β-O-4型木质素二聚体热解历程的密度泛函理论研究

为了解木质素的热解机理,利用密度泛函理论B3LYP方法,在6-31++G(d,p)基组水平上对含有C_α位羰基的β-O-4型木质素二聚体模型化合物(3-羟基-1-(4-羟基苯基)-2-苯氧基-1-丙酮)的热解过程进行了理论计算和分析。结果表明,C_α位上的羰基取代基可大大降低C_β—O的键解离能,提高C_α—C_β的键解离能,使得C_β—O的键解离能比C_α—C_β低91.5 k J/mol,因此该二聚体主要通过C_β—O键均裂的方式发生热解反应,其主要酚类热解产物是苯酚和4-羟基苯甲醛,次要产物是4-羟基苯乙酮,生成4-羟基苯甲醛的动力学最优路径是R7-a,其反应能垒为236.6 k J/mol。     

TG-FTIR联用下生物质废弃物的热解特性研究

采用TG-FTIR(热重-傅立叶红外光谱)联用的分析方法对红松锯屑的热解失重特性和产物生成特性进行了研究.结果表明,红松锯屑热解失重的主要阶段发生在200～450℃间,反应符合一级反应动力学模型,活化能在70～80 kJ·mol-1之间.小粒径有利于热解反应的进行,且该现象随着升温速率的增大而变得显著,但在本实验的梯度水平下粒径对热解特性的影响相对较小.升温速率对热解特性的影响相对较大,高的升温速率导致热解起始温度和失重峰温度向高温区移动,加快了热解进程,且升温速率达到50 K·min-1时,在735℃左右观察到特殊失重峰.FTIR的实时分析结果表明,热解的气态产物主要有CO2、CO、CH4和其他低分子烃类,通过对产物浓度变化的半定量分析,验证了粒径对热解特性的影响效果以及735℃左右特殊失重过程的存在.     

油料作物秸秆快速热解及其生物油特性的研究

以油菜秸秆、脱灰油菜秸秆、花生秸秆及芝麻秸秆等为原料,在小型流化床上进行了快速热解试验研究。从纤维素、半纤维素、木质素含量与灰分含量等原料品质方面,对热解产物分布以及生物油特性的影响进行了对比分析。结果表明,不同秸秆的纤维素、半纤维素、木质素的含量不同,其热解产物分布有所不同,纤维素与半纤维素含量高的秸秆,生物油产率较高。灰分对热解产物分布影响较大,脱除灰分有利于提高生物油的产率;脱除灰分对秸秆生物油品质有一定影响,其生物油的pH值、密度、运动粘度高于其它秸秆生物油。油菜秸秆、花生秸秆、芝麻秸秆生物油主要品质指标基本一致。     

8-甲氧基香豆素-3-甲酸薄荷酯的合成及其在卷烟加香中的应用

以薄荷醇和8-甲氧基香豆素-3-甲酸为原料,合成了一种新型、释放型清凉剂8-甲氧基香豆素-3-甲酸薄荷酯,产物的结构经IR、1H NMR、13C NMR和HRMS确证.采用在线裂解气相色谱-质谱联用技术,对8-甲氧基香豆素-3-甲酸薄荷酯在600℃下的裂解行为进行了研究,并对8-甲氧基香豆素-3-甲酸薄荷酯进行了卷烟加香试验.结果表明:(1)600℃时,香豆素-3-甲酸薄荷酯的热解产物中共鉴定出25种成分,其中多种为重要的烟草香味成分;(2)8-甲氧基香豆素-3-甲酸薄荷酯具有改善和修饰卷烟烟气,增加豆香与清凉香气,减轻刺激性的作用.     

