聚酯在超临界甲醇中的降解特性

研究在间歇高压反应器中聚对苯二甲酸乙二醇酯(PET)、聚对苯二甲酸丁二醇酯(PBT)及聚碳酸酯(PC)在超临界甲醇中的降解反应;通过建立聚酯在超临界甲醇中的降解反应模型,探讨了聚酯在甲醇中降解的机理。结果表明:PET、PBT和PC在甲醇溶液中的降解具有共性,均可分为超临界区、非临界区和中间过渡区三个区域。在超临界区聚酯完全溶于甲醇并降解为原料单体,且对苯二甲酸二甲酯(DMT)和碳酸二甲酯(DMC)的收率均大于90%;聚酯的降解是在聚合物分子链的无规断裂和聚酯进行酯交换反应的双重作用下发生的。     

典型醇类物质超临界水氧化反应途径研究

采用自主设计的连续流动气封壁超临界水氧化反应装置,研究了典型醇类物质甲醇、乙醇和异丙醇在超临界水中氧化的反应途径,并归纳了醇类物质超临界水氧化反应的规律及特点。研究结果表明,甲醇超临界水氧化反应的主要中间产物为甲醛,同样条件下转化率较乙醇和异丙醇低;乙醇和异丙醇超临界水氧化反应的主要中间产物为丙酮、乙酸、乙醛和甲醇等。三种醇超临界水氧化过程中均涉及到大量活性自由基的相互作用,表现为脱氢、裂解和聚合等反应形式;产物包括碳链增长、不变、降低三种类型。总体来看,醇类物质超临界水氧化反应的趋势是向碳链降低的方向进行,即通过一系列中间产物最后生成CO₂和水。     

典型醇类物质超临界水氧化反应途径研究

采用自主设计的连续流动气封壁超临界水氧化反应装置,研究了典型醇类物质甲醇、乙醇和异丙醇在超临界水中氧化的反应途径,并归纳了醇类物质超临界水氧化反应的规律及特点。研究结果表明,甲醇超临界水氧化反应的主要中间产物为甲醛,同样条件下转化率较乙醇和异丙醇低;乙醇和异丙醇超临界水氧化反应的主要中间产物为丙酮、乙酸、乙醛和甲醇等。三种醇超临界水氧化过程中均涉及到大量活性自由基的相互作用,表现为脱氢、裂解和聚合等反应形式;产物包括碳链增长、不变、降低三种类型。总体来看,醇类物质超临界水氧化反应的趋势是向碳链降低的方向进行,即通过一系列中间产物最后生成CO2和水。     

脂肪酸在超临界甲醇中的酯化反应研究

超临界甲醇中的酯化和酯交换反应是利用植物油、动物油或废油脂制备生物柴油的新工艺.它的最大特点是不需要添加催化剂,超临界甲醇既是反应媒介,又是反应物.     

超临界相CO加氢合成甲醇,异丁醇的研究

以正十一～十三烷的混合物为超临界介质,在反应温度３６０～４１０℃、合成气压力７５ＭＰａ、进气空速１７００ｈ－１、介质压力１７８ＭＰａ、总压９３ＭＰａ的实验条件下,研究了固定床反应器中Ｚｎ－Ｃｒ、Ｃｕ－Ｚｎ－Ｃｒ催化剂在超临界相和气相条件下合成甲醇、异丁醇的性能。结果表明,超临界相反应的ＣＯ转化率高于气相反应。在超临界条件下反应,醇类选择性随着温度升高下降较慢,而气相反应醇类选择性随着温度升高下降较快。气相反应产物以甲醇、异丁醇为主,含少量乙醇和正丙醇,超临界相反应的产物分布与气相反应的明显不同,甲醇含量减少,乙醇、正丙醇和异丁醇都有不同程度增加。超临界流体的存在对合成醇链增长有影响,在不同催化剂上的产物分布有较大差异     

Zr-Mn-K催化剂超临界相合成甲醇与异丁醇的研究

用共沉淀法和超临界流体干燥法,分别制备了Ｚｒ－Ｍｎ－Ｋ沉淀型催化剂和超细催化剂．以正十一～十三烷的混合物为超临界介质,在反应温度３６０～４１０℃、合成气压力７．５ＭＰａ、ＧＨＳＶ１７００ｈ－１及介质压力２．０８ＭＰａ的实验条件下,分别考察了超细催化剂和沉淀催化剂的气相和超临界相催化合成气制甲醇、异丁醇的性能．气相和超临界相反应的研究均表明,超细催化剂催化合成异丁醇的活性高于沉淀催化剂;在超临界条件下反应,超细催化剂上产物的异丁醇含量较高（为２３％～３２％）,甲醇含量为２２％～３３％,其它醇均在１０％左右．气相与超临界相反应结果的对比显示,超临界流体促进产物的脱附与传递,提高了ＣＯ的转化率．但超临界流体对甲烷的萃取作用强于对醇的萃取,醇选择性低于气相反应．在超临界条件下合成甲醇、异丁醇仍遵循异丁醇形成的链增长机理,超临界流体改变了链增长各步骤的相对速度,致使超临界相反应的产物分布不同于气相反应的产物分布．     

