失效锂离子电池有机物真空脱除和浸出研究

文章采用真空蒸发热处理的方法脱除废弃失效的锂离子电池中的有机物,加热温度为220~500℃,真空炉内压力150Pa,恒温处理时间1h。除有机物被脱除外,当处理温度为280℃时形成了CoO和Li2CO3。温度升高至350℃时,主要的物相为LiCoO2、CoO、Co3O4和Co,以及少量Li2CO3。在超声场中将电极材料与铝、铜箔集流体分离,然后分别用含亚硫酸钠的硫酸溶液和氨性溶液处理电极材料。当用含亚硫酸钠的硫酸溶液浸出经280℃脱除有机物的电极材料时,钴元素基本被浸出。而用氨性溶液浸出经350℃脱除有机物的电极材料时,钴元素的浸出率很低。为了提高钴的浸出率,真空热处理的温度应介于280~350℃之间。     

酒石酸浸出钴酸锂动力学机理研究

提出了一种绿色回收废旧钴酸锂电池正极活性物质的方法。采用酒石酸为浸出剂和还原剂,湿法回收废旧钴酸锂电池中的钴和锂。结果表明:钴酸锂与酒石酸摩尔比为1∶4,反应固液比为15 g/L,反应温度为90℃,反应时间为5 h时,金属钴和锂的浸出率分别为92.95%、91.86%;动力学分析显示,Co、Li浸出反应利用经典模型拟合效果最佳,其表观活化能分别为55.20,63.65 kJ/mol,浸出过程属于吸热反应和化学反应控制。该工艺可实现废旧钴酸锂正极活性物质的高效绿色回收,为其他废旧锂离子电池的回收提供理论基础。     

锂离子电池正极材料的回收及再制备

通过湿化学法从废旧锂离子电池中回收得到Li+、Co2+的硝酸溶液,以此为钴源,与Ni(NO3)2.6H2O、Mn(NO3)2按化学计量比混合,用草酸盐共沉淀法制备草酸盐前驱体,然后按Li过量5%加入Li2CO3混合,在空气中于800～950°C煅烧15 h得LiCo1/3Mn1/3Ni1/3O2,研究了煅烧温度对材料结构、形貌以及电化学性能的影响。结果表明,900℃保温15 h制备的LiCo1/3Mn1/3Ni1/3O2正极材料,为理想的(α-NaFeO2层状结构,颗粒为大小均匀的球形,在2.5～4.3 V的电压范围内,以0.1 C的恒定电流进行充放电,其首次充放电比容量分别为194.3和150.9 mAh/g,10次循环之后的容量保持率为89.9%,放电比容量为135.0 mAh/g。     

天然矿物负载Fe/Co催化H2O2氧化降解阳离子红3R

类Fenton反应关键是催化剂的活性,利用浸渍法负载铁、钴双金属对天然矿物材料进行改性,提高其催化活性,并运用扫描式电子显微镜(SEM)、X射线能谱仪(EDS)、X射线衍射(XRD)等表征手段对负载前后的材料进行表征分析.结果表明负载后材料中生成Fe2O3和Co Fe2O4两种新物质.将合成的催化剂用于催化H2O2氧化阳离子红3R染料废水,在催化剂投加量3 g·L-1,H2O2投加量0.3 m L·L-1,反应时间1 h条件下,100 mg·L-1阳离子红3R废水脱色率可达99.8%,TOC去除率可达58.4%,催化剂中活性组分主要为表面负载的Fe2O3和Co Fe2O4,电子自旋共振(ESR)分析表明催化氧化过程中产生羟基自由基,阳离子红3R发色基团在1 min已被完全破坏,光谱分析表明反应过程中有小分子物质生成.催化氧化效果受染料废水初始p H值影响小,适应p H范围广,解决了传统Fenton反应p H条件苛刻的问题.研究结果为印染废水处理提供了具有工程应用潜力的技术方法.     

