Lipase-catalyzed synthesis of biodiesel from acid oil in fixed bed reactor

Acid oil, which is a by-product in vegetable oil refining, mainly contains free fatty acids (FFAs) and acylglycerols and is a feedstock for production of biodiesel fuel now. The transesterification of acid oil and methanol to biodiesel was catalyzed by immobilized Candida lipase in fixed bed reactors. The reactant solution was a mixture of acid oil, water, methanol and solvent (hexane) and the main product was biodiesel composed of fatty acid methyl ester (FAME) of which the main component was methyl oleate. The effects of lipase content, solvent content, water content temperature and flow velocity of the reactant on the reaction were analyzed. The experimental results indicate that a maximum FAME content of 90.18% can be obtained in the end product under optimum conditions. Most of the chemical and physical properties of the biodiesel were superior to the standards for 0(#) diesel (GB/T 19147) and biodiesel (DIN V51606 and ASTM D6751).

Bio-syngas production from biomass catalytic gasification

A promising application for biomass is liquid fuel synthesis, such as methanol or dimethyl ether (DME). Previous studies have studied syngas production from biomass-derived char, oil and gas. This study intends to explore the technology of syngas production from direct biomass gasification, which may be more economically viable. The ratio of H-2/CO is an important factor that affects the performance of this process. In this study, the characteristics of biomass gasification gas, such as H-2/CO and tar yield, as well as its potential for liquid fuel synthesis is explored. A fluidized bed gasifier and a downstream fixed bed are employed as the reactors. Two kinds of catalysts: dolomite and nickel based catalyst are applied, and they are used in the fluidized bed and fixed bed, respectively. The gasifying agent used is an air-steam mixture. The main variables studied are temperature and weight hourly space velocity in the fixed bed reactor. Over the ranges of operating conditions examined, the maximum H-2 content reaches 52.47 vol%, while the ratio of H-2/CO varies between 1.87 and 4.45. The results indicate that an appropriate temperature (750 degrees C for the current study) and more catalyst are favorable for getting a higher H-2/CO ratio. Using a simple first order kinetic model for the overall tar removal reaction, the apparent activation energies and pre-exponential factors are obtained for nickel based catalysts. The results indicate that biomass gasification gas has great potential for liquid fuel synthesis after further processing.

