The effect of fire retardants on combustion and pyrolysis of sugar-cane bagasse

Experiments were conducted by thermal gravimetric analysis (TGA) and cone calorimetry to measure the affect of three fire retardants (ammonium sulphate, boric acid and borax) on the mass-loss rate and combustion characteristics of sugar-cane bagasse. Compared with untreated bagasse, bagasse impregnated with aqueous solutions of 0.1-0.5 M fire retardants exhibited an increase in char mass production from 16% up to 41% when pyrolysed and up to a 41% reduction in total heat release (THR) during combustion. Char mass production was only a weak function of additive concentration over the range of concentrations (0.1-0.5 M) used. Combining the additives did not show any synergistic effects for char production or heat release rate (HRR). Treatment of bagasse by these chemicals could be useful to enhance biochar yields in pyrolysis processes or to reduce flammability risk in composites containing bagasse.     

Preparation of carbon black from rice husk by hydrolysis, carbonization and pyrolysis

Carbon black is a form of amorphous carbon that is produced by incomplete combustion of petroleum- or some plant-derived materials and has a number of industrial uses. A process consisting of hydrolysis, carbonization and pyrolysis of rice husk was developed. Under optimal hydrolysis conditions (72 wt.% sulfuric acid, 50 °C, 10 min), a hydrolysis ratio of 52.72% was achieved. After carbonization of the hydrolysis solution by water bath, the solid carbon was further pyrolyzed. As the pyrolysis temperature was increased from 400 to 800 °C, the carbon content increased from 83.41% to 94.66%, the number of O-H, C-H, CO, and CC surface functional groups decreased, and based on Brunauer-Emmett-Teller (BET) results, the specific surface area and pore volume of carbon black increased from 389 to 1034 m²/g and from 0.258 to 0.487 cm³/g, respectively. X-ray diffraction pattern (XRD) and Raman spectroscopy analyses of samples pyrolyzed at 400-800 °C showed a localized graphitic structure. It is possible that the hydrolysis/carbonization/pyrolysis process developed in this study could also be applicable to the preparation of carbon black from other types of biomass.     

Bio-oil and bio-char from low temperature pyrolysis of spent grains using activated alumina

The pyrolysis of wheat and barley spent grains resulting from bio-ethanol and beer production respectively was investigated at temperatures between 460 and 540 °C using an activated alumina bed. The results showed that the bio-oil yield and quality depend principally on the applied temperature where pyrolysis at 460 °C leaves a bio-oil with lower nitrogen content in comparison with the original spent grains and low oxygen content. The viscosity profile of the spent grains indicated that activated alumina could promote liquefaction and prevent charring of the structure between 400 and 460 °C. The biochar contains about 10-12% of original carbon and 13-20% of starting nitrogen resulting very attractive as a soil amendment and for carbon sequestration. Overall, value can be added to the spent grains opening a new market in bio-fuel production without the needs of external energy. The bio-oil from spent grains could meet about 9% of the renewable obligation in the UK.     

A high-pressure form of sulfuric acid monohydrate as determined by X-ray and neutron diffraction

Two high-pressure polymorphs of sulfuric acid monohydrate (oxonium hydrogensulfate) have been obtained at ambient temperature by crystallisation at high pressure from the liquid at 1.3 GPa (form III) and by direct compression of the ambient-pressure form I first to 1.26 GPa (form II) and then to 1.72 GPa (form III). The structure of form III was solved by single crystal X-ray diffraction and this structure was used as the basis for the refinement of hydrogen positions using high-pressure neutron powder diffraction data. Form III crystallises in the orthorhombic crystal system at 1.97 GPa, and features parallel chains of hydrogensulfate ions linked by oxonium ions to form a three-dimensional hydrogen-bonded network. On further compression to 3.05 GPa, the direction of maximum compressibility is found to be along the a-axis and is associated with the shortening of a hydrogen bond between a hydrogensulfate ion and an oxonium ion. The structure of form II remains elusive although at ambient temperature it is stable (or metastable) at pressures as low as 0.42 GPa, perhaps indicating that it could be recoverable to ambient-pressure at low temperature.     

