活性炭纤维的改性及对Cu~(2+)吸附性能影响的研究

采用硝酸、磷酸、磷酸二氢铵和硝酸铜水溶液对聚丙烯腈基活性炭纤维(PAN-ACF)进行浸渍改性,制备了4种改性活性炭纤维(ACF1-ACF4)。测定了改性活性炭纤维表面含氧酸性官能团、零电荷点、比表面积和孔容,评价了改性纤维对铜离子的吸附性能。结果表明改性后活性炭纤维表面含氧酸性官能团明显增加,其零电荷点相应降低,比表面积和微孔孔容增大。改性活性炭纤维对Cu2+的吸附容量显著提高,其中ACF2吸附性能最佳,其吸附容量从改性前的4.80 mg/g增加到17.32 mg/g,提高了3.6倍。     

酸碱改性活性炭及其对甲苯吸附的影响

分别用酸溶液(H_2SO_4、HNO_3、H_3PO_4)和碱溶液(NaOH或NH_3·H_2O)浸渍方法对活性炭进行改性,并对酸改性活性炭进行碱溶液二次改性处理,通过表征改性前后活性炭BET比表面积、孔结构、表面官能团等理化特征和测定其对甲苯蒸气的饱和吸附量,研究了影响活性炭吸附甲苯蒸气的关键因素.结果表明,酸改性使BET比表面积、微孔面积、微孔容积减少、表面酸性官能团增加,而碱改性呈现相反的理化特征变化.活性炭理化特征的变化可能与改性溶液的酸碱性、氧化还原性有关,并且这种相反的变化直接关系到活性炭对甲苯蒸气的吸附.3种酸改性的活性炭对甲苯蒸气饱和吸附量相对于原活性炭减少9.6%~20.0%,而两种碱改性的活性炭则增加29.2%~39.2%.相关性分析显示甲苯吸附量与BET比表面积、微孔面积、微孔容积正相关,而与表面酸性官能团负相关;多元回归分析进一步表明微孔容积和酸性官能团数量是影响活性炭甲苯吸附的关键因素.二次改性活性炭甲苯吸附量与表面含氧酸性官能团拟合结果则表明,—COOH、C＝O和—OH都对活性炭甲苯吸附能力有影响,其中—COOH影响较大.研究结果表明有效提高活性炭对甲苯吸附能力,改性宜以提高活性炭微孔容积和减小活性炭表面酸性官能团数量,特别是—COOH数量为目标导向.     

富含中孔与酸性基团的生物质炭的制备与吸附性能

以棉秆基生物质纤维为原料,采用磷酸一步活化法制备了同时富含中孔与含氧酸官能团的新型高比表面棉秆纤维基生物质活性炭,分析了浸渍比、炭化温度及保温时间等操作参数对活性炭纤维组成、得率、孔结构及表面官能团含量的影响,测定了制得的棉秆纤维基活性炭对水中对Pb(Ⅱ)与对硝基苯胺的等温吸附性能,并初步探讨了其吸附机制.结果表明,棉秆纤维基生物质炭孔结构与含氧酸基团因制备条件不同有较大变化,实验条件下制备的棉秆基活性炭纤维产率、中孔孔容与比表面的最大值分别为35.5%、0.91 cm3·g-1、1731 m2·g-1;在3∶2的浸渍比,600℃活化90 min的工艺条件下,制备的样品ACF-01的总孔孔容达1.02 cm3·g-1,比表面积为1 731 m2·g-1,微、中孔比例分别为66%与31%,中孔集中在5 nm以内,富含含氧酸官能团.样品ACF-01对水中Pb(Ⅱ)与对硝基苯胺的Langmuir最大吸附量分别为123 mg·g-1和427 mg·g-1,吸附性能远高于微孔孔容相近的商业活性炭纤维ACF-CK,这表明活性炭ACF-01的中孔和含氧酸官能团在吸附过程中发挥了重要作用.     

改性ACF低温吸附脱除烟气中NO的研究

采用自制微型反应器对粘胶基活性炭纤维(R-ACF)进行脱硝的针对性实验研究,实验结果表明:经硫酸处理再经氨水溶液改性处理后,ACF表面含氧官能团特别是含氮官能团显著增加,对低温吸附氧化脱除NOx是十分有效的,通过连续测试记录NO的吸附情况,得到R-ACF脱附前后的NO吸附效率稳态时分别达到15.2%和11.5%;求出通过负吸热空气脱附法脱附后的R-ACF脱除效率达到78.7%。验证了R-ACF具有良好的循环脱附NO效率和再生性能,具有很高的工业应用价值。     

