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。     

Alkali catalyzed liquefaction of corncob in supercritical ethanol–water

Corncob liquefaction in supercritical ethanol–water was performed with and without the addition of an alkali catalyst by direct addition or biomass impregnation in a 250-cm³ batch reactor. The effects of temperature, solvent and alkali addition on the biomass conversion level and oil yield were investigated to find the optimum condition. For non-catalytic liquefaction using a 1:1 (v/v) ethanol: water ratio, a maximum oil yield and conversion level of 49.0% and 93.4%, respectively, were obtained at 340 °C. For alkali catalytic liquefaction, the oil yield with KOH addition (57.5%) was higher than that from KOH-impregnated corncob liquefaction (43.3%). The oil from liquefaction with KOH addition had higher heating value (26.7–35.3 MJ kg⁻¹) than the corncob (19.1 MJ kg⁻¹). The dominant components of the obtained oil were found by GC/MS analysis to be aldehyde, ester, phenol derivatives and aromatic compounds.     

Synthesis of highly efficient,structurally improved Li4SiO4 sorbents for high-temperature CO2 capture

Li₄SiO₄ sorbents for high-temperature CO₂ removal have drawn extensive attention owing to their potential application in carbon capture and storage (CCS). The major challenge in the application lies in the poor CO₂ capture performance under realistic conditions of low CO₂ concentrations, owing to the dense structure and poor porosity. In this work, Li₄SiO₄ sorbents were prepared with porous micromorphologies and large contact areas using a variety of organometallic Li-precursors, achieving fast CO₂ sorption kinetics, high capacity and excellent cyclic stability at a low CO₂ concentration (15?vol%). It was found that a high conversion of ~?74% was maintained for pure Li₄SiO₄ even after 100 sorption/desorption cycles. Moreover, by doping with Na₂CO₃ to reduce the CO₂ diffusion resistance, the conversion of the sorbent was further enhanced to 93.2%. The enhancement mechanism of alkali carbonate have been proven here to be ascribed to the formation of the eutectic melt of Li/Na carbonates, the existence and function of which has been confirmed in this study.     

燕皮传统加工工艺中碱液对肉糜特性的影响

燕皮是以猪肉和甘薯粉为原料,手工制成的薄如纸且经煮不烂的传统食品。在传统制作燕皮过程中添加山榉灰配制的碱液是影响肉糜品质的关键步骤。通过测定制作燕皮过程中各工序样品的氮溶解指数、持水性、乳化稳定性、pH值和粘度,利用SDS-PAGE分析样品中的蛋白质组分、利用光学显微镜观察它们的结构变化,证实植物碱液能够提高样品的氮溶解指数、持水性和乳化稳定性并且延迟了肉糜硬化。同时实验证明碳酸碱(Na2CO3或K2CO3)可替代传统工艺中的植物碱,为后续标准化、工业化生产提供可行条件。     

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     

Stages of surface erosion under ion irradiation

Initial stages of surface erosion have been studied for NaCl and LiF single crystals bombarded by Ar⁺ ions with 20 keV. For irradiation with doses D=10¹⁰-10¹¹ ions/cm², exoelectron emission has been used, whereas for higher doses, we have used electron microscopy. Two stages of initial surface erosion have been identified; for small doses, there is slow development of atomic-scale roughening, which reaches its peak when areas damaged by closest incident ions start to overlap, and then, beginning with D=10¹⁶ ions/cm², there is rapid etching, deep into the crystal, followed by the emergence of secondary microscopic structure, i.e. caverns, concentric closed steps and terraces. Ion-induced surface structure of alkali halide crystals has been shown to depend strongly on the presence of foreign particles on the surface, as well as on segregation. Topography of thin carbon films and some metals have been discussed.     

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.