葡萄糖脱水制备5-羟甲基糠醛的研究

研究了Br（o）nsted-Lewis复合催化体系催化葡萄糖脱水制备5-羟甲基糠醛,详细考察了溶剂种类和用量、催化体系种类和用量、反应时间和反应温度等因素对5-羟甲基糠醛收率的影响,得到最佳工艺条件：葡萄糖2.0g,复合催化体系HCl-CrCl3[m（HCl）∶m（CrCl3·6H2O）=5∶1]0.6 g,正丁醇20 mL,反应时间15 min,反应温度200℃.在该反应条件下,5-羟甲基糠醛的收率达42.5％.结果表明,同单酸型的催化剂相比,复合催化体系更有利于葡萄糖脱水制备5-羟甲基糠醛.     

紫外双波长法检测葡萄糖降解产物5-HMF的研究

5-羟甲基糠醛(HMF)是一种重要的平台化合物,是制取生物质液体燃料和其他化工产品的前体,可通过葡萄糖脱水制得。采用双波长紫外分光光度法测定葡萄糖转化为5-羟甲基糠醛的葡萄糖的转化率和HMF的产率。并通过验证实验验证了该方法的准确性。结果表明,该方法为大规模工业化检测提供一种简单有效的检测手段。     

糠醛和5-羟甲基糠醛双键加氢催化剂及催化作用研究进展

生物质基平台化合物糠醛和5-羟甲基糠醛来源广泛,可从绿色植物中提取得到。糠醛和5-羟甲基糠醛双键加氢制备四氢糠醇和2,5-二羟甲基四氢呋喃具有重要的研究价值。文章综述了近年来糠醛和5-羟甲基糠醛双键加氢反应的研究成果,重点阐述了反应机理的研究进展,讨论了不同催化体系(单金属、合金)对糠醛和5-羟甲基糠醛双键加氢的催化作用,并对后续催化剂的研究方向和应用前景作了展望。     

碱性离子液体催化单糖脱水制5-羟甲基糠醛

离子液体作为一种新型的环境友好溶剂和液体酸碱催化剂用于单糖脱水制备5-羟甲基糠醛日益成为研究热点,受到广泛重视。以典型的OH-为阴离子的碱性离子液体为催化剂,研究了其对果糖/葡萄糖转化为5-羟甲基糠醛反应的影响。结果表明,在二甲基亚砜中,160℃反应6 h,果糖转化率达90.4%,5-羟甲基糠醛收率为83.3%,5-羟甲基糠醛选择性为92.1%。这一新的碱性离子液体催化单糖脱水的体系,取代了传统酸性催化剂的使用,具有高效、环保、经济的特点,为5-HMF规模化生产奠定了基础。     

催化果糖脱水制备5-羟甲基糠醛的影响

果糖脱水降解为5-羟甲基糠醛是生物质资源综合利用的研究热点。以AlCl₃为催化剂,考察反应条件对果糖脱水制备5-羟甲基糠醛的影响,重点研究不同无机酸对AlCl₃催化果糖降解生成5-羟甲基糠醛反应的影响。以AlCl₃和无机酸为共催化剂,考察在不同溶剂（1,4-二氧六环、N,N-二甲基甲酰胺、2-甲基亚砜）、反应温度和硫酸与磷酸质量比（1∶2、2∶3、3∶2、2∶1）条件下对果糖脱水降解制5-羟甲基糠醛的影响。结果表明,以温和的N,N-二甲基甲酰胺为溶剂,在反应温度120 ℃、AlCl₃用量为7.5 mmol、硫酸为20 mmol·L^-1和磷酸为30 mmol·L^-1共催化剂条件下,5-羟甲基糠醛收率达92.1%。     

磷酸改性凹凸棒石催化葡萄糖脱水制备5-羟甲基糠醛研究

以磷酸改性的凹凸棒石作为固体酸催化剂,对葡萄糖脱水制备生物基平台化合物5-羟甲基糠醛进行研究。研究结果表明,凹凸棒石经磷酸改性后,催化剂表面同时含有Bronsted位点和Lewis酸位点,催化葡萄糖脱水转化5-羟甲基糠醛活性增强,且该催化剂在含水体系中表现出良好的稳定性,催化剂重复使用四次后,活性基本不变。     

