海泡石负载Cu催化糠醛气相加氢制糠醇反应

糠醇是一种重要的精细化学品，用于合成耐酸、耐碱和防腐蚀树脂，并用于合成纤维、橡胶、农药等行业，还是呋喃树脂、清漆和颜料的优良溶剂和一种火箭燃料．     

含铜类水滑石催化材料热分解过程的研究

共沉淀法合成了Cu0.13Mg0 6Al0.27(OH)2(CO3)0.135·xH2O类水滑石物质 (CuHTlc) ,采用XRD、DTA TG、BET、TEM和27AlMASNMR技术对其热分解过程进行了表征。结果表明 ,在较低焙烧温度时 (低于300℃ ),氢氧根和层间水部分脱除 ,但水滑石仍保持其层状结构 ;500℃时 ,其层状结构被完全破坏 ,出现氧化镁晶相结构 ,随着焙烧温度的进一步升高 ,尖晶石晶相生成。500℃时的焙烧产物具有最大比表面 (193m2·g-1)。当温度高于500℃ ,焙烧产物组成可表示为Cu0.13Mg0.6Al0.27O0.135,CuHTlc的热分解过程可表示为 :Cu0.13Mg0.6Al0.27(OH)2(CO3)0.135·xH2O→Cu0.13Mg0.6Al0.27O0.135 (1 x)H2O 0.135CO2。     

CuO-CaO/SiO2超细催化剂结构及糠醛加氢反应性能的研究

采用溶胶-凝胶法制备出超细CuO—CaO／SiO2催化剂，用XRD、BET、TEM、XPS、TPR对催化剂结构进行了表征．将催化剂用于糠醛催化加氢反应，制备2-甲基呋喃，研究了活性组分负载量对催化剂结构及性能的影响。结果表明，载体对活性组分的分散能力随着负载量的减少而增大；催化剂的比表面积和孔体积随负载量的增加而减小，而孔径逐渐增大；活性组分与载体之间存在较强的相互作用．催化剂在糠醛加氢反应中表现出很高的活性；选取适宜的活性组分负载量，可高选择性制取2-甲基呋喃．     

Cu/ZnO催化糠醛气相加氢制2-甲基呋喃的研究

通过共沉淀法制备一系列铜锌催化剂,用于固定床上糠醛气相加氢制2-甲基呋喃的研究。采用X射线衍射仪(XRD)、N_2吸附-脱附、扫描电子显微镜(SEM)、H_2-程序升温还原(H_2-TPR)、NH_3-程序升温脱附(NH_3-TPD)表征,分析催化剂中Cu0和ZnO在催化反应中的作用。结果表明,Cu~0是糠醛加氢的活性中心,氧化锌的加入减小了催化剂晶粒粒径、增大了催化剂比表面积、利于催化剂还原和增加催化剂表面弱酸性位。当Cu/Zn物质的量比为1∶2时,Cu_1Zn_2催化剂具有适宜氧化还原活性中心及弱酸位数量,对2-甲基呋喃表现出较高的选择性。Cu_1Zn_2催化剂在常压、反应温度为200℃、氢醛物质的量比为4∶1、糠醛体积空速为0.3 h-1条件下,糠醛转化率100.0%,2-甲基呋喃选择性最高为93.6%。反应稳定运行200 h后,糠醛转化率仍为100.0%,2-甲基呋喃选择性为80.0%,糠醇选择性为11.4%。     

Cu-Cr-Ca-Ba催化剂上糠醛加氢制备2-甲基呋喃

采用固定床反应器,研究了Cu Cr Ca Ba催化剂上糠醛常压选择加氢制2 甲基呋喃的反应.详细考察了反应条件对催化性能的影响.结果表明,添加Ca Ba助剂显著提高了催化剂对目的产物的选择性,Cu Cr Ca Ba催化剂在200～220℃,液时空速0.2～0.6h-1,氢醛摩尔比6～16的条件下,具有良好的活性和选择性,糠醛转化率 99.8%,2 甲基呋喃选择性 90.3%.     

