Effects of side-chain hydroxyl groups on pyrolytic <Emphasis Type="Italic">β</Emphasis>-ether cleavage of phenolic lignin model dimer

Effects of side chain hydroxyl groups on pyrolytic β-ether cleavage of phenolic model dimers were studied with various deoxygenated dimers under pyrolysis conditions of N₂/400°C/1 min. Although phenolic dimer with hydroxyl groups at the C _α ⁻ and C _γ ⁻positions was much more reactive than the corresponding nonphenolic type, deoxygenation at the C _γ -position substantially reduced the reactivity up to the level of the nonphenolic type. These results are discussed with the cleavage mechanism via quinone methide intermediate formation, which is activated through intramolecular hydrogen bonds between C _α ⁻ and C _γ ⁻ hydroxyl groups.     

Application and verification of simultaneous determination of cellulose δ13C and δ18O in Picea shrenkiana tree rings from northwestern China using the high-temperature pyrolysis method

Stable isotopes in tree-ring cellulose provide important data in ecological, archaeological, and paleoenvironmental researches, thereby, the demand for stable isotope analyses is increasing rapidly. Simultaneous measurement of cellulose δ¹³C and δ¹⁸O values from tree rings would reduce the cost of isotopic commodities and improve the analytical efficiency compared with conventional separate measurement. In this study, we compared the δ¹³C and δ¹⁸O values of tree-ring α-cellulose from Tianshan spruce (Picea schrenkiana) in an arid site in the drainage basin of the Urumqi River in Xinjiang of northwestern China based on separate and simultaneous measurements, using the combustion method (at 1050°C) and the high-temperature pyrolysis method (at 1350°C and 1400°C). We verified the results of simultaneous measurement using the outputs from separate measurement and found that both methods (separate and simultaneous) produced similar δ¹³C values. The two-point calibrated method improved the results (range and variation) of δ¹³C and δ¹⁸O values. The mean values, standard deviations, and trends of the tree-ring δ¹³C obtained by the combustion method were similar to those by the pyrolysis method followed by two-point calibration. The simultaneously measured δ¹⁸O from the pyrolysis method at 1400°C had a nearly constant offset with that the pyrolysis method at 1350°C due to isotopic-dependence on the reaction temperature. However, they showed similar variations in the time series. The climate responses inferred from simultaneously and separately measured δ¹³C and δ¹⁸O did not differ between the two methods. The tree-ring δ¹³C and δ¹⁸O values were negatively correlated with standardized precipitation evapotranspiration index from May to August. In addition, the δ¹⁸O was significantly correlated with temperature (positive), precipitation (negative), and relative humidity (negative) from May to August. The tree-ring δ¹³C and δ¹⁸O values determined simultaneously through the high-temperature pyrolysis method could produce acceptable and reliable stable isotope series. The simultaneous isotopic measurement can greatly reduce the cost and time requirement compared with the separate isotopic measurement. These results are consistent with the previous studies at humid sites, suggesting that the simultaneous determination of δ¹³C and δ¹⁸O in tree-ring α-cellulose can be used in wide regions.     

不同Si/Al的氢型分子筛催化热解对生物油特性的影响

为考察对于氢型分子筛(HZSM-5)的Si/Al变化和添加量对生物质热解液化的影响,该文通过离子交换法制备HZSM-5催化剂,采用激光粒度分析仪、比表面积及孔径分析仪和X射线衍射仪对催化剂的粒度、孔隙及晶体结构等性质进行表征,并在最佳油产率温度下进行木屑的催化热解。对无催化剂和不同催化条件下得到的生物油进行气相色谱质谱联用分析,结果表明,分子筛作用下,生物油产率明显降低(最大降幅8%),含水率增加。同时,液体产物中醛类、酯类、酮类、呋喃等含氧化合物及酸含量均有所降低,提高了烃类和酚类的含量,峰面积百分比最高达到12.57%和39.36%,对催化剂催化调控改善生物油品质提供了一定的科学依据。     

生物质热裂解生物油精制的研究进展

生物质热裂解生物油的高含氧量、低热值和化学不稳定等特性在一定程度上影响了生物油的广泛应用,因此必须对生物油进行精制,以改善生物油的品质.该文从催化加氢、催化裂解、气相催化、水蒸气重整和乳化等方面详细阐述了生物油精制的研究进展,指出了生物油精制的发展方向,以期为生物油的应用提供参考.     