5-羟甲基糠醛的合成研究

以葡萄糖为原料,在氯化铬的离子液中,经分子内变旋作用和脱水反应而生成5-羟甲基糠醛(5-HMF)。反应混合物通过闪蒸,将产物、副产物和剩余的原料等反应混合物与离子液分离,回收离子液套用。反应混合物采用超临界流体萃取法提纯得到产品5-羟甲基糠醛。合成工艺路线简捷,产品质量高、成本低和生产过程环保,总质量收率达到72%以上。     

L酸/B酸可调的磺酸功能化MIL-101(Cr)材料催化葡萄糖脱水制备5-羟甲基糠醛

以九水合硝酸铬和单磺酸钠对苯二甲酸为原料,水为溶剂,采用水热法合成系列磺酸功能化MIL-101(Cr),通过调节反应温度和时间,合成不同Lewis/Br?nsted催化位点比例的磺酸功能化MIL-101(Cr),采用PXRD、EDX、SEM、ICP-AAS及BET比表面积分析等技术对材料进行综合表征,并研究磺酸功能化MIL-101(Cr)催化葡萄糖脱水制备5-羟甲基糠醛的催化活性。催化反应动力学研究结果表明,MIL-101(Cr)-SO3H中的Cr(Ⅲ)作为葡萄糖异构化反应的Lewis酸位点,-SO3H作为果糖脱水反应的Br?nsted酸催化位点,当催化剂的Br?nsted酸和Lewis酸的摩尔比为1.1时,150℃下反应,5-羟甲基糠醛的选择性最高可以达到47.15%,5-羟甲基糠醛的产率最高达到46.0%。     

SO_4~(2-)/ZrO_2固体超强酸催化剂金属离子复合、改性及在乙酰丙酸制备中的研究

采用共沉淀法制备了SO42-/ZrO2-Fe2O3和SO42-/ZrO2-Al2O3双金属固体超强酸催化剂,其中SO42-/ZrO2-Fe2O3对葡萄糖水解生成5-羟甲基糠醛的反应有利,而SO42-/ZrO2-Al2O3对5-羟甲基糠醛脱羧生成乙酰丙酸的反应有利。采用沉淀-浸渍法制取两种金属离子改性的SO42-/ZrO2催化剂,该类催化剂对葡萄糖水解制5-羟甲基糠醛和5-羟甲基糠醛脱羧生成乙酰丙酸的反应均有利。     

葡萄糖制备5-羟甲基糠醛工艺研究

为实现5-羟甲基糠醛绿色化、低成本制备,以可再生资源葡萄糖为原料,固体酸为催化剂,在水-γ-戊内酯双相介质中经酸化水解制备出5-羟甲基糠醛。考察了反应温度、反应时间、催化剂用量、葡萄糖用量对5-羟甲基糠醛收率的影响。结果表明,最佳工艺条件:反应温度190℃,反应时间43 min,催化剂用量0. 3 g,葡萄糖用量0. 15 g,在此条件下,5-羟甲基糠醛的收率44. 7%。     

Greener,solvent free three component Biginelli reaction over different recyclable solid acid catalysts

Solid acids comprising 12-tungstophosphoric acid and 12-tungstosilicic acid anchored on to metal oxide (ZrO₂), zeolites (Hβ and HZSM-5), and mesoporous material (MCM-41) were synthesized, characterized and used as the catalysts. A solvent free green route to carry out the Biginelli cyclocondensation reaction is described over synthesized catalysts. The method provides an efficient and much improved protocol of Biginelli reaction in terms of solvent free conditions, high yields up to 98 %, very short reaction time of 15 min, and simple work-up procedure. Based on the above study a best catalyst among all is proposed and is recycled up to four times without any significant change in % yields of the product. Another important feature of this method is survival of a variety of functional groups under the reaction conditions.     

