Enantioselective Hydrogenation of N‐Acetyldehydroamino Acids over Supported Palladium Catalysts

The enantioselective hydrogenation of two N‐acetyldehydroamino acids over Cinchona alkaloid‐modified, supported palladium catalysts has been studied. Moderate enantioselectivities, up to 36 %, were obtained in the hydrogenation of 2‐acetamidocinnamic acid over cinchonidine‐modified Pd/TiO₂ under low hydrogen pressure. Increase in the pressure or use of benzylamine as additive led to a gradual decrease in the enantiomeric excess and eventually inversion of the sense of the enantioselectivity. On the contrary, the optical purity of the product resulting from the hydrogenation of 2‐acetamidoacrylic acid was significantly increased by addition of benzylamine to the reaction mixture. Enantiomeric excess values up to 58 % and 60 % were obtained over Pd/Al₂O₃ modified by cinchonidine and cinchonine, respectively. These optical purities are the best obtained in the hydrogenation of dehydroamino acid derivatives over chirally modified heterogeneous metal catalysts.     

苯甲酸气相加氢制苯甲醛负载型CeO2/Al2O3催化剂的研究

分别采用浸渍法和共沉淀法制备了一系列CeO2/A12O3催化荆,并考察了它们在苯甲酸加氢制备苯甲醛反应中的催化性能.结果表明,共沉淀法制备的催化剂的催化性能优于浸渍法制备的催化剂.采用共沉淀法制备催化剂时,焙烧温度为600℃和CeO2负载量为40%时的催化剂性能较好,进行苯甲酸加氢反应时,苯甲酸转化率可达98.4%,苯甲醛的选择性和收率分别为93.7%和92.2%.共沉淀法制得的催化剂在反应过程中因产生积炭而失活,再生后能恢复活性.对两种方法制备的催化剂分析,发现催化剂比表面、CeO2晶粒大小和CeO2在载体表面的分散性是造成活性不同的根本原因.     

层状前驱体法制备Cu-MnO双功能催化剂及其气相耦合加氢合成苯甲醛

以层状铜锰铝水滑石为前躯体制备Cu-MnO双功能催化剂,实现了甲醇水蒸气重整制氢与苯甲酸甲酯气相加氢反应耦合制备苯甲醛,选择性可达93.34％,要明显优于传统的外加氢方法.X射线衍射和热重-差热分析表明合成的CuMnAl-LDHs、Cu2Al-LDHs、Mn2Al-LDHs具有典型的层状水滑石结构.层状前躯体经氢气还原...     

Selective Hydrogenation of Citral Over Noble Metals Intercalated Montmorillonite Catalysts

Surfactant stabilized platinum and ruthenium nano particles were intercalated into the interlamellar space of montmorillonite. The XRD patterns of the metal intercalated montmorillonite reveal that there was a significant swelling during the intercalation of surfactant stabilized metal particles without affecting the crystallinity of montmorillonite. The success of the synthesis of nano particles into montmorillonite catalysts was confirmed from the TEM micrographs of the catalytic materials. The TEM micrographs clearly indicated well dispersion of particles and the average diameter (in nm) of the intercalated metal particles were also determined. The catalytic activity and selectivity of these newly developed catalysts towards the selective hydrogenation of citral in liquid phase was found to be appreciable. The conversion levels were found to be 38% and 18% at 30 °C and increased to 61% and 46% at 100 °C over Pt-CTA-MM 2 and Ru-CTA-MM 2 catalysts respectively at 9 bar hydrogen pressure. The best selectivity towards geraniol and nerol was observed to be 61% over Pt-CTA-MM 2 among the catalysts studied. The effect of temperature, hydrogen pressure, amount of catalyst and time on stream on the conversion and selectivity towards geraniol and nerol were also discussed in detail.     