废旧锂离子二次电池回收有价金属工艺研究

本文对从废旧锂离子二次电池中回收有价金属的工艺进行了研究。采用解体分选出塑料外壳、铜铁连接件、石墨负极和正极；采用碱浸－酸溶－净化－沉钴工艺回收政极废料中的铝和钴。LiCoO2在硫酸、双氧水体系中的分解反应为：2LiCoO2 3H2SO4 H2O2→Li2SO4 2CoSO4 4H2O O2↑。用硫酸中和碱浸液中的铝，制取化学纯氢氧化铝，回收率为94．89％；以草酸钴的形式回收钴，产品达到Q／GGHO1－89标准，直收率94．23％。     

以海泡石为载体的双金属多相类芬顿催化剂的制备及表征

以活性艳蓝为目标污染物,以改性海泡石为载体,以Fe(NO3)3浓度、MnSO4浓度、尿素浓度、水浴温度、煅烧温度与煅烧时间为影响因素,优化了均匀沉淀法制备双金属多相类芬顿催化剂的工艺条件,并利用SEM、XRD、FTIR对催化剂进行了表征.结果表明,随铁离子浓度的增大,所制得催化剂金属离子活性越高.少量的锰掺杂可抑制Fe2O3粒径的增长,提高催化剂的活性.尿素浓度增大,使得晶粒的生成速率愈快,有利于生成细小、均匀的金属颗粒.利用Box-Behnken实验得出催化剂制备的最佳工艺条件为:硝酸铁浓度为0.18 mol.L-1,硫酸锰浓度为0.05 mol.L-1,尿素的浓度为1.0 mol.L-1,海泡石的投加量为40 g.L-1,水浴温度为100℃,煅烧温度为370℃,煅烧时间为3 h.SEM表明本实验所采用的海泡石为α型海泡石,可作为良好的催化剂载体;在催化剂制得后,FTIR图谱显示海泡石的纯度得到提高,并出现了Fe-O的吸收峰.XRD图谱表明,在催化剂表面铁离子主要以α-Fe2O3和γ-Fe2O3的形式存在.     

杀菌剂对湖泊水体温室气体浓度分析的影响

通过往湖泊水样中添加杀菌剂(CuSO4和HgCl2),利用平衡法,用气相色谱仪测定CO2、CH4、N2O浓度,研究杀菌剂(CuSO4和HgCl2)添加对湖泊水体CO2、CH4、N2O浓度分析的影响.实验设计:对照组(CK)不加任何试剂;处理组T1加1mL CuSO4溶液,T2加5 mL CuSO4溶液,T3加0.5 mL HgCl2溶液;每组的水样分两批分析:(Ⅰ)预处理完成后立即分析和(Ⅱ)预处理完成后静置两天再分析.结果表明,CuSO4和HgCl2的添加均能明显增加水体中CO2的浓度,CK(Ⅰ)和CK(Ⅱ)的CO2平均浓度分别为(11.5±1.47)μmol·L-1和(14.38±1.59)μmol·L-1,T1(Ⅰ)和T1(Ⅱ)的CO2平均浓度分别为(376±70)μmol·L-1和(448±246.83)μmol·L-1;T2(Ⅰ)和T2(Ⅱ)的CO2平均浓度分别为(885±51.53)μmol·L-1和(988.83±101.96)μmol·L-1;T3(Ⅰ)和T3(Ⅱ)的CO2平均浓度分别为(287.19±30.01)μmol·L-1和(331.33±22.06)μmol·L-1.但CuSO4和HgCl2添加对水体中CH4和N2O的浓度没有影响.对比Ⅰ和Ⅱ的实验结果可知,在水样预处理完成后需当天分析其温室气体(CO2、CH4、N2O)浓度.本研究表明,杀菌剂的添加能显著增加水体CO2的浓度.     

盐析法从锂离子电池正极浸出液中回收钴盐的研究

根据电解质溶液的现代理论,探索利用盐析方法从锂离子电池正极浸出液中回收盐的可能性.在从LiCoO2为正极的盐酸浸出液中加入(NH4)2SO4饱和水溶液和无水乙醇,可使浸出液中的Co2 发生盐析,当浸出液、(NH4)2SO4饱和水溶液和无水乙醇的体积比控制为2:1:3时,Co2 的析出率可达到92%以上.所得盐析产品经X射线衍射分析可知为(NH4)2Co(SO4)2和(NH4)Al(SO4)2,且Co2 在Al3 之前从浸出液中析出,分段盐析可使这2种盐分离,得到不同的产品.     