Compression, compaction, and disintegration properties of low crystallinity celluloses produced using different agitation rates during their regeneration from phosphoric acid solutions

The tabletting characteristics of low crystallinity celluloses (LCPC)-LCPC-700, LCPC-2000, and LCPC-4000-prepared using agitation rates of 700, 2000, and 4000 rpm, respectively, during their regeneration from phosphoric acid, were evaluated and compared with those of Avicel PH-102 and Avicel PH-302. The mean deformation pressure values calculated from the linear region of the Athy-Heckel curves indicated LCPC-4000 to be the most ductile material. The area under the Athy-Heckel curve for LCPC-4000 was 330 MPa, whereas LCPC-700 and LCPC-2000 showed a corresponding value similar to that of Avicel PH-102 and Avicel PH-302 (192–232 MPa). The tensile strength of LCPC and Avicel compacts increased linearly with increasing applied pressures. A comparison of the area under the tensile strength-compression pressure curves indicated that LCPC-4000 formed the strongest tablets. The strengths of LCPC-700 and LCPC-2000 compacts, in contrast, were slightly lower than that of Avicel PH-302 and Avicel PH-102, respectively. The compacts of both LCPC-4000 and Avicel PH-102 were intact in water for 6 hours, whereas LCPC-2000 and Avicel PH-302 compacts disintegrated in 4 minutes and 2 minutes, respectively. In conclusion, LCPC-4000 was the most ductile material and exhibited the highest compression and compaction characteristics. The corresponding properties of LCPC-700 and LCPC-2000, in contrast, were comparable to that of Avicel PH-102 or Avicel PH-302.     

玉米芯低温热解特性研究

针对如何提高农田副产物玉米芯综合利用价值的问题,通过热重分析以及低温热解实验对热解过程中玉米芯组分、产率、热值的变化规律进行研究,得到热解产物的特性及其产率,热值随热解温度、时间的变化规律,为玉米芯的综合利用提供重要的理论依据。实验研究表明,在实际生产应用中应当选择的最佳工艺参数为：30 min、350 ℃,在此条件下热解产物的热值及密度都有较大的提高,生物质炭的产率为69.2%,热值为18.78 MJ/kg,相对于未经处理的玉米芯热值提高了19.7%。     

Thermal glycosylation and degradation reactions occurring at the reducing ends of cellulose during low-temperature pyrolysis

Thermal glycosylation and degradation reactions of cellulose (Avicel PH-101) were studied in the presence or absence of alcohols (glycerol, mannitol, 1,2,6-hexanetriol, 3-phenoxy-1,2-propanediol, and 1-tetradecanol) under N₂ at 60–280 °C. In the presence of glycerol (heating time, 10 min), the reducing ends were converted into glycosides when the temperature of the glycerol was >140 °C without the addition of any catalysts. A temperature of 140 °C is close to that required for the initiation of thermal polymerization (glycosylation). Although the conversion was only around 20% in the range of 140–180 °C, the reactivity increased above 200–240 °C where the thermal expansion of cellulose crystals is reported to become significant. Finally, all reducing ends were converted into glycosides at 260 °C. Such heterogeneous reactivity likely arose from the lower reactivities of the reducing ends in the crystalline region due to their lower accessibility to glycerol, although the reactivity in the non-crystalline region was similar to that of glucose. Alcohols that have a lower OH/C ratio did not react with the reducing ends, suggesting that the hydrophilicity of the alcohol was critical for the glycosylation reaction to proceed. The glycosylated cellulose samples were found to be significantly stabilized against pyrolytic coloration. The results of neat cellulose pyrolysis indicated that two competitive reactions, thermal glycosylation and degradation, formed a dark-colored substance at the reducing ends while the internal glucose units in the cellulose were comparatively stable.     

The preparation of high-grade bio-oils through the controlled, low temperature microwave activation of wheat straw

The low temperature microwave activation of biomass has been investigated as a novel, energy efficient route to bio-oils. The properties of the bio-oil produced were considered in terms of fuel suitability. Water content, elemental composition and calorific value have all been found to be comparable to and in many cases better than conventional pyrolysis oils. Compositional analysis shows further differences with conventional pyrolysis oils including simpler chemical mixtures, which have potential as fuel and chemical intermediates. The use of simple additives, e.g. HCl, H₂SO₄ and NH₃, affects the process product distribution, along with changes in the chemical composition of the oils. Clearly the use of our low temperature technology gives significant advantages in terms of preparing a product that is much closer to that which is required for transport fuel applications.     

