甲烷催化还原NOx中Co基/分子筛催化剂的助剂和载体优化

采用共浸渍法制备了系列Co基/分子筛催化剂,在固定床催化反应器中考察了不同催化剂在甲烷催化还原NO_x中的催化行为,优化了Co基/分子筛催化剂的助剂和载体,并通过催化表征手段阐明了其构效关系.结果表明,Fe和SAPO-34分别作为优化助剂和载体制备得到的Co-Fe/SAPO-34催化剂具有最高的催化活性,在450℃时,NO_x的最大转化率可以达到52.7%.CO_2对Co-Fe/分子筛催化剂活性无明显抑制作用,H_2O对催化剂的活性抑制是可逆的,SO_2对催化剂活性抑制作用明显.Co-Fe/SAPO-34催化剂表面钴物种以CoO和Co(OH)_2为主,Co-Fe/ZSM-5催化剂表面钴物种则以Co_3O_4和Co(OH)_2为主,Co-Fe/Beta催化剂则可能以CoO、Co Al2O_4和Co_3O_4为主.各Co-Fe/分子筛催化剂表面Fe~(2+)/Fe~(3+)含量比依次为Co-Fe/ZSM-5(3.98)Co-Fe/SAPO-34(0.52)Co-Fe/Beta(0.43).活性组分钴物种的形态和合适的Fe~(2+)/Fe~(3+)含量比对Co-Fe/分子筛催化剂上甲烷催化还原NO_x至关重要.Co-Fe/分子筛催化剂上CH_4-SCR反应机制为:NO在Br?nsted酸位上吸附氧化成NO~+,同时CH_4在Br?nsted酸位上吸附活化成—C=O和—COO等活性物种,生成的NO~+在Co2+和Fe~(3+)等催化活性位上转化成硝酸盐等中间产物,中间产物硝酸盐与活化物种(—C=O和—COO)反应生成N_2和CO_2.     

Effects of zeolites on cultures of marine micro-algae

GOAL, SCOPE AND BACKGROUND: The cation-exchange capacity of zeolites is well known and has been increasingly explored in different fields with both economic and environmental successes. In aquatic medium with low salinity, zeolites have found multiple applications. However, a review of the literature on the applications of zeolites in salt waters found relatively few articles, including some recently published papers. The purpose of this review is to present the state-of-the-art on applications of using zeolites for amending the trace elemental contents of salt water as well as the implications of this property for promoting marine micro-algal growth. MAIN FEATURES: This paper deals with the following features: Sorption capacity of zeolites including 1. application of zeolites in saltwater, 2. the role of silicon and zeolites on cultures of micro-algae, and 3. the role of organically chelated trace metals. RESULTS: The following competing factors have been identified as effects of zeolites on algal growth in salt water: (i) ammonia decrease: growth inhibition reduced; (ii) macro-nutrients increase, mainly silicon: stimulation of silicon-dependent algae; (iii) trace metals increase (desorption from zeolites) or decrease (adsorption): inhibition or stimulation, depending on the nature of the element and its concentration; and, (iv) changes in the chelating organics exudation: inhibition or stimulation of growth, depending on the (a) nature of the complexed element; (b) bioavailability of the complex; and (c) concentration of the elements simultaneously present in inorganic forms. DISCUSSION: Zeolites have been capable of stimulating the growth of the silicon-demanding marine micro-algae, like diatoms, mainly because they can act as a silicon buffer in seawater. Zeolites can also influence the yield of non-silicon-demanding algae, because the changes they can cause (liberation and adsorption of trace elements) in the composition of the medium. CONCLUSIONS: Zeolites have been capable of stimulating the growth of the marine micro-algae. However, the extent of ion exchange between zeolite and seawater, which conditions the effects, will depend on several factors: (1) initial metal concentration in seawater; (2) levels of trace metals in the zeolites (contaminants); (3) characteristics of the zeolites in terms of both ion-exchange capacity and specific affinities for the different cations; (4) quantity of zeolite per litre of solution; (5) pH and (6) response of the organism in terms of liberation of organic ligands. RECOMMENDATIONS AND PERSPECTIVES: RECOMMENDATIONS: Therefore, a previous investigation in each particular case is recommended, in order to select the zeolitic characteristics and concentrations that will maximize the algal yield. PERSPECTIVES: Stimulation of phytoplankton growth can be economically relevant since phytoplankton constitutes the basis of the marine food webs and is required in fish farming nurseries in the marine aquaculture industry. Zeolites are cheap, only small amounts (few milligrams per liter of culture) are required and the addition of some micro-nutrients may be omitted. Therefore, the inclusion of zeolites in algal cultures in aquaculture may have economic advantages.     