化学镀镍老化液中镍、磷的处理与回收

以 Ca(OH) 2 作为沉淀剂 ,调节溶液 p H =1 2 ,在 80℃条件下反应 1 h,使化学镀镍老化液中镍浓度降到1 / mg· L- 1 ;分离沉淀后的溶液用硫酸调节 p H=8,按 Ca(Cl O) 2 与总 P重量比为 3 .5∶ 1 .0的比例加入 Ca(Cl O) 2 ,老化液中的磷酸盐通过形成沉淀得到去除 ,从而使化学镀镍老化液中的镍、磷含量均达到国家排放标准。对于含 Ni(OH) 2 的沉淀 ,以稀硫酸溶解回收其中的镍 ,剩余沉渣建议填埋处理 ;磷酸盐沉淀可以作为磷肥资源回用于农业生产。     

利用硫铁矿烧渣和硫酸铵废液制备铵铁蓝

将氨法制铁黄所产生的硫酸铵废液净化后,加入硫铁矿烧渣制备得到的硫酸亚铁得到硫酸亚铁和硫酸铵混合溶液,其硫酸亚铁和硫酸铵Ё浓度分别为0.346和0.173 mol·L-1.按照硫酸亚铁与亚铁氰化钠物质的量比为1.15:1,将硫酸亚铁和硫酸铵混合溶液加入浓度为0.200 mol·L-1的亚铁氰化钠溶液中,80℃下反应10 min得到白浆.将所得白浆在100℃下热煮1 h,加入质量分数为50%的硫酸溶液酸煮2 h,降温至70℃后加入质量分数为10%的氯酸钠溶液氧化3 h得到铁蓝.将铁蓝过滤、洗涤、干燥、研磨得到铵铁蓝粉末.实验所得铵铁蓝质量优于国家标准GB 1860-88及HG/T 3001-1999行业标准.SEM实验表明,铵铁蓝颗粒大小均匀、粒径约为20 nm;XRD实验表明,铵铁蓝具有与Fe4[Fe(CN)6]3相同的立方晶体结构.     

Toxic effects of acetochlor, methamidophos and their combination on nifH gene in soil

Toxic effects of two agrochemicals on nifH gene in agricultural black soil were investigated using denaturing gradient gel electrophoresis （DGGE） and sequencing approaches in a microcosm experiment. Changes of soil nifH gene diversity and composition were examined following the application of acetochlor, methamidophos and their combination. Acetochlor reduced the nifH gene diversity （both in gene richness and diversity index values） and caused changes in the nifH gene composition. The effects of acetochlor on nifH gene were strengthened as the concentration of acetochlor increased. Cluster analysis of DGGE banding patterns showed that nifH gene composition which had been affected by low concentration of acetochlor （50 mg/kg） recovered firstly. Methamidophos reduced nifH gene richness that except at 4 weeks. The medium concentration of methamidophos （150 mg/kg） caused the most apparent changes in nifH gene diversity at the first week while the high concentration of methamidophos （250 mg/kg） produced prominent effects on nifH gene diversity in the following weeks. Cluster analysis showed that minimal changes of nifH gene composition were found at 1 week and maximal changes at 4 weeks. Toxic effects of acetochlor and methamidophos combination on nifH gene were also apparent. Different nifH genes （bands） responded differently to the impact of agrochemicals： four individual bands were eliminated by the application of the agrochemicals, five bands became predominant by the stimulation of the agrochemicals, and four bands showed strong resistance to the influence of the agrochemicals. Fifteen prominent bands were partially sequenced, yielding 15 different nifH sequences, which were used for phylogenetic reconstructions. All sequences were affiliated with the alpha- and beta-proteobacteria, showing higher similarity to eight different diazotrophic genera.     

Arsenic uptake by arbuscular mycorrhizal maize （Zea mays L.） grown in an arsenic-contaminated soil with added phosphorus

The effects of arbuscular mycorrhizal (AM) fungus (Glomus mosseae) and phosphorus (P) addition (100 mg/kg soil) on arsenic (As) uptake by maize plants (Zea mays L.) from an As-contaminated soil were examined in a glasshouse experiment.Non-mycorrhizal and zero-P addition controls were included.Plant biomass and concentrations and uptake of As,P,and other nutrients,AM colonization,root lengths,and hyphal length densities were determined.The results indicated that addition of P significantly inhibited root colonization and development of extraradical mycelium.Root length and dry weight both increased markedly with mycorrhizal colonization under the zero-P treatments,but shoot and root biomass of AM plants was depressed by P application.AM fungal inoculation decreased shoot As concentrations when no P was added,and shoot and root As concentrations of AM plants increased 2.6 and 1.4 times with P addition,respectively.Shoot and root uptake of P,Mn,Cu,and Zn increased,but shoot Fe uptake decreased by 44.6%,with inoculation, when P was added.P addition reduced shoot P,Fe,Mn,Cu,and Zn uptake of AM plants,but increased root Fe and Mn uptake of the nonmycorrhizal ones.AM colonization therefore appeared to enhance plant tolerance to As in low P soil,and have some potential for the phytostabilization of As-contaminated soil,however,P application may introduce additional environmental risk by increasing soil As mobility.     

