Mesoporous silicas synthesis and application for lignin peroxidase immobilization by covalent binding method

Immobilization of enzymes on mesoporous silicas (MS) allows for good reusability. MS with two-dimensional hexagonal pores in diameter up to 14.13 nm were synthesized using Pluronic P123 as template and 1,3,5-triisopropylbenzene as a swelling agent in acetate buffer. The surface of MS was modified by the silanization reagents 3-aminopropyltriethoxysilane. Lignin peroxidase (LiP) was successfully immobilized on the modified MS through covalent binding method by four agents: glutaraldehyde, 1,4- phenylene diisothiocyanate, cyanotic chloride and water-soluble carbodiimide. Results showed that cyanotic chloride provided the best performance for LiP immobilization. The loaded protein concentration was 12.15 mg/g and the immobilized LiP activity was 812.9 U/L. Immobilized LiP had better pH stability. Acid Orange II was used to examine the reusability of immobilized LiP, showing more than 50% of the dye was decolorized at the fifth cycle.     

Immobilization study of biosorption of heavy metal ions onto activated sludge

Activated sludge was immobilized into Ca-alginate beads via entrapment, and biosorption of three heavy metal ions, copper(Ⅱ), zinc(Ⅱ), and chromimum(Ⅱ), from aqueous solution in the concentration range of 10-100 mg/L was studied by using both entrapped activated sludge and inactivated free biomass at pH≤5. A biphasic metal adsorption pattern was observed in all immobilized biomass experiments. The biosorption of metal ions by the biosorbents increased with the initial concentration increased in the medium. The adsorption rate of immobilized pre-treated activated sludge(PAS) was much lower than that of free PAS due to the increase in mass transfer resistance resulting from the polymeric matrix. Biosorption equilibrium of beads was established in about 20 h and the adsorbed heavy metal ions did not change further with time. No significant effect of temperature was observed in the test for free biomass while immobilized PAS appeared to be strong temperature dependent in the test range of 10 and 40℃.Besides, the content of activated sludge in the calcium alginate bead has an influence on the uptake of heavy metals. The sorption equilibrium was well modeled by Langmuir isotherm, implying monomolecular adsorption mechanism. Carboxyl group in cell wall played an important role in surface adsorption of heavy metal ions on PAS.     

The key role of inoculated sludge in fast start-up of sequencing batch reactor for the domestication of aerobic granular sludge

Two types of inoculated sludges, granular sludge that had been stored at-20°C and activated sludge, were investigated for the domestication of aerobic granular sludges(AGSs in sequencing batch reactors(SBRs). The results showed that using the stored granular sludge as inoculation sludge could effectively shorten the domestication time of AGS and yielded mature granular sludge after 22 days of operation. The AGS domesticated by stored granular sludge had better biomass and sedimentation properties; its MLSS and SVI reached8.55 g/L and 35.27 mL/g, respectively. The removal efficiencies for chemical oxygen demand(COD), ammonium nitrogen(NH_4~+-N) and total phosphorus(TP) reached 90.76%, 97.39% and 96.40%, respectively. By contrast, 54 days were needed to obtain mature granules using activated sludge. The microbial community structure was probed by using scanning electron microscopy(SEM) and high-throughput sequencing. The results showed that the diversity of the microbial community in mature granules was reduced when stored granular sludge rather than activated sludge was employed as inoculation sludge, and the dominant microbes were changed. The dominant species in mature granules domesticated using stored granular sludge were Zoogloea, Acidovorax and Tolumonas at the genus classification level, while the dominant species were Zoogloea and TM7-genera in granules developed from activated sludge.     

Biodegradation of phenol by free and immobilized Acinetobacter sp. strain PD12

A new phenol-degrading bacterium with high biodegradation activity and high tolerance of phenol, strain PD 12, was isolated from the activated sludge of Tianjin Jizhuangzi Wastewater Treatment Facility in China. This strain was capable of removing 500 mg phenol/L in liquid minimal medium by 99.6% within 9 h and metabolizing phenol at concentrations up to 1100 mg/L. DNA sequencing and homologous analysis of 16S rRNA gene identified PD12 to be an Acinetobacter sp. Polyvinyl alcohol （PVA） was used as a gel matrix to immobilize Acinetobacter sp. strain PDI2 by repeated freezing and thawing. The factors affecting phenol degradation of immobilized cells were investigated, and the results showed that the immobilized cells could tolerate a high phenol level and protected the bacteria against changes in temperature and pH. Storage stability and reusability tests revealed that the phenol degradation functions of immobilized cells were stable after reuse for 50 times or storing at 4℃ for 50 d. These results indicate that immobilized Acinetobacter sp. strain PD 12 possesses a good application potential in the treatment of phenol-containing wastewater.     

