苯并咪唑衍生物缓蚀机理的理论研究

目的对五种苯并咪唑衍生物缓蚀剂的缓蚀性能进行理论评价,并对其缓蚀机理进行理论研究。方法采用量子化学计算与分子动力学模拟相结合的方法。结果苯并咪唑、2-丙基苯并咪唑、2-戊基苯并咪唑、2-己基苯并咪唑的最高占据轨道(HOMO)和最低空轨道(LUMO)均分布在苯并咪唑环上,而2-对氯苄基苯并咪唑的最高占据轨道分布在苯并咪唑环上,最低空轨道分布在取代基上。分子的苯并咪唑环平行吸附在金属表面,取代基含有的烷基链会垂直于表面并指向溶液,对分子吸附的影响较小,而取代基含有的苯环则会发生平行吸附。在五种缓蚀剂分子中,苯并咪唑的能隙差(ΔE)为5.572 e V,在金属表面上的吸附能为364.19 k J/mol,缓蚀性能最弱;2-对氯苄基苯并咪唑的能隙差为5.157 e V,吸附能为700.19 k J/mol,缓蚀性能最强。结论苯并咪唑衍生物分子的取代基官能团会对缓蚀性能造成一定影响,缓蚀剂分子通过其前线轨道与Fe原子形成的配位键和反馈键稳定吸附在金属表面,吸附形态和前线轨道分布有关。     

二氧化碳驱油工艺中油酸咪唑啉对碳钢的缓蚀行为研究

目的 研究CO2驱油工艺中咪唑啉缓蚀剂对油套管P110钢腐蚀的缓蚀机制与规律。方法 模拟长庆油田CO2驱工艺环境为实验条件,采用失重挂片、电化学测试、微观表征等手段,研究油酸咪唑啉缓蚀剂对P110碳钢的腐蚀抑制行为。结果 P110钢的腐蚀速度随着CO2分压的升高而增大,但是增大幅度不明显。当CO2分压为2、6 MPa时,油酸咪唑啉对P110钢腐蚀具有显著的抑制效果,缓蚀效率均超过98%,试片表面基本完整;当CO2分压升高到8 MPa时,油酸咪唑啉的缓蚀性能明显下降,缓蚀效率仅为64.33%,试片表面存在明显的腐蚀特征。结论 CO2分压升高到8 MPa时,P110钢表面携带过剩的正电荷,不利于油酸咪唑啉缓蚀剂的吸附。     

剩余污泥中活性成分提取及其酸洗缓蚀行为研究

文章采用失重法,考察了从剩余污泥中提取的活性成分对A3碳钢在10%盐酸中的缓蚀作用,然后通过热力学研究了缓蚀剂的吸附行为,研究结果表明,污泥水解时37%盐酸加入量8 mL、水解时间18 h、水解温度(99±0.5)℃可有效地提取污泥中的活性成分,失重法结果表明缓蚀剂的加入可有效抑制钢铁在HCl中的腐蚀,在(30±0.5)℃下缓蚀率可达到88%以上,随着温度升高,缓蚀性能下降。该缓蚀剂在A3碳钢表面的吸附符合校正的Langmuir吸附模型,吸附过程为放热、熵增的自发过程。     

金县1-1水源井缓蚀阻垢剂筛选的实验研究

目的解决金县1-1油田井下管柱腐蚀结垢问题。方法结合金县1-1油田水源井A1W井的实际工况,运用高温高压动态腐蚀测试仪对N80钢进行模拟井筒条件实验,明确A1W井含H2S的水对N80钢的腐蚀性和结垢性。运用室内实验分别对三种缓蚀剂和五种阻垢剂的单剂进行优选,结合扫描电镜对试片表面进行微观形貌分析,筛选出合适的缓蚀剂和阻垢剂的单剂。然后开展缓蚀剂和阻垢剂的单剂配伍性实验,明确缓蚀剂和阻垢剂二者混合后的配伍性以及得出缓蚀剂和阻垢剂的最佳配比。结果筛选出的AA/AMPS阻垢剂的阻垢率可达84.2%,HS-3缓蚀剂的缓蚀率达到87.3%。缓蚀剂和阻垢剂配伍性和配比实验结果表明,HS-3缓蚀剂和AA/AMPS配伍性较好,当缓蚀剂和阻垢剂按照11:1的配比时,缓蚀率可达87.7%,阻垢率可达94%。结论优选出的复合缓蚀阻垢剂的防腐阻垢性能,可满足油田腐蚀防垢控制指标。     

