Bamboo biochar-catalytic degradation of lignin under microwave heating

Abstract

Lignin biochar-catalytic depolymerization using biochar Fe-600, Fe-800, Ni-600, Ni-800 catalysts under microwave-heating (180?°C for 30?min) was explored in an ethanol/formic acid (1:1) media. Non-catalyst depolymerization was also studied and compared with the biochar-catalysts results. Characteristics of the bio-char catalysts were analyze by BET, XRD, and FT-IR. GPC, FT-IR, and MALDI-TOF MS spectrometry were also used to characterize the depolymerization products. The experimental results showed that the S_BET, V_t, and V_mec and average pore diameter of the biochars are considerably dependent on the preparation temperature and type of cation (Ni²⁺ or Fe³⁺). The maximum yield of bio-oil product was obtained as 85?wt% with the addition of biochar Ni-600 and the total amount of oligomers or monomers with a molecular weight of 164 to 446 reaches 80.4%.     

Low density polyethylene and grafted lignin polyblends using epoxy‐functionalized compatibilizer: mechanical and thermal properties

Lignin was graft copolymerized with methyl methacrylate using manganic pyrophosphate as initiator. This modified lignin was then blended (up to 50 wt%) with low density polyethylene (LDPE) using a small quantity of poly[ethylene‐co‐(glycidyl methacrylate)] (PEGMA) compatibilizer. The mechanical properties of the blend were substantially improved by using modified lignin in contrast to untreated lignin. Differential scanning calorimetry studies showed loss of crystallinity of the LDPE phase owing to the interaction between the blend components. Thermogravimetric analysis showed higher thermal stability of modified lignin in the domain of blend processing. This suggested that there is scope for useful utilization of lignin, which could also lead to the development of eco‐friendly products. Copyright © 2005 Society of Chemical Industry     

Peracetic acid pretreatment of sugarcane bagasse for enzymatic hydrolysis: a continued work

Previous work has shown that the enzymatic hydrolysis of sugarcane bagasse could be greatly enhanced by peracetic acid (PAA) pretreatment. There are several factors affecting the enzymatic digestibility of the biomass, including lignin and hemicelluloses content, cellulose crystallinity, acetyl group content, accessible surface area and so on. The objective of this work is to analyze the mechanism of the enhancement of enzymatic digestibility caused by PAA pretreatment. Delignification resulted in an increase of the surface area and reduction of the irreversible absorption of cellulase, which helped to increase the enzymatic digestibility. The Fourier transform infrared (FTIR) spectrum showed that the absorption peaks of aromatic skeletal vibrations were weakened or disappeared after PAA pretreatment. However, the infrared crystallization index (N.O'KI) was increased. X‐ray diffraction (XRD) analysis indicated that the crystallinity of PAA‐treated samples was increased owing to the partial removal of amorphous lignin and hemicelluloses and probable physical change of cellulose. The effect of acetyl group content on enzymatic digestibility is negligible compared with the degree of delignification and crystallinity. The results indicate that enhancement of enzymatic digestibility of sugarcane bagasse by PAA pretreatment is achieved mainly by delignification and an increase in the surface area and exposure of cellulose fibers. Copyright © 2008 Society of Chemical Industry     

Pyrolysis-field ionization mass spectrometry of modified bagasse fractions

The fractions obtained from bagasse after activation with 17.5% NaOH, alternative alkylation with quarternary ammonium groups and extraction with 80% ethanol, water and 5% NaOH, were analyzed using pyrolysis-field ionization mass spectrometry (Py-FIMS). The proposed degradation products from lignin were mostly symmetric fragments containing two aromatic rings while the compounds formed from polysaccharides were the result of dehydration reactions. From the temperature-resolved Py-FIMS it could be seen that ethanol-lignin starts to degrade at temperatures lower than 180°C before the degradation of the hemicellulose fraction. The lignin markers are eliminated from hemicellulose fractions before the polysaccharide gasification starts. The quarternary ammonium groups are cleaved from the fractions at temperatures lower than 200°C.     

Activity of two lignin biosynthesis enzymes during development of a maize internode

To ascertain the temporal relationships of phcnylpropanoid and lignin pathway enzymes, phenylalanine ammonia-lyase (PAL) and cinnamyl alcohol- NADPH dehydrogenase(CAD), with lignin concentration, PAL and CAD activities and lignin concentrations were assessed during progressive development of the 10th internode in maize (Zea mays L). Enzyme activities were quantified and lignin concentrations were determined by the detergent system of fiber fractiona- tion from lower, middle, and upper sections of the elongating internode harvested 3, 5, 7, 9, 11, 13, and 15 days after the internode had reached 10 mm in length. Over 15 days, a coordinated, sequential, and basipetal pattern of enzyme activities and lignin accumulation evolved through the internode, spanning the stages of rapid elongation, cellular differentiation, and secondary cell wall formation. PAL activity was initiated first, rising to peak activity in elongating tissue, and falling basipetally in tissues as they matured. CAD activity rose in fully elongated, maturing internode tissue where PAL activity was waning following its peak activity. Lignin accumulated in tissues with high CAD activity. CAD activity and lignin deposition patterns were similar: simultaneously increasing in activity and deposition over time while activity and deposition also shifting basipetally through the internode, keeping pace with secondary cell wall formation. Lignin concentration correlated significantly with CAD, but not with PAL.     

