CuCoMn-zeolite双功能催化剂转化生物质基合成气制取液态烃

选用四种不同的分子筛(SAPO-34, ZSM-5, Y, MCM-41)与CuCoMn(高醇合成组元)构成双功能催化剂,利用N₂吸脱附、H₂-TPR、XRD、NH₃-TPD等表征了催化剂的结构性质. 研究了催化剂在生物质基合成气一段法制取液态烃燃料的应用. 相比于CuCoMn催化剂,加入分子筛的双功能催化剂均不同程度地提高了液体烃燃料的选择性及收率,且收率按顺序递减呈CCM-ZSM-5>CCM-SAPO-34>CCM-Y>CCM-MCM-41. 同时,共沉淀法制备的CuCoMn-ZSM-5 (20wt%, Si/Al=100) 具有最佳的CO转化率(76%)及液体产物收率(30%). 相比于CuCoMn氧化物,双功能催化剂的比表面及孔容均得到提高. CCM-ZSM-5具有适中的微孔尺寸和中等强度的酸性,增加CCM-ZSM-5中ZSM-5含量或降低ZSM-5中的Si/Al比,均有利于提高酸性位的数量,主要是较弱的酸性位. 而共沉淀法制备的CCM-ZSM-5具有更好的金属分散性及还原性能.     

Effect of Calcination Temperature on La-Modified Al2O3 Catalysts for Vapor Phase Hydrofluorination of Acetylene to Vinyl Fluoride

利用沉积沉淀法制备出了La改性Al₂O₃催化剂,研究不同焙烧温度对La改性Al₂O₃催化剂用于乙炔气相氢氟化合成氟乙烯反应性能的影响．利用NH₃-TPD、Pyridine-FTIR、XRD和Raman等技术对不同温度焙烧的催化剂进行表征,发现焙烧过程能改变催化剂结构的同时也能调变催化剂表面的酸量．经400 °C焙烧的催化剂显示出最高的乙炔转化率(94.6%)、最高的氟乙烯选择性(83.4%)和较低的积炭选择性(0.72%)．催化剂的高活性与其表面的高酸量有关,同时积炭的选择性也与其表面的酸中心数量有关．     

1H NMR探究空间效应对表面活性剂复配体系中协同作用的影响

通过核磁共振氢谱（¹H NMR）实验测量了温度为298.0 K时3种表面活性剂——十六烷基三甲基溴化铵（CTAB）、辛基苯基聚氧乙烯醚（TX-100）和十二烷基硫酸钠（SDS）组成的复配体系CTAB/TX-100、SDS/TX-100和CTAB/TX-100/SDS中各组分的化学位移,得到了各混合体系中CTAB、TX-100和SDS的临界胶束浓度（CMC）.对不同体系中各组分CMC随摩尔分数的变化曲线进行比较,发现了空间效应对表面活性剂复配体系中协同作用的影响在一定的情况下并不逊于静电相互作用：表面活性剂分子的截面积越大,对体系中其他组分的协同作用越强;当组分间存在弱的静电相互作用时,空间效应对协同作用起到更主要的影响.     

KE型染料与Gemini阳离子表面活性剂T122的光谱研究

在室温(25℃)下,通过紫外-可见光谱法及稳态荧光法分别测定了Gemini型阳离子表面活性剂T122和传统阳离子表面活性剂十六烷基三甲基溴化铵(CTAB)与三种KE型活性染料相互作用后的临界胶束浓度(CMC),并对二者作用的机理进行了初步分析.实验结果表明,两种方法测出的CMC值基本吻合;KE型染料的加入都能使阳离子表面活性剂的CMC值有所提高;如染料黄KE-4R的加入使表面活性剂T122的CMC增至不加染料前的7.0倍,而CTAB的CMC值增加至原来的1.5倍;带有双亲分子结构的表面活性剂T122的性能要明显优于传统表面活性剂CTAB.     

Ni基催化剂在邻甲酚原位加氢反应中的催化性能

采用等体积浸渍法制备了一系列负载型Ni基催化剂,利用XRD、H₂-TPR、NH₃-TPD 等技术表征了催化剂的理化特性,考察了载体(CMK-3、SiO₂ZrO₂、MgO、Al₂O₃)、助剂(Cu、Ce、Fe)对Ni基催化剂理化特性的影响,测试了230 oC、0.1 MPa冷压下催化剂对邻甲酚原位加氢反应的性能．结果表明,在负载型镍基催化剂作用下,甲醇水相重整制氢反应可以与邻甲酚的原位加氢反应相耦合;以CMK-3为载体的催化剂活性明显优于其他三种载体,邻甲酚的转化率为45.35%;助剂的添加对催化剂性能影响显著,Fe 的引入使原位加氢体系的转化率降至40.49%,助剂Ce、Cu的加入提高了Ni/CMK-3催化剂的原位加氢反应性能,转化率分别提高至64.6%、66.8%,Cu的添加改变了产物的分布,在产物中出现了新产物甲苯;同时探讨原位加氢反应路径及反应机理．     

