CO加氢制备低碳烯烃Fe基和Co基催化剂研究进展

CO加氢制备低碳烯烃是非石油路线获得烯烃的重要反应,其反应路线有直接法和间接法.直接法制备低碳烯烃具有反应路线短、能源利用率高、经济高效等优势.综述了近年来Fe基催化剂、 Co基催化剂在CO直接制备低碳烯烃中的研究进展.分析认为:费托合成过程产物选择性遵循Anderson-Schulz-Flory(ASF)分布规律,助剂和载体的使用一定程度提高Fe基、 Co基催化剂的低碳烯烃选择性.     

Cu-Zn-Zr/SBA-15介孔催化剂的制备及CO2加氢合成甲醇的催化性能

以具有骨架结构的SBA-15介孔分子筛为载体,采用浸渍法合成了具有高比表面积、不同金属氧化物含量的Cu-Zn-Zr介孔催化剂CZZx/SBA-15(x=0.3,0.4,0.5,0.6).采用N2吸附-脱附(BET)、X射线衍射(XRD)、H2程序升温还原(H2-TPR)、CO2吸附(CO2-TPD)和透射电子显微镜(TEM)等手段对样品进行了表征.在固定床反应器上评价了其CO2加氢合成甲醇的催化性能.实验结果表明,CZZx/SBA-15催化剂具有介孔结构,负载的Cu O,Zn O和Zr O2能够很好地分散在表面,并且负载氧化物晶粒尺寸不同.催化剂的铜比表面积SCu与甲醇催化活性呈近似线性关系,其中CZZ0.4/SBA-15催化剂表现出最大甲醇选择性(54.32%),与CZZ相比,甲醇选择性增加24.85%.随着金属氧化物负载量的增大,催化剂比表面积和SCu明显减小,甲醇选择性与收率也相应减小,负载型CZZx/SBA-15催化剂表面结构对CO2加氢合成甲醇反应活性起关键作用.     

FeCoMnK/BeO催化剂上二氧化碳加氢合成低碳烯烃的反应性能和原位FT-IR研究

 研究了FeCoMnK/BeO新型多组分催化剂上二氧化碳加氢的反应性能,考察了反应温度、空速及原料气组成对反应性能的影响. 结果表明,二氧化碳的转化率及烯烃/烷烃比值均高于氧化铝、硅胶或活性炭担载的催化剂. 在647 K, 3000 h-1, CO2/H2体积比为1/3的条件下,低碳烯烃的收率最高. 利用原位FT-IR技术研究了该催化剂上二氧化碳加氢反应的程序升温过程,提出了可能的反应机理.     

Preparation and Characterization of SiO2/Co and C/Co Nanocomposites as Fisher-Tropsch Catalysts for CO2 Hydrogenation

To fabricate high-density cobalt-based catalysts, we first synthesized SiO₂/C composites via a hydrothermal method and removed C and SiO₂ by two different methods, respectively. The as-prepared SiO₂ and C supports then reacted with cobalt acetylacetonate and N,N-dimethylformamide(DMF) under hydrothermal conditions to prepare SiO₂/Co and C/Co nanocomposite catalysts. The catalysts were characterized by X-ray diffraction(XRD), scanning electron microscope(SEM), transmission electron microscopy(TEM), inductively coupled plasma mass spectrometry(ICP), energy dispersive X-ray fluoresence spectrometer(EDX), and nitrogen adsorption. It was found that hexagonal cobalt nanocrystals were successfully integrated with the mesoporous silica or carbon nanotube supports. SEM and TEM results show that SiO₂/Co composites with a hollow/mesoporous sphere structure and C/Co composites with a tubular structure have been successfully synthesized. Both composite samples show superparamagnetism exhibiting an S-type hysteresis loop, which originated from the cobalt nanoparticles in the samples. Nitrogen adsorption/desorption curves suggest that the SiO₂ and C supports have well-developed pore structures and large specific surface areas, and the loading and good dispersity of cobalt nanoparticles on the supports were proven by ICP and EDX. Moreover, the samples exhibited good and stable catalytic activity, demonstrating that the two composites are suitable catalysts for Fischer-Tropsch CO₂ hydrogenation.     

Review of Directly Producing Light olefins via CO Hydrogenation

Directly making light olefins via CO hydrogenation is a promising process to obtain a nonpetroleum based supply of alkenes.Limited by the ASF distribution function of Fischer-Tropsch synthesis,the yield of light olefins (C2-C4) can not reach the desired levels,which is a great challenge to overcome.Beginning thermodynamic analysis,the ASF distribution function,the reaction performance of CO hydrogenation and slurry reactor studies.The problems currently faced by this research area are presented at the end of the article.     