Potential of plant polyphenol oxidases in the decolorization and removal of textile and non-textile dyes

In this study an effort has been made to use plant polyphenol oxidases; potato （Solanum tuberosum） and brinjal （Solanum melongena）, for the treatment of various important dyes used in textile and other industries. The ammonium sulphate fractionated enzyme preparations were used to treat a number of dyes under various experimental conditions. Majority of the treated dyes were maximally decolorized at pH 3.0. Some of the dyes were quickly decolorized whereas others were marginally decolorized. The initial first hour was sufficient for the maximum decolorization of dyes. The rate of decolorization was quite slow on long treatment of dyes. Enhancement in the dye decolorization was noticed on increasing the concentration of enzymes. The complex mixtures of dyes were treated with both preparations of polyphenol oxidases in the buffers of varying pH values. Potato polyphenol oxidase was significantly more effective in decolorizing the dyes to higher extent as compared to the enzyme obtained from brinjal polyphenol oxidase. Decolorization of dyes and their mixtures, followed by the formation of an insoluble precipitate, which could be easily removed simply by centrifugation.     

Removal of heavy metals from sewage sludge by low costing chemical method and recycling in agriculture

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Single and joint effects of pesticides and mercury on soil urease

The influence of two pesticides including chlorimuron-ethyl and furadan and mercury （Hg） on urease activity in 4 soils （meadow burozem and phaeozem） was investigated. The soils were exposed to various concentrations of the two pesticides and Hg individually and simultaneously. Results showed that there was a close relationship between urease activity and organic matter content in soil. Chlorimuron-ethyl and furadan could both activate urease in the 4 soils. The maximum increment of urease activity by chlorimuronethyl was up to 14%-18%. There was almost an equal increase （up to 13%-21%） in the urease activity by furadan. On the contrary, Hg markedly inhibited soil urease activity. A logarithmic equation was used to describe the relationship （P〈0.05） between the concentration of Hg and the activity of soil urease in the 4 tested soils. Semi-effect dose （ED50） values by the stress of Hg based on the inhibition of soil urease in the 4 soils were 88, 5.5, 24 and 20 mg/kg, respectively, according to the calculation of the corresponding equations. The interactive effect of chlorimuron-ethyl or furadan with metal Hg on soil urease was mainly synergic at the highest tested concentrations.     

Isolation and preliminary characterization of a 3-chlorobenzoate degrading bacteria

A study was conducted to compare the diversity of 2-, 3-, and 4-chlorobenzoate degraders in two pristine soils and one contaminated sewage sludge. These samples contained strikingly different populations of mono-chlorobenzoate degraders. Although fewer cultures were isolated in the uncontaminated soils than contaminated one, the ability of microbial populations to mineralize chlorobenzoate was widespread. The 3- and 4-chlorobenzoate degraders were more diverse than the 2-chlorobenzoate degraders. One of the strains isolated from the sewage sludge was obtained. Based on its phenotype, chemotaxonomic properties and 16S rRNA gene, the organism S-7 was classified as Rhodococcus erythropolis. The strain can grow at temperature from 4 to 37℃. It can utilize several （halo）aromatic compounds. Moreover, strain S-7 can grow and use 3-chlorobenzoate as sole carbon source in a temperatures range of 10-30℃ with stoichiometric release of chloride ions. The psychrotolerant ability was significant for bioremediation in low temperature regions. Catechol and chlorocatechol 1,2-dioxygenase activities were present in cell free extracts of the strain, but no （chloro）catechol 2,3- dioxygenase activities was detected. Spectral conversion assays with extracts from R. erythropolis S-7 showed accumulation of a compound with a similar UV spectrum as chloro-cis,cis-muconate from 3-chlorobenzoate. On the basis of these results, we proposed that S-7 degraded 3-chlorobenzoate through the modified ortho-cleave pathway.     