稀酸水解玉米芯制备丁二酸

利用正交设计得到稀H2SO4水解玉米芯制备混合糖液的优化工艺:玉米芯料液比1∶5(质量体积比),物料粒径250~380μm、H2SO4用量3%(体积分数)、水解温度126℃、反应时间2.5 h。此工艺条件下的总糖收率达90%,总糖质量浓度为60 g/L,发酵抑制物糠醛含量为0.87 g/L,5-羟甲基糠醛含量为0.68 g/L。在此基础上利用活性炭吸附和Ca(OH)2中和对玉米芯混合糖液进行脱毒及脱盐处理,SO42-脱除率达96%,色素脱除率为96%,糠醛、5-羟甲基糠醛及多酚类物质脱除率均高于50%。处理后的玉米芯多组分糖液作为产琥珀酸放线杆菌(Actinobacillus succino-genes)NJ113的发酵C源,当培养基中初始总糖质量浓度为50 g/L时,丁二酸收率为61.68%,丁二酸质量浓度为30.8 g/L;初始总糖质量浓度为70 g/L时,丁二酸收率仍可达50%以上,丁二酸质量浓度为35.2 g/L。发酵实验表明,将经过脱毒脱盐处理的玉米芯多组分糖液替代葡萄糖作为C源发酵制备丁二酸具有可行性。     

低温环境中乳酸菌的开发利用

乳酸菌作为一种益生资源,越来越为人们所重视.在自然界存在的乳酸菌中,有一类虽然人们一直在利用,但是还没有充分的研究和开发,这类乳酸菌就是低温环境中生长的乳酸菌.国外目前所见有关低温乳酸菌的报道多集中于低温冷藏肉、鱼制品及泡菜中的乳酸菌,集中研究和应用的菌属主要包括Leuconostoc和Lactobacillus,而国内这方面的研究并不多见.笔者根据目前国内外低温乳酸菌的研究现状,阐述了其存在环境、种类及相应作用,并对其研究涉及的领域、趋势及应用前景进行了探讨和展望,以期为国内这类乳酸菌资源的研究开发提供参考和依据.     

Enhanced enzymatic hydrolysis of spruce by alkaline pretreatment at low temperature

Alkaline pretreatment of spruce at low temperature in both presence and absence of urea was studied. It was found that the enzymatic hydrolysis rate and efficiency can be significantly improved by the pretreatment. At low temperature, the pretreatment chemicals, either NaOH alone or NaOH-urea mixture solution, can slightly remove lignin, hemicelluloses, and cellulose in the lignocellulosic materials, disrupt the connections between hemicelluloses, cellulose, and lignin, and alter the structure of treated biomass to make cellulose more accessible to hydrolysis enzymes. Moreover, the wood fiber bundles could be broken down to small and loose lignocellulosic particles by the chemical treatment. Therefore, the enzymatic hydrolysis efficiency of untreated mechanical fibers can also be remarkably enhanced by NaOH or NaOH/urea solution treatment. The results indicated that, for spruce, up to 70% glucose yield could be obtained for the cold temperature pretreatment (-15 degrees C) using 7% NaOH/12% urea solution, but only 20% and 24% glucose yields were obtained at temperatures of 23 degrees C and 60 degrees C, respectively, when other conditions remained the same. The best condition for the chemical pretreatment regarding this study was 3% NaOH/12% urea, and -15 degrees C. Over 60% glucose conversion was achieved upon this condition.     

Increased production of eicosapentaenoic acid by Skeletonema costatum cells after decantation at low temperature

Coagulation of Skeletonema costatum biomass was induced at alkaline pH in enriched sea-water to concentrate the microalgal suspensions by decantation. Incubation of the concentrated cultures at 15 °C after return at pH 7.5 preserved cell viability and increased the yield of lipid extraction and the 20:5(n-3) fatty acid content of the diatom biomass.     

Auto-hydrolysis of lignocellulosics under extremely low sulphuric acid and high temperature conditions in batch reactor

Batch reactors were employed to investigate the kinetics of cellulose hydrolysis under extremely low acid (ELA) and high temperature condition. The sawdust was pretreated by Autohydrolysis prior to the batch reaction. The maximum yield of glucose obtained from the batch reactor experiment was about 70% for the pretreated sawdust, this occurred at 210 and 220°C. The maximum glucose yield from the untreated sawdust was much lower at these temperatures, about 55%. The maximum yields of glucose from the lignocellulosics were obtained between 15th and 20th minutes after which gradual decrease was observed.     