Analyzing organic matter composition at intact biopore and crack surfaces by combining DRIFT spectroscopy and Pyrolysis‐Field Ionization Mass Spectrometry#

In the clay‐illuvial horizons (Bt) of Luvisols, surfaces of biopores and aggregates can be enriched in clay and organic matter (OM), relative to the bulk of the soil matrix. The OM composition of these coatings determines their bio‐physico‐chemical properties and is relevant for transport and transformation processes but is largely unknown at the molecular scale. The objective of this study was to improve the interpretation of spectra from Fourier transform infrared spectroscopy in diffuse reflectance mode (DRIFT) by using thermograms and released ion intensities obtained with pyrolysis‐field ionization mass spectrometry (Py‐FIMS) for a more detailed analysis of the mm‐scale spatial distribution of OM components at intact structural surfaces. Samples were separated from earthworm burrow walls, crack coatings, uncoated cracks, root channels, and pinhole fillings of the Bt‐horizons of Luvisols. The information from Py‐FI mass spectra enabled the assignment of OM functional groups also from spectral regions of overlapping DRIFT signal intensities to specific OM compound classes. In particular, bands from C=O and C=C bonds in the infrared range of wave numbers between 1,641 and 1,605 cm^?1 were related to heterocyclic N‐compounds, benzonitrile, and naphthalene. The OM at earthworm burrow walls was composed of chemically labile aliphatic C‐rich and rather stable lignin and alkylaromatic compounds whereas the OM of thick crack coatings and pinholes was dominated by heterocyclic N and nitriles and high‐molecular compounds, likely originating from combustion residues. In combination with Py‐FIMS, DRIFT applications to intact samples seem promising for generating a more detailed mm‐scale spatial distribution of OM‐related sorption and wettability properties of crack and biopore surfaces that may serve as preferential flow paths in structured soils.     

生物质无轴螺旋连续热解装置送料器设计及中试

为解决有轴螺旋送料器存在质量大、能耗高、易产生机械干涉等问题,该文设计了送料能力为150 kg/h的生物质无轴螺旋送料器,并以稻壳为原料开展了冷态输送和热解试验。设计的无轴螺旋送料器关键尺寸为:螺旋外径为400 mm、螺旋轴径为80 mm、螺距为200 mm,送料器采用柴油燃烧机和热解气回烧的方式加热,计算出燃烧机需要提供的功率为95.43 k W。稻壳冷态输送试验表明,当送料频率为50 Hz即无轴螺旋的转速为2.03 r/min时,无轴螺旋送料器输送稻壳的送料量为224.3 kg/h150 kg/h,无轴螺旋送料器的实际送料量高于理论计算值。稻壳热解试验表明,当加热腔最高温度为(700±50)℃时,随着热解时间增加,稻壳炭的挥发分质量分数由22.45%减至13.6%,灰分质量分数由29.38%增至33.44%,固定碳质量分数由48.17%增至52.96%。稻壳炭的高位热值随热解时间增加而增加,但在试验范围内增幅不大。热解时间对生物炭品质影响较大,即传热速率是限制大型连续热解反应器处理效率提高的主要因素,因此,在工业化应用的大型热解反应器的设计中,应着重考虑提高热解传热效率的方法。     

保温时间与粒度对稻秆和棉秆热解产物组成及能量转化影响

热解炭化技术的开发对秸秆的能源化利用具有重要意义。试验研究了保温时间与粒度对水稻和棉花秸秆热解产物理化特性及能源转化的影响。结果表明,保温时间从0到120 min中,秸秆生物炭产率先降低后略增加,热解气中CH_4、C_nH_m和H_2百分含量增加,其高位热值和能量转化率增加,而生物炭的pH值、电导率、灰分、固定碳、C、高位热值增加,保温时间为90 min的生物炭的炭化程度最好。秸秆中能量有1.5%~5.4%保留在热解气中,有50%~57%保留在生物炭中。不同粒度相比,粗粉秸秆的生物炭的炭产率、挥发分、H、O、N及碳转化率最高,细粉秸秆热解气中CO和CH_4百分含量、高位热值和能量转化率最高,而超微秸秆生物炭的pH值、灰分、C最高。棉花秸秆生物炭的挥发分、固定碳、C、H、碳转化率、高位热值和能量转化率高于水稻秸秆生物炭。     

