用Lewis酸或Brnsted酸催化剂和N2汽提法使木糖脱水为糠醛（英文）

The activity of Lewis (Nb2O5) and Br nsted (Amberlyst 70) acid catalysts for the cyclodehydration of xylose to furfural was studied. The nature of the acidity resulted in significant changes in the reaction mechanism. Lewis acid sites promote the formation of xylulose, while Br nsted acid sites are required to further dehydrate the sugar to furfural. Amberlyst 70 in water/toluene at 175 ℃ showed lower activity but gave a higher furfural yield. Using N2 as the stripping agent considerably improved the furfural yield and product purity in the stripped stream. Catalyst stability was also studied.     

Selective aqueous-phase hydrogenation of furfural to cyclopentanol over PdRu/C catalyst

The bimetallic PdRu catalyst supported on carbon nanotubes were found ot provide an efficient synthesis of cyclopentanol in aqueous-phase hydrogenation of furfural. Under the chosen reaction conditions (temperature of 473 K, total pressure of 8 MPa), the selectivity towards cyclopentanol reaches 77% at a complete conversion of furfural. A high activity of this catalyst can be associated with changes in the electronic state and dispersion of the supported metals caused by their mutual interaction and formation of PdRu alloy.     

铜镍双金属催化剂上糠醛水相选择性偶联加氢-重排制环戊酮

生物质资源高效催化转化制备高附加值化学品具有重要的科学意义与工业应用潜力.生物质基糠醛催化加氢-重排制备环戊酮是一条具有吸引力的"非石油"制备路线,但该过程面临副产物多、环戊酮选择性难以提高等难题,除糠醛外,中间物种也很容易发生多种聚合副反应.因此,探索中间物种聚合副反应的条件和作用机制,是提高目标产物环戊酮的选择性和收率的关键.本文制备了CuNi/Al-MCM-41双金属纳米过渡金属催化剂,通过精确调控介质水的pH值和原料浓度,实现了糠醛加氢-重排耦合制备环戊酮的高选择性和高收率.在2.0 MPa H2,160oC和近中性条件下反应5 h,糠醛的转化率为99.0％,环戊酮的选择性达到97.7％;其催化性能远远高于单组份铜或镍催化剂以及其它分子筛载体(MCM-41,SBA-15,HY,ZSM-5)负载的CuNi双金属催化剂.研究结果表明,高度分散在MCM-41上的少量Al组分,有利于Cu,Ni金属组分相互均匀分散.XPS结果表明,双金属催化剂CuNi/Al-MCM-41中Cu和Ni具有明显的电子结合能偏移,表明Ni向Cu转移电子;耦合催化反应性能的提高可能与CuNi双金属协同作用及电荷转移效应有关.傅立叶变换红外光谱和质谱结果表明,聚合副反应对反应体系的pH值敏感.在酸性条件下,中间产物糠醇在反应体系中容易发生聚合,导致糠醇重排生成3-羟基环戊烯酮的选择性降低;在碱性条件下,3-羟基环戊烯酮转化为4-羟基-环戊-2-烯酮后,容易进一步发生聚合副反应.在近中性条件下可有效避免中间体的聚合,提高加氢重排生成环戊酮的选择性.此外,降低原料糠醛的初始浓度,有利于降低聚合等副反应,能够进一步提高目标产物环戊酮的收率.本文为研制双金属纳米过渡金属催化剂以及利用双金属协同作用等方面提供新的启示,为解决生物质原料转化过程中普遍存在的聚合副反应和碳平衡降低等问题提供了新思路.     

水/二甲基亚砜体系中无机盐高效催化木糖脱水制备糠醛(英)

提出了一种高效的均相催化木糖制备糠醛的方法,探讨了水/二甲基亚砜（DMSO）均相体系中不同类型的无机盐对催化木糖制备糠醛的影响.结果表明,氯盐较硫酸盐和硝酸盐表现出较高的催化活性,其中以SnCl₄的催化效果最高.且它与LiCl复配时催化性能更高.当SnCl₄的摩尔分数为0.8时,催化效果最好,糠醛收率达56.9%.反应条件优化实验发现,当催化剂与木糖的摩尔比为0.5:1,固液比为1:20,水与DMSO体积比为5:5时,于130℃下反应6h,糠醛收率达63%.     