土壤生物炭的生产：三种窑模型的比较研究

Biochar has potentials for soil fertility improvement, climate change mitigation and environmental reclamation, and charred biomass can be deliberately incorporated into soil for long-term carbon stabilization and soil amendment. Many different methods have been used for biochar production ranging from laboratory to industrial scales. However, in countryside of developing countries,biomass is generally used for cooking but not charred. Biochar production techniques at farmer scale have remained poorly developed.We developed and tested biochar production kilns for farmers with a dimension of 50.8 cm × 38.1 cm(height × diameter), using three different setups for optimizing oxygen(O2) limitation and syngas circulation: airtight with no syngas circulation(Model I),semi-airtight with external syngas circulation(Model II) and semi-airtight with internal syngas circulation(Model III). A comparative assessment of these biochar production kiln models was made considering biochar pyrolysis time, fuel to biomass ratio, biochar to feedstock ratio and thermogravimetric index(TGI). Among the models, the best quality biochar(TGI = 0.15) was obtained from Model I kiln taking the longest time for pyrolysis(12.5 h) and the highest amount of fuel wood(1.22 kg kg-1biomass). Model III kiln produced comparatively good quality biochar(TGI = 0.11), but with less fuel wood requirement(0.33 kg kg-1biomass) and shorter pyrolysis time(8.5 h). We also tested Model III kiln in a three times larger size under two situations(steel kiln and pit kiln). The biochar to feedstock ratio(0.38) and quality(TGI = 0.14) increased slightly for the larger kilns. Quality of biochar was found to be mainly related to pyrolysis time. The costs for the biochar stove and pit kiln were US$ 65–77, while it was US$ 154 for the large size steel kiln. Model III kiln can potentially be used for both cooking and biochar production at farmer scale.     

Mg2+作用下水稻秸秆热裂解特性及动力学模拟

为研究Mg2+对水稻秸秆热裂解特性及动力学的影响,分别将MgO、MgCl2、KCl、NaCl、MgCl2-KCl、MgCl2-NaCl、KCl-MgCl2-NaCl与水稻秸秆按0.3∶1的质量比进行干混,并分别在10、30和50℃/min的升温速率下进行了非等温热裂解试验。试验结果表明：NaCl和KCl作用下的水稻秸秆热裂解只存在一个质量损失峰,Mg2+盐作用下水稻秸秆热裂解均出现肩状峰;水稻秸秆在MgCl2作用下的热裂解残留量最低,为11%;二元和三元盐降低了挥发分的初始析出温度,对裂解促进作用明显;Mg2+盐作用下水稻秸秆热裂解特性综合指数均大于纯水稻秸秆的综合指数,混合盐增大效应更显著;模拟所得模型的第一步反应多属于符合Jander方程的三维扩散反应,第二步反应为n阶反应;3种熔盐体系对水稻秸秆热裂解的作用大小依次为：三元盐>二元盐>一元盐;两步反应模型能较好地描述熔盐作用下的水稻秸秆热裂解反应。该研究为熔盐热裂解生物质制生物油的研究提供了参考。     