NMR法研究胶束的增溶作用

本文用高分辨~1H.NMR谱研究了多种短链芳烃及其衍生物在阳离子表面活性剂—十六烷基三甲基溴化铵(CTAB)水溶液胶束和非离子表面活性剂—月桂基聚氧乙烯(4)醚(Brij30)非水溶液胶束中的增溶作用。得到这些不同种类的增溶物在两种不同类型的胶束中增溶位置的详细结果。并讨论了增溶物与表面活性剂分子之间的相互作用。这一研究对深入探讨增溶机理十分有益。     

Enhancement in Magnetorheological Effect of Magnetorheological Elastomers by Surface Modification of Iron Particles

为了研制具有高磁流变效应的磁流变弹性体,从新的化学修饰的角度制备了各向异性的橡胶基磁流变弹性体. 阴离子表面活性剂、非离子表面活性剂和复合表面活性剂等三种不同类型的表面活性剂分别用于修饰铁颗粒. 使用力磁耦合动态测试仪测量磁流变弹性体的动态剪切模量,并计算材料的磁流变效应. 测试结果表明,当Span 80的含量为15%时,材料的相对磁流变效应可达到188%,除了表面活性外,Span 80的增塑效应也有利于相对磁流变效应的增加. 当使用具有强表面活性的复合表面活性剂修饰铁颗粒时,用量只需0.4%,便可使相对     

糠醇辅助的聚合凝胶法制备纳米Li4Ti5O12负极材料

以硝酸锂、钛酸正丁酯和糠醇为反应物,采用糠醇聚合凝胶法制备了纳米Li₄Ti₅O₁₂粉体．利用XRD、SEM和BET比表面测试对产物进行了表征,并研究了纳米Li₄Ti₅O₁₂粉体作为锂离子电池负极材料的电化学性能．在700℃或更高温度烧结时产物为纯相的尖晶石型．通过柠檬酸、聚乙烯吡咯烷酮、十六烷基三甲基溴化铵(CTAB)表面活性剂的加入能够减少产物颗粒的团聚程度,增大粉体的比表面积,提高其电化学性能．加入0.5 g CTAB、700℃烧结12 h的Li₄Ti₅O₁₂粉体展示出最高的比容量和最佳的循环性能,10 C下充电比容量高达156.7 mAh/g．     

四氯化碳-水-十六烷基三甲基溴化铵三元体系凝胶的生成机理初探

自从1921年凝胶首次由小分子制得以来,小分子凝胶研究已经有了一定的进展。特别是近几十年小分子凝胶在医药、化妆品、食品、卫生用品等各个领域应用,被人们广泛关注。但到目前为止,人们对基于表面活性剂的小分子凝胶的结构和生成机理,特别是水、有机溶剂和表面活性剂在形成小分子凝胶过程中的作用仍认识十分有限。可使用水、四氯化碳和三甲基十六烷基溴化铵(CTAB)制出了一种小分子凝胶,并根据滴定和XRD实验结果提出了水和四氯化碳协同增溶表面活性剂CTAB形成凝胶的机理。红外光谱与核磁共振实验结果证明CTAB在凝胶中通过分子堆砌形成准有序结构。     

表面活性剂对纳米制冷剂颗粒团聚的影响

为通过表面活性剂抑制纳米制冷剂中的颗粒团聚,需要了解不同种类和浓度的表面活性剂对纳米制冷剂颗粒团聚的影响。本文采用动态光散射技术测量纳米制冷剂中的颗粒尺度,来定量分析纳米制冷剂的颗粒团聚特性;实验所用纳米制冷剂为TiO_2-R141b;表面活性剂种类包括SDBS(阳离子型)、CTAB(阴离子型)和NP-10(非离子型)。实验结果表明,SDBS、CTAB和NP-10均可降低纳米制冷剂的颗粒尺度,即抑制纳米制冷剂中的颗粒团聚。对SBDS、CTAB和NP-10,当其浓度分别为400 mg·L~(-1)、200 mg·L~(-1)和300mg·L~(-1)时纳米制冷剂的颗粒尺度最小,最小值分别是未加表面活性剂时的58.4%、56.9%和38.0%。     