糠醛一锅法制备γ-戊内酯的多相催化研究进展

γ-戊内酯(GVL)是一种重要的生物质平台化合物, 可以用作绿色溶剂、聚合物前体、燃料和燃料添加剂等, 催化转化生物质制备GVL是资源化利用生物质和缓解资源、能源危机的重要途径之一。糠醛经麦尓外因-彭多夫-沃莱(MPV)还原一锅制备GVL具有操作简单、经济环保、安全可靠等优点, 是GVL合成研究领域极具工业化潜质的路线, 受到学术界和工业界的广泛关注。本文阐述了糠醛转化为GVL各步所需Brønsted酸(B酸)和Lewis酸(L酸)催化活性中心, 从催化剂构筑方法、载体结构等方面总结了糠醛一锅法制备GVL的高效固体催化剂。发现水热稳定且具有良好传质效果的分子筛(如beta分子筛、ZSM-5分子筛等)是该反应中常用的载体, 以及通过分子筛脱Al改性, 或引入具有L酸位的Zr、Hf化合物、具有B酸位的磷钨酸(HPW)等活性中心是构筑该反应的高效双功能催化剂的常用手段。并对催化剂失活的原因和再生方法进行了总结, 分析了溶剂、温度等催化反应条件对反应活性的影响, 同时还对设计该反应的新型高效催化提出了建议。     

硅钨酸稀土盐催化合成丁基多苷

以硅钨酸铈为催化剂。以葡萄糖和正丁醇为原料,采用直接法合成了丁基多苷。详细地研究了醇糖摩尔比、反应温度、催化剂用量和反应时间等因素对葡萄糖转化率的影响,得出最佳反应条件。结果表明：当反应中醇糖比为5：1,油浴温度120℃,反应时间2h,催化剂的量为葡萄糖质量的3％,反应的转化率最高,可达到96．81％。比较了不同硅钨酸稀土盐的催化活性。同时以二氧化硅负载硅钨酸镧和硅钨酸铈作为催化剂．考察活性组分的负载量对葡萄糖转化率的影响。并考察了债载催化剂的萤复利用性能。     

Prins反应的研究和应用现状

结合Prins反应的发展历史,概述了近年来Prins反应的最新研究及应用现状。目前Prins反应有直接热缩合反应和催化合成反应两大类,本文分析了这两大类反应的优势和不足,指出了未来催化合成反应是Prins反应研究的重点。Prins反应的催化剂包括液体酸催化剂、固体酸催化剂和固体碱催化剂等,而离子液体催化剂、杂多酸催化剂、竹炭磺酸催化剂等高效且环境友好型催化剂是今后研究发展的重点。同时概述了Prins反应在化工、农药、香料、医药、天然大分子合成等方面的应用,最后提出了Prins反应未来在新型催化剂、相关合成方法学、石油化工和天然产物全合成等相关领域发展方向的展望。     

Reactions of conjugated fatty acids. III. Kinetics of the Diels-Alder reaction

Summary The kinetics of a Diels-Alder-type reaction between diethylazodicarboxylate andt,t-9,11-octadecadienoic acid has been studied in various solvent systems and with acidic catalysts. The rate of the reaction was found to vary as follows: a) the reaction rate is faster in polar solvents than in nonpolar solvents; b) addition of acidic catalysts to nonpolar solvents increases the rate of the reaction, and acidic catalysts appear to have no effect on the rate of reaction in polar solvents; c) when compatibility can be maintained, addition of water to polar solvent systems appears to increase the reaction rate in proportion to the amount of water added. The reaction follows second-order or pseudo second-order kinetics. Probably it is more complex than the over-all reaction kinetics indicate. Certain reactions were studied at two temperatures, and information on activation energy of the reaction has been obtained. Presented at fall meeting, American Oil Chemists’ Society, Philadelphia, Pa., Oct. 10–12, 1955.     

A novel route for green conversion of cellulose to HMF by cascading enzymatic and chemical reactions

In this work, a novel route to deconstruct cellulose into 5‐hydroxymethylfurfural (HMF) by cascading enzymatic and chemical reactions is reported. For biocatalyst preparation, Fe₃O₄ nanoparticles encapsulated SBA‐15 with appropriate pore size was synthesized and utilized as magnetic scaffolds for the immobilization of cellulase. For chemical catalyst preparation, sulfated zirconium dioxide conformed monolayers were grafted on SBA‐15 template to create thermally robust mesoporous catalysts with tunable solid basic/Lewis acid and Brønsted acid sites. Catalytic performance of biocatalyst and chemical catalyst was explored in the aqueous phase conversion of IL pretreated cellulose to glucose, and in the iPrOH/water solvent conversion of glucose to HMF conversion, respectively. After the optimization of reaction conditions, a sequential conversion of pretreated cellulose to glucose and glucose to HMF was performed, and 43.6% HMF yield can be obtained. The cascaded enzymatic and chemocatalytic reaction system demonstrates an effective and economically friendly process for biomass energy conservation. A novel route for green conversion of IL pretreated cellulose to 5‐hydroxymethylfurfural (HMF) by cascading an enzymatic catalysis in an aqueous system with chemocatalysis in an iPrOH/water solvent mixture is reported. © 2017 American Institute of Chemical Engineers AIChE J, 2017     