生物质焦油模型化合物的催化转化（简报）

生物质热解焦油对气化装置及气体运输装置都有极大危害,该文以脂肪烃类化合物正庚烷与环己烷作为焦油的模型化合物,在微型固定床反应器上采用商用Z417镍基催化剂研究了温度、S/C（水蒸气与焦油模型化合物中碳的摩尔比）和试验停留时间对正庚烷与环己烷催化转化率的影响。结果表明,在600～800℃范围内正庚烷与环己烷的转化率随温度的升高而提高,750℃时正庚烷转化率可达到95%,环己烷转化率达到88.7%左右。水蒸气量对于正庚烷和环己烷的转化率有一定的影响,并且可以促进气体产物成分调整与缓解催化剂表面积碳;延长停留时间增加了反应物与催化剂的接触时间,因此正庚烷和环己烷的转化率随停留时间增加而升高。试验结果表明,在水蒸气参与反应条件下,Z417镍基催化剂对生物质焦油模型化合物正庚烷与环己烷的催化效果良好。     

天然微藻水热炭理化特性及热解动力学研究

为探索天然微藻资源化的利用途径,该文以天然栅藻为原料,采用傅立叶转换红外线光谱分析, X射线衍射分析,X射线荧光光谱分析,环境扫描电子显微镜与热重分析仪对水热炭进行测试分析。研究结果表明,随着水热温度的升高,水热炭产率从47.29%(180℃)降低至43.01%(240%);水热炭的O/C摩尔比从1.45减小至0.28,碳化程度加强,水热炭具有应用于固体燃料的潜力。鉴于水热炭含有大量灰分,其热值为8.43～9.67 MJ/kg,因此脱灰预处理是必要的过程。经过水热碳化处理,天然栅藻的比表面积从4.36 m~2/g增加到35.26 m~2/g。热解动力学结果表明随着水热温度的提高,水热炭的热稳定性增强。研究结果对天然微藻的资源化利用提供了一定的理论参考。     

HZSM-5和MCM-41分子筛催化剂比例对油菜秸秆热解的影响

选取油菜秸秆为原料,利用不同比例均匀混合的HZSM-5/MCM-41进行在线催化热解油菜秸秆制备生物油试验,根据生物油有机相的理化特性、FT-IR、GC-MS分析和催化剂的BET分析结果,研究HZSM-5与MCM-41的混合比例对生物油品质的影响规律.结果表明随着混合催化剂中MCM-41质量分数的增加,生物油有机相产率、密度、运动黏度及O质量分数先减少后增加,C质量分数及高位热值先升高后降低,1,8-二甲基萘、对二甲苯、甲基萘等芳香烃类物质的选择性呈现先增加后减少的变化趋势,生物油有机相中羰基类物质的质量分数先减少后增加,酸性物质持续减少.当HZSM-5与MCM-41以1∶1混合时,生物油产率为18.68％,高位热值高达34.31 MJ/kg,生物油中烃类物质的质量分数为53.83％,羰基类物质的质量分数为6.35％.混合催化剂活性随MCM-41质量分数增加逐渐提高,当MCM-41质量分数超过50％时,混合催化剂的催化活性趋于稳定.     

Microwave pyrolysis of cellulosic materials for the production of anhydrosugars

Large-scale microwave rapid pyrolysis of cellulosic materials has been investigated. Levoglucosan (1,6-anhydro--d-glucopyranose) was obtained from a larch log as the main anhydrosugar in 2.6% yield on the basis of dry wood weight. This yield would be much higher than that obtainable by conventional pyrolysis in the largescale reaction. Levoglucosenone (1,6-anhydro-3,4-dideoxy--D-glycero-hex-3-enopyranos-2-ulose) was found to be produced in one-quarter the amount of levoglucosan. Other anhydrosugars, such as mannosan (1,6-anhydro--D-mannopyranose), galactosan (1,6-anhydro--d-galactopyranose), and xylosan (1,4-anhydro--d-xylopyranose), were also confirmed to be produced as minor components depending on the proportion of the monosaccharide content in the larch. When microwave pyrolysis of used papers and filter papers was performed, the yields of levoglucosan were about 6% and 12%, respectively, suggesting that a higher content of cellulose gives a larger amount of levoglucosan.