厌氧好氧一体化生物反应器处理发酵废水的中试研究

一体化反应器由于投资少、占地小、管理运行方便等优点而备受青睐。但现有的一体化反应器大都适用于处理中低浓度废水，耐受负荷普遍偏低。本课题研制出新型高效的厌氧好氧一体化生物反应器，旨在通过反应器结构优化、高效微生物载体研制、配合高效微生物菌剂技术处理中高浓度有机废水，实现高效和低耗，降低设备造价，提高反应器运行稳定性。 首先开展了菌剂对废水的适配试验。采用15种不同的微生物菌剂，以葡萄糖配水、中药提取废水、啤酒废水、氨氮配水为基质，分别测定了微生物菌剂的耗氧速率和厌氧比产甲烷速率，以其为指标比较了各菌剂对废水的适配性。根据结果选择活性高的14＃、8＃、10＃菌剂，在试验室进行了菌剂对废水的连续处理试验，取得良好的处理效果，为菌剂在厌氧好氧一体化生物反应器的小试、中试中的应用奠定了基础。 经小试研究后，又对厌氧好氧一体化生物反应器进行了处理发酵废水的中试研究。试验结果表明，反应器启动快，系统有机负荷2.72 kgCODm-3d-1时整个反应器去除率保持在84.5％～93.19％，在30多天内一次启动成功。冲击负荷试验中，系统总有机负荷最高可达到8.88 kgCODm-3d-1，系统去除率稳定在88.10％～96.88%，说明反应器处理效率高，抗冲击能力强。稳定运行期间，COD去除率可达90％以上，各项指标都能达到国家排放标准。 此外，对反应器配套系统高效菌剂、高分子复合颗粒载体进行了研究。结果显示，菌剂与反应器适配良好，各功能区形成了丰富、高活性的微生物，厌氧区颗粒污泥TS高达83.9 gL-1，VS/TS为56.9％～57.4％，比产甲烷活性为280～350 mLCH4 gvss-1d-1；好氧区固定化微生物TS高达1.921 gL-1，VS/TS为94.02～94.30％。对载体性能的研究表明，此高分子复合颗粒载体密度适中，易于流化，不易流失；粗糙多空，易于挂膜；且无生物毒害作用，稳定安全，是一种优良的生物载体。反应器各功能区对废水的降解过程分析，说明了反应器、菌剂、载体适配良好，在其协同作用下，实现了污染物的高效降解。 The integrated reactors were popular because of their characteristics such as little investment, small occupation of land, convenient of manage and running etc. But the present integrated reactors were mostly applied for treating wastewater of low concentration, the load tolerance was generally on the low side. A new type integrated anaerobic-aerobic bio-reactor was developed, which was conducted to treating organic wastewater of middle or high concentration by optimization of reactor structure, development of efficient microbe carrier and adaptation of high active microbial blends, to achieve high efficiency and low consume, reduce equipment cost, enhance running stabilization of reactor. The adaptability test of microbial blends on different wastewater was carried on firstly. Oxygen consumption rate and anaerobic specific activity of methane producing of 15 different microbial blends were measured separately taking glucose artificial wastewater, Chinese herb extracting wastewater, brewery wastewater and ammonia nitrogen artificial wastewater as substrate, by which the adaptabilities of different microbial blends to wastewater were compared. According to the results high active microbial blends 14#, 8# and 10# were selected and used in the continuous treatment of wastewater in the laboratory and had obtained good effect, which had laid a foundation for application microbial blends to small scale test and pilot test of integrated anaerobic-aerobic bio-reactor. After the small scale test, the pilot test of the integrated anaerobic-aerobic bio-reactor treating fermentation wastewater was carried on. The test results showed fast initiation of the reactor. When system organic load reached 2.72 kgCODm-3d-1the COD removal rate of the reactor was stable between 84.5%～93.19% and it initiated successfully in more than 30 days at a time. In the load shock test the maximum organic load of system could reach to 8.88 kgCODm-3d-1 and the COD removal rate could be stable between 88.10%~96.88% which indicated that the reactor was efficient for treating wastewater and had strong resistance to shock load. At stable running period the COD removal rate of the reactor was over 90% and each index of wastewater could reach to the national discharge standards. In addition, the high active microbial blends and the macromolecule compound granule carrier, the matching system of the reactor was studied. It showed that the microbial blends adapted well to the reactor and abundant and high active microbes were formed in each functional field. The TS of granule sludge in anaerobic field was as high as 83.9 gL-1, the VS/TS was 56.9%~57.4%, the specific activity of methane producing was 280~350 mLCH4 gvss-1d-1. And the TS of immobilized biological granule was as high as 1.921 gL-1, the VS/TS was 94.02%~94.30%. Study on the carrier showed that the self-made macromolecular compound granule carrier was moderate of density, easy of fluidization, unease of running off, rough and porous, easy of films fixation, no bio-toxic, stable and safe, was a kind of superior carrier. Analysis of degradation process in each functional field confirmed the reactor, microbial blends and carriers were in good adaptation and wastewater was decontaminated by their cooperation.

High-throughput characterization of heterogeneous catalysts by temperature-programmed analysis method

A multistream reactor for high-throughput examining the surface acidity by NH3-TPD method by application of multistream mass spectrometer screening (MSMSS) technique has been developed. This method allows for examining the surface acidity of 10 catalyst samples in about 6 h, which is an improvement over the traditional process. The demonstration of the feasibility of high-throughput TPD can be significant in convincing the hardened traditionalists in the heterogeneous catalysis community that, combinatorial methods indeed should have an important place in scientific catalyst research and development. The developed method could also be used for almost all the temperature-programmed analysis theoretically with careful designed multistream reactors. (C) 2003 Elsevier B.V. All rights reserved.

Investigation of the gel effect in reactive extrusion processes for free radical polymerization

The gel effect in the reactive extrusion process for free radical polymerization in a closely intermeshing co-rotating twin screw extruder was investigated. First the reaction kinetic model was constructed mainly on the basis of entanglement theory. Next, numerical calculation expressions for the initiator and monomer concentrations, monomer conversion, average molecular weight and apparent viscosity were deduced. Finally, the evolution of the above variables were shown and discussed for the example of butyl methacrylate. The simulated results of the monomer conversion are in good agreement with experimental results.

Free radical grafting of polyethylene with vinyl monomers by reactive extrusion

The free radical grafting of polyethylene with vinyl monomers by reactive extrusion was studied numerically. Numerical computation expressions of key variables, such as the concentrations of the initiator and polymer, grafting degree, average molecular weight and apparent viscosity, were deduced. The evolutions of the above variables were predicted by means of an uncoupled semi-implicit iterative algorithm. The monomer conversion monotonically increases with decreasing throughput or increasing initial initiator concentration; with increasing barrel temperature, the monomer conversion first increases then decreases. The simulated results are nearly in good agreement with the experimental results.