Reduction of dehydroascorbic acid at low pH

Ascorbic acid and dehydroascorbic acid are unstable in aqueous solution in the presence of copper and iron ions, causing problems in the routine analysis of vitamin C. Their stability can be improved by lowering the pH below 2, preferably with metaphosphoric acid. Dehydroascorbic acid, an oxidised form of vitamin C, gives a relatively low response on the majority of chromatographic detectors, and is therefore routinely determined as the increase of ascorbic acid formed after reduction. The reduction step is routinely performed at a pH that is suboptimal for the stability of both forms. In this paper, the reduction of dehydroascorbic acid with tris-[2-carboxyethyl] phosphine (TCEP) at pH below 2 is evaluated. Dehydroascorbic acid is fully reduced with TCEP in metaphosphoric acid in less than 20 min, and yields of ascorbic acid are the same as at higher pH. TCEP and ascorbic acid formed by reduction, are more stable in metaphosphoric acid than in acetate or citrate buffers at pH 5, in the presence of redox active copper ions. The simple experimental procedure and low probability of artefacts are major benefits of this method, over those currently applied in a routine assay of vitamin C, performed on large number of samples.     

Enhancing the enzymatic digestibility of sugarcane bagasse through the application of an ionic liquid in combination with an acid catalyst

Various ionic liquids have been identified as effective pretreatment solvents that can enhance the cellulose digestibility of lignocellulose by removing lignin, one of the main factors contributing to the recalcitrant nature of lignocellulose. 1-Butyl-3-methylimidazolium methylsulfate ([BMiM]MeSO(4)) is a potential delignification reagent, hence its application as a pretreatment solvent for sugarcane bagasse (SB) was investigated. The study also evaluated the benefit of an acid catalyst (i.e., H(2) SO(4)) and the effect of pretreatment conditions, which varied within a time and temperature range of 0-240 min and 50-150°C, respectively. The use of an acid catalyst contributed to a more digestible solid and a higher degree of delignification. However, the [BMiM]MeSO(4)-H(2) SO(4) combination failed to produce a fully digestible solid, as a maximum cellulose digestibility of 77% (w/w) was obtained at the optimum pretreatment condition of 125°C for 120 min. Furthermore, up to half of the lignin content could be extracted during pretreatment, while simultaneously extensive, sometimes complete, removal of xylan, the presence of which, also hampers cellulose digestibility. Hence, [BMiM]MeSO(4) has been identified an effective pretreatment solvent for SB as the application thereof both significantly improved digestibility, and simultaneously removed two of the main factors contributing to the recalcitrant nature of lignocellulose. As xylan and lignin have potential value as precursor chemicals, the existing process may in future be extended toward substrate fractionation, a biorefinery concept where value is added to all feedstock constituents.     

Chiral separation of D,L-mandelic acid through cellulose membranes

This work reports the chiral separation of D,L-mandelic acid with cellulose membranes. Cellulose was chosen as membrane material because it possesses multichiral carbon atoms in its molecular structure unit. The flux and permselective properties of membrane using aqueous solutions of D,L-mandelic acid as feed solution was studied. The top surface and cross-section morphology of the resulting membrane were examined by scanning electron microscopy. When the membrane was prepared with 8.1 wt % cellulose and 8.1 wt % LiCl in the DMA casting solution, and the operating pressure and feed concentration of racemate were 0.0125 MPa and 0.5 mg/ml, respectively, over 90% of enantiomeric excess could be obtained. This is the first report that the cellulose membrane is used for isolating the optical isomers of D,L-mandelic acid. Chirality, 2011.     

温度胁迫对马铃薯叶片抗坏血酸代谢系统的影响

采用盆栽试验,研究了高温（40 ℃）和低温（5 ℃）胁迫下,马铃薯叶片抗坏血酸（AsA）含量、L-半乳糖-1,4-内酯脱氢酶（GalLDH）和脱氢抗坏血酸还原酶（DHAR）基因表达与相应酶活性,以及抗坏血酸过氧化物酶（APX）、单脱氢抗坏血酸还原酶（MDHAR）、谷胱甘肽还原酶（GR）活性及H₂O₂和丙二醛（MDA）含量的变化规律,探讨温度胁迫对AsA代谢系统的影响.结果表明：40 ℃下,AsA含量快速增加,在6 h达到最高值,最高值比对照增加43.7％,而后急速减少;5 ℃下,在9 h达到最高值,最高值比对照增加27.7％,而后也开始减少.GalLDH、DHAR、APX、MDHAR和GR活性在40 ℃和5 ℃下均呈先升后降的变化趋势;GalLDH和DHAR基因表达与其酶活性的变化趋势一致.温度胁迫下,H₂O₂和MDA含量均显著增加.说明在温度胁迫初期,马铃薯叶片以AsA为核心的抗氧化系统对抵御高温和低温胁迫发挥了重要作用,但是随着胁迫时间的延长,AsA代谢系统的抗氧化功能逐渐降低.