城市污水处理厂污泥低温热解技术

介绍了污泥低温热解技术的反应机理和影响因素,分析了热解产物的经济性,总结了污泥低温热解技术的优缺点.     

Tandem size exclusion chromatography-Polyacrylamide gel electrophoresis of humic acids

Humic acids (HAs) from four soils were fractionated by size exclusion chromatography (SEC) on Sephadex G-75. Three fractions were obtained in all humic acids, collected and assayed by Polyacrylamide gel electrophoresis (PAGE). The unfractionated HA from each soil was used as reference. Each chromatographic fraction formed one electrophoretic zone corresponding closely to one band of the reference sample with some admixture of the fractions preceding or following. The results indicate that fractionation of HAs by tandem SEC-PAGE can be successfully used for obtaining fractions of reduced polydispersity and different electrophoretic mobilities. Pyrolysis/methylation-gas chromatography-mass spectrometry of the full size preparations of HA and fractions with exactly defined molecular size and electrophoretic mobility showed a different distribution in humic components, mainly lipids, lignin derivatives and N-containing compounds.     

原料和热解温度对生物油分子蒸馏分离特性的影响

针对生物油组分复杂,难以直接应用的问题,该研究开展了不同生物油的分子蒸馏馏分分布规律的研究,并考察了不同原料和温度对生物油分子蒸馏分离特性的影响。热解液化试验结果表明,生物油组分以酸、醛、酮、酚、糖为主。随着热解温度的升高,松木生物油中轻质组分产率由21%不断降低至11%,而秸秆生物油中轻质组分产率稳定在20%左右。高温生物油各组分的平均分子自由程两极化程度加强,600℃制备轻质油蒸出比例最高,可以达到92%（松木）和86%（秸秆）。酚类化合物中酚羟基的数量可以显著影响其分离特性,较高的热解温度促进了酚羟基的产生,从而使酚类物质从蒸出部分（distillation fraction, DF）向残留部分（residual fraction, RF）中转移。分子蒸馏技术能够实现对不同生物油的有效分离,得到的DF中主要包含酸、酮和小分子酚类,RF则以糖和大分子酚为主,除了羟乙醛和苯并呋喃等化合物外,生物油中的大部分化合物的富集程度都可以达到90%以上。该研究可为快速热解生物油的分离及其后续提质研究提供一定的参考。     

盐酸预处理对生物质热解特性和热力学特性的影响

为深入探讨盐酸预处理对生物质热解特性的影响,采用热重法对比分析了酸洗前后玉米秸秆和银中杨在低升温速率(10、20、30、40、50℃/min)下的热解特性,利用分布活化能模型(DAEM)计算了热解过程的动力学参数和相应的热力学参数,采用傅里叶变换红外光谱(FTIR)分析了酸洗前后生物质化学结构的变化。结果表明:生物质热解过程经历了失水、玻璃化转变、快速热解和碳化4个阶段;酸洗预处理提高了生物质热解的最大失重速率和最终失重率,减少了焦炭的产生。在转化率为20%～70%时,用DAEM模型计算得到酸洗前后玉米秸秆和银中杨热解活化能分别为218.27～340.08 kJ/mol、225.17～291.73 kJ/mol、227.35～254.76 kJ/mol、197.39～235.52 kJ/mol。盐酸酸洗预处理整体上降低了生物质热解过程中的活化能、焓变和熵变,增加了吉布斯自由能(ΔG),促进了热解反应。酸洗前后玉米秸秆和银中杨红外光谱图相似,但在相同吸收峰处存在明显的强度变化,说明酸洗预处理对不同生物质有机官能团的影响程度不同。     

