在线流动注射液-液萃取非水介质汞还原原子荧光光谱法的研究及应用

提出了一种流动注射在线液－液萃取有机相汞还原原子荧光光谱法测定汞的新方法。该法以KI＋HNO3＋（NH2）2CS／TBP为萃取体系，将汞萃取到有机相中，汞还原反应是在金属络合萃取液与含NaBH4的N，N－二甲基甲酰铵（DMF）溶液和冰乙酸中发生。应用流动注射技术实现了液－液萃取非水介质汞还原反应原子荧光测定的在线分析。研究了反应的最佳条件和流动注射流路及运行程序。该法提高了测定灵敏度并消除了干扰。用于地质样品中汞的测定得到好的准确度和精密度。     

萃金体系第三相的产生及其谱学研究

利用^198Au示踪法研究了十四烷基二甲基苄基氯化铵从碱性氰化液中萃取金第三相的产生过程，同时用傅里叶变换红外光谱（FTIR），核磁共振（NMR），激光光散射（DLS）等方法分析了第三相形成后上下两有机相的微观结构，结果表明，随着有机相中金浓度的增大，有机相中有纳米级的聚集体形成；当金浓度继续增大时，有机相分为上下两相，有机相中的金，磷酸三丁酯（TBP）和水主要集中在下层，下层有机相有明显的水特征吸收峰，TBP的P=O伸缩振动向低频移动，核磁共振（^31P-NMR)的化学位移明显移向高场；用激光光散射技术测定了两有机相中聚集体的大小。     

双水相液膜微萃取咖啡因的动力学

自行设计了双水相支撑液相膜微萃取装置,以聚四氟乙烯徽孔膜为支撑,以磷酸三丁酯为有机萃取相,紫外光谱法研究了咖啡因稀水溶液的双水相液萃取。发现咖啡因以分子形式通过磷酸三丁酯有机液膜萃取进入HCl溶液中,萃取动力学受浓度差和收集液相中的化学反应控制,萃取率与咖啡因浓度成反比。     

用三正辛胺-苯萃取分离体系-原子吸收光谱对铬作形态分析

研究了痕量铬形态分析的三正辛胺(TOA)-苯萃取分离体系-原子吸收光谱法。用三正辛胺(TOA)和苯在H₂SO₄介质中把水相中的Cr(Ⅵ)萃入到有机相而Cr(Ⅲ)留在水相中,使两种形态的Cr分离到两相中后对有机相的Cr(Ⅵ)和水相的Cr(Ⅲ)进行AAS测定,可求得Cr(Ⅵ)和Cr(Ⅲ)的含量,该方法对实际水样加标回收率分别在95.0%～102% 和94.8%～103%之间,相对标准偏差分别为2.9%和2.6% ,体系对Cr(Ⅵ)有富集作用,对Cr(Ⅵ)和Cr(Ⅲ)的检出限分别为6.6 μg·L-1和0.20 mg·L-1,TOA对Cr(Ⅵ)的最佳萃取量为4.6 mg·mL-1,该法简单、快速、准确。     

镍基金属有机骨架催化制藻基生物航油

本文研制了镍基金属有机骨架催化剂,考察了其催化微藻生物质及其水热提取油脂进行脱氧断键制航油性能。当金属有机骨架负载镍金属后,碳氧钴元素含量降低而镍元素含量提升到22.25%。由于金属骨架中钴的电子部分转移给成功担载的镍金属,故催化微藻亚临界水热提取油脂制航油的转化率和选择性分别达到90.51%和37.83%,显著高于微藻生物质直接催化转化效果。以微藻油脂的典型成分十六烷酸为例,量子化学计算揭示了其脱氧断键的竞争反应机理:Ni-H加成到羰基碳原子使得羰基碳与α位碳的键长由0.08007 nm拉长为0.08132 nm,有助于十六烷酸脱羧;同时Ni-H加成到羰基碳原子上的反应焓变为-40.8 kJ/mol,低于Ni-H加成到羰基氧原子上的158.8 kJ/mol,故脱羧反应更倾向于沿Ni-H加成到羰基碳原子的路径进行。     

水-四氢呋喃混合溶剂中硫酸氢钠催化生物质转化制备5-羟甲基糠醛及糠醛

报道了在水-四氢呋喃组成的混合溶剂中,采用硫酸氢钠催化各种生物质原料(玉米芯、玉米秸秆、麦秆、稻秆和甘蔗渣)制备重要的生物质基平台化学品5-羟甲基糠醛和糠醛的研究. 考察了反应温度(160～200 oC)、反应时间(30～120 min)、水与四氢呋喃的溶剂比例(1:1～1:10)和原料质量分数(2.4wt%～11.1wt%)等反应工艺的影响.在优化的工艺条件下(190 oC, 90 min, 10:1 THF:H₂O),转化玉米芯得到了47mol%的HMF和56mol%的糠醛. 此外,原料中的木质素也被有效地转化为有机溶木质素.     