Comparison of four supports for adsorption of reactive dyes by immobilized beads

Four materials, sodium carboxymethylcellulose （Na-CMC）, sodium alginate （SA）, polyvinyl alcohol （PVA）, and chitosan （CTS）, were prepared as supports for entrapping fungus Aspergillusfumigatus. The adsorption of synthetic dyes, Reactive Brilliant Blue KN- R, and Reactive Brilliant Red K-2BP, by these immobilized gel beads and plain gel beads was evaluated. The adsorption efficiencies of Reactive Brilliant Red K-2BP and Reactive Brilliant Blue KN-R by CTS immobilized beads were 89.1% and 93.5% in 12 h, respectively. The adsorption efficiency by Na-CMC immobilized beads was slightly lower than that of mycelial pellets. But the dye culture mediums were almost completely decolorized in 48 h using the above-mentioned two immobilized beads （exceeding 95%）. The adsorption efficiency by SA immobilized beads exceeded 92% in 48 h. PVA-SA immobilized beads showed the lowest adsorption efficiency, which was 79.8% for Reactive Brilliant Red K-2BP and 92.5% for Reactive Brilliant Blue KN-R in 48 h. Comparing the adsorption efficiency by plain gel beads, Na-CMC plain gel beads ranked next to CTS ones. SA and PVA-SA plain gel beads hardly had the ability of adsorbing dyes. Subsequently, the growth of mycelia in Na-CMC and SA immobilized beads were evaluated. The biomass increased continuously in 72 h. The adsorption capacity of Reactive Brilliant Red K-2BP and Reactive Brilliant Blue KN-R by Na-CMC immobilized beads was 78.0 and 86.7 mg/g, respectively. The SEM micrographs show that the surface structure of Na-CMC immobilized bead is loose and finely porous, which facilitates diffusion of the dyes.     

Effect of seed sludge on characteristics and microbial community of aerobic granular sludge

Aerobic granular sludge was cultivated by using different kinds of seed sludge in sequencing batch airlift reactor.The influence of seed sludge on physical and chemical properties of granular sludge was studied;the microbial community structure was probed by using scanning electron microscope and polymerase chain reaction-denaturing gradient gel electrophoresis(PCR-DGGE).The results showed that seed sludge played an important role on the formation of aerobic granules.Seed sludge taken from beer wastewater treatment plant(inoculum A) was more suitable for cultivating aerobic granules than that of sludge from municipal wastewater treatment plant(inoculum B).Cultivated with inoculum A, large amount of mature granules formed after 35 days operation, its SVI reached 32.75 mL/g, and SOUR of granular sludge was beyond 1.10 mg/(g·min).By contrast, it needed 56 days obtaining mature granules using inoculum B.DGGE profiles indicated that the dominant microbial species in mature granules were 18 and 11 OTU when inoculum A and B were respectively employed as seed sludge.The sequencing results suggested that dominant species in mature granules cultivated by inoculum A were Paracoccus sp., Devosia hwasunensi, Pseudoxanthomonas sp., while the dominant species were Lactococcus raffinolactis and Pseudomonas sp.in granules developed from inoculum B.     

Advanced treatment of biologically pretreated coal gasification wastewater by a novel heterogeneous Fenton oxidation process

