane (methoxychlor) and 1,1,1-trichloro-2,2-bis-(4-chlorophenyl)ethane (DDT) removed in 4–6 weeks. Residual fractions of these pesticides persisted till the end of the 16-week experiment. DDT was degraded through 1,1-dichloro-2,2-bis-(4-chlorophenyl)ethane (DDD). Accumulation of this product corresponded stoichiometrically only to 34–53% of removed DDT, supposedly due to its further transformations, finally resulting in formation of detected 4,4′-dichlorobenzophenone (DBP). Addition of 0.5 mM Tween 80 nonionic surfactant resulted in about a twofold decrease of γ -HCH and methoxychlor residual concentrations, as well as considerably lower DDD accumulation (7–29%) and higher DBP production. However, 1.25 mM dose of this surfactant applied together with granular sludge brought DDD levels back to that observed for treatments with the sludge alone, also impairing DBP formation.     

MnxCe1-xO2／γ-Al2O3催化剂的制备及其催化甲苯的燃烧性能

以γ-Al2O3为载体,以MnxCe1-xO2为催化活性组分,采用浸渍法制备了一系列负载型MnxCe1-xO2／γ-Al2O3催化剂（x=0、0．2、0．4、0．6、0．8、0．9、1）,在固定床反应器中评价了催化剂对甲苯的催化燃烧性能。结果表明,MnxCe1-xO2／γ-Al2O3催化剂的催化活性与催化剂的焙烧温度、活性组分MnxCe1-xO2的负载量以及Mn、Ce摩尔比有显著关系,其中焙烧温度550℃、负载量为20％、Mn、Ce摩尔比为4：1时,即MnxCe1-xO2／γ-Al2O3催化剂对甲苯的催化性能最佳,反应温度为180℃时,甲苯的转化率达到95％。并在连续100h的稳定性操作后,催化剂的活性基本无变化。采用XRD、BET以及SEM等分析测试手段对催化剂的结构以及表面进行了表征。     

Investigation in the sorption mechanism and behavior of nano γ-Al2O3 for the removal of fluorine ions

研究了纳米γ-Al2O3吸附剂对氟离子的吸附行为,考查了吸附平衡时间、温度、溶液的pH等对吸附过程的影响.结果表明,在室温下,纳米γ-Al2O3对氟离子的吸附在3min基本达到平衡;在pH3～9范围内,吸附率达95%以上;吸附过程符合准二级反应动力学模型,其反应的表观活化能（Ea）为10.99kJ.mol-1;颗粒内扩散过程是吸附的主要控制步骤,而颗粒外扩散过程对吸附也有影响;吸附过程符合Langmuir、D-R等温模型,常温下,纳米γ-Al2O3对氟离子的平均吸附能为11.15kJ.mol-1.吸附反应的ΔGθ〈0,ΔHθ〉0,说明该吸附过程是自发的吸热反应.共存阴离子HCO3-和PO43-、阳离子Cu2＋对氟离子的吸附影响较大.纳米γ-Al2O3在动态和静态吸附实验中的除氟效果相近.     

Photocatalytic remediation of γ-HCH contaminated soil induced by α-Fe2O3 and TiO2

Heterogeneous photocatalytic degradation of γ-HCH on soil surfaces was carried out to evaluate the photocatalytic effectiveness of α-Fe2O3 and TiO2 toward degrading γ-HCH on soil surfaces. After being spiked with γ-HCH, soil samples were loaded with α-Fe2O3 or TiO2 and exposed to UV-light irradiation. Different catalyst loads(0%, 2%, 5%, 7%, and 10% (wt). α-Fe2O3; 0%, 0.5%, 1%, 2% wt. TiO2) were tested for up to 7 d irradiation. The effects of soil thickness, acidity, and humic substances were also investigated. The obtained results indicated that the γ-HCH photodegradation follows the pseudo-first-order kinetics. The addition of α-Fe2O3 or TiO2 accelerates the photodegradation of γ-HCH, while the photodegradation rate decreases when the content of α-Fe2O3 exceeds 7%(wt.). The degradation rate increases with the soil pH value. Humic substances inhibit the photocatalytic degradation of γ-HCH. Pentachlorocyclohexene, tetrachlorocyclohexene, and trichlorobenzene are detected as photodegradation intermediates, which are gradually degraded with the photodegradation evolution.     

g 辐照预处理促进剩余污泥发酵产氢的研究

为降低能耗,提高辐照技术的经济性,探讨了在0~9.5kGy范围内,γ辐照剂量对生活污水处理厂二沉池剩余污泥中耗氢菌的抑制效果和对发酵产氢的影响,建立了描述发酵产氢过程及辐照影响的动力学模型.结果表明,γ辐照剂量从0增加至9.5kGy时,污泥溶解率从0增加至4%,上清液中可检测出一定的蛋白质和多糖等物质,其中蛋白质中的氮素占溶出总氮素的90%,表明较低剂量辐照即对污泥菌体造成较明显的破解,这可在一定程度上抑制无法形成芽孢的耗氢菌活性;与之相对应的是污泥发酵产氢能力的明显提升,以葡萄糖为底物(1.0g/L),在35℃和初始pH值为7.0时,当辐射剂量仅为0.5kGy时,累积产氢量即比未辐照时有70%的提升,进一步增加辐照剂量至5kGy,累计产氢量和产氢得率均继续增长且达到最大值,分别为240mL/g葡萄糖和1.93mLH2/mol葡萄糖(发酵液的污泥量达2.0g VSS/L);此后,污泥发酵产氢能力随辐射剂量的增加而降低.修正的Logistic模型能很好地描述本研究中累积产氢量随时间的变化规律,而修正的Han-Levenspiel模型能很好地描述辐照剂量对平均产氢速率的影响.     

催化湿式氧化处理造纸废水的研究

以过渡金属氧化物CuO为活性组分,采用催化湿式氧化法处理造纸废水,考察Cu负载量、催化剂用量、反应温度对废水COD去除率的影响。结果表明:固定氧气分压在2.5MPa和反应时间3h,催化剂用量为3g,Cu负载量为4%,反应温度为220℃,500mL浓度为3250mg/L造纸废水的COD去除率为90%,色度去除率为89%,pH值由9.6变为7.8。另外,对催化剂进行再生处理和稳定性测试。结果表明:450℃下活化3h,在上述相同反应条件下,对原废水的COD去除率降低为88%,重复使用9次后对废水的COD去除率仍能保持在85%左右。