生物法改性纤维素纳米纤维制备高效CO2缓蚀剂

目的 以绿色天然材料为原料,制备高效CO2缓蚀剂.方法 以植物乳杆菌为改性工具,采用生物法对纤维素纳米纤维进行改性,制备功能化的纳米材料.采用红外光谱对产物结构进行表征,使用失重测试和电化学测试相结合对碳钢在饱和CO2盐溶液中的缓蚀性能进行评价.结果 功能化的纤维素纳米纤维对碳钢的腐蚀具有明显的抑制作用.失重测试证实,当添加浓度达到10?4时,缓蚀效率可达到88.6％.极化曲线测试表明,改性后纳米缓蚀剂的作用机制属于混合抑制型,对阴极电荷的传递过程和阳极溶解过程均产生抑制作用,且纳米粒子在高过电位下会发生脱附.不同时间的电化学阻抗谱测试表明,纳米缓蚀剂的缓蚀作用在溶液中达到稳定的时间约8 h,明显长于传统的缓蚀剂.结论 功能化的纤维素纳米纤维是一种缓蚀性能优异的新型纳米缓蚀剂,它独特的组成结构使其能在金属表面吸附成膜.这种特殊的改性方法为缓蚀剂的绿色安全生产提供了新的思路.     

桐油水解制备咪唑啉缓蚀剂及其量子化学研究

目的 开发原料价廉易得、能实际应用的缓蚀剂。方法 以桐油为原料,水解后得到桐油酸,然后与二乙烯三胺经过酰胺化和环化反应,生成桐油咪唑啉缓蚀剂。在模拟现场环境的条件下对所合成的桐油咪唑啉缓蚀剂进行电化学测试和高温高压性能评价。利用量子化学计算对桐油咪唑啉缓蚀剂的分子动力学进行模拟,探讨其在Fe表面的吸附作用。结果 红外光谱显示,桐油水解后可生成桐油酸,最终合成物为桐油咪唑啉。电化学测试表明,随着桐油咪唑啉缓蚀剂添加量的增大,20#测试钢片的自腐蚀电位逐渐提高,腐蚀电流降低。高温高压模拟实验显示,加入油酸咪唑啉后,腐蚀速率明显降低,由0.3181 mm/a降到了0.0392 mm/a。量子化学计算表明,桐油咪唑啉分子中的咪唑啉环会平行吸附于铁表面,形成一层缓蚀剂膜。结论 价廉易得的桐油经水解后可得桐油酸,再与二乙烯三胺经过酰胺化和环化反应最终合成了桐油咪唑啉缓蚀剂。该缓蚀剂添加量越大,对20#钢片的缓蚀效果越好,呈现出了较好的缓蚀效果,其分子结构中的咪唑环能平行吸附于铁表面,属于抑制阳极型缓蚀剂。     

一种船舶用钢预膜缓蚀剂的研究

目的研究CP-CI021海水介质预膜缓蚀剂的缓蚀行为及复配工艺。方法主要采用失重法和电化学阻抗谱(EIS)研究CP-CI021对Q235碳钢在海水介质中的缓蚀行为,并优化出预膜缓蚀剂最佳复配工艺。结果 CP-CI021预膜缓蚀剂具有优异的缓蚀性能,经预膜处理的Q235碳钢测试的EIS阻抗模值增大了2个数量级。结论得到了预膜缓蚀剂的最佳复配工艺,有机膦PHA质量浓度为7.3 g/L,助剂A质量浓度为3 g/L,助剂B质量浓度为5 g/L,缓蚀效率高达98.4%。     

钼酸盐复合缓蚀剂对海水中碳钢缓蚀性及机理研究

采用失重法、电极化法和X-射线光电子能谱XPS技术对钼酸盐复合缓蚀剂的缓蚀性及缓蚀机理进行了研究。实验结果表明:单一钼酸盐对海水中碳钢的缓蚀率随着钼酸盐使用浓度的增加而增加,但低浓度使用缓蚀率较低。通过失重法确定了与钼酸盐有较好协同效应的缓蚀剂配方-钼酸盐、柠檬酸钠、有机膦酸盐(HEDP)和锌盐,当缓蚀剂各组分浓度分别为10mg/L、40mg/L、10mg/L和4mg/L时,该缓蚀剂对海水中碳钢的缓蚀率超过93%。动电位极化曲线测试结果表明:单一钼酸盐缓蚀剂和钼酸盐复合缓蚀剂均为抑制阳极反应为主的阳极型缓蚀剂;X-射线光电子能谱XPS实验结果表明:添加了缓蚀剂的碳钢表面形成了以氧化铁和有机铁络合物为主要成分,钼与磷也参与成膜的不溶性沉淀膜,有效的抑制了海水对碳钢表面的腐蚀。     

