超临界流体技术在化学研究中的应用

对超临界流体技术的应用和研究进行了综述。     

溶出温度对乙醇木质素超临界解聚特性影响研究

通过控制溶出温度(160、180和200℃),制备了三种毛竹乙醇木质素EOL(EOL-160、EOL-180和EOL-200),并采用红外光谱仪(FT-IR)、凝胶渗透色谱(GPC)和热重分析(TG)分别对乙醇木质素的官能团、分子量分布及热稳定性进行了分析;采用微型高温高压反应釜,在超临界乙醇体系,进行三种乙醇木质素的解聚实验,通过气相色谱/质谱联用仪(GC/MS)及FT-IR对解聚产物进行分析,探讨乙醇木质素特性对其超临界乙醇环境解聚产物组成的影响规律。结果表明,随着溶出温度的升高,乙醇木质素溶出率呈上升趋势。EOL-160、EOL-180和EOL-200三种乙醇木质素在超临界条件解聚液相产物主要成分分别为对乙基苯酚、2,6-二甲氧基苯酚和4-羟基-3-甲氧基-苯甲酸酯。     

亚/超临界乙醇液化秸秆纤维素解聚反应研究与机理初探

利用间歇式高压反应釜,在反应温度200～330 ℃、乙醇用量0～150 mL条件下,考察了亚/超临界乙醇直接液化秸秆纤维素的解聚行为,并初步探讨了其液化机理。结果表明,反应温度、乙醇用量和反应停留时间对秸秆纤维素的液化均有显著影响,反应温度由200 ℃升高至330 ℃,重油和气体收率分别增加了12.55%、28.83%;乙醇用量增加,反应压力随之升高,乙醇进入超临界状态,残渣和气体收率相比单纯热裂解分别降低11.10%和8.44%。通过GC/MS、FT-IR分析生物油组分和残渣特性,表明秸秆纤维素在亚/超临界乙醇中断键裂解,且酮类和乙酯类化合物是生物油的主要成分。     

超临界流体在有机合成中的应用

超临界化学反应是一种新型的反应体系，本文对超临界流体在有机合成反应中应用的最新进展进行了综述。     

超临界流体色谱在金属络合物和金属有机化合物中的分析应用

超临界流体色谱（SFC）在色谱分离过程中能在较低的温度下分析对热不稳定性的化合物,包括金属络合物和金属有机化合物。本文总结了近来文献报道的各种过渡金属、重金属、镧系和锕系以及铅、汞和锡的金属有机化合物的SFC分离,还讨论了SFC检测系统和金属有机化合物的溶解度的测定。     

木质素催化转化制取苯、甲苯和二甲苯

对HZSM-5、HY和MCM-22三种催化剂进行了比较,其中HZSM-5催化裂解木质素制备苯、甲苯和二甲苯（BTX）的结果最优．确定了木质素催化裂解的最佳反应条件,包括反应温度、载气流速、催化剂／木质素配比．当反应温度为550-600℃,载气流速为300mL／min,催化剂／木质素配比为2时,使用HZSM-5催化裂解制备BTX的最高C产率和芳香选择性分别可达25．3％和90．9％。     

以水、甲苯及其混合溶剂超临界萃取煤的研究

在半连续萃取装置上,以水、甲苯及其混合物为溶剂对黄县褐煤进行了非等温超临界萃取,考察了不同溶剂对萃取过程的影响。结果表明,以甲苯为溶剂的萃取率高于以水为溶剂的。以水为溶剂萃取物中的沥青烯和预沥青烯的H/C原子比高于以甲苯为溶剂的,而O/C原子比则低。在水中加入适量甲苯,能够明显改善萃取效果,大幅度提高萃取率。     

在超临界CO2流体中的化学反应

超临界CO2流体中的化学反应是继超临界流体应用于萃取分离过程之后进一步将其应用于化学反应的新尝试。本文重点综述了超临界CO2流体中的化学反应研究进展, 并对其发展前景作了展望。     

超临界流体色谱仪在天然产物研究中的应用

超临界流体可以用做色谱的流动相，使混合物质在色谱柱上得到分离，这种分离方法被称为超临界流体色谱(Supercdtical Fluid Chromatography,简称SFC)。作为色谱流动相的超临界流体，其作用与超临界流体萃取(Supercritical Fluid Extraction，简称SFE)类似。超临界流体对物质的溶解能力远比一般气体大的多，     

