Ni-P/HZSM-5催化木质素降解制备酚类化学品

采用Ni-P复合改性HZSM-5催化剂催化木质素降解制备高附加值的单酚类化学品，探讨了催化剂种类、金属负载量、反应温度、反应时间以及溶剂种类对木质素催化降解制备酚类化合物的影响。同时采用X射线衍射仪（XRD）、比表面积和孔径分析仪（BET）、化学吸附仪（NH₃-TPD）、热重分析仪（TG）以及气相色谱质谱联用仪（GC/MS）对催化剂以及液相产物进行分析表征，同时探讨其催化失活以及再生机制。结果表明：Ni、P高度分散在HZSM-5催化剂的表面，Ni的添加有效地弱化了C－C键，致使β-O-4和α-O-4发生断裂，有效地提高了木质素加氢解聚的活性，减少了焦炭的生成，但催化剂的再生水热稳定性较差，重复使用性较低。当采用甲醇为供氢试剂，在反应温度为220℃，氢气压力为2MPa，反应时间为8h，催化剂负载量为10%，NaOH为共催化剂时，其木质素的转化率为98.6%，酚类化合物的含量达到74.97%。产物以苯酚、愈创木酚和紫丁香酚为主，低温促进了紫丁香酚的产生。     

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%.     

木质素基表面活性剂研究现状

木质素作为一种天然高分子化合物，其来源丰富，可以用来代替石油资源制备表面活性剂，缓解当前石油资源枯竭的问题。常见的木质素基表面活性剂有阳离子表面活性剂、阴离子表面活性剂、两性离子表面活性剂以及非离子表面活性剂。木质素基表面活性剂在工业领域具有广泛的应用范围，可以作为染料分散剂、混凝土减水剂、沥青乳化剂以及原油采集过程中的驱油剂等。木质素基表面活性剂的开发利用为生物质产品的高值化利用开辟了一条新的路径。     

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.