CO Hydrogenation Catalyzed by Supported Ni-Cu Bimetallic Catalysts

A series of Ni-Cu/ZnO and a series of Ni-Cu/SiO₂ catalysts were prepared by coprecipitation and impregnation methods, respectively, and studied in CO hydrogenation. The results revealed the presence of metal-support interactions between Cu and ZnO, and between Ni and ZnO, and a bimetallic interaction between Ni and Cu. The bimetallic interaction affected the metal-support interactions.     

Pt3Co Octapods as Superior Catalysts of CO2 Hydrogenation

As the electron transfer to CO₂ is a critical step in the activation of CO₂, it is of significant importance to engineer the electronic properties of CO₂ hydrogenation catalysts to enhance their activity. Herein, we prepared Pt₃Co nanocrystals with improved catalytic performance towards CO₂ hydrogenation to methanol. Pt₃Co octapods, Pt₃Co nanocubes, Pt octapods, and Pt nanocubes were tested, and the Pt₃Co octapods achieved the best catalytic activity. Both the presence of multiple sharp tips and charge transfer between Pt and Co enabled the accumulation of negative charges on the Pt atoms in the vertices of the Pt₃Co octapods. Moreover, infrared reflection absorption spectroscopy confirmed that the high negative charge density at the Pt atoms in the vertices of the Pt₃Co octapods promotes the activation of CO₂ and accordingly enhances the catalytic activity.     

助剂Mn对CO2加氢制二甲醚CuO-ZnO-ZrO2/HZSM-5催化剂的结构和性能影响

以无水乙醇为溶剂,草酸为沉淀剂,采用悬浮共沉淀法,一步合成Mn改性的CuO-ZnO-ZrO2/HZSM-5双功能催化剂.并研究了该催化剂在CO2加氢合成二甲醚反应中的催化性能,考察了助剂锰的添加量对催化剂性能的影响,并采用XRD、BET、TPR、NH3-TPD和XPS对催化剂结构进行表征.结果表明,双功能催化剂性能与助剂锰的添加量有密切联系,适量锰的加入可提供合适的表面酸性,提高二甲醚的选择性,降低副产物CO的选择性.表征结果表明,加入Mn可以促进CuO的分散,并降低CuO的还原温度,增加催化剂的比表面积,提高Cu+/Cu0比,从而能促进CO2的转化,有利于提高催化剂的活性.     

Effects of potassium on MgO-supported Fe-Mn catalysts for the hydrogenation of carbon monoxide to light alkenes

A series of potassium-promoted, MgO-supported Fe-Mn catalyst were prepared by the wetness impregnation method and characterized by nitrogen adsorption, TPR and X-ray photoelectron spectroscopy (XPS) techniques. The CO hydrogenation activity test indicated that with the addition of potassium, significant changes in CO conversion and selectivity to light alkenes are observed. 2 wt.% potassium-promoted Fe-Mn catalyst exhibited better catalytic performance. The CO hydrogenation reaction temperature and space velocity were also investigated and optimized.     

表面金属有机化学Ⅱ—SiO_2担载的三钌乙烯酮原子簇化合物[PPN]_2[Ru_3(CO)_9(CCO)]在CO加氢反应中的催化行为

本文分别通过三种不同的钌原子簇化合物[HRu_3(CO)_(11)]~-、Ru_6C(CO)_(17)和[Ru_3(CO)_9(CCO)~(2-)]制备了三种SiO_2担载型的钌催化剂,并研究了它们在CO加氢反应中的催化行为.结果表明,若和用[HRu_3(CO)_(11)]~-制备的催化剂相比较,用[Ru_3(CO)_9(CCO)]~(2-)制备的催化剂在CO加氢反应中显示了较高的活性.通过比较以上三种催化剂的催化行为以及所进行的红外和质谱表征,初步提出了用[Ru_3(CO)_9(CCO)]~(2-) 制备的催化剂上,CCO基团经脱羰基后可能转化成表面碳化物(Carbide),它是形成烃类产物的中间体.     

担载型铁金属簇催化剂催化CO2加氢制低碳烯烃的研究

担载型铁金属簇催化剂催化ＣＯ_２加氢制低碳烯烃的研究黄友梅，翁善至，孟宪波，张传安（中国科学院兰州化学物理研究所，兰州７３００００）关键词低碳烯烃，ＣＯ_２加氢，担载型铁金属簇催化剂近年来，储量极丰富而又极便宜的二氧化碳重新引起世界各国科学家的兴趣，我...     