Organochlorine pesticides in soils under different land usage in the Taihu Lake region, China

A field study was conducted in the Taihu Lake region, China in 2004 to reveal the organochlorine pesticide concentrations in soils after the ban of these substances in the year 1983. Thirteen organochlorine pesticides (OCPs) were analyzed in soils from paddy field, tree land and fallow land. Total organochlorine pesticide residues were higher in agricultural soils than in uncultivated fallow land soils. Among all the pesticides, ΣDDX (DDD, DDE and DDT) had the highest concentration for all the soil samples, ranging from 3.10 ng/g to 166.55 ng/g with a mean value of 57.04 ng/g and followed by ΣHCH, ranging from 0.73 ng/g to 60.97 ng/g with a mean value of 24.06 ng/g. Dieldrin, endrin, HCB and α-endosulfan were also found in soils with less than 15 ng/g. Ratios of p,p'-(DDD DDE)/DDT in soils under three land usages were: paddy field ＞ tree land ＞ fallow land, indicating that land usage inlfuenced the degradation of DDT in soils. Ratios of p,p'-(DDD DDE)/DDT ＞1, showing aged residues of DDTs in soils of the Taihu Lake region. The results were discussed with data from a former study that showed very low actual concentrations of HCH and DDT in soils in the Taihu Lake region, but according to the chemical half-lives and their concentrations in soils in 1980s, the concentration of DDT in soils seemed to be underestimated. In any case our data show that the ban on the use of HCH and DDT resulted in a tremendous reduction of these pesticide residues in soils, but there are still high amounts of pesticide residues in soils, which need more remediation processes.     

Sorption of 1-naphthol by plant cuticular fractions

The contribution of aliphatic-rich plant biopolymer to sorption of hydrophobic organic compounds is significantly important because of their preservation and accumulation in the soil environment,but sorption mechanism is still not fully understood.In this study, sorption of 1-naphthol by plant cuticular fractions was examined to better understand the contributions of respective fraction.Toward this end,cuticular materials were isolated from the fruits of tomato by chemical method.The tomato cuticle sheet consisted of waxes (6.5 wt%),cuticular monomer (69.5 wt%),and polysaccharide (24.0 wt%).Isotherms of l-naphthol to the cuticular fractions were nonlinear (N value (0.82-0.90)) at the whole tested concentration ranges.The KodKow ratios for bulk cuticle (TC1),dewaxed cuticle (TC2),cutin (TC4),and desugared cuticle (TC5) were larger than unity,suggested that tomato bulk cuticle and cutin are much powerful solption medium.Sorption capability of cutin (TC4) was 2.4 times higher than the nonsaponifiable fraction (TC3).The 1-naphthol interactions with tomato cuticular materials were governed by both hydrophobic-type interactions and polar (H-bonding) interactions. Removal of the wax and polysaccharide materials from the bulk tomato cuticle caused a significant increase in the sorption ability of the cuticular material.There was a linear negative trend between K_(oc) values and the amount of polysaccharides or fraction's polarities ((N O)/C);while a linear positive relationship between K_(oc) values and the content of cutin monomer (linear R~2=0.993) was observed for present in the cuticular fractions.Predominant sorbent of the hydrophobic organic compounds (HOCs) in the plant cuticular fraction was the cutin monomer,contributing to 91.7% of the total sorption of tomato bulk cuticle.     

Alterations of organ histopathology and metallolhionein mRNA expression in silver barb, Puntius gonionotus during subchronic cadmium exposure

Common silver barb,Puntius gonionotus,exposed to the nominal concentration of 0.06 mg/L Cd for 60 d,were assessed for histopathological alterations(gills,liver and kidney),metal accumulation,and metallothionein(MT)mRNA expression.Fish exhibited pathological symptoms such as hypertrophy and hyperplasia of primary and secondary gill lamellae,vacuolization in hepatocytes,and prominent tubular and glomerular damage in the kidney.In addition,kidney accumulated the highest content of cadmium,more than gills and liver.Expression of MT mRNA was increased in both liver and kidney of treated fish.Hepatic MT levels remained high after fish were removed to Cd-free water.In contrast,MT expression in kidney was peaked after 28 d of treatment and drastically dropped when fish were removed to Cd-free water.The high concentrations of Cd in hepatic tissues indicated an accumulation site or permanent damage on this tissue.     

Seed selections for crystallization of calcium phosphate for phosphorus recovery

Seed induces and promotes the crystallization of calcium phosphate, and acts as carrier of the recovered phosphorus （P）. In order to select suitable seed for P recovery from wastewater, three seeds including Apatite （AP）, Juraperle （JP） and phosphate-modified Juraperle （M-JP） were tested and compared. Batch and fixed-bed column experiments of seeded crystallization of calcium phosphate were undertaken by using synthetic wastewater with 10 mg/L P phosphate. It shows that AP has bad enduring property in the crystallization process, while JP has better performance for multiple uses, and M-JP is a hopeful seed for P recovery by crystallization of calcium phosphate.