K-Co-Mo/CNTs催化剂合成低碳醇性能研究

A series of carbon nanotubes-supported K-Co-Mo catalysts were prepared by a sol-gel method combined with incipient wetness impregnation.The catalyst structures were characterized by X-ray diffraction,N₂ adsorption-desorption,transmission electron microscopy and H₂-TPD,and its catalytic performance toward the synthesis of higher alcohols from syngas was investigated.The as-prepared catalyst particles had a low crystallization degree and high dispersion on the outer and inner surface of CNTs.The uniform mesoporous structure of CNTs increased the diffusion rate of reactants and products,thus promoting the reaction conversion.Furthermore,the incorporation of CNTs support led to a high capability of hydrogen absorption and spillover and promoted the formation of alkyl group,which served as the key intermediate for the alcohol formation and carbon chain growth.Benefiting from these characteristics,the CNTs supported Mo-based catalyst showed the excellent catalytic performance for the higher alcohols synthesis as compared to the unsupported catalyst and activated carbon supported catalyst.     

利用生物质气化合成气在FeCuZnAlK催化剂上高效制备清洁生物燃料

研究了生物质气化合成气在Fe_1.5Cu₁Zn₁Al₁K_0.117催化剂上高效转化为清洁生物燃料的合成过程. 利用生物质气化合成气合成的生物燃料最大产率为1.59 kg/(kgcatal·h), 其中醇占0.57 kg/(kgcatal·h), 液体烃占1.02 kg/(kgcatal·h). 在生物燃料中, 醇类产物主要为C2⁺醇(主要为C2-C6高碳醇), 其含量占总醇的7     

利用生物质合成气在钼基催化剂上制备混合醇

采用柠檬酸作络合剂的溶胶凝胶法制备了一系列的钼基催化剂,并应用到从生物质气化合成气有效合成低碳混合醇的实际过程中. 在钼基催化剂中,Cu₁Co₁Fe₁Mo₁Zn_0.5-6%K催化剂具有相对较高的混合醇时空产率. 通过实验发现, 反应温度在340 oC以下时,碳转化率随着反应温度的增加而不断上升,总醇的选择性却逐渐下降. 在试验测试的条件内,从生物质气化合成气合成的混合醇最大产率为494.8 g/(kg_catal·h),其中C2⁺醇(C2-C6高碳醇)占总醇含量的80.4%. 在不同的钼基催化剂上合成的混合醇,其醇分布除甲醇以外均符合Schulz-Flory方程. 在醇类产物中,C2以上的高级醇含量占总醇重量的百分比为70%-85%. 同时,利用X射线衍射和BET等表征手段对钼基催化剂的形态和结构进行了表征. 从生物质合成气生产的洁净生物质燃料混合醇具有较高的辛烷值,可以用作运输燃料或汽油的添加剂.     

Mn助剂对K-Co-Mo催化剂结构及CO加氢合成低碳醇性能的影响

通过溶胶-凝胶法合成了一系列Mn掺杂K-Co-Mo催化剂,并利用X射线衍射、N₂吸脱附、NH₃程序升温脱附、原位漫反射红外光谱以及X射线吸收谱等技术对催化剂的结构进行了表征.活性测试结果显示Mn掺杂催化剂比未掺杂催化剂表现更高的合成低碳醇的催化活性,尤其是C₂₊醇的选择性得到了明显的提高.醇产物分布偏离了ASF分布规律,甲醇的含量显著减少,乙醇成为主要醇产物.表征结果表明Mn助剂的加入增强了Co和Mo之间的相互作用,促进了醇生成活性中心Co-Mo-O物种的生成.显著减少了催化剂强酸性位的数量,促进了弱酸性位的产生,有利于醇产物的生成.助剂的加入有利于催化剂对CO的线性和桥式吸附,促进了醇产物的生成和碳链的增长,提高了催化剂对C₂₊醇的选择性.     

Size controlled synthesis of Co nanoparticles by combination of organic solvent and surfactant

Co particles were synthesized with mean particle sizes in the range of 3.2-171.4 nm in ambient atmosphere by reduction of cobalt salt with sodium borohydride as the reducing reagent, a combination of alcohols as solvents and a triblock copolymer P123 (EO₂₀PO₇₀EO₂₀) as the surfactant. The particle size and its distribution were controlled by varying the synthesis parameters such as the viscosity of the medium, the amount of alcohols or P123 in the reaction system. FT-IR and X-ray photoelectron spectroscopy (XPS) measurements confirmed the interaction between the oxygen atoms of P123 and Co²⁺ or Co⁰. Detailed surface analyses by XPS and HRTEM revealed that the synthesized particles consisted of Co⁰ metal surrounded by amorphous CoO, Co₂B and chemisorbed P123.     

