费托合成制低碳烯烃铁基催化剂研究进展

综述了费托合成制低碳烯烃铁基催化剂方面所取得的研究进展,重点介绍了催化剂活性相、助剂和载体等方面的关键因素,探讨了催化剂制备条件对合成气制烯烃的影响,最后对费托合成直接法制烯烃的研究提出了一些展望。     

费托合成制低碳烯烃钴基催化剂研究进展

概述了费托合成制低碳烯烃的背景和发展趋势,综述了费托合成制低碳烯烃反应机理和钴基催化剂的研究进展,重点评述了钴基催化剂活性相、助剂和载体等关键因素,探讨了活性相、助剂和载体对合成气制低碳烯烃的影响,并对费托合成制烯烃的研究提出了展望和建议。     

Co基费托合成催化剂研究进展

概述了co基费托合成催化剂的制备方法,介绍了Co盐种类、浸渍方法、浸渍溶液的pH值、Co盐溶剂、金属Co负载量和干燥温度等制备条件对Co基催化剂活性的影响,介绍了Co基催化剂的改性方法。并在此基础上对Co基催化剂今后的研究发展方向进行了展望。     

合成气制低碳烯烃研究进展

国内低碳烯烃产业发展受资源、技术发展及环境状况等因素影响,合成气制低碳烯烃已经成为非石油路线制备烯烃的新途径。阐述了间接法和直接法制低碳烯烃2种工艺的特点,其中直接法具有流程短、效率高、能耗低等优点,成为合成气制低碳烯烃研究热点。展望了今后合成气制低碳烯烃的研究方向,指出合成气制低碳烯烃今后的研究重点为提高催化剂的可靠性、降低催化剂成本。     

高选择性钴基费托合成催化剂的研究进展

费托合成反应催化剂的开发是费托合成技术研究和产业化的关键,钴基费托合成催化剂是制备长链烃类的较理想的催化剂之一,具有良好的工业应用前景。对催化剂预处理方法、载体、助剂及制备方法等方面进行了介绍,分析了钴基催化剂在费托合成反应中提高反应活性及选择性的作用,并指出选择适宜的钴基催化剂制备方法可以较好地提高费托合成反应转化率、选择性及稳定性。     

合成气直接制低碳烯烃铁基催化剂助剂研究进展

综述了合成气直接制低碳烯烃铁基催化剂助剂的研究进展,主要分析了电子助剂和结构助剂对催化剂结构与性能的影响,认为碱金属、碱土金属、过渡金属、稀土金属及非金属等电子助剂在调变催化剂酸碱性与氧化还原性上各自表现出不同的正作用,抑制了链增长反应,增加低碳烯烃选择性,结构助剂的表面性质与孔道结构可控,方便低碳烯烃从催化剂中扩散,可以减少低碳烯烃的二次加氢副反应。最后指出了催化剂存在的问题并对以后的研究工作进行了展望。     

费托合成钴基催化剂助剂研究进展

针对助剂对钴基催化剂的促进作用,介绍了近年来钴基催化剂助剂的研究进展。综述了助剂添加方式、助剂功能和助剂作用、详细分析了助剂对钴基催化剂的还原度、分散度、稳定性和费托反应性能的影响、重点讨论了助剂的结构作用、电子作用和协同作用,并对今后催化剂的研究提出了一些建议。     

合成气直接法制取低碳烯烃铁基催化体系研究进展

合成气直接法制取低碳烯烃因具有原料易得、流程简单和能源效率高等优势,成为了目前合成气应用领域一个新的热门研究方向。直接法转化方式主要有经由费托合成反应直接制取低碳烯烃（FTO）路径和经由氧化物-分子筛（OX-ZEO）过程直接制取低碳烯烃的双功能催化路线。本文简述了合成气制取低碳烯烃的主要工艺流程,重点聚焦在近年来费托合成反应直接制取低碳烯烃过程中铁基催化体系的研究进展,主要讨论了通过费托合成反应制取低碳烯烃中的反应机理,以及活性相、助剂和载体等因素对铁基催化剂反应性能的影响。此外,指出了当前研究存在的高低碳烯烃选择性与高反应活性难以兼得,产物中甲烷选择性过高等不足之处并对合成气直接法制取低碳烯烃的发展方向进行了展望。     