大港油田官109-1断块稠油油藏碱/表面活性剂吞吐采油技术

大港油田官109-1断块稠油油藏的油井由于井筒、近井地带发生原油有机沉积,储层原油流动性差,采用多种方法都不能正常生产。为此研制了一种碱性解堵液,用于油井化学吞吐。该解堵液为复配碱和抗硬剂等添加剂的10%两性木质素表面活性剂溶液,能使玻璃片表面由亲油变强亲水,在石英上的接触角为6°(稀释至1/2和1/4浓度时为11°和12°),与羊大站原油间的界面张力为1.75×10-3~3.18×10-3mN/m。该解堵液与黏度1~50 Pa.s的不同区块稠油按体积比1∶1混合形成的乳状液,60℃、175 s-1黏度为2~6 mPa.s,在配液水矿化度高达6000mg/L以上或钙镁离子浓度高达250 mg/L时,该解堵液仍能保持对稠油的乳化降黏能力。该解堵液从实验岩心中驱出的原油量比地层水多75%,驱出液为乳状液。通过一个井例介绍了化学吞吐工艺:先用一种降黏解堵液对油井进行预处理,清洗油管、炮眼及近井地带,再注入碱性解堵液(该井例中为500 m3),注入时间约15小时,然后开井生产。2000年2月至2002年6月在16口新投产井实施化学吞吐(第一轮次),15口井有效,其中2口井先后转注水,其余13口井到2005年底仍继续产油。图1表6参5。     

Anaerobic digestion of alkaline black liquor using an up-flow anaerobic sludge blanket reactor

The anaerobic digestion of alkaline black liquor from a cereal straw pulping mill was studied in batch (serum bottles) and continuous systems (up-flow anaerobic sludge blanket reactor—UASB). The batch digestion studies confirmed that lignin and related compounds (LRC) in the alkaline black liquor were the main inhibitory substances and could not be decomposed by anaerobic bacteria. At organic loading rates of 5–10 kg COD m^?3 day^?1, the UASB reactor achieved 50–60% COD removal efficiencies. Gas production was 2–3 dm³ per dm³ of alkaline black liquor. Two different sludge types were examined in the reactor: granular and cluster-like sludges. Sludge in a cluster, which involved many small granules and flocs, tended to form larger aggregates and possessed good settling ability.     

木质素单体模化物的热解与产物分析

采用苯酚、邻苯二酚、愈创木酚和紫丁香酚为木质素单体模化物,利用两段裂解反应器-在线气相色谱仪（GCs）进行热解实验和产物分析,采用多色谱柱对无机气体（IGs）、C₁~C₅烃（C₁~C₅ LHs）、非芳基含氧化合物、酚和芳烃进行定量分析,以确定羟基和甲氧基对木质素热解过程中开环反应及产物分布的影响. 结果显示：羟基和甲氧基可以提高模化物的转化率,且羟基和甲氧基的存在影响芳基开环反应、芳基取代反应和重排反应间的竞争关系,使热解产物分布存在明显差异. 4种模化物热解产物主要是芳环的开环反应产物,包括IGs（质量分数为27.29%~33.56%）和C₁~C₅烃（20.46%~39.51%）. 一氧化碳产率（23.82%~29.18%）随羟基数增加而升高,随甲氧基数增加而降低;二氧化碳产率（0.19%~9.61%）随甲氧基数增加而升高. 羟基和甲氧基的存在降低了C₁~C₅烃的质量选择性,促进了烷基苯、大分子化合物和焦炭的形成.     

木质素液化研究进展

介绍了木质素的液化、液化产物的改良的方法及其研究进展,对将来研究发展方向以及目前面临的一些问题作了简要的叙述。     

黑液中的多糖对合成本素胺乳化剂的影响

直接以浓缩黑液为原料，通过环氧氯丙烷引入季铵基团制取阳离子型木素胺乳化剂。对产品和原料黑液做了剖析，证明黑液中的非本素有机物发生了胺化反应．应用试验证明这部分胺化产物具有助乳化和稳定乳液的作用。