Dehydrogenation of methanol to methyl formate: deuterium labeling studies

Different synthetic AlPO₄ systems are effective yet mild acid catalysts for the heterogeneous cycloaddition reaction of cyclopentadiene with (-)-menthyl acrylate. The reaction proceeds selectively under mild conditions and in a relatively short reaction time with an almost total conversion, a high endo/exo ratio, and a reasonable asymmetric induction. When the reactions are carried out without solvent, some correlations are obtained between the number of acid sites, titrated with pyridine, and reaction yields, endo/exo and diastereofacial selectivities. The positive influence of surface area of catalysts is also determined. However, the lack of good correlations between reaction results and surface properties of the catalysts indicates the influence of some other factors.     

Platinum‐Catalysed Hydrosilylation of Unsaturated Fatty Acid Esters

Different Pt(IV), Pt(II) and Pt(0) catalysts were screened for the hydrosilylation of fatty acid esters containing terminal as well as internal double bonds. The reaction of terminally unsaturated fatty acid esters proceeded smoothly with short reaction times for nearly all examined catalysts, whereas Pt(IV) species and Pt(II) or Pt(0) species with labile ligands were sufficiently active in the reaction of internally unsaturated compounds. For methyl linoleate, a conjugation of the two internal double bonds before the hydrosilylation was observed. The reaction was carried out in substance as well as in solvent systems permitting a catalyst recycling and reuse. In these systems, however, hydrogenation and double bond isomerisation were found as side reactions.     

混合酸催化葡萄糖选择性转化合成乙酰丙酸甲酯

将生物质原料直接转化制备乙酰丙酸甲酯(MLE)具有经济价值高、对环境友好和可持续性强等优点。详细研究了Lewis酸(Sn-β分子筛)、Brønsted酸(对甲苯磺酸,PTSA)及混合酸(Sn-β/PTSA)在葡萄糖直接转化合成乙酰丙酸甲酯中的催化效果,取得了较高的产物收率。首先,将各种分子筛和PTSA组合成催化体系并将其应用于葡萄糖醇解合成MLE的反应过程,发现Sn-β分子筛与PTSA的混合体系效果最佳(其中,Sn-β分子筛是借助简单的研磨法制备),产物MLE的收率可达68.3%左右。进而,对分子筛催化剂进行了XRD、FT-IR和TG-DTG等表征;由实验结果可知,Sn-β分子筛的主要作用在于将葡萄糖异构生成果糖,而PTSA的催化作用是加速醇解过程;最后,针对催化剂组分的比例、反应时间和反应温度进行了优化,得到了最佳反应条件。     

SELECTIVE OXIDATION OF ALCOHOLS BY REDOX MOLECULAR SIEVES

High-throughput synthesis and screening of libraries consisting of redox zeolites and molecular sieves have been developed for the selective oxidation of 2-butyl-5-hydroxymethyl-imidazole to the corresponding aldehyde in the liquid phase. Libraries consisting of 96 catalysts were prepared and screened for catalytic activity using high-throughput software, robotics, reactor, and screening technologies. The integrated synthesis and screening workflow allowed ～5000 samples to be screened in less than one month. Promising hits identified in the high-throughput primary screens were successfully scaled up and optimized in conventional laboratory test units. Best results have been obtained with doubly or triply doped mesoporous sieves containing both an impregnated and framework-substituted metal. PtBi-doped framework-substituted V-MCM-41 redox mesoporous sieves were found to be efficient catalysts for aerobic oxidation under relatively mild reaction conditions (100–150°C, 15–400 psi air, 4–10 h reaction time). MIBK/H₂O/t-BuOH mixtures were identified as efficient solvent systems for this reaction. Isolated yields confirm high selectivities of more than 90% with quantitative conversions. Spent catalysts were shown to be fully regenerable by high temperature calcination in air.