四元共聚物的热裂解色谱-质谱分析

报道了2－丁烯、甲基丙烯酸甲酯、丙烯酸丁酯、丙烯酸辛酯四元共聚物在不同裂解温度下的热裂解行为。用热裂解色谱－质谱分析方法，研究了裂解温度对裂解产物的影响，并讨论了四元共聚物的热裂解规律。     

High temperature pyrolysis of novolac resin biomass composites

Composites of novolac resin (N.R.) and biomass derived from olive stones (OL.B.), in various proportions, were cured with hexamethylenetetramine (HTA) and pyrolyzed up to 900°C. The pyrolysis mechanism was monitored using TGA and gas chromatography. The pyrolysis regions, as well as important pyrolysis parameters of the materials used, were determined. Cured and pyrolyzed composites of N.R./OL.B. varied from 20/80 to 75/25, exhibiting at temperatures up to approx. 600°C lower weight losses than expected by the rule of mixtures, owing to additional cross linkages of lignin with HTA. This stabilization effect vanished during pyrolysis at higher temperatures because of the breaking of other chemical bonds, e.g. cross linkages. The release of CH₄ during the pyrolysis of OL.B. is derived from the lignin contained in OL.B. The other gases, CO, CO₂ and H₂, could be formed from celluose, hemicellulose and lignin which are the main components of OL.B. The use of N.R. in the initial mixture with OL.B. reduces the weight losses during pyrolysis compared with OL.B. alone. A heating rate of 10°C/min was necessary for the carbonization processes of OL.B. and its mixtures with N.R. in order to promote minimum weight loss of material and minimum pyrolysis time.     

热裂解气相色谱法测定动物源性食品中敌百虫残留量

通过对热裂解气相色谱及气-质联用技术测定动物源性食品中敌百虫的探讨,建立了气相色谱进样口裂解产物的检测方法,并确定了气相色谱的主要分析条件(进样口280℃,DB-225毛细管色谱柱及FPD检测器)。样品前处理结合动物源性食品的特点,采用V(乙腈)∶V(水)=9∶1提取,乙酸锌水解除酯,并利用三氯化碳相转移的方式,建立了一套前处理方法。检测方法的回收率在80.7%~96.5%之间,RSD<5.5%,线性相关系数为0.9991,检出限为0.02mg/kg。该方法是按照我国关于兽药残留分析方法要求建立的,适合进出口及日常动物源性食品中敌百虫残留量的检测。     

Real-time method for the identification and quantification of hydrocarbon pyrolysis products: Part II. Application to transient pyrolysis and validation by numerical simulation

A real-time quantification infra red method has been developed with a gas cell to determine the composition of hydrocarbon pyrolysis products. The aim is to chemically characterise the fuel decomposition in case of regenerative cooling. The method can be extended to a large variety of applications. A transient analysis of the method behaviour is conducted to estimate its capacity to be applied to unsteady conditions (one measure per second), which can be encountered in cooling activity and unsteady processes. A numerical tool called RESPIRE (French acronym for Supersonic Combustion Ramjet Cooling with Endothermic Fuel, Transient Reactor Programming) is used to help in understanding the complex phenomena involved in such a chemical reactor. The validation of transient behaviour with respect to the computations shows negligible time delay (lower than few seconds with gasification rate higher than 60 wt.%) due to residence time in the experimental setup. The quantification accuracy is confirmed to be around 2 mol%. The agreement obtained on gas cell measurements is found to be correct over 10-20 wt.% of gasification rate and very satisfactory over 60 wt.% but this depends on the species. An extension of the method has been developed with a dedicated online cell to be specifically applied to supercritical and multiphase flows. The quantification of the gas phase in the pyrolysis mixture in case of biphasic flow is proposed and validated with an uncertainty around 3 wt.%. The coke formation is monitored as a function of time and its quantification is even tested with 50% of uncertainty after a numerical calibration with respect to simulation.     

In-situ pyrolysis and silylation for analysis of lipid materials used in paint layers

Summary Although pyrolysis coupled with gas chromatography and mass spectrometry (Py-GC-MS) is a useful technique for the rapid characterization of the organic materials used by artists, diagnostic pyrolysis products bearing polar groups, for example carboxylic acids, require derivatization (e. g. methylation) before GC separation. In this study we propose the use of hexamethyldisilazane (HMDS) as an effective on-line derivatizing reagent to prepare the trimethylsilyl (TMS) derivatives of fatty acids released from the pyrolysis of fats. Pyrolysis in combination with HMDS has been applied to the analysis of lipid materials employed as painting media, for example siccative oils and egg.     