血浆中丁丙诺啡提取方法研究

报道了液相萃取法、固相萃取法提取血浆中丁丙诺啡的方法.血浆中添加丁丙诺啡,液相萃取时调pH至7用三氯甲烷提取、固相萃取时调pH至10.8用401有机担体作吸附剂、用三氯甲烷作洗脱剂,GC/NPD法进行检测.液相萃取血浆中丁丙诺啡萃取率可达85.8%以上,固相萃取血浆中丁丙诺啡萃取率可达87.7%以上.该提取方法萃取率高,可用于血浆中丁丙诺啡的提取.     

双水相体系中Cu(Ⅱ),La(Ⅲ),U(Ⅵ),Ce(Ⅳ)光谱行为及萃取分离

利用聚乙二醇2000(PEG)-(NH)2SO4-萃取剂(铜试剂)双水相体系,采用液-液萃取的方法,研究了PEG相、单纯水相中金属离子络合物及萃取剂的光谱行为,探讨了金属离子络合物在PEG相中存在形态及萃取机理。同时实验了在不同酸度,不同盐用量,不同萃取剂用量,以及在不同表面活性剂的影响下,铜、镧、铀、铈的萃取率,通过控制一定条件,实现了Cu(Ⅱ)与La(Ⅲ),Cu(Ⅱ)与Ce(Ⅳ)之间的定量萃取分离。     

TBP对部分皂化的DMHPA—正庚烷体系及萃取稀土有机相的影响

研究了部分皂化的二（１甲基庚基）磷酸（ＤＭＨＰＡ）磷酸三丁酯（ＴＢＰ）—正庚烷（Ｃ７Ｈ１６）体系及萃取稀土有机相的聚集状态。结果表明，ＴＢＰ可以扩大ＤＭＨＰＡＣ７Ｈ１６Ｈ２Ｏ微乳状液形成的区间，并且对萃取有机相的存在状态及水的行为有明显的影响，在一定的条件下有凝胶形成。ＦＴＩＲ光谱分析表明，该类凝胶中ＤＭＨＰＡ和ＴＢＰ与稀土离子以多种形式配位，ＴＢＰ与ＤＭＨＰＡ及水的氢键结合对凝胶网状结构的形成也起了一定的作用。     

TBP-Pd(Ⅱ)-HCI萃取体系微乳的生成及溶液聚集态的谱学研究

采用动态激光光散射(DLS)、Fourier变换红外光谱(FTIR)、核磁共振波谱(31P-/1H NMR)等谱学技术,研究了TBP-Pd(Ⅱ)-HCI萃取有机相中微乳的形成以及溶液聚集态结构的变化.结果表明:(1)伴随钯的萃取,TBP萃取有机相中形成微乳.(2)萃取有机相中酸含量的变化导致溶液结构发生相应改变:胶团聚集体平均流体力学半径随有机相中酸含量的增加先增大而后又减小.微乳"内核水"的O-H伸缩振动吸收谱带逐渐宽化,与邻近的C-H伸缩振动区形成交迭,且有机相含酸量越高,交迭程度越大.水分子O-H-O弯曲变角振动吸收峰形也发生很大变化.TBP的P=O伸缩振动明显向低频移动.核磁共振31P化学位移与活泼氢1H化学位移变化行为相反,说明TBP分子与酸和水分子发生缔合,形成RP=0·H 或RP-O·H3O ,并与PdC2-4存在相互作用.(3)有机相形成微乳水团后,由于大量H 的进入,微乳水团中酸浓度表现出明显的"增浓效应".微乳水池内部微观环境的改变是导致钯萃取行为变化的主要原因.     