Conversion of xylose and xylan into furfural in biorenewable choline chloride–oxalic acid deep eutectic solvent with the addition of metal chloride

An environmentally benign processing approach for furfural production from xylose and xylan under very mild conditions(353–373 K) was developed with the addition of metal chlorides in ChCl–oxalic acid(a deep eutectic solvent(DES)) synthesized from cheap and renewable starting materials). ChCl–oxalic acid acted as both a Br?nsted acid catalyst and a reaction medium in this catalytic route. In addition, a biphasic system with methyl isobutyl ketone as an extracting reagent(DES/MIBK) to further increase furfural yield was also proposed. This processing approach for producing furfural eliminated the large energy consumption for high pressure saturated steam and the generation of acidic effluent, which was very difficult to handle. The whole catalytic system was more environmentally friendly compared with the commercial process for furfural production.     

Dehydration characteristics of struvite-K pertaining to magnesium potassium phosphate cement system in non-isothermal condition

Struvite-K (KMgPO₄·6H₂O) is the main hydration product of magnesium potassium phosphate cement. Its thermal stability is critical to the properties of magnesium potassium phosphate cement. Therefore, in this study, the dehydration behavior of struvite-K was investigated at N₂ atmosphere in non-isothermal condition. The process was conducted and controlled in a simultaneous TG/DTA analyzer, at heating rates of 2, 5, 10, 15, and 20 K min^?1. The residual mass was always around 58.5% of the initial one, regardless of the heating rate, which corresponds to the dehydration reaction through one step, KMgPO₄·6H₂O → KMgPO₄. The activation energy (E _a) corresponding to the dehydration of struvite-K was evaluated by non-isothermal kinetic analysis based on the application of isoconversional methods (Flynn–Wall–Ozawa and Kissinger–Akahira–Sunose methods). The calculated results show that Flynn–Wall–Ozawa has slightly higher values of activation energy (E _a) and correlation coefficients (R ²). Both methods have been proved to be suitable for analyzing dehydration behavior of struvite-K.     

Selective hydrogenolysis of 5-(hydroxymethyl)furfural over Pd/C catalyst to 2,5-dimethylfuran

Several metal supported catalysts were prepared and evaluated for 5-(hydroxymethyl)furfural (5-HMF) hydrogenolysis to 2,5-dimethylfuran (2,5-DMF) which is a renewable potential fuel additive. Among the prepared catalysts, 3%Pd/C showed excellent performance in terms of complete conversion of 5-HMF along with the highest selectivity of 99% to 2,5-DMF. Detailed physico-chemical characterisation was done in order to understand structure-activity correlation. Uniformly dispersed Pd nanoparticles on activated carbon provided the adsorption surface to enhance the hydrogenation of 5-HMF. Reaction was well optimised and established by extensive study of different reaction parameters like temperature, pressure, reaction time, stirring effect, substrate loading and metal loading.     

Effect of promoter on selective hydrogenation of furfural over Cu-Cr/TiO2 catalyst

The selective hydrogenation of furfural has been investigated over the titania-supported monometallic (Cu) and bimetallic (Cu–Cr) catalysts. The catalytic performances were assessed over 4 h of run length under atmospheric pressure at the hydrogen-to-hydrocarbon ratio of 10.6 and 453 K. The results represented that the level of furfural conversion over the non-promoted catalyst was very low (below 10%) while the promoted one showed considerable furfural conversion during this period (higher than 70%). However, both catalysts exhibited high durability and selectivity towards furfuryl alcohol.

     

醋酸溶液中Pd-CuPc/Y催化甲烷选择氧化制甲醇

以氯化铜、钼酸铵、苯酐、氯化铵、尿素和NaY分子筛为原料,采用苯酐-尿素法制备了酞菁铜/分子筛复合物CuPc/Y.采用等体积浸渍法将金属钯担载在CuPc/Y上制备了Pd-CuPc/Y催化剂,并在醋酸水溶液中考察了其催化甲烷选择氧化合成甲醇反应的性能,结果表明,催化性能与反应温度、溶剂中CH₃COOH与H₂O的混合比例、对苯醌用量、反应时间等因素有关,在0.5%Pd-0.5%CuPc/Y添加量0.5 g、CH₃COOH与H₂O体积比4∶1、对苯醌用量1 000 μmol、反应时间3 h、反应温度150 ℃的条件下,甲醇的最佳生成量为1 840 μmol.Pd-CuPc/Y催化剂可以多次循环使用,但由于催化剂流失和催化剂表面的钯粒子聚集的原因,循环使用后的催化剂催化活性有所下降.Pd-CuPc/Y在醋酸溶液中催化甲烷选择氧化合成甲醇是亲电取代反应和活性氧物种氧化共同作用的结果.     

