液相法苯选择加氢制环己烯反应条件的探讨

采用化学还原法制备负载型钌催化剂,进行了苯选择加氢制环己烯。研究了反应温度、氢气压力、搅拌速率、反应时间对苯转化率、环己烯选择性及收率的影响。结果表明:在最佳反应条件下,反应温度为140℃、氢气压力为6.0MPa、搅拌速率为900r/min、反应时间为20min时,苯转化率为76.27%,环己烯选择性为68.33%,环己烯收率为52.12%。     

新型碳三液相选择加氢催化剂的工业应用

报道了新型碳三选择加氢催化剂在200 kt/a乙烯装置上工业应用24个月的试验结果.工业应用结果表明:BC-H-30A催化剂适用工况范围广,抗波动能力强,催化活性高,选择性好.既有BC-L-83催化剂的高空速、再生周期长等方面的性能,又在催化剂活性、选择性、耐高浓度甲基乙炔和丙二烯入口的能力、控制出口甲基乙炔和丙二烯浓度的能力等方面有显著提升,与同类催化剂相比,处于国际先进水平.两年来,新增利税176.8万元.     

固相合成纳米炭球

首次用乙炔黑为碳源,利用高温炭化的方法制备出了纳米炭球,其直径为20～50 nm,并伴随有直径约为200～500 nm的炭空心球生成.结合SEM和XRD分析手段,研究了预处理时间、催化剂和降温速度对纳米炭球形成的影响.研究表明:用浓硫酸和浓硝酸(体积比3∶1)的混酸处理100 h的乙炔黑,在较快的降温速度下易生成分散较好的纳米炭球.     

On the effects of confinement within a catalyst consisting of platinum embedded within nanoporous carbon for the hydrogenation of alkenes

In heterogeneous catalysis, pore size exerts an influence on reaction pathway, selectivity, equilibrium and adsorption constants. This effect can in principle cause noticeable changes in selectivity. Here, we present an analysis of a diffusion–reaction process in the pores of a catalyst comprised of platinum nanoparticles embedded within a molecular sieving carbon. When the alkenes are hydrogenated over this catalyst, the reaction takes place within the ultramicropores of the carbon. Experimental data for the liquid phase hydrogenation of different alkenes over platinum supported on the carbon versus platinum embedded within the same carbon were collected. From these data kinetic parameters and diffusion coefficients for reactions were evaluated. The forward rate constant for 2-methyl-1-pentene hydrogenation was found to be almost one order of magnitude larger within the embedded platinum catalyst versus the supported platinum catalyst. The variation in pore size and reactant molecule dimension, were also found to affect the adsorption equilibrium constants and diffusion coefficients. For 2-methyl-1-pentene molecule with the highest steric hindrance, K increased to 500 g/mol in embedded catalyst compared to 100 g/mol on supported catalyst. At the same time the diffusion coefficient for 2-methyl-1-pentene was one order of magnitude smaller than 1-hexene.     

Recent development of supported monometallic gold as heterogeneous catalyst for selective liquid phase hydrogenation reactions

The great potential of gold catalysts for chemical conversions in both industrial and environmental concerns has attracted increasing interest in many fields of research. Gold nanoparticles supported b...     

新型碳三液相加氢催化剂工业侧线评价

以兰州石化24万吨乙烯车间裂解料为原料,模拟工业装置工况,LY-C3-A与对比催化剂1000 h活性和稳定性试验结果表明：在其它工艺相同条件下,LY-C3-A入口温度比对比剂低5～8℃、床层温升高2.3 ℃,LY-C3-A丙烯转化率优于对比剂4个百分点,且LY-C3-A催化剂丙烯选择性高于对比剂10个百分点。评价结果证明LY-C3-A综合性能优于对比剂且达到工业装置应用要求。     

负载金作为非均相催化剂催化选择性液相加氢反应的研究进展(英文)

The great potential of gold catalysts for chemical conversions in both industrial and environmental concerns has attracted increasing interest in many fields of research. Gold nanoparticles supported by metal oxides with high surface area have been recognized as highly efficient and effective green heterogeneous catalyst even at room temperature under normal reaction conditions, in gas and liquid phase reactions. In the present review, we dis-cuss the recent development of heterogeneous, supported monometal ic gold catalysts for organic transforma-tions emphasizing mainly liquid phase hydrogenation reactions. Discussions on the catalytic synthesis procedures and the promoting effect of other noble metals are omitted since they are already worked out. Appli-cations of heterogeneous, supported monometal ic catalysts for chemoselective hydrogenations in liquid phase are studied including potential articles during the period 2000–2013.     