Pd/C催化剂上烯酮的选择性加氢反应

采用釜式反应器,在无溶剂条件下考察了金属Pd的负载量、催化剂粒度、载体预处理方式和反应温度等因素对Pd/C催化剂6,10,14-三甲基-13-烯-2-十五烷酮(FA-4H)选择性加氢性能的影响规律。实验结果表明:随着Pd负载量的增加,Pd/C催化剂FA-4H加氢的活性逐渐增加;当Pd负载量在0.5%~3.0%(wt),FA-4H完全转化时目标产物六氢法呢基丙酮(PA)的选择性为99.3%~99.5%。较小的催化剂粒度对应较短的催化剂孔道,有利于减少产物PA在催化剂孔道内停留的时间,从而在一定程度上防止了C=O双键的过度加氢。此外,活性炭载体的硝酸或氨水预处理、较低的反应温度等也有利于减少Pd/C催化剂上FA-4H完全转化时加氢副产物6,10,14-三甲基-13-烯-2-十五烷醇(FA-alcohol)和6,10,14-三甲基-2-十五烷醇(PA-alcohol)的生成量,从而使目标产物PA的选择性接近100%。     

Alkynes Hydrogenation over Pd-Supported Catalysts

The liquid-phase stereoselective hydrogenation of phenyl alkyl acetylenics at 298 K and atmospheric pressure on Pd-supported catalysts has been studied. The catalysts were prepared by impregnation of Pd(acac)₂ precursor (1 wt% of Pd) on different siliceous substrates such as amorphous SiO₂, mesoporous MCM-41 and silylated MCM-41. The poisoning effect of lead incorporation on the supported palladium was also studied. All the catalysts displayed high selectivity to cis-alkene isomer, with Pd/MCM-41 being the most active catalyst. Deliberately adding lead to the base, palladium catalysts underwent changes in the selectivity to cis-alkene isomer and a significant drop in the activity. All the solids were characterized by nitrogen adsorption–desorption isotherms at 77 K, TGA, TPR, H₂ and CO chemisorption, XRD, XPS, and TEM.     

负载型纳米贵金属催化剂的催化氢化反应研究

研究了负载型的高分散纳米贵金属催化剂和含钌的双金属催化剂对2-吡啶甲酸甲酯加氢反应的催化活性.结果表明,单金属催化剂Ru(5 %)/C对吡啶及其衍生物具有较好的催化活性.用XRD、HRTEM和XPS对还原后的Ru/C催化剂表征,表明钌处于高分散零价态,其平均粒径小于5 nm.在50 ℃、5.0 MPa的条件下,催化2-吡啶甲酸甲酯,其加氢转化率达100 %,TOF达到了10.     

A Study of Nitrobenzene Hydrogenation Over Palladium/Carbon Catalysts

The hydrogenation of nitrobenzene has been studied over three palladium/carbon catalysts using methanol and isopropanol as solvents. A solvent and palladium particle size effect have both been observed, with the nature of the particle size effect dependent upon the solvent. This may be related to a change in the rate-determining step.     

离子液体及负载型钯催化剂在加氢反应中的研究进展

离子液体是在小于100℃条件下呈液态的盐,易溶解,热稳定性、催化性强,被誉为绿色溶剂与催化体系,现已得到了广泛应用。负载型钯催化剂具有表面积大,金属分散性,热稳定性强的特点,不过价格昂贵且目标产物选择性不高、反应机理不稳定。对此,就离子液体与负载型钯催化剂在加氢反应中的应用展开分析。     

钯金属催化氯代硝基苯加氢的研究进展

以钯金属催化剂催化氯代硝基苯加氢制备氯代苯胺的工艺具有催化活性高、催化剂可回收套用、绿色环保等优点,然而该类催化剂在催化过程中经常发生脱氯氢解生成副产物,影响产品品质,因此寻找合适的方法抑制脱氯副反应成为了目前该类反应研究的热点问题。本文阐述了钯金属催化剂的多种改性方法,重点介绍了钯金属纳米颗粒的制备,合适载体的选择,以及水溶性钯金属催化剂的制备等改性途径,通过钯金属催化剂的改性可以提高其催化氯代硝基苯加氢反应中反应物的转化率与目标产物的选择性。目前钯金属负载型催化剂已经成为工业抑制脱氯副反应的主要方法,其中高分子聚合-钯络合催化剂效果最优。     

Hydrodechlorination of CFC-12 over Novel Supported Palladium Catalysts

Novel supported palladium catalysts were prepared through organometallic Pd compounds including dichlorobistriphenylphosphine palladium (DCTPPP) and dithiocyanatobistriphenylphosphine palladium (DTTPPP) for the hydrodechlorination of CFC-12. These catalysts exhibited excellent catalytic activities in hydrodechlorination of CFC-12. Particularly, high selectivities of CH₂F₂ formation were achieved over the catalysts, DCTPPP/MgF₂ with 88.1% and DTTPPP/MgF₂ with 85.8%, at a limited conversion level (<5%). No obvious deactivation was observed for DCTPPP/MgF₂ and DTTPPP/MgF₂ catalysts within 60 h. The higher catalytic activity, CH₂F₂ selectivity and catalyst stability may be mainly attributed to high dispersions of palladium.     