Reductive amination of furfural toward furfurylamine with aqueous ammonia under hydrogen over Ru-supported catalyst

Poly(N-vinyl-2-pyrrolidone)-capped ruthenium-supported hydroxyapatite (Ru-PVP/HAP) shows significant activity for the synthesis of furfurylamine (FAM) via the reductive amination of furfural. As-prepared 5 wt% Ru-PVP/HAP affords 50 % yield of FAM in 25 % NH₃ aqueous solution under pressurized H₂ gas (2.5 atm), and the highest yield approaches 60 % at 4.0 H₂ atm. Comparison between the activities over four Ru-supported HAP catalysts prepared with different methods and the results of X-ray absorption spectroscopy suggested that the metallic Ru cluster is the active center for the reductive amination of furfural. Transmission electron microscope and inductively-coupled plasma analysis indicated that the as-prepared 5 wt% Ru-PVP/HAP catalyst possessed 4.0 wt% PVP-capped Ru clusters with average diameter of 1.7 ± 0.3 nm on HAP support. It was also demonstrated that the reductive amination approach with Ru-PVP/HAP catalyst, NH₃ aq. and pressurized H₂ gas has capability for transformation of aromatic aldehydes to the corresponding aromatic amines. According to these results, it is concluded that Ru(0) cluster supported on HAP will represent a suitable catalyst for widely-usable reductive amination to convert an aldehyde functionality towards an amine.     

Catalytic transfer hydrogenation of biomass-derived furfural to furfuryl alcohol with formic acid as hydrogen donor over CuCs-MCM catalyst

Catalytic transfer hydroge nation(CTH) of furfural(FF) to furfu ryl alcohol(FFA) has received great intere st in recent years.He rein,Cu-Cs bimetallic supported catalyst,CuCs(2)-MCM,was developed for the CTH of FF to FFA using formic as hydrogen donor.CuCs(2)-MCM achieved a 99.6% FFA yield at an optimized reaction conditions of 170℃,1 h.Cu species in CuCs(2)-MCM had dual functions in catalytically decomposing formic acid to generate hydrogen and hydrogenating FF to FFA.The doping of Cs made the size of Cu particles smaller and improved the dispersion of the Cu active sites.Impo rtantly,the Cs species played a favorable role in enhancing the hydrogenation activity as a promoter by adjusting the surface acidity of Cu species to an appropriate level.Correlation analysis showed that surface acidity is the primary factor to affect the catalytic activity of CuCs(2)-MCM.     

Cu/SBA-15-SO3H催化木糖一锅转化制备糠醇（英文）

糠醇是一种重要的高附加值化学品,目前工业上由含半纤维素或木聚糖的生物质原料经过酸脱水先制备糠醛,糠醛再进一步加氢制备糠醇.在实际生产中,这两步反应分别在不同的设备中进行,增加了分离纯化和运输成本;目前也很少有研究偶联这两步反应.本工作中,我们制备了一种多功能介孔Cu/SBA-15-SO3H催化剂用于一锅法一步转化木糖到糠醛,并且通过X射线粉末衍射(XRD)、透射电子显微镜(TEM)、傅里叶变换红外光谱(FT-IR)、热重分析(TGA)、电感耦合等离子体发射光谱(ICP-OES)、X射线荧光(XRF)、NH3-程序升温脱附(NH3-TPD)和N2物理吸附等表征检测了负载的酸和金属位点的可用性以及催化剂的物理化学性质,优化了反应温度、氢气压力、反应时间和溶剂体系等反应条件,研究了酸和金属位点的比例以及介孔尺寸对合成糠醇的影响.XRD表征和TEM及HRTEM图像均表明,在负载了磺酸和Cu之后,均会一定程度上破坏SBA-15的形貌,但是依然可以保持原本的有序介孔结构.XPS表明还原后的Cu主要以+1价的形式存在,也有少量的0价和+2价.红外光谱表明磺酸基团和SBA-15载体以共价键形式紧密结合.氮气吸脱附和相关的BET和BJH计算表明,我们的原位制备方法相比于传统浸渍法,磺酸位点的含量提高了7倍以上.通过对反应条件的优化,该体系在140℃和4MPaH2下可以实现62.6%的糠醇收率.过高的温度会引起产物过度加氢生成2-甲基呋喃,而过高的压力会导致原料过度加氢生成木糖醇.合适的溶剂也是反应的关键因素,使用1:3的水/丁醇双相体系,一方面可以有效促进糖的溶解,另一方面可以有效萃取产物,保证了反应的碳平衡.在对催化剂的筛选中发现,单独的SBA-15几乎无催化活性,Cu/SBA-15主要催化木糖加氢生成木糖醇,SBA-15-SO3H主要催化木糖脱水生成糠醛,而物理混合的Cu/SBA-15和SBA-15-SO3H的效率远不如双功能Cu/SBA-15-SO3H催化剂.通过调节磺酸含量和探究产物时间曲线发现,提高酸性位点可以促进木糖转化,但是过多的酸性位点会导致结焦,降低糠醇收率.共同存在的磺酸酸性位点和铜金属位点保持平衡,协同催化串联反应进行.通过调节SBA-15的孔道结构发现,4 nm的孔道最适合反应进行,孔道过大会降低反应的整体碳收率和糠醇收率.本催化体系实现了从木糖一锅多步法制糠醇,并对催化剂的构效关系进行了研究,对反应条件进行了系统的优化,有希望实际应用到糠醇生产中.     