食用菌菌糠的热解特性及动力学分析

为考察食用菌菌糠的热解特性和机理,该研究采用热重和热重-红外联用对香菇菌糠在氮气气氛下的热解特性进行研究,考察不同升温速率下菌糠的热重(TG)曲线和微分热重(DTG)曲线的变化规律,并对DTG曲线进行分峰分析,通过计算得到香菇菌糠热分解的反应活化能E、反应级数n及频率因子A,以及热解产物析出特性;在固定床上开展了香菇菌糠的定温热解试验,试验温度分别为500、550、600℃,并对三相产物产率和成分组成等进行了分析。结果表明:香菇菌糠热解可以分为3个阶段,水分析出段,热解段和炭化段,其中主要热解阶段为250～550℃,失质量率达到58%;升温速率对香菇菌糠热解影响不明显,但是随着升温速率的增大,试样的TG和DTG曲线向高温区移动;菌糠热解的表观活化能为66.33 kJ/mol,较低的表观活化能表明菌糠更容易发生热解。固定床定温热解结果表明菌糠热解气的主要成分为CO_2、CO、CH_4、H_2,4种气体成分含量由高到低为:CO_2、CO、CH_4、H_2;随着热解温度的升高,菌糠热解所得生物油成分以CxHyOz为主,表明菌糠热解生成的生物油具有一定的潜在利用价值;香菇菌糠热解半焦的主要成分是固定碳,相较于原料,挥发分的占比大幅度减少。     

温度梯度对秸秆炭化物质产率及特性的影响

在300～700℃温度区间,玉米秸秆、水稻秸秆以每100℃为间隔,大豆秸秆以200℃为间隔,研究炭化热解,量化对比产物。结果表明,秸秆热解炭比表面积、总孔容积、pH和碱式官能团随温度升高而增加,孔径和酸式官能团随温度升高而降低;热解液随热解温度升高,酸度降低;热解气中氢气和甲烷含量随温度升高而增加。热解温度平均每升高100℃,热解炭产率平均减少9.31%,热解液产率平均增加4.55%,热解气产率平均增加4.35%。玉米秸秆热解炭、热解液和热解气产率拐点分别为600、611和666℃,水稻秸秆热解炭、热解液和热解气产率拐点分别为666、600和666℃。量化参数可为优化秸秆炭化工艺提供技术支持。     

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.     

生物质热解液与壳聚糖处理对圣女果保鲜效果的影响

为了提高生物质资源利用率，开发低毒无害的新型果蔬保鲜剂，进行了3.3%生物质热解液以及热解液和不同浓度（0.50、0.75、1.00 g/L）的壳聚糖复合涂被液处理对圣女果保鲜效果的研究，主要观察了多聚半乳糖醛酸酶（PG）、过氧化物酶（POD）和多酚氧化酶（PPO）的活性及相关物质含量的变化。结果表明：生物质热解液与壳聚糖复合可较好地抑制圣女果PG和PPO活性的增长并减缓POD活性的下降速率，同时可减缓可溶性果胶和过氧化氢含量的增长并延缓酚类物质含量的下降，说明生物质热解液与壳聚糖复合涂被液处理有利于圣女果的贮藏与保鲜。     

浅析生物质快速热裂解反应器

[目的]研究生物质快速热裂解反应器。[方法]根据文献资料对现行几种主流热裂解反应器做了详细的介绍,并对新兴的斜板槽式反应器做了简要介绍。[结果]反应器是生物质快速热裂解液化技术的核心,不同的反应器类型决定了不同的工艺类型和工艺参数,目前热裂解反应器普遍还存在一些问题,实现工业化高效节能生产还不容易;斜板槽反应器作为一种新的尝试,其有一定的优势,但也存在着许多问题,需要进一步改进。[结论]该研究为生物质能代替常规能源提供理论依据。     

生物质水蒸气氛围烘焙对后续热解影响

为了探究余热烟气中水蒸气对生物质烘焙及后续热解影响,该研究以榆木为研究对象,在立式炉中进行不同氛围（氮气及氮气-水蒸气）和不同温度（200、230、260、290 ℃）的烘焙试验,然后利用热重-质谱联用仪（TG-MS）和热裂解-色谱质谱联用仪（Py-GC/MS）进行惰性氛围的热解试验。结果表明：榆木在烘焙过程中发生了脱水、脱羰基、脱甲基反应,水蒸气的存在对后续热解油中乙酸的去除更有利。在所有样品中氮气氛围下290 ℃烘焙样品的失重速率峰值最低,仅为0.3%/℃。同时水蒸气的存在使氮气-水蒸气烘焙样品的最大失重峰后移。在热解主反应区,200、290 ℃烘焙温度下,水蒸气会提高热解反应活化能,而230、260 ℃烘焙温度下热解反应活化能却降低。此外,同一烘焙温度下水蒸气会抑制热解过程中H2、CH4、H2O、CO和CO2的生成。研究结果可为复杂气氛对生物质烘焙以及后续热解影响的研究提供参考。