DETRITUS ABUNDANCE AND BENTHIC INVERTEBRATE CATCH IN ARTIFICIAL SUBSTRATE SAMPLES FROM MOUNTAIN STREAMS1

ABSTRACT: Artificial substrates were designed using rock filled polyethylene bags which were perforated with holes. The substrates trapped waterborne sediment and detritus which enhanced microhabitat complexity. Colonization was compared in side-by-side tests with multiple plate samplers in mountain streams ranging from second to seventh order. After 41 days the bag samples contained more sediment and detritus and more animals than did multiple plates. Plastic bags exceeded multiple plate samples by a factor of nearly 8 for individuals and 1.5 for taxa expressed as numbers/sampler. Although detritus amounts differed significantly between samplers, catch composition was similar in habitat preference and functional groups. Most taxa were “lotic erosional” or “lotic erosional-depositional” detritivores. The plastic bags better represented the streambed fauna judged by their greater similarity to dip net samples. Bag samplers had 4.5 × the colonization area of multiple plates, hence would be expected to support more species. Catch/m² of colonization area was not significantly different between samplers. Functionally the plastic bags act as detritus retention devices, offering a diverse, highly dynamic microhabitat for colonization. Results are interpretable in terms of research on microdistribution of stream benthos and the river continuum model. This study supports the conclusion that stream benthos abundance and diversity are related to the amount of detritus. Maximum diversity and numbers of individuals occurred in samples from third and fourth order streams. Grazers reached peak abundances in the same streams where the continuum model predicts P>R Shredders reached maximum abundances in third and fourth order streams where the riparian canopy was greatest. Predator abundance changed little with stream size. Although bag samples required more sorting time, the samplers are catch effective, inexpensive, and adaptable.     

2种孔径沸石分子筛对水中土霉素的去除研究

选择2种不同孔径的亲水性沸石分子筛5A和13X作为吸附材料,对水中的土霉素(OTC)进行吸附和脱附实验,重点考察pH、温度对吸附的影响,进行吸附动力学和热力学的计算,分析亲水性沸石分子筛的吸附机制.结果表明,2种分子筛对OTC均有较大的吸附量,吸附过程可用单层吸附模型拟合,在温度为298K、pH=7.0条件下5A和13X的饱和吸附量分别为667mg/g和1429mg/g;同一温度下13X的吸附量明显大于5A;二级动力学方程能较好地描述2种分子筛对OTC的吸附动力学,在解吸时,5A和13X分别得到91%和95%的OTC脱附率;溶液pH值对吸附影响较大,中性条件下分子筛对OTC的吸附量达到最大;热力学计算显示2种分子筛对OTC的吸附均属于自发的吸热反应,综合表观为化学氢键力占主导作用.     

改性沸石和铁粉的复合材料处理水中六价铬的研究

利用海藻酸盐的凝胶化将零价铁粉固定于改性沸石表面,制得复合材料,以期在保留改性沸石的吸附性的同时增加铁粉的还原性.复合材料的扫描电镜图片可以看出铁粉分散嵌于海藻酸钙薄层,同时海藻酸钙不会阻碍Cr(VI)与改性沸石的接触.实验考察材料去除水中Cr(VI)性能,结果表明:复合材料,改性沸石,铁粉的除Cr(VI)效率分别为:74.1%,38.4%,9.1%,这得益于改性沸石和铁粉相互的协同作用. 对反应后复合材料进行XPS检测,其表面含有Cr3+,Cr6+表明了材料吸附能力同时还具有还原性.并且对Cr(VI)去除的现象能用伪二级吸附动力学方程描述.平衡吸附量qe和反应速率常数k呈相反的变化趋势.铁粉含量为5.4%的材料性能较好:qe为0.96mg/g, k为0.011g/(mg×h);在Cr(VI)浓度为70mg/L时,上述铁含量的复合材料仍具有较高的处理性能,其qe和k分别为 1.29mg/g, 0.0094g/(mg×h).     

A long-term study comparing membrane filtration with Colilert defined substrates in detecting fecal coliforms and Escherichia coli in natural waters

Assessment methods for determining the presence and number of fecal bacteria and Escherichia coli (E. coli) in waters, foodstuffs, sewage effluent, and soils have evolved from multiple tube fermentations (MTF's) to membrane filtrations (MF's) to, most recently, defined substrate technologies (DST's). Mounting evidence indicates Colilert DST (IDEXX, Westbrook, ME) to be a versatile assessment technique for detecting and enumerating E. coli over a range of applications. This study compared the performance of Colilert DST with a confirmed standard MF technique using m-FC broth (Millipore, Bedford, MA) in assessing E. coli in ten different environmental water samples obtained monthly over a 3-year period from the upper Appomattox River, VA. For the duration of the study, E. coli counts measured by Colilert DST were positively correlated (Pearson's correlation coefficient=0.956; slope=0.979; p<0.0001) with E. coli counts measured by confirmed MF procedures. The results of a two-factor ANOVA revealed that Colilert DST counts compared equally to confirmed MF counts by year (p=0.974), by stream sampled (p=1.0), and by season (p=0.696). E. coli counts were significantly lower during cold season months (Dec/Jan/Feb) than during warm season months (Jun/Jul/Aug) for each year contributing to marked variation in sample quality. Counts obtained by Colilert DST compared equally to those obtained by MF across all samples and dates for the three years. Colilert DST presents a laboratory protocol that is simpler to manage, quicker to process, and easier to quantify results than MF. These factors, plus the enhanced precision and versatility of Colilert DST over the span of this three-year study attests to its suitability for testing ambient surface waters.     