铜基催化剂上甘油脱水制备羟基丙酮

采用共沉淀法制备了一系列铜基催化剂,在N2中于高压釜中,考察了其催化甘油脱水制备羟基丙酮的反应性能.结果表明,Cu/SiO2催化剂具有较高的催化甘油脱水活性,但目的产物羟基丙酮易与反应产生的H2生成1,2-丙二醇,使得羟基丙酮选择性不高.因此,在固定床反应器上详细考察了在优选的Cu/SiO2催化剂上反应气氛、温度和空速...     

Decarbonylation of furfural over oxide catalysts

Gas chromatography has been used to investigate the products accompanying tetrahydrofuran prepared by hydrogenation of furan, without isolating the latter pure from the gas mixture obtained by decarbonylating furfural over oxide catalysts. A number of unknown impurities accompanying tetrahydrofuran and furan, are identified. It is found that tetrahydrofuran contains isopropanol, along with furan,-methylfuran, and-methyltetrahydrofuran. Furan itself contains-methylfuran, and a number of unknown impurities, among them acetone. Ethane is found among the gaseous products of decarbonylation. Thus over Zn and Mn oxide catalysts there is joint hydrogenolysis of the furan ring, and ring opening at positions 1–5 and 3–4.     

Selective conversion of cellulose to levulinic acid and furfural in sulfolane/water solvent

Direct conversion of cellulose into levulinic acid and furfural in sulfolane media with the aid of water and H₂SO₄ was performed at 140–220 °C under the pressures of 0–1.5 MPa. This approach could obtain 72.5 mol% levulinic acid and 11.5 mol% furfural formation under an optimal condition in which the mass ratio of sulfolane, water and H₂SO₄ was 90:10:1. It was found that the decrease of water content led to an increasing yield of furfural and that the maximum furfural yield (51.1 mol%) could be obtained in the absence of water. The synergism of sulfolane and water in the selective liquefied system was demonstrated to be responsible for not only reinforced effect of optimizing and isolating the target products but also for reducing re-polymerization and side reactions. Furthermore, sulfolane in our case could be recycled and re-used for the conversion of cellulose with the same yield, which shed light on the remarkable potential for future industrial application.     