分子模拟在超临界流体领域中的应用

"分子模拟作为一种全新的研究手段已经在化学、化工、材料、生物等领域受到了广泛的关注。特别是在超临界流体技术方面,其应用不但可以获得许多结构、传递以及热力学信息,而且可以部分取代昂贵的超临界实验。本文从超临界流体在主体相和受限空间中的特性以及超临界萃取、反应等几个方面对现有的分子模拟方法和成果进行总结与评述,并对进一步发展的方向和面临的困难进行了讨论。     

超临界甲醇处理对活性炭表面性质及钌炭催化性能的影响

采用超临界甲醇处理活性炭,水浸渍制备负载钌炭催化剂,用N2物理吸附、Boehm滴定、X光电子能谱（XPS）和程序升温还原（TPR）等测试技术研究了超临界甲醇处理对活性炭表面结构及表面基团相对含量的影响,并以葡萄糖加氢生产山梨醇为模型反应对钌基催化剂的性能进行了评价。 研究结果表明,超临界甲醇处理活性炭,活性炭的孔结构性能变化不大,但可有效降低活性炭表面含氧酸性基团的含量,使催化剂的还原温度升高,增强了载体和活性组分间的相互作用,有效的提高了钌的分散度,从而提高所负载催化剂的催化活性。 在实验范围内,当超临界甲醇的温度为300 ℃,处理时间为12 h时,在4.0 MPa、120 ℃、葡萄糖的质量分数为50%的反应条件下,催化剂的反应速率（按Ru单位质量计）达到了118.65 mmol/(min·g),是未处理活性炭的1.96倍。     

反相液相制备色谱法结合超临界流体制备色谱法分离纯化海风藤中的化合物

建立了基于反相液相制备色谱和超临界流体制备色谱的组合方法,用于分离纯化醇提水沉后石油醚层中的海风藤。首先以甲醇作为改性剂,采用醇提水沉法去除海风藤甲醇提取物中的叶绿素,加入硅藻土后用石油醚回流富集目标成分。选用反相C18制备色谱柱将其分为18个组分,然后将组分在SFC模式下进行制备。选用酰胺色谱柱,以甲醇为改性剂,在柱温30℃、背压15.0 MPa的条件下进行分离。基于反相色谱和超临界流体色谱不同的分离选择性,最后分离得到6个高纯度化合物。该法展示了反相制备色谱和超临界流体制备色谱在海风藤分离纯化方面的优势,特别是超临界流体色谱在天然产物的分析和制备方面的巨大潜力。     

可调变流体与绿色化工过程

介绍了可调变流体特性及其在绿色化工过程中的应用。重点介绍了利用超临界流体(主要是超临界C02)、亚临界水和气体(主要是CO2)膨胀的流体这三类可调变流体进行绿色化工过程设计的特点与途径。     

CO2/离子液体体系热力学性质的分子动力学模拟

超临界CO2和离子液体(ILs)是两种绿色溶剂. 离子液体可以溶解超临界CO2, 而超临界CO2不能溶解离子液体. 由此设计构成的CO2/IL二元系统, 同时具备了超临界CO2和离子液体的许多优点: 既可以降低离子液体的粘度, 还便于相分离, 是新型的耦合绿色溶剂. 其物理化学性质对于设计反应、分离等过程非常重要. 因此, 本文以CO2/IL二元系统为研究对象, 通过选择合适的分子力场和系综, 运用分子动力学(MD)模拟方法研究了CO2/[bmim][PF6]、CO2/[bmim][NO3]等体系的热力学性质. 结果表明, CO2对ILs膨胀度的影响非常小, 当CO2摩尔分数为0.5时, ILs膨胀仅为15%. CO2/ILs的扩散系数远小于CO2膨胀甲醇、乙醇溶液的扩散系数. 随着CO2含量的增加, ILs的扩散系数提高, 粘度显著下降, 表明CO2能有效地改善ILs扩散性, 减小其粘度. 因此CO2可用以改善离子液体溶剂体系的传递特性, 增强反应分离过程在其中的进行.     

超临界二氧化碳二元体系相平衡性质的研究

采用固定体积可视观察法测定了CO₂+甲苯、CO₂+环己烷、CO₂+正丁醛、CO₂+异丁醛、CO₂+甲醇及CO₂+乙醇二元体系的临界点性质,为超临界萃取和化学反应提供基础数据.在对二元体系相行为与单组分超临界相行为进行比较的基础上,对不同化学物质及不同配比的二元体系临界点与二氧化碳临界点之间的关系进行了讨论.     