固载化瓜环的制备及其对磺胺间甲氧嘧啶的吸附性能研究

在微波无极灯下将烯氧基瓜环固载到巯基硅胶(MSG)上,制得固载化瓜环(ACB[6]-SG).通过红外光谱表征固载产物,并研究固载化瓜环对磺胺间甲氧嘧啶(SMM)的吸附性能.结果表明,SMM在固载化瓜环上的吸附基本在2 min内即可达到平衡;Henry方程和Freundlich方程均能较好地拟合SMM在固载化瓜环和巯基硅胶上的等温吸附曲线,但是SMM在固载化瓜环上的吸附主要是在瓜环中的分配,而SMM在巯基硅胶上的吸附则主要是多分子层的表面吸附作用;SMM在固载化瓜环上的平衡吸附量远大于在巯基硅胶上的平衡吸附量;SMM在两者上的吸附过程是一个放热过程,温度越低吸附效果越好.     

羧甲基壳聚糖接枝聚丙烯酸阻垢缓蚀性能研究

结垢和腐蚀是工业循环冷却水系统应用中存在的两大重要问题.以一种性能优越且绿色环保的天然高分子材料—壳聚糖为原材,制备了一系列不同接枝率的羧甲基壳聚糖接枝聚丙烯酸（CMCS-g-PAA）阻垢缓蚀剂.通过静态阻垢法、扫描电子显微镜（SEM）、X射线衍射（XRD）、失重法、电化学法、量子计算等详细考察了CMCS-g-PAA聚丙烯酸接枝率（内部结构因素）与药剂投加量、温度等（外部环境因素）对碳酸钙的阻垢及对碳钢的缓蚀性能影响.结果表明,CMCS-g-PAA具有较好的阻垢缓蚀效果,CMCS-g-PAA的阻垢与缓蚀性能均随着接枝率的增加呈先增加后减少的变化趋势.SEM和XRD结果分析表明,CMCS-g-PAA作为阻垢剂对CaCO3的阻垢作用是螯合作用、分散增溶和晶格畸变等多种效应共同作用的结果 .在CMCS-g-PAA缓蚀机制研究中,失重法及电化学法结果大体一致,CMCS-g-PAA是一种混合型缓蚀剂,能同时抑制阴极和阳极反应;抑制机理主要是CMCS-g-PAA上羟基、氨基及羧基等活性功能基团上孤对电子易与Fe外层空轨道有效配位形成单分子层保护膜,从而隔绝腐蚀介质达到对碳钢缓蚀的目的 .与CMCS...     

Distribution and ecological effect of mercury in Laogang landfill, Shanghai, China

Laogang landfill near Shanghai is the largest landfill in China, and receives about 10000 t of daily garbage per day, Samples of topsoil and plants were analyzed to evaluate mercury pollution from the landfill. For topsoil samples, there were significant correlations among total mercury （HgT）, combinative mercury （Hgc） and gaseous mercury （HgG）, and content of total organic carbon （TOC）, but, no significantly relationship was found between Hg content and filling time. Hg content changes in vertical profiles with time showed that the average Hgv of profiles 1992, 1996, and 2000 was similar, but their average HgG was quite different. HgT was significantly correlated with Hgc in profile 1992 and 2000, and Hgv was significantly correlated with Hg6 in profile 1996. HgG/Hgv ratio in profile samples decreased in the order of （HgG,/HgT）1992〉（HgG/HgT）1996〉〉（HgG/HgT）2000. A simple outline of Hg release in landfill could be drawn： with increasing of filling time, degradation undergoes different biodegradation, accordingly, gaseous mercury goes through small, more, and small proportion to total mercury. Distribution of Hg in plants was inhomogeneous, following the order of leaf〉root〉stem. The highest value of leaf may be associated with higher atmospheric Hg from landfill. Ligneous plants （e.g. Phyllostachys glanca, Prunus salicina and Ligustrum lucidum） are capable of enriching more Hg than herbaceous plants.     