Sewage sludge from a biological wastewater treatment plant was converted into sewage sludge based activated carbon(SBAC) with Zn Cl2 as activation agent, which was used as a support for ferric oxides to form a catalyst(Fe Ox/SBAC) by a simple impregnation method.The new material was then used to improve the performance of Fenton oxidation of real biologically pretreated coal gasification wastewater(CGW). The results indicated that the prepared Fe Ox/SBAC significantly enhanced the pollutant removal performance in the Fenton process, so that the treated wastewater was more biodegradable and less toxic. The best performance was obtained over a wide p H range from 2 to 7, temperature 30°C, 15 mg/L of H2O2 and 1 g/L of catalyst, and the treated effluent concentrations of COD, total phenols,BOD5 and TOC all met the discharge limits in China. Meanwhile, on the basis of significant inhibition by a radical scavenger in the heterogeneous Fenton process as well as the evolution of FT-IR spectra of pollutant-saturated Fe Ox/BAC with and without H2O2, it was deduced that the catalytic activity was responsible for generating hydroxyl radicals, and a possible reaction pathway and interface mechanism were proposed. Moreover, Fe Ox/SBAC showed superior stability over five successive oxidation runs. Thus, heterogeneous Fenton oxidation of biologically pretreated CGW by Fe Ox/SBAC, with the advantages of being economical, efficient and sustainable, holds promise for engineering application.     

Comparison of four supports for adsorption of reactive dyes by immobilized Aspergillus fumigatus beads

Four materials, sodium carboxymethylcellulose (Na-CMC), sodium alginate (SA), polyvinyl alcohol (PVA), and chitosan (CTS), were prepared as supports for entrapping fungus Aspergillus fumigatus. The adsorption of synthetic dyes. Reactive Brilliant Blue KN-R, and Reactive Brilliant Red K-2BP, by these immobilized gel beads and plain gel beads was evaluated. The adsorption efficiencies of Reactive Brilliant Red K-2BP and Reactive Brilliant Blue KN-R by CTS immobilized beads were 89.1% and 93.5% in 12 h, respectively. The adsorption efficiency by Na-CMC immobilized beads was slightly lower than that of mycelial pellets. But the dye culture mediums were almost completely decolorized in 48 h using the above-mentioned two immobilized beads (exceeding 95%). The adsorption efficiency by SA immobilized beads exceeded 92% in 48 h. PVA-SA immobilized beads showed the lowest adsorption efficiency, which was 79.8% for Reactive Brilliant Red K-2BP and 92.5% for Reactive Brilliant Blue KN-R in 48 h. Comparing the adsorption efficiency by plain gel beads, Na-CMC plain gel beads ranked next to CTS ones. SA and PVA-SA plain gel beads hardly had the ability of adsorbing dyes. Subsequently, the growth of mycelia in Na-CMC and SA immobilized beads were evaluated. The biomass increased continuously in 72 h. The adsorption capacity of Reactive Brilliant Red K-2BP and Reactive Brilliant Blue KN-R by Na-CMC immobilized beads was 78.0 and 86.7 mg/g, respectively. The SEM micrographs show that the surface structure of Na-CMC immobilized bead is loose and finely porous, which facilitates diffusion of the dyes.     

Immobilized reactor for rapid destruction of recalcitrant organics and inorganics in tannery wastewater

The wastewater discharged from tanneries lack biodegradability due to the presence of recalcitrant compounds at significant concentration. The focal theme of the present investigation was to use chemo-autotrophic activated carbon oxidation(CAACO) reactor, an immobilized cell reactor using chemoautotrophs for the treatment of tannery wastewater. The treatment scheme comprised of anaerobic treatment, sand filtration, and CAACO reactor, which remove COD, BOD, TOC, VFA and sulphides respectively by 86%, 95%, 81%,71% and 100%. Rice bran mesoporous activated carbon prepared indigenously and was used for immobilization of chemoautotrophs. The degradation of xenobiotic compounds by CAACO was confirmed through HPLC and FT-IR techniques.     

Catalysts for decomposing ozone tail gas

The preparation of immobilizing-catalysts for decomposing ozone by using dipping method was studied. XRD, XPS and TEM were used to characterize the catalysts. The three kinds of catalysts were selected preferentially, and their catalytic activities were investigated. The results showed that the catalyst with activated carbon dipping acetate( active components are Mn:Cu = 3:2, active component proportion in catalyst is 15%, calcination temperature is 200℃ ) has the best catalytic activity for ozone decomposing. One gram of catalyst can decompose 17.6g ozone at initial ozone concentration of 2.5g/m^3 and the residence time in reactor of 0.1s. The experimental results also indicated that humidity of reaction system had negative effect on catalytic activity.     