Temporal temperature measurement on burning biomass pellets using phosphor thermometry and two-line atomic fluorescence

We report accurate in-situ optical measurements of surface temperature, volatile gas temperature, and polycyclic aromatic hydrocarbon (PAH) emission over the whole burning history of individual biomass pellets in various combustion atmospheres. Two biomass fuels, wood and straw, were prepared in cylindrical pellets of ～300 mg. The pellets were burned in a well-controlled combustion atmosphere provided by a laminar flame burner with temperature ranging from 1390 K to 1840 K, and oxygen concentration from zero to 4.5%. The surface temperature of burning biomass pellets was accurately measured, for the first time, using phosphor thermometry, and the volatile gas temperature was measured using two-line atomic fluorescence thermometry. PAH emission was monitored using two-dimensional laser-induced fluorescence. During the devolatilization stage, a relatively low surface temperature, ～700 K, was observed on the burning pellets. The volatile gas temperature was ～1100 K and ～1500 K 5 mm above the top of the pellets in a gas environment of ～1800 K with 0.5% and 4.5% oxygen, respectively. PAH mainly released when the temperature of the pellet exceeded ～600 K with the highest concentration close to the surface and being consumed downstream. The weight of the released PAH molecules shifted towards lighter with a reduction of gas environment temperature. The wood and straw pellets had almost the same surface and volatile gas temperature but different compositions in the released volatile gases. The temperature information provided in the present work aids in revealing the reactions in the burning biomass fuels regarding species release, such as various hydrocarbons, nitrogen compounds, and potassium species, and is valuable for further development of biomass thermal conversion models.     

Ultrasound-ionic liquid enhanced enzymatic and acid hydrolysis of biomass cellulose

The purpose of this paper was to investigate the effect of ultrasound-ionic liquid (IL) pretreatment on the enzymatic and acid hydrolysis of the sugarcane bagasse and wheat straw. The lignocellulosic biomass was dissociated in ILs ([Bmim]Cl and [Bmim]AOC) aided by ultrasound waves. Sonication was performed at different frequencies (20, 28, 35, 40, and 50 kHz), a power of 100 W, a time of 30 min and a temperature of 80 °C. The changes in the structure and crystallinity of the cellulose were studied by Fourier transform infrared (FT-IR), X-ray diffraction (XRD) and thermal gravimetric analysis (TGA). The amounts of the total reducing sugars, glucose, cellobiose, xylose and arabinose in the hydrolysates were determined. The results of FT-IR, XRD and TGA revealed that the structure of cellulose of both biomass samples remained intact after the pretreatment, but the crystallinity decreased. The enzymatic and acid hydrolysis of the biomass samples pretreated with the ultrasound-IL result in higher yields of the reducing sugars compared with the IL-pretreated sample. Enzymatic hydrolysis of bagasse and wheat straw pretreated with [Bmim]Cl-ultrasound resulted in maximal yields of glucose at 20 kHz (40.32% and 53.17%) and acid hydrolysis resulted in maximal yields of glucose at 40 kHz (33.32% and 48.07%). Enzymatic hydrolysis of bagasse and wheat straw pretreated with [Bmim]OAc-ultrasound show maximal yields of glucose at 28 kHz and acid hydrolysis at 50 kHz. Combination of ultrasound with [Bmim]OAc is more effective than [Bmim]Cl in terms of the yields of reducing sugar.     

共聚焦显微拉曼光谱在木质纤维细胞壁预处理中的应用进展

在能源紧缺和环境恶化的双重压力下,利用农林生物质替代化石资源生产生物燃料、生物基化学品和材料逐步发展成为世界范围内的研究热点,而细胞壁中纤维素、半纤维素、木质素以及其他少量组分的空间分布不均一性和化学结构复杂性构成了天然抗降解屏障,严重阻碍生物质的转化效率,因此需要对木质纤维原料进行预处理,以期破坏细胞壁的宏观壁垒,实现生物质的低成本高效转化。在此过程中,全面了解木质纤维细胞壁的化学组成、结构特性及其在生物质转化过程中的解构机理是高效利用农林生物质的重要前提。由于拉曼光谱具有样品制备要求低、灵敏度高、且能在原位状态下对样品进行定性、定量分析等特点,使得拉曼光谱成为研究木质细胞壁结构的有力工具。尤其与显微技术相结合时,可以同时获得木质纤维细胞壁主要组分的微区分布与超分子结构信息,实现生物质转化过程中化学组分动态变化的可视化研究。首先介绍了拉曼光谱成像的工作原理,并对纤维素、半纤维素和木质素的拉曼特征信号进行了归属。其次,总结了近几年拉曼光谱在生物质转化领域内的应用与研究进展,综述了拉曼光谱在未处理状态下以及稀酸、水热、稀碱等不同预处理过程中的分析方法,对细胞壁主要组分的分布进行表征,以揭示预处理过程中各组分的溶出过程及迁移规律,为在细胞及亚细胞水平探究预处理诱导细胞壁主要组分动态溶解机制提供了有效路径。此外,针对检测中收集的光谱数量过多、分析难等问题,文章重点介绍了主成分聚类分析法和顶点成分分析法两种拉曼数据分析方法,用于提取特征信息并对光谱进行分类研究,以深入探究特定组分的空间分布和分子结构。最后,根据上述分析展望了拉曼光谱在生物质转化领域的研究趋势,为相关研究提供技术参考。     