活性炭孔结构和表面化学性质对吸附硝基苯的影响

通过对活性炭HNO3氧化及随后的N2:气氛中热处理,研究了活性炭性质对其吸附硝基苯性能的影响.以低温液氮(N2/77K)吸附测定活性炭的比表面积和孔容、孔径分布,以SEM观测活性炭表面形貌,以Boehm滴定、FTIR、零电荷点pHpzc测定及元素分析定量表征活性炭表面含氧官能团变化.结果表明, HNO3氧化可以显著改变活性炭表面化学性质,增加活性炭表面酸性含氧官能团数量,对活性炭孔隙结构影响不大.随后N2:气氛中热处理可以造成活性炭表面酸性含氧官能团分解,外表面积增大,微孔烧蚀为中孔.硝基苯在活性炭上的吸附基本符合Langmuir方程,改性后活性炭对硝基苯的吸附容量明显改变, ACNO-T、ACraw、ACNO吸附容量分别为1011.31、483.09、321.54 mg·g-1.较大的外表面积、适宜数量的中孔以及较少的酸性含氧官能团是ACNO-T对硝基苯表现出较高吸附容量的主要原因.     

ZnCl_2溶液对褐煤半焦表面性质及其中高温脱汞性能的影响

利用ZnCl_2溶液对褐煤进行浸渍后在700℃条件下热解制备改性半焦,采用N2吸附/脱附、傅里叶变换红外光谱、X射线光电子能谱等手段对ZnCl_2处理前后两种半焦表面物化性质进行了表征,在小型固定床反应器上研究了ZnCl_2溶液浸渍处理前后褐煤半焦对气态单质汞(Hg~0)的脱除性能.结果表明,经过ZnCl_2处理得到的半焦(ZSC)具有发达的孔隙结构,其表面含氧官能团含量和数量有所提高,并出现了新的C-Cl基团;在100~360℃温度范围内,制备的改性半焦ZSC的脱汞效率随温度升高而降低,但在中高温条件下仍表现出良好的脱汞性能;在化学吸附过程中,气态Hg0被C-Cl基团氧化为HgCl或HgCl_2,同时Hg~0与半焦表面含氧官能团结合生成HgO,Hg~0最终以HgCl_2或HgO的形式附着在半焦表面.     

活性炭纤维对铅镉二元离子吸附作用的研究

以活性炭纤维(Activated Carbon Fiber,ACF)为吸附剂,研究吸附剂投加量、时间、初始溶液pH和重金属浓度等影响因素对二元溶液中Pb(II)和Cd(Ⅱ)去除效果的影响。实验结果表明,ACF适应的pH范围宽(3.0～5.6),吸附平衡时间短(2 min),对Pb(Ⅱ)和Cd(Ⅱ)的吸附容量随溶液pH增加而增大。在溶液pH为5.6,ACF用量为0.004 g/L时,ACF对Pb(Ⅱ)和Cd(Ⅱ)的吸附容量分别为232.4和33.8 mg/g。ACF对Pb(Ⅱ)的吸附满足Freundlich等温吸附模型,对Cd(II)的吸附满足Langmuir等温吸附模型。环境扫描电镜照片显示ACF在吸附铅镉二元溶液后,表面聚集很多细小颗粒物,能量色散X射线光谱仪分析进一步验证颗粒物的主要组成为铅和镉元素,红外光谱分析则表明Pb(Ⅱ)和Cd(Ⅱ)与ACF的表面官能团结合实现了ACF对废水中Pb(Ⅱ)和Cd(Ⅱ)的去除。     

腐殖酸定向修饰Ce-Co铁基生物焦汞吸附机理

使用腐殖酸对铁基改性生物焦进行定向修饰,并借助固定床吸附装置考察改性后生物焦汞吸附性能,探究了不同腐殖酸负载量下的铁基改性生物焦的汞吸附能力.采用BET、XPS、FTIR表征手段,考察了定向修饰后生物焦的孔隙结构、表面元素价态及表面功能基团的组成,通过SEM扫描电镜探究生物焦微观形貌,并利用EDS能谱分析生物焦表面活性金属成分分布.结果表明,使用腐殖酸对铁基改性生物焦定向修饰后的生物焦汞脱除性能大幅提高,使用5%质量分数包裹后的生物焦汞脱除性能最高,3h单位累积汞吸附量为18025ng/g,相较于未被修饰的铁基改性生物焦汞吸附性能提高65%;负载腐殖酸后的生物焦以介孔为主,表面活性金属种类丰富,有利于单质汞的氧化;样品表面羧基、醇羟基等含氧官能团数量增加,定向修饰后生物焦表面出现大量氨基等利于重金属吸附的含氮官能团;定向修饰后的生物焦表面出现团聚现象,包裹量过高会将生物焦表面活性位点完全包裹,阻碍了氧化还原反应的进行,不利于汞的进一步氧化;汞在生物焦表面的吸附过程同时存在化学吸附与物理吸附.     