Investigation of oxide catalysts activity in the NOx neutralisation with organic reductants

Temperature-programmed desorption of NO (TPD) and temperature-programmed reduction of NO by propene and ethanol (TPSR) over the catalyst with redox properties and the structure of spinels - Co₃O₄ and CoFe₂O₄ - were investigated.The TPD experiments can determine the temperature range in which the deNO_x proceeds and provide information about the heat of adsorption of NO on the surface of catalysts. The values of the adsorption heat are much higher in the case of the catalyst with weaker redox properties (CoFe₂O₄), because of stronger bonds between the adsorbate and the surface of catalyst. The TPD and TPSR experiments show that ethyl alcohol is a more active reductant in the deNO_x process than propene. The maximum of NO_x conversion is higher with ethyl alcohol used as a reductant in both cases of investigated catalysts. Moreover, the temperature of the maximum degree of NO_x reduction is lower in the case of alcohol used as an reductant. Co₃O₄ is a more active and suitable catalyst for the deNO_x process than CoFe₂O₄.     

Effects of Poly(Propylene Oxide)–Poly(Ethylene Oxide)–Poly(Propylene Oxide) Triblock Copolymer on the Gelation of Poly(Ethylene Oxide)–Poly(Propylene Oxide)–Poly(Ethylene Oxide) Aqueous Solutions

Poly(ethylene oxide)-poly(propylene oxide)–poly(ethylene oxide) ((EO)_n–(PO)_m–(EO)_n) block copolymers, commercially available as Pluronics (BASF Corp.) and Poloxamers (ICI Corp.), have been widely applied in medicine, biochemistry, and other fields because of their ability to form reversible micelles and physical gels in aqueous solution. Generally, for PEO–PPO–PEO block copolymers with higher ethylene oxide concentration, the micellization and gelation in aqueous solution are easier. However, if we introduce the reverse block copolymer PPO–PEO–PPO into PEO–PPO–PEO aqueous solutions, the micellization and gelation of the system will be more complex. In this work, the reverse block copolymer PO₁₄–EO₂₄–PO₁₄ (17R4) was added to the Pluronics EO₂₀–PO₇₀–EO₂₀ (P123), EO₁₀₀–PO₆₅–EO₁₀₀ (F127), and EO₁₃₃–PO₅₀–EO₁₃₃ (F108) aqueous solutions with different molar ratios. The rheological properties of different mixtures were measured to study the additive effect on the gelation behavior. The sol–gel transition temperature of the P123, F127, and F108 solutions shifted to a higher temperature when 17R4 was added to the solutions. In addition, the existence of 17R4 greatly affected the stability of gels. These results help to better understand the gelation of Pluronic aqueous solutions.     

Metal-free activation of H<Subscript>2</Subscript>O<Subscript>2</Subscript> by synergic effect of ionic liquid and microwave: chemoselective oxidation of benzylic alcohols to carbonyls and unexpected formation of anthraquinone in aqueous condition

H₂O₂ mediated oxidation of alcohols in ionic liquid is revisited, wherein, ionic liquids under the influence of microwave irradiation have been found to facilitate activation of H₂O₂ without any metal catalyst in aqueous condition. The method utilizes a neutral ionic liquid [hmim]Br both as catalyst and solvent for efficient and chemoselective oxidation of benzyl alcohol derivatives on aromatic (β, γ) alcohols, cyclic and aliphatic analogues, which can be a useful synthetic approach in total synthesis of complex organic compounds/natural products. Moreover, an unexpected oxidation of 9-anthracenyl propanol, a polyaromatic benzyl alcohol, resulting in the formation of 9,10-anthraquinone by the loss of propyl side chain was observed. Plausible mechanism and further exploration of this method on various other related substrates are discussed in detail.     

在Ni/HZSM-5催化剂上低温水蒸汽重整生物油制氢

利用浸渍方法制备的Ni/HZSM-5催化剂在生物油低温水蒸汽重整合成中表现了较高的催化活性． 探讨了催化剂的组成、重整温度、水碳比例对重整过程的影响．在电催化重整研究中,发现催化剂上通过的电流可以显著地促进生物油水蒸汽重整．通过对不同负载量的Ni/HZSM-5催化剂和Ni₂₀/Al₂O₃催化剂的催化活性的比较,NiO在催化剂中负载量为20%(Ni₂₀/ZSM)时表现出了最高的催化活性; 即使在450 oC时, 在Ni₂₀/ZSM催化剂上也可以达到碳转化率接近完全, 氢气产率约为90%的效果． 利用XRD、ICP/AES、H₂-TPR、BET等表征手段对Ni/HZSM-5催化剂的形态和结构进行了表征.