不同硅源的Cu/SiO2催化糠醛加氢制2-甲基呋喃

以硅溶胶和气相二氧化硅为载体,采用氨蒸法制备了Cu/SiO₂-sol和Cu/SiO₂-aer两种催化剂,采用N₂吸附脱附、X射线衍射（XRD）、傅里叶红外光谱（FT-IR）、透射电子显微镜（TEM）、N₂O-H₂滴定、氢气程序升温还原（H₂-TPR）、氨程序升温脱附（NH₃-TPD）及X射线光电子能谱（XPS）对样品进行表征,在固定床反应器中考察两种催化剂对糠醛气相加氢制2-甲基呋喃的催化性能。结果表明,Cu/SiO₂-sol催化剂具有更好的催化活性,在150 h反应时间内,糠醛转化率为100%,2-MF选择性在91%以上。这主要归因于以硅溶胶为硅源可以生成更多页硅酸铜,还原后催化剂表面Cu的分散性更高、弱酸位更多,有利于提高糠醛的转化率与2-甲基呋喃的选择性。同时Cu/SiO₂-sol具有较大的孔容孔径,有利于降低反应过程中积炭,延长催化剂寿命。     

K-Ce改性类水滑石前驱体Co-M—Al复合氧化物催化分解N2O

采用共沉淀法制备不同组分类水滑石前驱体Co-M—Al和Co—M—Ce—Al（M=Zn,Ni,Cu）复合氧化物催化剂催化分解N2O．结果表明,Co—M—Al系列氧化物催化剂的催化活性Co—Ni-Al系列〉Co—Zn-Al系列〉Co—Cu-Al系列;CeO2添加使得催化剂催化活性进一步提高,N20分解温度T50和马0均下降80℃;继续负载碱金属K也使氧化物催化剂催化活性提高,N2O分解温度T50和T90下降约50℃.     

含铜MCM-48催化剂上糠醛选择性加氢制糠醇

 以MCM-48为载体,采用新颖的负载方法(有机官能团化法)制备了铜基负载型催化剂. 结果表明,活性组分以较高的负载量均匀地分散在载体MCM-48表面,且负载活性组分后,分子筛的结构未被明显破坏. 本文首次将采用此负载方法制备的铜基MCM-48催化剂用于糠醛选择性加氢制糠醇反应,并得到了较高的活性、稳定性及糠醇选择性,该催化剂可以与商业催化剂相比,具有潜在的工业应用价值. 与一维结构的MCM-41相比,三维孔道结构的MCM-48有效避免了孔堵塞,大大提高了催化剂的稳定性. 引入助剂镧有利于羰基加氢,明显提高了糠醛的转化率. 使用后的催化剂并未被氧化,催化剂失活的主要原因之一是积炭.     

以类水滑石CuZnAl为前驱体制备的催化剂对C—N交叉偶联反应的性能研究

以类水滑石Cu Zn Al为前驱体,经600℃焙烧制备了一系列不同Cu/Zn/Al摩尔比的催化剂.对催化剂进行了XRD、BET、AAS及XPS等表征,并测定了该催化剂催化碘苯与咪唑C—N交叉偶联合成1-苯基咪唑的催化性能.结果表明,当Cu/Zn/Al摩尔比为2∶1∶1时,其活性组分Cu分散均匀且催化性能达到最佳.在130℃空气气氛中,KOH存在的条件下,反应24 h,1-苯基咪唑的产率可达到85.8%,实现了C—N偶联反应在多相催化体系中进行.催化剂可回收不产生环境污染,经5次重复使用其催化性能下降不明显.     