聚乙烯醇固定化微生物新方法的研究

为克服聚乙烯醇(PVA)固定化微生物存在的缺点,本文以聚乙烯醇(PVA)和海藻酸钠(SA)为固定化载体,采用5种不同固定化方法,即PVA-硼酸法、PVA-硝酸盐法、PVA-磷酸盐法、PVA-硫酸盐法、PVA冻融法,制备固定化活性污泥颗粒,研究了固定化微生物颗粒的机械稳定性及生物活性.结果表明,PVA-硫酸盐法制得的固定化微生物颗粒具有较高的机械稳定性和生物活性,该法为固定化微生物的较好方法.对PVA-硫酸盐法固定化条件进行了优化,当PVA浓度为12％、Na2SO4浓度为0.5 mo1·L-1,在含有2％ CaCl2的饱和硼酸中交联1h,Na2SO4溶液中交联4h,得到的固定化微生物颗粒活性较高.通过对PVA-硫酸盐法制备的固定化颗粒的稳定性考察发现,颗粒的机械稳定性和生物活性随时间变化,最后逐渐趋于稳定,使用寿命在30 d以上,具有良好的稳定性.     

选择性抑制技术测定活性污泥细菌、真菌活性分布的适用性分析

以葡萄糖为唯一碳源,采用放线菌酮和硫酸链霉素作为真菌、细菌抗生素以抑制其活性,以基质诱导耗氧速率为考察指标,以好氧污泥、土壤污泥以及厌氧污泥为研究对象,对选择性抑制技术测定活性污泥中细菌、真菌分布的适用性进行了系统评估.随抗生素的投加,好氧污泥和土壤污泥的耗氧速率减小,厌氧污泥的耗氧速率反而增大,此方法对厌氧污泥不适用.当放线菌酮为1mg/g、硫酸链霉素为2mg/g时,抗生素对好氧污泥的抑制功效即D值为1,但并不能通过改变投药量使土壤污泥D值接近于1,说明所用抗生素对好氧污泥活性具有选择性抑制作用,而对土壤污泥活性抑制不具选择性.结果表明,选择性抑制技术能够用于测定好氧活性污泥中细菌和真菌的数量分布,但也存在着抗生素抑制作用失效、不完全抑制和实验结果精确度不高等问题,因此需要在抗生素选择、微生物活性指标选择等方面进行更深入的研究.     

固定化硝化菌去除废水中氨氮工艺的研究

采用聚乙烯醇－硼酸包埋固定化法,选用ＰＶＡ为包埋载体,粉末活性炭作为无机载体,包埋固定Ａ／Ｏ生物脱氮系统中的再经驯化过的硝化污泥,制成固定化硝化菌颗粒。     

Immobilization of microorganisms using carrageenan gels coated with chitosan and application to biodegradation of 4 chlorophenol

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不同方法处理乳品废水效果的比较研究

采用SBR工艺对悬浮活性污泥法、包埋固定化活性污泥法和活性炭吸附活性污泥法处理乳品废水效果进行了比较研究。试验结果表明,进水CODcr为395.55 mg/L的乳品废水,在水力停留时间（HRT）为24 h,采用活性炭吸附活性污泥法处理后的乳品废水CODcr的去除率为77.31%;采用包埋固定化法处理后的乳品废水CODcr的去除率为73.18%;采用悬浮活性污泥法处理后的乳品废水CODcr去除率为55.14%。结果表明,上述三种方法处理进水CODcr相同的乳品废水的效果排序为：活性炭吸附活性污泥法〉包埋固定化活性污泥法〉悬浮活性污泥法。     

ECOSUNIDE工艺中活性污泥生物代谢活性的测定研究

利用差压仪测定原理,设计了在差压瓶中密闭投加基质的试验方法,测定了ECOSUNIDE工艺和其它4个不同工艺的污水处理厂曝气池混合液中活性污泥的生物代谢能力,通过内源呼吸速率和投加基质后的外源呼吸速率来表达生物代谢能力,采用各自的比呼吸速率用来比较单位污泥浓度的生物代谢活性能力。研究结果表明,具有高效脱氮除磷能力的ECOSUNIDE工艺中活性污泥在1～2 d时段内的比内源呼吸速率为43 mg O2(/gVSS.d),投加醋酸钠和氨氮后比外源呼吸分别为450和283 mg O2(/gVSS.d),均高于其它不同工艺的普通进水方式污水处理厂混合液相应的呼吸速率。该工艺在提高活性污泥中异养菌和自养菌代谢能力,缩短污染物去除时间上有较明显的优势。     