Oxygen permeating properties of the mixed conducting membranes without cobalt

A new series of mixed conducting oxides, Sr10-n/2BinFe20Om (n = 4, 6, 8, 10), were synthesized by a solid state reaction method, and they have high oxygen permeability. The oxygen permeation rate at 1150 K is 0.41 ml(STD)/ cm(2).min for n = 6 and 0.90 ml(STD)/cm(2).min for n = 10, which is two times higher than that for Sr1-xBixFeO3 (x = 0.5). For the Sr1-xBixFeO3 (x = 0.1, 0.3, 0.5) series, the oxygen flux increases with increasing Bi content. (C) 1998 Elsevier Science Ltd.

Diversity and spatial distribution of sediment ammonia-oxidizing crenarchaeota in response to estuarine and environmental gradients in the Changjiang Estuary and East China Sea

Ammonia-oxidizing archaea (AOA) have recently been found to be potentially important in nitrogen cycling in a variety of environments, such as terrestrial soils, wastewater treatment reactors, marine waters and sediments, and especially in estuaries, where high input of anthropogenic nitrogen is often experienced. The sedimentary AOA diversity, community structure and spatial distribution in the Changjiang Estuary and the adjacent East China Sea were studied. Multivariate statistical analysis indicated that the archaeal amoA genotype communities could be clustered according to sampling transects, and the station located in an estuarine mixing zone harboured a distinct AOA community. The distribution of AOA communities correlated significantly with the gradients of surface-water salinity and sediment sorting coefficient. The spatial distribution of putative soil-related AOA in certain sampling stations indicated a strong impact of the Changjiang freshwater discharge on the marine benthic microbial ecosystem. Besides freshwater, nutrients, organic matter and suspended particles, the Changjiang Diluted Water might also contribute to the transport of terrestrial archaea into the seawater and sediments along its flow path.

A bioaugmentation failure caused by phage infection and weak biofilm formation ability

Two biological aerated filters (BAF) were setup for ammonia removal treatment of the circulation water in a marine aquaculture. One of the BAFs was bioaugmented with a heterotrophic nitrifying bacterium, Lutimonas sp. H10, where the ammonia removal was not improved and the massive inoculation was even followed by a nitrification breakdown from day 9 to 18. The nitrification was remained stable in control BAF operated under the same conditions. Fluorescent in situ hybridization (FISH) with rRNA-targeted probes and cultivable method revealed that Lutimonas sp. H10 almost disappeared from the bioaugomented BAF within 3 d, and this was mainly due to the infection of a specific phage as revealed by flask experiment, plaque assay and transmission electron observation. Analyses of 16S rRNA gene libraries showed that bacterial groups from two reactors evolved differently and an overgrowth of protozoa was observed in the bioaugmented BAR Therefore, phage infection and poor biofilm forming ability of the inoculated strain are the main reasons for bioaugmentation failure. In addition, gazing by protozoa of the bacteria might be the reason for the nitrification breakdown in bioaugmented BAF during day 9-18.

Gas phase catalytic partial oxidation of toluene in a microchannel reactor

Gas phase partial oxidation of toluene over V/Ti oxide catalysts has been successfully performed in a microchannel reactor, which provides very good mass and heat transfer conditions. With the elimination of hot spots, which are known as the most negative factors for partial oxidation of hydrocarbons, steady and uniform reaction conditions can be achieved in the catalyst bed by using, the microreactor. Since the best performance of the catalysts might be exploited, the selectivity of partial oxidation products of toluene has remarkably increased compared to the traditional packed fixed-bed reactor, even without the bother of modifying the catalysts, diluting the reactants or catalysts with inert contents to avoid hot spots or improve the diffusion and mixing. Furthermore, in virtue of its inherent safety features, when using pure oxygen as oxidant, the reactions were handled safety within the explosion limits in the microreactor. With TiO2 carried V2O5 as catalysts, the total selectivity of benzaldehyde and benzoic acid reaches around 60%, and the toluene conversion is about 10%. The conversion can go up without violent decline of selectivity, unlike most fixed bed reactors. Space time yield of 3.12 kg h(-1) L-1 calculated on the basis of the channel volume has been achieved. The influence of operating conditions has been investigated in detail in the microreactor. (c) 2005 Elsevier B.V. All rights reserved.