苯乙炔选择性加氢滴流床反应器内的液相轴向返混特性

苯乙炔选择性加氢是从裂解汽油C₈馏分中回收苯乙烯的关键反应,本文采用滴流床反应器对该反应体系的液相轴向返混行为进行了研究。首先利用脉冲示踪法测得了不同操作条件下的液相停留时间分布密度;然后基于固定床轴向扩散模型,通过有限元正交配置法和Levenberg-Marquardt非线性最小二乘法,计算得到了Péclet数和液相平均停留时间;最后考察了主要操作条件对液相轴向返混的影响。研究结果表明,增大液体流量、气体流量、温度以及压力均可减小液相返混,而增大颗粒粒径会使液相返混加剧。     

碳纳米管负载催化剂在对硝基甲苯液相催化加氢中的应用

用对硝基甲苯液相加氢生成对甲基苯胺为探针反应研究了碳纳米管负载铂锡催化剂的催化性能,分别评价了铂锡负载在碳纳米管、γ-Al2O3、SiO2上的催化活性。实验结果表明:在实验条件下,碳纳米管负载铂锡催化剂时反应物的转化率和产物的选择性分别是99.1%和100%。转化率分别是二氧化硅负载铂锡催化剂的1.5倍,三氧化二铝负载铂锡催化剂的1.8倍。     

Pt nanoparticles deposited over carbon nanotubes for selective hydrogenation of cinnamaldehyde

Two kinds of carbon nanotubes (CNTs) with different inner diameter (less than 10 nm: CNTs-1 and between 60 and 100 nm: CNTs-2) were used as catalyst supports. The platinum particles were simply deposited on the outside surface (CNTs-1) and inside (CNTs-2) and were easily reduced to Pt⁰ by refluxing. The catalysts exhibit high activities in the selective hydrogenation of cinnamaldehyde which contains both CC and CO bonds. But the selectivity of these two catalysts was quite different under same reaction conditions. The high selective hydrogenation of CO bond was observed over catalyst 3%Pt/CNTs-2, while the completely hydrogenation of both CC and CO bonds was found over catalyst 3%Pt/CNTs-1.     

Impact of nitrogen doping of carbon nanospheres on the nickel-catalyzed hydrogenation of butyronitrile

Three nickel catalysts supported on carbon and nitrogen-doped carbon nanospheres have been prepared by deposition-precipitation (DP) with urea (ca. 2% w/w). The nanospheres were prepared by thermal pyrolysis of benzene (CNS_B), aniline (CNS_A) and nitrobenzene (CNS_N) and characterized by transmission electron microscopy (TEM), N₂ adsorption–desorption, temperature-programmed oxidation (TPO), X-ray diffraction (XRD), elemental (CHN) analysis, X-ray photoelectron spectroscopy (XPS), temperature-programmed decomposition (TPD) and acid/base titrations, revealing different graphitic characteristics and different distribution of nitrogen (when present) functionalities. Upon Ni introduction, the catalysts were characterized by temperature-programmed reduction (TPR), XRD and TEM. Surface area weighted mean Ni particle diameters (post activation at 603 K) were in the range 10.5–18.2 nm. Ni particle size exhibited a big dependence on CNS nitrogen doping, where nitrogen introduction, essentially in the quaternary form, enhanced metal sintering by enriching the surface electron density of the support. The catalysts were tested in the gas phase hydrogenation of butyronitrile (T = 493 K). Extracted specific reaction rates in the steady state followed the sequence: Ni/CNS_B < Ni/CNS_A < Ni/CNS_N. When the active metal was physically mixed with the support, the following sequence was obtained: Ni + CNS_B < Ni + CNS_A < Ni + CNS_N. Our results demonstrate that doping carbon nanospheres with nitrogen strongly impacts on reactant adsorption and metal sintering, both critical aspects in the hydrogenation of nitriles. Selectivity was not sensitive to the support (or the physical mixture) employed and was in all cases close to 100% to the primary amine.     

溶剂对Pd/C催化四氯化碳液相加氢反应的影响

考察了活性组分、载体、Pd含量及溶剂对四氯化碳液相催化加氢转化为氯仿反应的影响。实验结果表明,质量分数0.5%的Pd/C是四氯化碳液相催化转化的较优催化剂。溶剂对该反应的速率和产品分布有显著影响,在正庚烷、甲苯和甲醇3种溶剂中,甲醇最利于提高Pd/C催化剂的活性,且四氯化碳转化的平均反应速率随着甲醇含量的增加呈现先增大后减小的趋势,氯仿的选择性随着甲醇含量的增加有所降低。当甲醇和四氯化碳的体积比为2∶1时,四氯化碳转化速率最高。甲醇和四氯化碳的体积比为1∶10时,氯仿的选择性达90%。     