Effects of biochars produced from different feedstocks on soil properties and sunflower growth

The use of biochar as a soil amendment is gaining interest to mitigate climate change and improve soil fertility and crop productivity. However, studies to date show a great variability in the results depending on raw materials and pyrolysis conditions, soil characteristics, and plant species. In this study, we evaluated the effects of biochars produced from five agricultural and forestry wastes on the properties of an organic‐C‐poor, slightly acidic, and loamy sand soil and on sunflower (Helianthus annuus L.) growth. The addition of biochar, especially at high application rates, decreased soil bulk density and increased soil field capacity, which should impact positively on plant growth and water economy. Furthermore, biochar addition to soil increased dissolved organic C (wheat‐straw and olive‐tree‐pruning biochars), available P (wheat‐straw biochar), and seed germination, and decreased soil nitrate concentration in all cases. The effects of biochar addition on plant dry biomass were greatly dependent upon the biochar‐application rate and biochar type, mainly associated to its nutrient content due to the low fertility of the soil used. As a result, the addition of ash‐rich biochars (produced from wheat straw and olive‐tree pruning) increased total plant dry biomass. On the other hand, the addition of biochar increased the leaf biomass allocation and decreased the stem biomass allocation. Therefore, biochar can improve soil properties and increase crop production with a consequent benefit to agriculture. However, the use of biochar as an amendment to agricultural soils should take into account its high heterogeneity, particularly in terms of nutrient availability.     

纤维素与半纤维素热解过程的相互影响

以微晶纤维素为纤维素模型物,以木聚糖为半纤维素模型物,采用同步热分析仪(STA)及热重和傅立叶红外光谱仪联用技术(TG-FT-IR)对微晶纤维素、木聚糖以及两种成分不同比例的混合组分进行了研究,以考察纤维素和半纤维素在热解过程中的相互影响。结果表明微晶纤维素和木聚糖均有一狭窄的快速热解温度区间,而且两者热解区间不重合。在微商热失重(DTG)峰对应温度区间微晶纤维素热解有一明显的吸热峰,吸热量为547.98 J/g,木聚糖热解则有一个比DTG峰较晚出现的小吸热峰,吸热量为45.01 J/g。木聚糖与微晶纤维素的混合组分的热解研究中发现,在DTG曲线上有两个分别由它们热解引起的失重峰,随着组分中比例的变化两个热失重峰此消彼长。微晶纤维素的热解失重峰不仅往高温区移动,而且热解速率减缓,热失重范围变宽。在DSC曲线上有两个分别由木聚糖和微晶纤维素热解所引起的吸热峰,木聚糖的吸热峰受组分中比例的变化影响较小,而微晶纤维素吸热峰随着纤维素比例的下降而明显减小。FT-IR检测到的主要有气体产物为H2O、CH4、CO2和CO。木聚糖与微晶纤维素的混合组分热解产物析出规律总体上是两者热解产物析出的叠加,与单独热解相比组分的混合有利于CH4、CO的生成,而CO2的产量则有较大幅度的下降。     

畜禽粪便热解气体的红外光谱分析

为了解畜禽粪便热解过程析出气体的主要成分以及气体析出规律,该文在30℃/min的升温速率条件下进行了猪粪、牛粪、羊粪和鸡粪的热解试验,利用傅里叶变换红外光谱（FTIR）技术对热解过程中气体产物的排放特性进行了分析。试验结果表明,畜禽粪便气体产物主要在250～500℃析出,其主要成分为H2O,CO,CO2和CH4等,其中H2O、CO和CO2的析出峰为双峰,H2O和CO2均在350℃附近形成最大析出峰,H2O约在150℃形成第1个析出峰,CO2约在710℃附近形成的第2个析出峰,CO在350℃处形成第一个析出峰,其最大析出峰形成于710℃处左右,CH4析出特性为一单峰,在530℃附近形成最大峰值。该文研究结果为热解反应器的设计和优化提供参考。