负载Pd-Fe双金属催化剂催化含氟芳香硝基化合物的选择性加氢

采用浸渍法制备了负载Pd-Fe双金属催化剂,考察了催化剂常压下催化3-氯-4-氟硝基苯的选择性加氢性能。结果表明,用硼氢化钾还原,在500℃焙烧4h,钯和铁的质量分数分别为5％和0．2％的TiO2负载Pd-Fe催化剂,具有很好的催化活性和选择性。在3-氯-4-氟硝基苯0．1mol,催化剂0．26g,无水乙醇80mL,50℃,0．1MPa和反应2h的条件下,TiO2负载Pd-Fe催化剂催化3-氯-4-氟硝基苯加氢反应,反应产率98．1％,3-氯-4-氟苯胺选择性99．1％。TiO2负载的Pd-Fe催化剂用于催化其他含氟芳香硝基化合物的常压加氢也表现出很高的催化活性和选择性,无脱卤现象。     

Structure-Sensitivity of Propylene Hydrogenation over Cluster-Derived Bimetallic Pt-Au Catalysts

A series of Pt and Pt-Au catalysts supported on TiO₂ has been studied using C₃H₆ hydrogenation as a probe reaction to determine the composition of the active catalytic surface. The catalysts were characterized by H₂ chemisorption and TEM analysis to determine concentrations of surface Pt sites for TOF calculations and metal particle size distributions, respectively. Similar TOF values for C₃H₈ formation (approximately 30 sec⁻¹) were observed for a monometallic Pt/TiO₂ and a bimetallic Pt–Au/TiO₂ sample prepared by impregnation from individual salt precursors. In contrast, the TOF for C₃H₈ formation over a Pt₂Au₄/TiO₂ sample prepared from an organometallic Pt₂Au₄ cluster precursor was decreased to 0.07 sec⁻¹, suggesting strong structure sensitivity for the hydrogenation reaction over this catalyst. Characterization results indicate that Pt on the surface of the Pt₂Au₄/TiO₂ catalyst is heavily diluted by Au atoms. In combination with the kinetic results, this suggests that the highly diluted surface ensembles of Pt are too small to effectively catalyze C₃H₆ hydrogenation, although electronic effects induced by the presence of Au adjacent to Pt sites can not be excluded.     

加氢法制苯甲醛的MnOx/Al2O3催化剂研究

采用等体积浸渍法制备了MnOx/Al2O3催化剂,在固定床连续反应器上考察了MnOx负载量对苯甲酸加氢制备苯甲醛的催化性能的影响,采用TG-DSC、H2-TPR、NH3-TPD和CO2-TPD等手段对催化剂进行了表征,并与催化剂活性和苯甲醛选择性关联。研究表明,在常压、380℃、氢气空速为760 h-1、氢/酸物质的量比为68的条件下,锰负载量为10%~15%的催化剂苯甲酸转化率在92%以上,苯甲醛选择性接近90%。H2-TPR表明,苯甲酸加氢反应与催化剂的氧化还原性有很大的关联,催化剂表面氧空位增加对苯甲酸加氢反应有利。NH3-TPD和CO2-TPD表明催化剂的表面酸碱性对反应活性有很大影响,具有表面弱酸性和中等强度碱性的催化剂活性和苯甲醛选择性比较高。     

Palladium Containing Catalysts Based on Hypercrosslinked Polystyrene for Selective Hydrogenation of Acetylene Alcohols

This paper reports palladium nanoparticle formation and stabilization by hypercrosslinked polystyrene and the catalytic properties of the nanocomposites obtained. The nanocomposites were characterized using low-temperature nitrogen physisorption, X-ray photoelectron spectroscopy and transmission electron microscopy. The inorganic nanoparticle size was found to depend on the Na₂PdCl₄ loading with the smallest nanoparticles formed at 0.1?wt% of Pd. The nanocomposites synthesized showed high activity [up to 27?mol/(mol Pd?s)] and selectivity (up to 98.5?% at 100?% conversion) in selective hydrogenation of acetylene alcohols.     