CuCr／γ—Al2O3催化剂结构及其对糠醛加氢制糠醇的影响

Cu-CrCa系列复合氧化物催化剂用于糠醛液相加氢制糠醇已有较多报道。已知的气相加氢催化剂有低铬铜系复合氧化物,Cu/SiO_2、Cu/Al_2O_3等。我们发现CuCr/γ-Al_2O_3用于常压糠醛气相加氢制糠醇时负荷量大,活性组分用量少,加氢转化率高,选择性好。本文讨论催化剂结构对加氢反应的影响。     

Highly Dispersed CoNi Alloy Embedded in N-doped Graphitic Carbon for Catalytic Transfer Hydrogenation of Biomass-derived Furfural

The development of efficient, stable, and cost-effective heterogeneous catalysts for catalytic transfer hydrogenation (CTH) of biomass-derived furfural (FAL) is highly desired. Herein, series of N-doped graphitic carbon embedded CoNi bimetallic alloy nanoparticles were fabricated and used for the CTH of FAL to value-added furfuryl alcohol (FOL) with renewable isopropanol as hydrogen donor. Intrinsic catalytic activity examination indicated the catalytic performance of Ni_xCo_y@NGC (x:y=1 : 3, 1 : 1, 3 : 1) nanocatalysts were sensitive to their chemical compositions. The optimal Ni₁Co₁@NGC nanocatalyst with Ni/Co mole ratio of 1 : 1 afforded a largest FOL yield of 89.3% with nearly full conversion of FAL. The synergistic effect enabled by bimetallic alloys and the abundant N-based Lewis base sites and surface Co−N active species were revealed based on systematic structural characterization, responsible for the excellent catalytic efficiency of bimetallic Ni₁Co₁@NGC nanocatalyst for CTH of FAL.     

Furfural Hydrogenation on Nickel‐promoted Cu‐containing Catalysts Prepared from Hydrotalcite‐Like Precursors

The nickel‐promoted Cu‐containing catalysts (Cu_xNi_y‐MgAlO) for furfural (FFR) hydrogenation were prepared from the hydrotalcite‐like precursors, and characterized by X‐ray powder diffraction, inductively‐coupled plasma atomic emission spectroscopy, N₂ adsorption‐desorption, UV‐Vis diffuse reflectance spectra and temperature‐programmed reduction with H₂ in the present work. The obtained catalysts were observed to exhibit a better catalytic property than the corresponding Cu‐MgAlO or Ni‐MgAlO samples in FFR hydrogenation, and the CuNi‐MgAlO catalyst with the actual Cu and Ni loadings of 12.5 wt% and 4.5 wt%, respectively, could give the highest FFR conversion (93.2%) and furfuryl alcohol selectivity (89.2%). At the same time, Cu⁰ species from the reduction of Cu²⁺ ions in spinel phases were deduced to be more active for FFR hydrogenation.     

Cu－Zn／γ－Al2O3催化剂的制备及其在选择加氢反应中的催化性能

 通过浸渍法制备了不同Cu／Zn比的γ－Al2O3和改性γ－Al2O3负载的Cu－Zn催化剂，并用XRD，XPS和SEM等手段对催化剂进行了表征．XRD表征结果表明，还原活化前催化剂中的Cu和Zn分别以CuO和ZnO的形式存在；还原活化后Cu以单质的形式存在；催化剂失活后，单质Cu又转变成CuO．XPS和SEM分析结果表明，催化剂中金属的价态及颗粒的形貌在反应前后发生了变化．所制备的催化剂在糠醛加氢制糠醇反应中表现出较高的选择性．用Co改性的γ－Al2O3负载的Cu－Zn催化剂不仅具有较高的催化活性和选择性，而且还呈现出较长的寿命．催化剂中的Cu晶相是催化活性中心；催化剂中的Cu晶相转变成CuO和烧结是催化剂失活 的主要原因．     

氮掺杂多级孔碳负载钴纳米颗粒促进糠醛催化转移加氢

将钴金属纳米粒子负载在具有高比表面积的氮掺杂多级孔碳(Co/HNPC)上,并用于糠醛(FF)的催化转移加氢反应。实验结果表明,Co/HNPC在120℃、4 h的温和条件下,获得了97.6%的FF转化率和95.3%的糠醇(FOL)选择性。优异的催化性能主要取决于金属与HNPC载体之间的协同作用,以及金属本身的负载量。此外,由于HNPC载体的高比表面积和氮掺杂,Co/HNPC催化剂的稳定性也得到了提高。     