Reduction effect of co-firing of torrefied straw and bituminous coal on PM1 emission under both air and oxyfuel atmosphere

Straw sample was torrefied at 260 °C and 300 °C in N₂, respectively, to prepare torrefied straw named as T-260 and T-300, and the reduction effect of co-firing straw or torrefied straw and steam coal on PM₁ is investigated. The combustion experiments were conducted in a high temperature drop tube furnace (DTF) at 1400 °C to collect the inorganic PM₁₀ for further analysis. Combustion atmosphere was air for all cases and 50% O₂/50% CO₂ (OXY50) for coal, T-260 and their blends of 1:1 and 4:1. The results show that all three biomass fuels show obvious emission reduction of PM with aerodynamic diameters of ≤?0.3?µm (PM_0.3) under both mix ratios. Reduction ratios of co-firing are overall higher at mix ratio of 1:1 than 4:1, and co-firing of T-260 or T-300 with coal shows higher reduction ratio than co-firing of straw. The higher ash content in torrefied straw leads to higher contents of alkali and alkaline earth metals (AAEM), which will further react with both Si and S during co-firing and coagulate into particles of larger sizes, leading to higher reduction ratios of PM_0.3 and unconspicuous reduction effects in PM_0.3–1 emitted from co-firing. During co-firing in oxyfuel atmosphere, a higher combustion temperature compared to air leads to an intensitive gasification, may resulting in effective and even higher reduction ratio in PM_0.3.     

High-throughput heterogeneous catalyst research

With the discovery of abundant and low cost crude oil in the early 1900’s came the need to create efficient conversion processes to produce low cost fuels and basic chemicals. Enormous investment over the last century has led to the development of a set of highly efficient catalytic processes which define the modern oil refinery and which produce most of the raw materials and fuels used in modern society. Process evolution and development has led to a refining infrastructure that is both dominated and enabled by modern heterogeneous catalyst technologies. Refineries and chemical manufacturers are currently under intense pressure to improve efficiency, adapt to increasingly disadvantaged feedstocks including biomass, lower their environmental footprint, and continue to deliver their products at low cost. This pressure creates a demand for new and more robust catalyst systems and processes that can accommodate them.Traditional methods of catalyst synthesis and testing are slow and inefficient, particularly in heterogeneous systems where the structure of the active sites is typically complex and the reaction mechanism is at best ill-defined. While theoretical modeling and a growing understanding of fundamental surface science help guide the chemist in designing and synthesizing targets, even in the most well understood areas of catalysis, the parameter space that one needs to explore experimentally is vast. The result is that the chemist using traditional methods must navigate a complex and unpredictable diversity space with a limited data set to make discoveries or to optimize known systems.We describe here a mature set of synthesis and screening technologies that together form a workflow that breaks this traditional paradigm and allows for rapid and efficient heterogeneous catalyst discovery and optimization. We exemplify the power of these new technologies by describing their use in the development and commercialization of a novel catalyst for the hydrodesulfurization of gasoline distillates having 50% more selectivity and 30% more activity for sulfur removal than the state-of-the-art commercial reference.     