Acetophenone Hydrogenation on Polymer–Palladium Catalysts. The Effect of Polymer Matrix

Catalytic properties of Pd supported on two polymers of similar basicity but different electrical properties, a π-conjugated conducting-polypyrrole (PPY) and the electro-inactive poly(4-vinylpyridine) (PVP) have been studied in the hydrogenation of acetophenone (ACT) and compared with that of γ-Al₂O₃ supported Pd. Experimental evidences provided by several techniques: X-ray photoelectron spectroscopy (XPS), scanning (SEM) and transmission electron (TEM) microscopy, X-ray diffraction (XRD) and temperature programmed desorption (TPD) of hydrogen show that both polymers PVP and PPY exhibited ability to stabilize finely dispersed palladium nanoparticles, better this ability is offered by electro-inactive PVP. Palladium nanoparticles within a narrow range of size 2–20nm as well as very high surface concentration of Pd (22.2at %) in agglomerates were established in the latter polymer supported catalysts. Distinctly lower surface concentration of Pd (1.8at %) and crystalline Pd particles of dimension within a wide range, from 5nm up to ca. 1500nm appeared in the matrix of electroactive polymer – PPY. The hydrogenation of ACT to ethylbenzene (ETB) via 1-phenylethanol (ACP) (as the intermediate) proceeded over all studied catalysts. The effects of solvents, Pd content, ACT concentration and the additives of ACP, ETB were also studied. The catalytic properties of Pd/PPY in terms of activity and selectivity significantly differ from those of Pd/PVP and Pd/Al₂O₃. Both latter catalysts offered high activity and selectivity in the C=O in ACT to C–OH reduction. Definitely lower activity and higher tendency towards the hydrogenolysis of C–OH in ACP reflected Pd/PPY catalysts. Such unprofitable properties of Pd/PPY can be attributed to relatively strong adsorption of all organic reactant ACT, ACP, ETB. A competition of the ACP and ETB with the ACT occurred only in the case of Pdcentres created in the electroactive polymer, whereas Pd sites dispersed in the electro-inactive PVP similarly as the ones in Al₂O₃ exhibited definitely more substrate – ACT specific character.     

Hydrogenation of But-1-yne and But-1-ene on Palladium Catalysts: Particle Size Effect

The hydrogenation of but-1-yne and but-1-ene was studied on highly (D = 97%) and lowly (D = 26%) dispersed palladium on alumina catalysts. The activity calculated in terms of accessible palladium atoms was found to depend on the particle size. For the hydrogenation of but-1-ene, the turnover number was higher on highly dispersed catalysts than on the lowly dispersed one. The reverse was true for the hydrogenation of but-1-yne. During the hydrogenation of but-1-yne the quantity of but-1-ene produced without further hydrogenation was higher on small particles. A study by X-ray photoemission spectroscopy showed an increase of the binding energy by 1 eV for the 3d core level of palladium in 0.2% Pd/Al₂O₃ (D > 80%) , either before or after a catalytic run (no coalescence occurred). The catalytic results were interpreted as being due to the variation of the adsorption strength of the hydrocarbons. The unsaturated hydrocarbons could be more strongly adsorbed on very small palladium particles which may be considered as “electron deficient”. A calculation showed that the sticking coefficient of but-1-yne was at least 2.5 times as high on small particles as on larger ones.     

钯蜂窝催化剂用于硝基苯气液固三相加氢反应

以Pd/Al2O3/堇青石为催化剂,硝基苯与氢气为原料,系统地考察了氧化铝涂层的上载量、氢气流速、反应温度以及液体空速对硝基苯气液固三相加氢反应的影响规律。结果表明:较高的涂层上载量能产生较大的Pd颗粒,而在较大的Pd颗粒上反应的活性较高;氢气流速对反应并无明显的影响,表明反应器内的流型处于膜状流;反应的表观活化能为6.1 k J/mol,显示外扩散过程对反应的影响很大;硝基苯转化率随着液体空速的增加而不断下降,通过计算不同液相空速时的总传质系数,并与硝基苯的转化率进行关联,发现总传质系数与硝基苯转化率呈良好的线性关系。     

可聚合性季铵盐—膨润土嵌入复合物的制备

本文合成了三种含有可聚合基团的季铵盐,用它们膨润土夹层中的阳离子进行离子交换,制得可聚合性季铵盐－膨润土嵌入复合物。这些嵌入复合物在苯乙烯中具有很好的防沉降性,表观密度比膨润土小,而白度比膨润土有较显著的提高。