EDTA-enhanced phytoremediation of lead contaminated soil by Bidens maximowicziana

Phytoremediation is a potential cleanup technology for the removal of heavy metals from contaminated soils.Bidens maximowicziana is a new Pb hyperaccumulator,which not only has remarkable tolerance to Pb but also extraordinary accumulation capacity for Pb.The maximum Pb concentration was 1509.3 mg/kg in roots and 2164.7 mg/kg in overground tissues.The Pb distribution order in the B. maximowicziana was:leaf>stem>root.The effect of amendments on phytoremediation was also studied.The mobility of soil Pb and the Pb concentrations in plants were both increased by EDTA application.Compared with CK(control check),EDTA application promoted translocation of Pb to overground parts of the plant.The Pb concentrations in overground parts of plants was increased from 24.23-680.56 mg/kg to 29.07-1905.57 mg/kg.This research demonstrated that B.maximowicziana appeared to be suitable for phytoremediation of Pb contaminated soil,especially,combination with EDTA.     

Decomposition of alachlor by ozonation and its mechanism

Decomposition and corresponding mechanism of alachlor, an endocrine disruptor in water by ozonation were investigated. Results showed that alachlor could not be completely mineralized by ozone alone. Many intermediates and final products were formed during the process, including aromatic compounds, aliphatic carboxylic acids, and inorganic ions. In evoluting these products, some of them with weak polarity were qualitatively identified by GC-MS. The information of inorganic ions suggested that the dechlorination was the first and the fastest step in the ozonation of alachlor.     

Enzymatic oxidation of aqueous pentachlorophenol

The influence of the nonionic surfactant Tween 80 on pentachlorophenol （PCP） oxidation catalyzed by horseradish peroxidase was studied. The surfactant was tested at concentrations below and above its critical micelle concentration （CMC）. Enhancement of PCP removal was observed at sub-CMCs. The presence of Tween 80 in the reaction mixture reduced enzyme inactivation which occurred through a combination of free radical attack and sorption by precipitated products. A simple first-order model was able to simulate time profiles for enzyme inactivation in the presence or absence of Tween 80. At supra-CMCs, the surfactant caused noticeable reductions in PCP removal, presumably through micelle partitioning of PCP which precluded the hydrophobic PCP molecule from interacting with the enzyme.     

基于综合水质标识指数和对应分析法的校园河道水质评价

以三峡大学的校园河道求索溪为研究对象,利用综合水质标识指数法确定求索溪水质类别,分析其水质时空变化规律,并利用对应分析法得出求索溪中不同监测点的主要污染因子.研究结果表明:求索溪整体的综合水质标识指数为7.423,整体水质为劣V类(地表水环境质量标准GB 3838-2002)且黑臭.从时间变化来看,求索溪4月份的水质最差,5月份次之,4、5月份所有监测点的水质都劣于V类且黑臭;8月份水质最好,水质为Ⅳ类;从空间分布来看,8个监测点综合水质标识指数均超过6.0,水质为劣V类,其中6号监测点的水质相对最好,监测点3号的水质相对最差;对应分析法得出求索溪的整体水体污染程度受总氮因子的影响最大,其次为总磷.该研究拟为求索溪及类似校园河道的水环境治理研究提供基础依据和参考.     

Effects of chitosan on growth of an aquatic plant (Hydrilla verticillata) in polluted waters with different chemical oxygen demands

Effects of chitosan on a submersed plant, Hydrilla verticillata, were investigated. Results indicated that H. venicillata could prevent ultrastructure phytotoxicities and oxidativereaction from polluted water with high chemical oxygen demand (COD). Superoxide dismutase (SOD) activity and malondialdehyde (MDA) contents in H. verticillata treated with 0.1% chitosan in wastewater increased with high COD (980 mg/L) and decreased with low COD (63 mg/L), respectively. Ultrastructural analysis showed that the stroma and grana of chloroplast basically remained normal. However, plant cells from the control experiment (untreated with chitosan) were vacuolated and the cell interval increased. The relict of protoplast moved to the center, with cells tending to disjoint. Our findings indicate that wastewater with high COD concentration can cause a substantial damage to submersed plant, nevertheless, chitosan probably could alleviate the membrane lipid peroxidization and ultrastructure phytotoxicities, and protect plant cells from stress of high COD concentration polluted water.     