木质素二聚体模型化合物热解机理的量子化学研究

β-O-4连接是木质素主体结构单元之间的主要联结方式。采用密度泛函理论方法B3LYP,在6-31G (d, p)基组水平上,对β-O-4型木质素二聚体模型化合物(1-愈创木基-2-(2-甲氧基苯氧基)-1,3丙二醇)的热解反应机理进行了研究。提出了三种热解反应途径:C_β-O键均裂的后续反应、C_α-C_β键均裂的后续反应以及协同反应。对各种反应的反应物、产物、中间体和过渡态的结构进行了能量梯度全优化,计算了各热解反应途径的标准动力学参数。分析了各种主要热解产物的形成演化机理以及热解过程中温度对热解机理的影响。计算结果表明,C_β-O键的均裂反应和协同反应路径(1)和(3)是木质素二聚体热解过程中主要的反应路径,而C_α-C_β键的均裂反应和协同反应路径(2)和(5)是主要的竞争反应路径;热解的主要产物是酚类化合物如愈创木酚、1-愈创木基-3-羟基丙酮、3-愈创木基-3-羟基丙醛、愈创木基甲醛和乙烯等。在热解低温阶段协同反应是热解过程中的主要反应形式,而在高温阶段自由基均裂反应是热解过程的主要反应形式。     

Determination of biogenic quaternary ammonium compounds on fused silica capillary columns with a splitless injector as a chemical reactor/pyrolysis chamber

A conventional splitless injector is used as a pyrolysis chamber or chemical reactor for the N-demethylation of acetylcholine and other choline esters. The novel uses of 2-aminoethanol as a N-demethylation reagent in splitless injection and bonded-phase fused silica capillary columns in the separation of the tertiary amine derivatives of choline esters are described. A comparison is made between non-polar and moderately polar fused silica capillary columns in the separation of choline esters.     

Dimethyl carbonate as a novel methylating reagent for fatty acids in analytical pyrolysis

Dimethyl carbonate (DMC) was investigated as a mild, harmless and odorless reagent for pyrolytic methylation of fatty acids. Soybean oil was selected as test material for its high content of (poly)unsaturated fatty acids. Pyrolyses were performed at 500, 700 and 900 degrees C by means of a heated platinum filament pyrolyser on-line and off-line to the GC-MS apparatus. Methyl esters of palmitic, linoleic, oleic and stearic acid were formed as prominent products from off-line pyrolysis of soybean oil in the presence of DMC and zeolite 13X. Fatty acid methyl esters (FAMEs) were not observed at important levels in the absence of zeolite, while on-line Py-GC-MS experiments resulted principally in the formation of free fatty acids and hydrocarbons. The FAME profiles obtained from the DMC/zeolite off-line pyrolysis were compared to those resulting from tetramethylammonium hydroxide (TMAH) thermochemolysis and BF3-methanol procedure. The observed differences between pyrolysis and methanolysis methods were principally attributed to the thermal degradation of unsaturated fatty acids. The effectiveness of the DMC/zeolite pyrolytic methylation was further demonstrated by the analysis of tripalmitine and soybean seeds.     

Determination of sodium dodecylbenzene sulfonate in ternary mixtures by curie-point pyrolysis gas chromatography coupled to multivariate analysis

Summary Multivariate analysis was used to develop a viable method for determination of sodium dodecylbenzene sulfonate (DBS) by Curie-point pyrolysis gas chromatography. The pyrograms obtained were normalized against a maximum peak area and peak height. Normalized values were used for Quantification IV, which is one of the multivariate analysis methods, to select useful values initially. Then cluster analysis was carried out using both the selected values and their deviations. This method corresponds to qualitative analysis and indicates which data-base is similar to the sample. On the basis of this data-base, calibration data-bases are chosen. Principal component analysis (PCA) was performed using the calibration data-base and a set of sample data simultaneously. The principal component scores and contribution coefficients obtained were used to construct a calibration curve from which the DBS content of the sample was calculated. The results are in fair agreement with theoretical values.     