Hydrogenation of Furfural to Furfuryl Alcohol over Co-B Amorphous Catalysts Prepared by Chemical Reduction in Variable Media

Five Co-B amorphous alloy catalysts were prepared by chemical reduction in different media, including pure water and pure ethanol as well as the mixture of ethanol and water with variable ethanol content, Their catalytic properties were evaluated using liquid phase furfural hydrogenation to furfuryl alcohol as the probe reaction. It was found that the reaction media had no significant influence on either the amorphous structure of the Co-B catalyst or the electronic interaction between metallic Co and alloying B. This could successfully account for the fact that all the as-prepared Co-B catalysts exhibited almost the same selectivity to furfuryl alcohol and the same activity per surface area （ Rs ）, which could be considered as the intrinsic activity, since the nature of active sites remained unchanged. However, the activity per gram of Co （ R^mH ） of the as-prepared Co-B catalysts increased rapidly when the ethanol content in the water-ethanol mixture used as the reaction medium for catalyst preparation increased. This could be attributed to the rapid increase in the surface area possibly owing to the presence of more oxidized boron species which could serve as a support for dispersing the Co-B amorphous alloy particles.     

膜反应器中Ni-Cu催化剂上CO加氢合成乙烯的研究

 将硅藻土－TiO2－聚乙烯（或聚丙烯）疏水复合膜反应器应用于\r\nCO加氢合成乙烯的反应过程，以Ni－Cu／TiSiO和Ni－Cu／MgSiO为催化\r\n剂，考察了反应温度、空速和进料组成等因素对CO转化率和乙烯选择性\r\n的影响．结果表明：膜催化反应的产物与常规催化反应相同，催化反应\r\n机理没有区别，在适宜条件下，膜催化反应的CO转化率和乙烯选择性较\r\n之常规催化反应提高了10％左右，二氧化碳和甲烷的选择性降低，而乙\r\n烷的选择性略有增加．     

不同方法制备的Cu-Cr/γ-Al2O3的结构及其对糠醛加氢制2-甲基呋喃反应的催化性能

 利用普通浸渍法、共沉淀法和溶剂化金属原子浸渍法制备了一系列Cu－Cr／γ－Al2O3催化剂，并用X射线衍射、扫描电镜、透射电镜和X射线光电子能谱等技术对这些催化剂进行了表征．结果表明，不同方法制备的催化剂的金属粒度的顺序为溶剂化金属原子浸渍法＜共沉淀法＜普通浸渍法；金属还原程度的顺序为溶剂化金属原子浸渍法＞普通浸渍法≈共沉淀法．糠醛加氢反应实验结果表明，催化活性顺序为溶剂化金属原子浸渍法＞普通浸渍法＞共沉淀法；生成2－甲基呋喃选择性顺序为共沉淀法＞普通浸渍法＞溶剂化金属原子浸渍法．     

Catalytic transfer hydrogenation of furfural into furfuryl alcohol over Ni–Fe‐layered double hydroxide catalysts

Layered double hydroxides (LDHs) and their derivatives have been reported to be widely used as heterogeneous catalysts in various reactions. Herein, Ni‐Fe LDHs with the controlled Ni/Fe molar ratios (2:1, 3:1, 4:1) were synthesized via an easy hydrothermal method, which were used to catalyze the selective reduction of biomass‐derived furfural into furfuryl alcohol using 2‐propanol as a H‐donor under autogenous pressure and characterized using FT‐IR, XRD, TGA, BET, SEM, NH₃‐TPD, and CO₂‐TPD. It was found that the LDH with a Ni/Fe molar ratio of 3:1 demonstrated the best catalytic activity among the LDHs with different Ni/Fe molar ratios, which showed 97.0% conversion of furfural and 90.2% yield of furfuryl alcohol at 140°C for 5 hr. This was attributable to the synergistic effect of acidic sites and basic sites of the catalyst.