超临界流体色谱法在农药分析中的应用

本文介绍了超临界流体色谱仪器装置的主要部件，对其所用的检测器系统作了较详细的阐述，综述了近年来国外ＳＦＣ在氨基甲酸酯，拟除虫菊酯，有机磷，有机氯，有机硫及有机氮类等农药分析中的应用情况，展示了该技术在农药分析中广阔前景。     

Carbon nanotube synthesis in supercritical toluene

Multiwall carbon nanotubes (MWNTs) were synthesized in supercritical toluene at 600 degrees C and approximately 12.4 MPa using ferrocene, Fe, or FePt nanocrystals as growth catalysts. Toluene serves as both the carbon source for nanotube formation and the solvent. In contrast to vapor-phase synthetic routes, the supercritical solvent provides high precursor concentration and a homogeneous reaction environment with dispersed growth catalyst particles. Both carbon filaments and MWNTs are produced by this approach, and a growth mechanism is proposed to explain the factors that determine the nanotube versus filament morphology. The plasmon energies of the pi and pi + sigma valence electrons were measured using electron energy-loss spectroscopy (EELS) of individual carbon fibers and MWNTs as a characterization tool to complement the imaging data obtained from electron microscopy.     

碱木质素超/亚临界乙醇体系解聚机理研究

采用微型高温高压反应釜,在超/亚临界乙醇体系,进行麦草碱木质素的解聚实验,通过扫描电子显微镜(SEM)、气相色谱/质谱联用仪(GC/MS)及红外光谱仪(FT-IR)对解聚产物进行分析,探讨大分子结构的解聚机理。结果表明,碱木质素在乙醇临界点条件(240℃,7.2 MPa)解聚获得最低残焦得率,数值为16.5%。碱木质素在亚临界乙醇体系解聚过程,碱木质素熔融形成直径1.0-2.0μm的微球分散于乙醇中,结构单体间少量醚键和苯环侧链Cα均裂断裂,形成酚类、酯类、酮类和酸类产物;碱木质素在超临界乙醇体系解聚过程,熔融微球直径明显缩小,解聚时发生大量结构单体间醚键、苯环侧链Cα断裂及酯类产物的二次分解反应,解聚产物中酯类产物含量(11.94%)降低,酚类产物得率(52.14%)提高。     

Kinetics of pyrolysis and properties of carbon black from a scrap tire

The pyrolysis of rubber from the sidewall and tread of a passenger car tire was carried out in a nitrogen flow at a wide range of final temperatures. Derivative thermogravimetric analysis (DTG) was applied to examine the kinetics at the different process conditions of completed pyrolysis. Two characteristic stages were observed in the DTG curves. The first stage corresponded to the decomposition of processing oil, plastifier, and additives, whereas the rubber polymer was decomposed in the second stage. Several properties of the carbon black formed by the pyrolysis such as ash content, specific surface area, and pore size distribution were determined. A change of the internal structure of the rubber particle in the meso-and macroregions of the pore size was observed. Presented at the 33rd International Conference of the Slovak Society of Chemical Engineering, Tatranské Matliare, 22–26 May 2006.     

轮胎橡胶多组分分析方法的研究

轮胎橡胶物证是涉车案件中常见物证,对于相关案件的侦破具有重要的物证价值。本文根据轮胎橡胶组分体系的特点,设计了以大型仪器为主线的多组分分析方案。所选用的仪器设备及方法有:裂解气相色谱仪(Py-GC)、裂解气相色谱与质谱联用仪(Py-GCMS)、差示扫描量热仪(DSC)、热重分析仪(TGA)、原子吸收分光光度计(AAS)、化学法;实验中,测试了轮胎橡胶的胶型、配合剂定性(防老剂定性、促进剂定性、其他助剂定性)、玻璃化温度,焓值,高聚物含量、配合剂含量、炭黑含量、无机填料(盐酸不溶物、氧化锌含量、二氧化硅含量)、硫含量等十三个测试项目;并将已知配方的硫化胶理论值与测试样品结果比对分析。分析结果表明:建立的系列方法的测试结果准确、可靠,可以为轮胎橡胶的分析鉴别提供技术支持。     