Gas- and solid/liquid-phase reactions during pyrolysis of softwood and hardwood lignins

Pyrolytic reactions of Japanese cedar (Cryptomeria japonica, a softwood) and Japanese beech (Fagus crenata, a hardwood) milled wood lignins (MWLs) were studied with thermogravimetry (TG) and by pyrolysis in a closed ampoule reactor (N₂/600 °C). The data were compared with those of guaiacol/syringol as simple lignin model aromatic nuclei. Several DTG peaks were observed around 300-350, 450, 590 and 650 °C. The first DTG peak temperature (326 °C) of beech was lower than that (353 °C) of cedar. This indicates that the volatile formation from cedar MWL is slightly delayed in heating at 600 °C. The gas-phase reactions via GC/MS-detectable low MW products were explainable with the temperature-dependent reactions observed for guaiacol/syringol in our previous paper. The methoxyl groups became reactive at ∼450 °C, giving O-CH₃ homolysis products (catechols/pyrogallols) and OCH₃ rearrangement products (cresols/xylenols). The former homolysis products were effectively converted into gaseous products (mainly CO) at >550-600 °C. However, the GC/MS-detectable tar yields, especially syringyl unit-characteristic products, were much lower than those from guaiacol/syringol. Thus, contributions of higher MW intermediates and solid/liquid-phase reactions are more important in lignin pyrolysis. From the results of stepwise pyrolysis of char + coke fractions at 450 and 600 °C, the methoxyl group-related reactions (450 °C) and intermediates gasification (600 °C) were suggested to occur also in the solid/liquid phase. This was consistent with the DTG peaks observed around these temperatures. These solid/liquid-phase reactions reduced the tar formation, especially catechols/pyrogallols and PAHs. Different features observed between these two MWLs are also focused.     

NaOH后处理对多级孔Hβ分子筛上木质素催化热解性能的影响

采用碱性条件下"后处理"脱硅的方法,制备了一系列多级孔Hβ分子筛,考察了Na OH浓度对Hβ分子筛上木质素催化热解性能的影响。结果表明,当Na OH浓度小于0.2 mol/L时,碱处理后的多级孔Hβ分子筛的介孔数量增加,木质素热解液体产物的收率随着Na OH浓度提高而显著增加。当Na OH浓度小于0.5 mol/L时,碱处理可以保持多级孔Hβ分子筛的微孔结构基本不被破坏,木质素催化热解具有较好的脱氧效果;产物以芳烃为主,含氧化合物的收率始终小于3%。当Na OH的浓度增加到1 mol/L时,会造成Hβ分子筛过度脱硅,骨架坍塌;由于Hβ分子筛的多级孔结构被破坏,此时不仅木质素热解液体产物的收率降低,而且脱氧效果变差。     

聚合物/无机纳米粒子复合膜在气体分离中的研究进展

由于聚合物膜具有可高度设计、机械性能好、易于加工 等优点,是理想的气体分离材料。然而,聚合物膜在气体选择性和渗透性方面存在平衡限制,在聚合物中引入纳米粒子,是提高气体分离性能的一种有效手段。本文基于聚合物/无机纳米粒子复合膜在气体分离领域的研究现状,重点阐述了零维纳米粒子（二氧化硅、二氧化钛）、一维纳米粒子（碳纳米管）、二维纳米粒子（氧化石墨烯、二维过渡金属氧化物）、三维纳米粒子（金属有机框架、沸石）对气体分离性能的影响,并展望了聚合物复合分离膜的发展趋势,为未来高效分离膜的研发提供了参考。     

Evaluation of factors affecting pyrolysis in A microfurnace system

A styrene isoprene block copolymer, known as Kraton 1107, is used to study some of the parameters involved in the pyrolysis process. Using a continuous mode microfurnace pyrolysis system interfaced to a capillary gas chromatography system, the effect of pyrolysis temperature and gas flows through the pyrolysis chamber were studied. Comparisons in sample introduction methods were made. Introducing the sample in solution, rather than conventional solid sample introduction, was found to offer some advantages.     

Pore size control and gas permeation kinetics of silica membranes by pyrolysis of phenyl-substituted ethoxysilanes with cross-flow through a porous support wall

A silica membrane was produced by chemical vapor deposition using tetraethoxysilane (TEOS), phenyltriethoxysilane (PTES) or diphenyldiethoxysilane (DPDES) as the Si source. Amorphous silica was deposited in the mesopores of a γ-alumina film coated on a porous -alumina tube, by evacuating the reactant through the porous wall. Hydrogen permeance at a permeation temperature of 600°C was of the order of 10⁻⁷ mol m⁻² s⁻¹ Pa⁻¹, and was not greatly dependent on the Si sources. The silica membrane produced using TEOS contained micropores permeable to both helium and hydrogen, but CO₂ and larger molecules were only slightly permeated through those mesopores which were left unplugged. The silica membrane produced from DPDES showed a single-component CO₂ permeance equivalent to that of single-component He, and CO₂/N₂ selectivity was approximately 9 at a permeation temperature of 30°C. When a mixture of CO₂ and N₂ was fed, however, CO₂ permeance decreased to the level of N₂ permeance. The H₂/N₂ selectivity, determined from single-component permeances to H₂ and N₂, was approximately 100, and these permeances remained unchanged when an equimolar mixture of H₂ and N₂ was fed. Thus, the DPDES-derived membrane possessed two types of micropores, abundant pores through which helium and hydrogen permeated and a small number of pores in which molecules of CO₂ and N₂ were permeable but not able to pass one another. Neither meso or macropores remained in the DPDES membrane.     