Removal of cadmium using MnO2 loaded D301 resin

MnO2 loaded weak basic anion exchange resin D301 （Anion exchange resin, macroreticular weak basic styrene） as adsorbent has been prepared and applied to the removal of cadmium. The adsorption characteristics have been investigated with respect to effect of pH, equilibrium isotherms, removal kinetic data, and interference of the coexisting ions. The results indicated that the Cd^2＋ could be efficiently removed using MnO2 loaded D301 resin in the pH range of 3-8 from aqueous solutions with the co-existence of high concentration of alkali and alkaline-earth metals ions. The saturate adsorption capacity of the Cd^2＋ was 77.88 mg/g. The adsorption process followed the pseudo first-order kinetics. The equilibrium data obtained in this study accorded excellently with the Langmuir adsorption isotherm.     

Effect of coagulation pretreatment on the fouling of ultrafiltration membrane

The purpose of this study is to understand the effect and mechanism of preventing membrane fouling, by coagulation pretreatment, in terms of fractional component and molecular weight of natural organic matter （NOM）. A relatively higher molecular weight （MW） of hydrophobic compounds was responsible for a rapid decline in the ultrafiltration flux. Coagulation could effectively remove the hydrophobic organics, resulting in the increase of flux. It was found that a lower MW of neutral hydrophilic compounds, which could remove inadequately by coagulation, was responsible for the slow declining flux. The fluxes in the filtration of coagulated water and supernatant water were compared and the results showed that a lower MW of neutral hydrophilic compounds remained in the supernatant water after coagulation could be rejected by a membrane, resulting in fouling. It was also found that the coagulated flocs could absorb neutral hydrophilic compounds effectively. Therefore, with the coagulated flocs formed on the membrane surface, the flux decline could be improved.     

Penetration analysis of elements and bioleaching treatment of spent refractory for recycling

Acidithiobacillus ferrooxidans ATCC23270 and Acidithiobacillus thiooxidans TM-32 were used for bioleaching of spent refractories of aluminium and copper melting furnaces for their recycling.Firstly,penetration of elements into aluminium melting furnace refractory was investigated and it was found that up to 7 cm from surface was contaminated.Comparison on leaching efficiency by the strains ATCC23270 and TM-32 found that the strain ATCC23270 could treat larger amount of the refractories than the strain TM-32 could do.In the experiment of bioleaching of spent refractory aluminium melting furnace by the strain ATCC23270,high leaching efficiency were obtained on Al,Si,and Ca,and extremely low leaching performance was,however,shown on the rest of elements i.e.,Na,Mn,and Zn.Under the strain TM-32 use,relatively high leaching performance was recognized on Al,Si,Ca,Na,Mn,and Zn.In the experiment of bioleaching for spent refractory copper melting furnace,almost the same leaching trends were shown on Cu,Zn,Al,and Si under the strains ACTT23270 and TM-32 uses.     

Simultaneous removal of ammonium and phosphate by zeolite synthesized from coal fly ash as influenced by acid treatment

Zeolite synthesized from fly ash （ZFA） without modification is not efficient for the purification of NH4＋ and phosphate at low concentrations that occur in real effluents, despite the high potential removal capacity. To develop an effective technique to enhance the removal efficiency of ammonium and phosphate at low concentrations, ZFA was modified with acid treatment and the simultaneous removal of ammonium and phosphate in a wide range of concentration was investigated. It was seen that when compared with untreated ZFA, only the treatment by 0.01 mol/L of H2SO4 significantly improved the removal efficiency of ammonium at low initial concentrations. The behavior was well explained by the pH effect. Treatment by more concentrated H2SO4 led to the deterioration of the ZFA structure and a decrease in the cation exchange capacity. Treatment by 0.01 mol/L H2SO4 improved the removal efficiency of phosphate by ZFA at all initial P concentrations, while the treatment by concentrated H2SO4 （≥0.9 mol/L） resulted in a limited maximum phosphate immobilization capacity （PIC）. It was concluded that through a previous mild acid treatment （e.g. 0.01 mol/L of H2SO4）, ZFA can be used in the simultaneous removal of NH4＋ and P at low concentrations simulating real effluent.