不同类型组合与滞留时间下串联型基质床净污效果

研究了不同基质床组合和不同滞留时间下对模拟生活污水的净化效果,并对2个影响因素进行二维方差分析。选取砾石、炉渣和沸石作为级配基质,构建由表流型基质床和潜流型基质床组成的4种三级串联基质床组合,设定污水滞留时间为1、3和5h。结果表明,不同基质床组合的净污效果存在显著性差异,其中由2个表流型基质床和1个潜流型基质床组成的系统对CODMn、NH4＋-N和PO34--P的去除率最高。不同滞留时间的净污效果也存在显著性差异,且污水在系统中滞留时间越长,去污效率越高。尽管不同基质床组合和滞留时间都对CODMn、NH4＋-N和PO34--P去除率有着显著性影响,但基质床组合与滞留时间的交互作用对去除率影响却不显著。     

Transportation fuel production by combination of LDPE thermal cracking and catalytic hydroreforming

Fuel production from plastics is a promising way to reduce landfilling rates while obtaining valuable products. The usage of Ni-supported hierarchical Beta zeolite (h-Beta) for the hydroreforming of the oils coming from LDPE thermal cracking has proved to produce high selectivities to gasoline and diesel fuels (>80%). In the present work, the effect of the Ni loading on Ni/h-Beta is investigated in the hydroreforming of the oils form LDPE thermal cracking. h-Beta samples were impregnated with Ni nitrate, calcined and reduced in H₂ up to 550 °C to achieve different Ni contents: 1.5%, 4%, 7% and 10%. Larger and more easily reducible metal particles were obtained on Ni 7%/h-Beta and Ni 10%/h-Beta. Hydroreforming tests were carried out in autoclave reactor at 310 °C, under 20 bar H₂, for 45 min. Ni content progressively increased the amount of gases at the expenses of diesel fractions, while gasoline remained approximately constant about 52–54%. Maximum selectivity to automotive fuels (～81%) was obtained with Ni 7%/h-Beta. Ni loading also enhanced olefins saturation up to Ni 7%/h-Beta. High cetane indices (71–86) and octane numbers (89–91) were obtained over all the catalysts. Regarding the different studied Ni contents, Ni 7%/h-Beta constitutes a rather promising catalyst for obtaining high quality fuels from LDPE thermal cracking oils.     

1株高效BBP降解菌的分离与特性研究

从湖北省荆沙河泥样中富集培养分离得到了1株能够以邻苯二甲酸丁基苄基酯为唯一碳源和能源生长的细菌并命名为HS-B1.采用形态学、生理生化和16S rDNA序列分析对其进行了鉴定,发现HS-B1是1株杆状、需氧、革兰氏阴性细菌,接触酶呈阳性反应,氧化酶呈阴性反应,不产硫化氢气体,且该菌的16S rDNA序列与琼氏不动杆菌(Acinetobacter junii)的相似性高达99%.因此初步鉴定该菌株为不动杆菌(Acinetobacter sp.).摇瓶实验表明,菌株HS-B1生长和BBP降解的最适培养条件为35℃,pH 8.0.采用0.10 mmol.L-1非离子型表面活性剂吐温-80提高了BBP在水溶液中的表观溶解度,发现在最适培养条件下,HS-B1能够在48 h内将浓度为1 000 mg.L-1BBP完全降解,证明是一株高效降解菌.底物广谱性实验中,菌株HS-B1也能够有效利用DMP、DEP、DBP等邻苯二甲酸酯类化合物,说明该菌株在处理邻苯二甲酸酯类化合物的污染治理中有独特的应用潜力.     

4种人工湿地填料的f2噬菌体吸附特性

以无烟煤、钢渣、沸石和镁橄榄石这4种人工湿地填料为研究对象,以f2噬菌体为模型病毒,通过静态和动态吸附试验,考察和比较了4种填料的f2噬菌体吸附效果与特性.静态吸附结果表明,4种填料的f2噬菌体吸附去除效果依次为无烟煤>钢渣>镁橄榄石≈沸石,其中无烟煤对f2噬菌体的吸附过程经历了快、中、慢3个吸附阶段,且随着无烟煤投加量的增加,f2噬菌体去除率逐渐增加,优化的无烟煤投加量为8.0 g(固液比1∶12.5);4种填料的f2噬菌体等温吸附满足Freundlich和Langmuir等温吸附方程;无烟煤和钢渣的f2噬菌体吸附满足准二级吸附动力学,它们的理论平衡吸附量分别为3.35×108PFU·g-1和2.56×108PFU·g-1,与试验条件下得到的平衡吸附量基本一致;液膜扩散过程为无烟煤和钢渣吸附f2噬菌体的速率控制步骤,但不是唯一控制步骤.动态吸附结果表明,吸附柱的f2噬菌体吸附过程经历了适应、吸附、脉冲吸附和动态平衡这4个阶段,达到动态平衡时的f2噬菌体对数去除率大于2.55 lg.