EB-promoted recycling of waste tire rubber with polyolefins

Despite the fact that more and more methods and solutions are used in the recycling of polymers, there are still some problems, especially in the recycling of cross-linked materials such as rubber. Usually the biggest problem is the lack of compatibility between the cross-linked rubber and the thermoplastic matrix. In this study we applied ground tire rubber (GTR) as recycled material. The GTR was embedded into polyethylene (PE) and polyethylene/ethylene-vinyl acetate copolymer (PE/EVA) matrices. In order to increase the compatibility of the components electron beam (EB) irradiation was applied. The results showed that the irradiation has a beneficial effect on the polymer–GTR interfacial connection. The EB treatment increased not only the tensile strength but also the elongation at break. The irradiation had also positive effect on the impact strength properties.     

Utilization of waste tire rubber in hybrid plywood composite panel

The aim of this work was to use waste tire rubber (WTR) in the middle layer of hybrid plywood materials. The effects of four variable parameters, namely, WTR contents (430 and 720 g), resin contents (120 and 160 g/m²), hot pressing (single‐stage and two‐stage), and arrangements of veneer layers on the mechanical, physical, and acoustical properties, were studied. Beech (Fagus orientalis) and alder (Alnus glutinosa) veneers having 1.8‐mm thickness were used in the production of hybrid plywood panels. Rubber layers of 3‐ and 5‐mm thickness were used in the middle layer of plywood samples. To produce plywood panels, single‐stage and two‐stage hot‐pressing processes were used. Bonding of wood layers was performed using 120 and 160 g/m² urea‐formaldehyde resins, and to form the rubber layers and bond them to wood layers, methylene diisocyanate resin (150 g/m²) was used. Overall trend showed that with the increase in rubber content, the physical properties (water absorption, thickness swelling, and sound absorption) of the manufactured panels were improved, while the mechanical properties (modulus of rapture, modulus of elasticity, and impact strength) of the panels were reduced. Both physical and mechanical performances of plywood panels were improved with increase in resin content. An increase in the WTR content in plywood improved the composite's acoustical property. The production process of the wood/rubber plywood did not significantly affect their properties. The order of improvement in the physical properties of the panels is rubber content > resin content > arrangement of layers > pressing process. Copyright © 2015 John Wiley & Sons, Ltd.     

Depolymerization and ionic conductivity of enzymatically deproteinized natural rubber having epoxy group

Preparation of liquid epoxidized natural rubber (ENR) was made by oxidative depolymerization of ENR in latex stage without loss of epoxy group. Epoxidation of fresh natural rubber latex, which was purified by deproteinization with proteolytic enzyme and surfactant, was carried out with freshly prepared peracetic acid. The glass transition temperature (T_g) and gel content of the rubbers increased after the epoxidation, both of which were dependent upon an amount of peracetic acid. The gel content was significantly reduced by oxidative depolymerization of the rubber with (NH₄)₂S₂O₈ in the presence of propanal. The resulting liquid epoxidized rubber (M_n≈10⁴) was found to have well-defined terminal groups, i.e. aldehyde groups and α-β unsaturated carbonyl groups. The novel rubber was applied to transport Li⁺ as an ionic conducting medium, that is, solid polymer electrolyte.     

Synthesis of carbon nanotubes using scrap tyre rubber as carbon source

Carbon nanotubes(CNTs) were successfully synthesized through chemical vapor deposition(CVD) method over cobalt catalysts using scrap tyre rubber as carbon source.The CNTs as produced were investigated by means of X-ray diffraction, thermogravimetric analysis,scanning electron microscope,transmission electron microscopy and Raman spectrum techniques.It was found that the obtained carbon material mainly existed in the form of CNTs.     

Partial oxidation of toluene with nitrous oxide under supercritical conditions

The partial oxidation of toluene with nitrous oxide over the H-ZSM-5 catalyst under supercritical conditions at temperatures of 370–420°C and pressures of 70–160 atm has been investigated for the first time. The maximum cresol selectivity under these conditions is 32%. The amounts of the resulting cresol isomers form the following decreasing sequence: m-cresol > o-cresol > p-cresol. The partial oxidation of toluene is accompanied by disproportionation and biphenyl formation.