Organosilicon compounds in supercritical carbon dioxide: Synthesis,polymerization, modification,and production of new materials

The main promising opportunities for the advantageous combination of organosilicon compounds and supercritical carbon dioxide both as a solvent and as a reagent in chemical processes are analyzed. The main processes of polymerization and modification of polymer matrices that are performed in supercritical СО₂ with the use of organosilicon materials of various types are outlined. Methods for the obtaining organosilicon polymers and polymer-inorganic composites and methods for the application of siloxane stabilizers in the dispersion polymerization of monomers in supercritical СО₂ are described. Studies of the insertion of a СО₂ molecule into Si–H, Si–N, and Si–O–Me bonds in reactions that feature exceptionally high chemical selectivity and afford a wide spectrum of products potentially useful for application in the chemistry of polymer materials are considered. It is shown that the silylation of surfaces of various types and morphologies in the medium of supercritical СО₂ is a rapidly developing green approach that makes it possible to obtain highly uniform defect-free coatings with variable desired functionality.     

PdCl_2-catalyzed heterocyclotrimerization in MeOH/scCO_2:A versatile approach to dimethyl pyridine-3,5-dicarboxylate from methyl acrylate and urea

A novel and green method for the synthesis of dimethyl pyridine-3,5-dicarboxylate has been developed. It is PdCl2-catalyzed heterocyclotrimerization of methyl acrylate with urea in methanol/supercritical carbon dioxide. The target compound was obtained with a 75% isolated yield under the optimized con-ditions.     

PdCl2-catalyzed heterocyclotrimerization in MeOH/scCO2: A versatile approach to dimethyl pyridine-3,5-dicarboxylate from methyl acrylate and urea

A novel and green method for the synthesis of dimethyl pyridine-3,5-dicarboxylate has been developed. It is PdCl₂-catalyzed heterocyclotrimerization of methyl acrylate with urea in methanol/supercritical carbon dioxide. The target compound was obtained with a 75% isolated yield under the optimized conditions.     

Thermal decomposition and stability of fatty acid methyl esters in supercritical methanol

In recent years, non-catalytic supercritical processes for biodiesel production have been proposed as alternative environmentally friendly technologies. However, conditions of high temperature and pressure that occur while biodiesel is in supercritical fluid can cause fuel degradation, resulting in low yield. In this study, we performed the thermal decomposition of fatty acid methyl esters (FAMEs) in supercritical methanol at temperatures ranging from 325 °C to 420 °C and pressure of 23 MPa to investigate the degradation characteristics and thermal stability of biodiesel. The primary reactions we observed were isomerization, hydrogenation, and pyrolysis of FAMEs. The main pathway of degradation was deduced by analyzing the contents of degradation products. We found that if FAME has shorter chain length or is more saturated, it has higher thermal stability in supercritical methanol. All FAMEs remained stable at 325 °C or below. Based on these results, we recommend that transesterification reactions in supercritical methanol should be carried out below 325 °C (at 23 MPa) and 20 min, the temperature at which thermal decomposition of FAMEs begins to occur, to optimize high-yield biodiesel production.     

Comparison of supercritical fluid and ultrasound-assisted extraction of carotenoids and chlorophyll a from Dunaliella salina

In the work described here the extraction processes of carotenoids and chlorophylls were analysed using two extraction techniques, namely ultrasound-assisted extraction and supercritical fluid extraction, and the results are compared. The solvents used for the ultrasound-assisted extraction were N,N′-dimethylformamide and methanol and for the supercritical fluid extraction, carbon dioxide. The raw material studied was Dunaliella salina, a microalgae characterized by the high levels of carotenoids present in its cellular structure. The results indicate that the supercritical fluid extraction process is comparable to the ultrasound-assisted extraction when methanol is used as solvent. In addition, the supercritical extraction process is more selective for the recovery of carotenoids than the conventional technique since it leads to higher values for the ratio carotenoids/chlorophylls. Finally, the effects of pressure and temperature on the extraction yields of the supercritical fluid extraction process were studied.     

Chemical conversion of cellulose as treated in supercritical methanol

The chemical conversion of cellulose as treated in supercritical methanol was studied using a batch-type reaction vessel at temperatures from 220 to 450°C and pressures from 14 to 72MPa. Supercritical methanol treatment at 350°C and 43MPa for 7min was sufficient to convert microcrystalline cellulose (avicel) to the methanol-soluble. To study the kinetics of the decomposition of cellulose, the decomposition rate constants were obtained, and rapid increase was observed at about 270°C which was about 30°C higher than the critical temperature of methanol. The main products from cellulose decomposition were methylated cellotriose, methylated cellobiose, methyl - and -D-glucosides, levoglucosan and 5-hydroxymethylfurfural. Monomeric compounds such as methyl - and -D-glucosides were stable in supercritical methanol, allowing high yields of monomeric products by supercritical methanol treatment. Based on these results, a pathway of cellulose decomposition treated in supercritical methanol was proposed. These findings suggest that the supercritical methanol treatment of various cellulosic materials may be suitable to obtain useful chemicals and liquid fuels without using fossil resources.