On the feasibility of the numerical Laplace Transform in the calculation of the statistical moments in GC

Summary Statistical moments may be used to augment the information content of stored GC data. Their calculation can be performed either directly by the methods of statistics or by the numerical Laplace Transform. It was found that the direct statistical computation will yield the better results.

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Zur Frage der Anwendbarkeit der numerischen Laplace-Transformation in der Berechnung der Statistischen Momente in der Gas-Chromatographie

Zusammenfassung Die statistischen Momente können zur Erhöhung der Aussagekraft von GC-Daten verwendet werden. Diese Berechnungen können auf dem Weg der Statistik direkt oder mittels numerischer Laplace-Transformation durchgeführt werden. Es wurde festgestellt, daß die direkte statistische Bestimmung der numerischen Laplace-Transformation vorzuziehen ist.

     

Rapeseed oil methyl ester pyrolysis: on-line product analysis using comprehensive two-dimensional gas chromatography

Thermochemical conversion processes play a crucial role in all routes from fossil and renewable resources to base chemicals, fuels and energy. Hence, a fundamental understanding of these chemical processes can help to resolve the upcoming challenges of our society. A bench scale pyrolysis set-up has been used to study the thermochemical conversion of rapeseed oil methyl ester (RME), i.e. a mixture of fatty acid methyl esters. A GC×GC, equipped with both a flame ionization detector (FID) and a time-of-flight mass spectrometer (TOF-MS), allows quantitative and qualitative characterization of the reactor feed and product. Analysis of the latter is accomplished using a dedicated high temperature on-line sampling system. Temperature programmed analysis, starting at -40°C, permits effluent characterization from methane up to lignoceric acid methyl ester (C(25)H(50)O(2)), in a single run of the GC×GC. The latter combines a 100% dimethylpolysiloxane primary column with a 50% phenyl polysilphenylene-siloxane secondary column. Modulation is started when the oven temperature reaches 40°C, thus dividing the chromatogram in a conventional 1D and a comprehensive 2D part. The proposed quantification approach allows to combine the quantitative GC×GC analysis with 2 other on-line 1D GC analyses, resulting in a complete and detailed product composition including the measurement of CO, CO(2), formaldehyde and water. The GC×GC reveals that the product stream contains a huge variety of valuable products, such as linear alpha olefins, unsaturated esters and aromatics, that could not have been identified and quantified accurately with conventional 1D GC because of peak overlap.     

Evaluation of fast gas chromatography and gas chromatography-mass spectrometry in the analysis of lipids

Fast and conventional gas chromatography (GC) techniques were applied to nine different lipidic matrices (butter, lard, tallow, and peanut, corn, sunflower, soya, olive, menhaden oils). Simultaneous methylic transesterification was performed on all samples prior to GC analysis. Several practical aspects concerning high speed analysis were investigated, such as the great increase in linear velocity, the use of fast temperature ramps, column sample capacity and detection systems. Analytical results showed certain losses in resolution, balanced by a consistent reduction in analysis time. The actual time savings were variable (60-70 min) as they were dependent on the complexity of the sample while the speed enhancement factor was equal to 10.5. Peak identification was achieved by means of different information sources, such as fast GC-mass spectrometry (MS), linear retention indices and comprehensive two-dimensional (2D) gas chromatography group patterns. The method developed was shown to be applicable in routine applications on complex natural samples.     

Towards identification of traditional European and indigenous Australian paint binders using pyrolysis gas chromatography mass spectrometry

We report a pyrolysis GC–MS method capable of analysing Indigenous Australian and European binders typically used in the manufacture of culturally important painted works. Eleven different traditional European binders and ten different Indigenous Australian binders were examined. The method allows discrimination between highly complex and impure lipid, resin, polysaccharide, wax, and protein-based binders. Each was found to have characteristic pyrolysis products that were unique to the binder material, demonstrating the potential for differentiation of these binders on Australian Aboriginal artworks towards identification and conservation of cultural heritage.