MgO-CNTs复合载体负载的铁基催化剂用于CO加氢制备低碳烯烃催化性能研究(英文)

通过将Mg(NO3)3沉淀于碳纳米管(CNTs)上,制备了一系列质量比不同的MgO-CNTs混合物并用于费托合成的载体.实验结果表明,在2 MPa,350℃条件下大部分以MgO-CNTs为载体制备的催化剂有着很高的CO转化率,同时,当MgO∶CNTs的比例为2∶1时,烯烃的选择性高于其它载体制备的催化剂.我们还用扫描电镜(SEM),程序升温还原(H2-TPR),X射线衍射(XRD)和N2物理吸附对催化剂进行了表征.     

CO2加氢制低碳醇CuFe基催化剂中的Mn助剂效应

采用共沉淀法制备了一系列Mn掺杂的CuFeZnK催化剂, 研究了Mn助剂对催化剂的结构及催化CO₂加氢制低碳醇合成性能的影响. 结果表明, 引入适量的Mn(质量分数2.1%)能有效提高低碳醇的选择性和时空收 率(STY), 在320 ℃和5 MPa的条件下, CO₂的转化率为29.4%, 低碳醇选择性(CO-free)达到23.2%, 时空收率达到41.1 mg·{\mathrm{g}}_{\mathrm{c}\mathrm{a}\mathrm{t}}^{-\mathrm{1}}·h^?1, 且低碳醇在总醇中的比例达到96.9%. 利用X射线衍射(XRD)、 N₂吸附-脱附实验、 X射线光电子能谱(XPS)、 透射电子显微镜(TEM)和氢气程序升温还原(H₂-TPR)等手段对制得催化剂进行表征, 结果表明, 适量Mn可以起到结构助剂的作用, 减小Cu颗粒尺寸的同时促进Fe₅C₂相的形成, 从而构建丰富的Cu-Fe₅C₂活性界面, 用于低碳醇合成. 而过量的Mn反而会堵塞催化剂的孔道, 覆盖活性位点, 降低了催化性能.     

Rh/ZnO-Al2O3催化剂用于巴豆醛选择性加氢（英文）

Gas phase hydrogenation of crotonaldehyde was performed over 1 wt% Rh/ZnO-Al2O3 catalysts with various Zn/Rh atomic ratios. Monometallic Rh/Al2O3 was also prepared for comparison. The samples were prepared by the successive impregnation of Al2O3 with chlo-ride precursors of zinc and rhodium. The solids have been characterized by H2 chemisorption,temperature-programmed reduction,scanning electron microscopy,and cyclohexane dehydrogenation. Their catalytic behaviour in the gas phase crotonaldehyde hydrogenation reaction after reduction treatment in flowing hydrogen at 723 K was investigated. The relationship between catalytic activity,selectivity for crotyl alcohol,and physicochemical properties of the catalysts was examined. Results obtained showed that the presence of Zn clearly promotes the hydrogenation of the carbonyl bond. The catalyst with Zn/Rh atomic ratio of 5 displayed good catalytic stability and the highest selectivity for crotyl alcohol(70%) along with alloy formation.     

SMAI法制备的Cu催化剂的CO加氢催化

用溶剂化金属原子浸渍（SMAI）法制备了SiO2、Cr2O3负载Cu催化剂.XPS测定表明三种载体上的Cu几乎全部以零价态存在．X射线增宽法测定表明随着Cu含量增加Cu颗粒增大．Cu催化剂在CO加氢中的催化活性与载体、Cu颗粒大小和Cu价态有关．Cr2O3对Cu催化活性有促进效应．Cr2O3负载Cu催化剂活性随Cu颗粒减小而增大，而SiO2作载体时，颗粒大小对活性无影响，零价Cu0为催化活性中心     

Selective Hydrogenation of CO2 to Ethanol over Cobalt Catalysts

Methods for the hydrogenation of CO₂ into valuable chemicals are in great demand but their development is still challenging. Herein, we report the selective hydrogenation of CO₂ into ethanol over non‐noble cobalt catalysts (CoAlO_x), presenting a significant advance for the conversion of CO₂ into ethanol as the major product. By adjusting the composition of the catalysts through the use of different prereduction temperatures, the efficiency of CO₂ to ethanol hydrogenation was optimized; the catalyst reduced at 600 ° gave an ethanol selectivity of 92.1 % at 140 °C with an ethanol time yield of 0.444 mmol g^?1 h^?1. Operando FT‐IR spectroscopy revealed that the high ethanol selectivity over the CoAlO_x catalyst might be due to the formation of acetate from formate by insertion of *CH_x, a key intermediate in the production of ethanol by CO₂ hydrogenation.     