果糖一步转化制备呋喃基燃料：溶剂效应及离子液体修饰活性金属对产物选择性的决定作用

在众多生物基化合物中,2,5-二甲基呋喃(DMF)是一种有实用前景的可再生液体生物质燃料,也是一种具有重要价值的化学品,可作为生产对苯二甲酸的原料.2,5-二甲基四氢呋喃(DMTF)是DMF进一步加氢产物,该化合物比DMF更稳定,适合长期保存;由于具有更高的氢碳比,用作生物燃料燃烧时能够释放更多能量.研究生物质资源制备DMF和DMTF对可再生资源制备液体燃料和化学品具有重要意义.从生物质多糖出发制备这两类化合物,中间经历了水解、脱水、加氢、加氢脱氧等多个反应步骤,每一步反应都十分复杂,包含许多副反应途径.此外,由于每一步反应条件的不兼容性,大多数研究集中在分步反应阶段,鲜有文献能够实现从碳水化合物原料直接转化为DMF和DMTF.发展由生物质一锅法多步耦合转化技术制备化学品和燃料,不仅具有科学意义,而且可大大简化反应过程,避免中间产物分离和损失,节省资源和时间,历来受到化学家和工业界的关注.本文利用离子液体对Ru/C催化剂电子性质的修饰作用以及溶剂效应的影响,设计了离子液体/THF双相体系中果糖直接催化转化制备2,5-二甲基呋喃(DMF)和2,5-二甲基四氢呋喃(DMTF)的新路线.该转化过程耦合了果糖脱水制HMF、HMF加氢及加氢脱氧生成DMF和DMTF等多步反应.通常在HMF加氢转化过程中, Ru/C催化剂的高活性易导致HMF深度加氢生成大量开环产物及气体,我们借助离子液体与有机溶剂的不同溶解性,筛选出[BMIm]Cl/THF双相溶剂体系,使极性HMF在离子液体层反应,生成弱极性的DMF和DMTF能及时被THF萃取出来,有效稳定了目标产物.其次,果糖转化为HMF会产生少量水,通常水的存在易导致HMF发生水合等副反应,对下一步的加氢转化是不利因素;然而在本催化体系中,由于[BMIm]Cl能与水以较强的氢键结合形成水合物,对水分子起到了束缚作用,减少了HMF发生水解、水合等副反应的机会.另一方面,离子液体粘度较大,微量水的存在能降低离子液体层粘度,改善传质,从而提高反应速率.在HMF加氢处理过程中,离子液体对DMF和DMTF的生成起了决定作用.当反应体系中不添加离子液体,以THF为溶剂,反应结束后未检测到DMF生成, DMTF的收率仅为2%,但HMF已经完全转化.取气体样品进行GC分析,发现有部分气相产物生成,包括CO2、CH4和C2H6等.液体混合物进行GC-MS检测,发现产物主要包括DHMTF、5-甲基四氢糠醇(MTFA)、四氢糠醇(TFA)、1,2-戊二醇、DMTF、2-己醇和少量戊醇,产物中所有呋喃环结构的双键都发生加氢反应.以上结果表明,没有离子液体的THF中, Ru/C催化的HMF涉氢反应平衡已发生改变.当反应体系中添加0.2 g离子液体[BMIm]Cl进行HMF的加氢时,此时开始有DMF生成,随着[BMIm]Cl量依次增加, DMF以及DMTF的收率也呈上升趋势.1.0 g离子液体获得两种产物最高收率为68%.然而,如果进一步增加[BMIm]Cl的量到2.0 g,呋喃基液体燃料DMF和DMTF的收率却开始下降.综合以上实验结果,我们认为适量的[BMIm]Cl存在有可能会对催化剂物理化学性质造成影响,从而对产物的选择性起了决定性作用.通过对催化剂进行元素分析、XPS、H2-TPR表征以及一系列对比实验证明,离子液体不仅促进果糖脱水转化为HMF,同时在HMF选择性加氢反应中可修饰活性金属电子性质,改变催化路径,是多步串联反应能够耦合的关键因素.在[BMIm]Cl/THF双相溶剂体系中,离子液体的“溶剂笼效应”促进DMF和DMTF高效生成, THF的萃取功能对目标产物的稳定起了关键作用.以上对催化剂和溶剂的合理设计共同促进高产率呋喃基燃料的获得.该研究实现由六碳糖直接选择转化获取DMF和DMTF,为生物质高效催化转化制备生物基能源化学品提供了新思路.     

Aqueous biphasic hydroformylation of higher alkenes and highly efficient catalyst recycling in the presence of a polar low boiling solvent

The hydroformylation of higher alkenes under aqueous biphasic reaction conditions with a rhodium catalyst derived from BISBIS (sodium salt of sulfonated 2,2′-bis (diphenylphosphinomethyl)-1,1′-biphenyl) in the presence of a polar low boiling point solvent was studied. The addition of ethanol greatly accelerated hydroformylation, such that the turnover frequency (defined as the moles of converted alkene per mole of Rh per hour) and the selectivity for linear aldehyde were up to 2095 h^?1 and 99 %, respectively. The catalytic system could be recycled for at least five runs without significant loss of activity in the aqueous biphasic hydroformylation of 1-octene; the rhodium content leaching in product mixtures detected by inductively coupled plasma atomic emission spectroscopy was < 0.1 ppm.     

A novel ytterbium/perfluoroalkylated-pyridine catalyst for Baylis-Hillman reaction in a fluorous biphasic system

Ytterbium perfluorooctanesulfonate [Yb(OPf)₃] catalyses the highly efficient Baylis-Hillman reaction in the presence of a catalytic amount of a novel perfluoroalkylated-pyridine as a ligand in a fluorous biphasic system (FBS) composed of toluene and perfluorodecalin. The new process can be carried out successfully without the use of a stoichiometric amount of Lewis base. The fluorous phase containing the active catalytic species is easily separated and can be reused several times without significant loss of catalytic activity.