生物炭的制备及其性能研究

以生物质(小麦秸秆、稻壳和木屑)为原料,KOH为浸渍剂,采用控制热分解的方法制备生物炭,并利用差热/热重分析、Boehm滴定、红外光谱、X射线衍射、碘吸附及亚甲基蓝吸附等方法对原料和生物炭的结构及性质进行了表征。实验结果表明:木屑在热解过程中质量损失最大,其次是稻壳和小麦秸秆;不同原料在相同炭化温度下制得的生物炭所含表面含氧官能团种类和总量相近,均含有烷基、芳香基及一些含氧官能团,但pH值和吸附能力差别较大,其中小麦秸秆制备的生物炭pH值最大,木屑制备的生物炭吸附能力最强;随着炭化温度的升高,生物炭表面含氧官能团总量减少,pH值升高,芳构化程度增加;生物炭吸附性能总体呈上升的趋势。     

表面酸碱2步改性对活性炭吸附Cr(Ⅵ)的影响

研究了酸碱2步改性对活性炭吸附水相中Cr(Ⅵ)的影响.将活性炭(AC₀)在HNO₃溶液中氧化(AC₁),然后在NaOH和NaCl的混合液中处理(AC₂).分别采用平衡和连续吸附试验,测试Cr(Ⅵ)的吸附特征.以Boemh滴定法定量检测活性炭表面酸性官能团数量,结合元素分析结果定量表征活性炭的表面含氧官能团变化;以低温液氮(N₂/77K)吸附法分析活性炭的比表面积和孔径结构.结果表明:活性炭经2步改性后,其Cr(Ⅵ)的吸附容量和吸附速度均显著改变.吸附容量和吸附速度大小依次为AC₂>AC₁>AC₀.改性活性炭表面积下降,表面含氧酸性官能团数量增加.HNO₃液相氧化处理可使活性炭表面生成带正电含氧酸性官能团,第2步改性后活性炭表面酸性官能团H⁺部分被Na⁺取代,使活性炭表面酸性降低.表面较多的含氧酸性官能团(与AC₀相比)、适宜的表面pH(与AC₁相比)是AC₂所表现出较高Cr(Ⅵ)吸附容量的主要原因.     

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.     

Degradation of metabolites accumulated of benzo[a]pyrene by coupling Penicillium Chrysogenum with KMnO4

Several main metabolites of benzo[a]pyrene （BaP） formed by Penicillium chrysogenum, Benzo[a]pyrene-1,6-quinone （BP 1,6- quinone）, trans-7,8-dihydroxy-7,8-dihydrobenzo[a]pyrene （BP 7,8-diol）, 3-hydroxybenzo[a]pyrene （3-OHBP）, were identified by high-performance liquid chromatography （HPLC）. The three metabolites were liable to be accumulated and were hardly further metabolized because of their toxicity to microorganisms. However, their further degradation was essential for the complete degradation of BaP. To enhance their degradation, two methods, degradation by coupling Penicillium chrysogenum with KMnO4 and degradation only by Penicillium chrysogenum, were compared; Meanwhile, the parameters of degradation in the superior method were optimized. The results showed that （1） the method of coupling Penicillium chrysogenum with KMnO4 was better and was the first method to be used in the degradation of BaP and its metabolites; （2） the metabolite, BP 1,6-quinone was the most liable to be accumulated in pure cultures; （3） the effect of degradation was the best when the concentration of KMnO4 in the cultures was 0.01% （w/v）, concentration of the three compounds was 5 mg/L and pH was 6.2. Based on the experimental results, a novel concept with regard to the bioremediation of BaP-contaminated environment was discussed, considering the influence on environmental toxicity of the accumulated metabolites.     

Impact of atrazine and nitrogen fertilizers on the sorption of chlorotoluron in soil and model sorbents

Sorption of chlorotoluron in ammonium sulfate, urea and atrazine multi-solutes system was investigated by batch experiments. The results showed application of nitrogen fertilizers to the soil could affect the behavior of chlorotoluron. At the same concentration of N, sorption of chlorotoluron decreased as the concentration of atrazine increased on the day 0 and 6 in soil, respectively. The sorption of chlorotoluron increased from 0 to 6 d when soils were preincubated with deionized water, ammonium sulfate and urea solution for 6 d. That indicated incubation time was one of the most important factors for the sorption of chlorotoluron in nitrogen fertilizers treatments. The individual sorption isotherms of chlorotoluron in rubbery polymer and silica were strictly linear in single solute system, but there were competition sorption between pesticides or between pesticides and nitrogen fertilizers. That indicated the sorption taken place by concurrent solid-phase dissolution mechanism and sorption on the interface of water-organic matter or water-mineral matter.     

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.