合成气制低碳烯烃用Fe／AC催化剂的制备及性能表征

 研究了以活性炭（AC）作为载体制备的铁基催化剂，通过对不同铁盐、活性炭和助剂的筛选，研制出对合成气转化为低碳烯烃具有高活性和高选择性的催化剂．对反应前及反应过程中催化剂体相结构的XRD测试结果表明，Fe－Cu－K／AC催化剂在反应前主要由α－Fe，Fe3O4和Cu0组成，经合成气反应后主要由α－Fe，Fe5C2，Fe7C3，Cu0和K2O组成．Fe－Mn－K／AC催化剂的晶体结构主要以Fe嵌入MnO中形成的（Fe，Mn）O结构存在．实验中得出的α－Fe，FexCy及（Fe，Mn）O与激光热解法制备的催化剂的的晶体结构相似．对催化剂的制备方法进行了筛选，考察了不同助剂Cu，Mn，Si和K等元素对催化剂性能的影响．结果表明，以草酸铁为铁源，椰壳炭为载体制备的Fe－Mn－K／AC催化剂的催化效果最佳，在空速600h－1，压力1．5MPa和温度320℃条件下，CO转化率可达97．4％，C＝2～C＝4选择性可达68．0％．     

Zn Doping Effect on the Performance of Fe-Based Catalysts for the Hydrogenation of CO2 to Light Hydrocarbons

In this work, we studied the role of zinc in the composition of supported iron-containing catalysts for the hydrogenation of CO₂. Various variants of incipient wetness impregnation of the support were tested to obtain catalyst samples. The best results are shown for samples synthesized by co-impregnation of the support with a common solution of iron and zinc precursors at the same molar ratio of iron and zinc. Catalyst samples were analyzed by various methods: Raman, DRIFT-CO, TPR-H₂, XPS, and UV/Vis. The introduction of zinc leads to the formation of a mixed ZnFe₂O₄ phase. In this case, the activation of the catalyst proceeds through the stage of formation of the metastable wustite phase FeO. The formation of this wustite phase promotes the formation of metallic iron in the composition of the catalyst under the reaction conditions. It is believed that the presence of metallic iron is a necessary step in the formation of iron carbides—that is, active centers for the formation and growth of chain in the hydrocarbons. This leads to an increase in the activity and selectivity of the formation of hydrocarbons in the process of CO₂ hydrogenation.     

Pd基多相催化剂上CO2加氢反应的研究进展

随着二氧化碳(CO₂)排放量的不断增加, 全球变暖和气候变化的加剧对人类的生存环境产生了巨大的影响. CO₂作为廉价、 可再生的碳氧资源, 将其转化为高附加值化学品是绿色化学及能源领域的重要研究课题之一, 受到广泛关注. Pd基催化剂由于具有优异的加氢能力以及良好的抗烧结、 抗毒化性能, 作为CO₂催化转化最有前途的催化剂被广泛应用和研究. 本文主要对Pd基催化剂上CO₂加氢制备HCOOH, CO, CH₄和甲醇等小分子能源化合物的研究进展进行综合评述, 重点关注Pd基催化剂上CO₂分子的吸附/活化位点、 催化剂的金属-载体强相互作用及表界面组成等对催化剂活性和选择性的影响以及催化反应机理.     

稀土改性CuO-ZnO-ZrO_2/SAPO-34分子筛催化CO_2加氢合成低碳烯烃

采用共沉淀法分别制备了Y_2O_3,La_2O_3和Ce O_2改性的Cu O-Zn O-Zr O_2,表征结果表明,稀土改性的Cu O-Zn O-Zr O_2分散性良好,比表面积增大.将稀土改性的Cu O-Zn O-Zr O_2与SAPO-34分子筛机械混合用于催化CO_2加氢一步法合成了低碳烯烃,在反应温度400℃,压力3 MPa,空速为1800 m L·g~(-1)_(cat)·h~(-1),氢碳体积比为3∶1,Ce O_2改性Cu O-Zn O-Zr O_2与SAPO-34质量比为1∶1,催化剂用量为1.0 g时,CO_2的单程转化率为54.6%,低碳烯烃的选择性和产率分别为51.1%和27.9%.