Ultrasonic-assisted catalytic transfer hydrogenation for upgrading pyrolysis-oil

Recent interest in biomass-based fuel blendstocks and chemical compounds has stimulated research efforts on conversion and upgrading pathways, which are considered as critical commercialization drivers. Existing pre-/post-conversion pathways are energy intense (e.g., pyrolysis and hydrogenation) and economically unsustainable, thus, more efficient process solutions can result in supporting the renewable fuels and green chemicals industry. This study proposes a process, including biomass conversion and bio-oil upgrading, using mixed fast and slow pyrolysis conversion pathway, as well as sono-catalytic transfer hydrogenation (SCTH) treatment process. The proposed SCTH treatment employs ammonium formate as a hydrogen transfer additive and palladium supported on carbon as the catalyst. Utilizing SCTH, bio-oil molecular bonds were broken and restructured via the phenomena of cavitation, rarefaction, and hydrogenation, with the resulting product composition, investigated using ultimate analysis and spectroscopy. Additionally, an in-line characterization approach is proposed, using near-infrared spectroscopy, calibrated by multivariate analysis and modeling. The results indicate the potentiality of ultrasonic cavitation, catalytic transfer hydrogenation, and SCTH for incorporating hydrogen into the organic phase of bio-oil. It is concluded that the integration of pyrolysis with SCTH can improve bio-oil for enabling the production of fuel blendstocks and chemical compounds from lignocellulosic biomass.     

基于工业分析/元素分析和可见-近红外光谱预测农作物秸秆高位热值

越来越多的农作物秸秆用于生产生物质成型燃料(生物质颗粒),作为民用和工业锅炉的生物质燃料。高位热值是衡量生物质燃料燃烧性能的主要参数之一,反映了生物质可用能含量,但利用传统的氧弹分析法测试高位热值费时费力,急需一种快速准确的方法评估农作物秸秆的高位热值,以制备高质量的生物质颗粒燃料。基于工业分析/元素分析和可见-近红外光谱分析,对比分析了五种农作物秸秆(稻秸、麦秸、棉秆、油菜秆和玉米秆)的高位热值预测模型。首先,利用多元线性回归(MLR)、逐步回归(SWR)和反向传播人工神经网络(BPNN)模型,在基于五种农作物秸秆工业分析和元素分析基础上,提出了高位热值预测模型并进行验证。MLR模型具有较好的相关系数(R2),预测均方根误差(RMSEP)和预测标准差与参比标准差比值(RPD),分别为0.921 1,0.135 1和3.49。此外,利用可见-近红外光谱分析了农作物秸秆,发现对光谱数据作最小二乘法回归(PLR),可建立高位热值预测模型,预测R2和RMSEP分别为0.881 2和0.412 9。研究结果表明MLR模型和PLR模型分别适用于基于工业分析/元素分析和可见-近红外光谱建模,对农作物秸秆的高位热值快速检测设备研发能提供基础模型支持。     

Ultrasonic vibration-assisted pelleting of wheat straw: A predictive model for energy consumption using response surface methodology

Cellulosic biomass can be used as a feedstock for biofuel manufacturing. Pelleting of cellulosic biomass can increase its bulk density and thus improve its storability and reduce the feedstock transportation costs. Ultrasonic vibration-assisted (UV-A) pelleting can produce biomass pellets whose density is comparable to that processed by traditional pelleting methods (e.g. extruding, briquetting, and rolling). This study applied response surface methodology to the development of a predictive model for the energy consumption in UV-A pelleting of wheat straw. Effects of pelleting pressure, ultrasonic power, sieve size, and pellet weight were investigated. This study also optimized the process parameters to minimize the energy consumption in UV-A pelleting using response surface methodology. Optimal conditions to minimize the energy consumption were the following: ultrasonic power at 20%, sieve size at 4 mm, and pellet weight at 1 g, and the minimum energy consumption was 2.54 Wh.     

Modeling of chemical tracer transport in the atmospheric environment and its impact on the global climate

Continental regions are experiencing rapid environmental changes due to expansion of industrial activities and land uses in different types of agricultural productions, burning of fossil fuels, etc., which lead to the emanation of huge amount of smog aerosol particulates and chemicals in the atmosphere. Information about these chemical tracers has been found from Indian Ocean Experiment (INDOEX), Intergovernmental Panel for Climate Change (IPCC) assessment reports as well as from other sources. The results of these computations may be interpreted by the chemical tracer transport model. In this paper, we have used a global atmospheric model in which the optical properties and the concentrations of the chemical tracers and aerosols have been incorporated. The aerosols and chemicals are transported in the atmospheric environment by the model cumulus convection and through the model semi-Lagrangian advection process . Thus, they are globally distributed along with the wind flow. The model has been used in studying the impact of the tropospheric chemical perturbations on the global environment.