印染废水活性污泥代谢状态光偏转快速检测法

针对现有活性污泥检测方法过程繁琐、耗时长、检测结果滞后的局限,提出了光偏转快速检测法.在污泥负荷为0.33KgCOD/（kg MLSS·d）、水力停留时间为15h的印染废水完全混合式活性污泥系统中,投放粒径4mm、具有20μm微孔结构的聚乙烯醇（PVA）凝胶小球以负载微生物,并在小球达到稳定状态后,对其表面处因外界溶液与微生物代谢产物交换产生的浓度梯度变化,借助光斑分析仪进行光偏转检测,同时测定与光偏转检测结果相对应的15h后的出水COD及COD去除率.连续10个月的检测发现,小球中富集的主要为细菌,当进水COD由91.95mg/L增至519.4mg/L时,小球的光偏转值从229.51μm增加至299.97μm,COD去除率从16.03%提高至66.99%;当DO浓度为1.5mg/L~5mg/L时,小球光偏转值在DO=4mg/L时增至最大为309.3mg/L,对应状态下COD去除率增至最大为61.18%;在pH值为6~9时,小球光偏转值在pH=7时增至最大为293.96μm,对应状态下COD去除率也达到最大值为64.83%;当重金属Cr³⁺浓度增至50mg/L时,微生物活性逐渐受到抑制,小球光偏转值在Cr³⁺浓度为20mg/L时降至269.7μm,随后随着Cr³⁺浓度的增加,微生物细胞受损,胞内物质溶出,小球光偏转值有所增大,对应状态下COD去除率从52.5%持续降低至25.73%.结果表明：该方法可快速获得活性污泥代谢状态变化信息,且依据特定条件下小球光偏转值变化能够预测随后印染废水COD的去除效果.利用三维荧光光谱初步探究了微生物代谢引发光偏转的机理,发现参与微生物代谢的主要有机物为酪氨酸、芳香类蛋白及色氨酸.     

固定化蛋白酶对废水中蛋白质的水解效果与机理

采用吸附方法将蛋白酶固定于活性炭、大孔树脂和硅胶载体上,分别研究了3种载体蛋白酶固定化效果,酶活性以及对淀粉加工黄浆废水中蛋白质的水解效果.批次试验结果表明,3种载体蛋白酶固定效果分别为:硅胶20.31%,大孔树脂37.85%,活性炭61.95%;酶活性最高时pH均为5.5;酶活性分别为3.6mg/min、21.48mg/min和18.68mg/min .水解后,大孔树脂和活性炭固定酶的水解产物氨基酸总量分别较水解前增加21.26倍和14.6倍;产物中检出1 6种氨基酸,较水解前增加2种.以大孔树脂为载体构建固定化酶反应器进行连续进水试验,结果表明:进水中蛋白质浓度明显影响反应器的水解效果,当其蛋白质浓度与反应器的酶浓度匹配时(500mg/L) ,反应器能获得80 %蛋白质水解率和36.1%有机物水解酸化率.挥发性水解产物组成以乙醇和乙酸为主,分别占50.3%,33.3%.为乙醇型水解.     

菌株qy37吸附包埋固定化的脱氮效果研究

以对异养硝化好氧反硝化菌菌株qy37固定化后的脱氮效果为考察标准,分别研究了不同的吸附、包埋固定化载体和方式对固定化脱氮效果的影响。研究结果表明:以碳纳米管、多孔陶粒、活性炭、石墨四种材料为吸附固定化载体时,纳碳纳米材料的吸附固定化脱氮效果最好,脱氮率可达94%;以海藻酸钠(SA)和聚乙烯醇(PVA)制成的SA、PVA、PVA-SA、PVA-SA-活性炭和PVA-SA-纳米材料小球为包埋固定化载体时,PVA和SA混合作为包埋剂固定效果要好于单独作为包埋剂,包埋剂PVA和添加剂SA最佳包埋比是10:1;吸附材料作为强化剂一起包埋的复合式包埋有助于提高固定化小球的稳定性和固定化效果,脱氮率提高5%。其中纳米材料作为强化剂的包埋固定化脱氮效果要优于活性炭,脱氮率可达到85%。强化剂活性炭、纳米材料最佳包埋比是5:4。吸附固定化整体脱氮效率优于包埋固定化。