碳纳米管负载镍基催化剂上乙炔选择性加氢

分别采用浸渍法、化学还原法和超声辅助的浸渍-化学还原法,制备晶态Ni/CNTs、非晶态NiB和NiB/CNTs催化剂,对非晶态NiB/CNTs催化剂热处理使其晶化.表征了催化剂,并考察催化剂的乙炔选择性加氢性能.结果表明非晶态NiB/CNTs合金的催化性能优于晶态Ni/CNTs以及晶化NiB/CNTs催化剂的性能,其在乙炔选择性加氢反应中有较好的稳定性,连续使用650 min后乙炔转化率达80%以上.乙烷选择性随反应进行逐渐下降,最终趋于7.5%;乙烯选择性随反应进行逐渐上升,最终趋于55%.     

Highly selective palladium supported catalyst for hydrogenation of phenol in aqueous phase

Hydrogenation of phenol to cyclohexanone in aqueous phase, under mild conditions, has been carried out using palladium on different supports such as hydroxyapatite (HA), carbon (C), alumina (γ-Al₂O₃) and Al₂O₃-CWE synthesized with high surface area. High activity (100%) and selectivity (98%) to cyclohexanone was obtained using Pd/ Al₂O₃-CWE catalyst in 50 min under mild reaction conditions.     

Porous membrane catalysts with Pd-M-clusters for liquid phase hydrogenation of dehydrolinalool

New membrane catalysts with less than 1.5% of Pd in porous stainless steel have been prepared for liquid phase hydrogenation of unsaturated organic compounds. Ultradispersed Pd modified with catalytically active Pb, Mn, or Bi was prepared using Metal Vapour Synthesis techniques. Rates of over 12 mol/m²h with selectivities of up to 96% in hydrogenation of dehydrolinalool into linalool under atmospheric pressure of H₂ were observed. The ease of separation of this catalyst from reaction products, its regenerability, along with its corrosion, thermal stability, and mechanical strength give good prospects for these materials.     

Bimetallic Pt–Sn/γ-alumina catalyst for highly selective liquid phase hydrogenation of diethyl succinate to γ-butyrolactone

Platinum–tin bimetallic catalyst on γ-alumina support was prepared by impregnation method and was reduced by sodium borohydride at room temperature. XRD and XPS characterization revealed that platinum was reduced to Pt⁰ while, tin was probably partially reduced to Sn²⁺ due to the low temperature reduction method and Sn⁰ was completely absent, avoiding the formation of Pt–Sn alloy. Pt–Sn/γ-alumina (Pt 1%, Sn 9%) thus prepared was found to give almost complete selectivity to γ-butyrolactone in liquid phase hydrogenation of diethyl succinate. A plausible reaction pathway is proposed involving Pt–O–Sn state and high selectivity to GBL is due to the Lewis acidity of Sn^2+/4+.     

加氢除炔和液相烷基化双功能催化剂的研究开发

利用离子交换法负载贵金属钯,对β沸石FX-01催化剂进行改性,制成具有加氢除炔及烷基化双重催化功能的新型沸石催化剂,以提高催化剂对原料的适应性并延长催化剂的寿命。采用加速失活的方法进行寿命实验,通过热重分析和气相色谱-质谱(GC-MS)对积炭进行表征。实验结果表明,改性后的催化剂选择性和稳定性提高,异丙基苯的收率增加;钯元素改性制成的双功能催化剂具有较好的抗积炭性能,催化剂寿命延长,钯元素适宜的负载量为0.2%。     

炭材料负载Pt催化肉桂醛选择性加氢性能的研究

采用液相还原法分别制备了碳纳米管(MWCNT)、活性炭(AC)、碳纳米纤维(CNF)和炭气凝胶(CA)负载质量分数3%的Pt催化剂,并对催化剂的结构和形貌进行了XRD和TEM等表征。以肉桂醛加氢作为探针反应,研究了其催化肉桂醛加氢的活性和产物选择性。结果表明,炭材料的结构对其催化肉桂醛加氢行为具有重要影响,纳米炭材料催化剂（Pt/MWCNT、Pt/CNF）表现出较高的CO选择性加氢行为,而无定形碳催化剂表现为C=C选择性加氢,同时Pt/MWCNT的催化活性最高。     

Supported liquid phase catalysis in selective oxidation

The application of supported liquid-phase catalysis (SLPC) to selective oxidation examples is discussed to provide valuable alternatives to the purely homogeneous or heterogenous processes. Specific examples discussed are the Wacker type ethylene oxidation on heterogenous catalysts and the vinyl acetate production by ethylene acetoxylation. The potential industrial application of SLPC for these oxidations and the possible extensions of this technology to other oxidation processes are also discussed.