EDTA辅助制备高活性费托合成催化剂

费托合成（FTS）对天然气、煤炭和生物质向清洁运输燃料和增值化学品的转化至关重要。传统上,用于FTS的负载型铁催化剂主要是以氧化铝和二氧化硅为载体。然而,金属与载体的相互作用阻碍了活性相碳化铁的形成,使得催化剂活性较低。本文通过乙二胺四乙酸（EDTA）络合浸渍制备了Fe/Al₂O₃催化剂,通过带正电荷的羟基（OH{}_{\mathrm{2}}^{+}）与[Fe(EDTA)]^-配合物阴离子之间的库仑相互作用来提高氧化铝载体上铁物种的分散度。采用X射线衍射（XRD）、扫描电子显微镜（SEM）、透射电子显微镜（TEM）、X射线光电子能谱（XPS）、比表面积（BET）、原位红外（In-situ IR）等手段进行表征分析。结果表明,添加EDTA有助于增强Fe的抗烧结性。在煅烧络合浸渍制备样品的过程中,EDTA可以分解为具有还原性质的有机小分子,将催化剂中的铁物种还原为Fe²⁺,有利于催化剂的还原;更多活性中心增强了催化剂对CO的吸附量。原位红外实验表明,EDTA辅助制备的催化剂更容易富集活性物种,从而提高CO的转化率。调节体系中碱金属钠的含量改善了烃内产物分布。在较低的氢碳比（H₂/CO=1/1）下,EDTA络合制备的Fe-Na/Al₂O₃催化剂显示出高的CO转化率（88.5%）以及最大的C₂~C₄=和C₅~C₁₁选择性,总选择性达71.2%。     

FT合成反应器概述

介绍ＦＴ合成反应器的研究进展，详细论述了工业化的高气速固定床、循环流化床和固定流化床反应器的基本原理和开发过程，分析了操作多数对高气速固定床Ｆｒ合成反应结果的影响。并对固定床、流化床和浆态床反应器的结构、生产能力、原料及产物组成和操作条件等进行了比较。     

Effect of hierarchical meso-macroporous silica supports on Fischer-Tropsch synthesis using cobalt catalyst

Hierarchical meso-macroporous (HS-X) silica with different mesopore diameters synthesized by using rice husk ash as a silica source and chitosan as a natural template were applied for the first time as the cobalt support for Fischer-Tropsch synthesis. Unimodal mesoporous silica (MS-X) supports with equivalent mesopore diameters to HS-X supports have also been prepared for comparison. Effects of diffusion in MS-X and HS-X supports of different particle sizes on the catalytic activity and hydrocarbon selectivity were investigated. The cobalt crystallite sizes were increased with increasing mesopore diameters, whereas the highest amount of H₂ chemisorbed was found for the catalyst with the medium mesopore diameter. The HS-X supports revealed lower surface area and higher macroporosity which led to the formation of larger cobalt crystallite size and less chemisorbed H₂. However, the catalytic activity was much higher for cobalt supported on HS-X silica of both small and large catalyst particle sizes. Moreover, with the large catalyst particle size, the C₅₊ selectivity of cobalt supported on HS-X silica was much higher than that on MS-X silica, indicating the influence of mass transfer of reactants and products in macropores of HS-X supports.     

含镁添加剂的铁基费-托合成催化剂

采用连续共沉淀与喷雾干燥技术相结合的方法制备了一系列不同镁添加剂含量的微球状沉淀型Fe/Cu/K/Mg/SiO_2(Mg/Fe质量比0～0.11)催化剂.采用H_2/CO体积比为2的合成气在523 K、2.0 MPa、2 000 h~(-1)的条件下于固定床反应器上考察了这一系列催化剂的F-T合成(FTS)反应性能.结果表明,适量镁添加剂的加入可以提高催化剂FTS反应活性,增加稳定性,提高C_(5+)、总烃的时空产率和C_(5～11)汽油馏分段产物的选择性,降低CO_2的选择性,抑制铁基催化剂的水煤气变换(WGS)反应,但过高的Mg添加剂含量易使催化剂的稳定性变差,反应活性下降.结果表明,Mg/Fe=0.07的催化剂在该反应条件下,CO最高转化率达到90%,且具有良好的稳定性;在整个运行期间,有效烃(C_(5+)+C_(2～4)~=)选择性在83%左右,甲烷选择性维持在8%左右.     

费托合成反应器应用研究进展及展望

费托合成反应是强放热的气液固三相反应,为有效移热及提高目标产物产率,应加强费托合成反应器的研发,系统介绍了工业上几种费托合成反应器的特点、应用规模等,论述了近几年已经或有望进行工业化应用的几种费托合成反应器,如固定床反应器、流化床反应器、浆态床反应器等,并比较了各类反应器的优劣,最后对费托合成反应器的选型和发展提出了建议和展望。固定床反应器技术成熟,产品容易分离,催化剂损失少,但是移热效果较差;浆态床反应器,反应物混合均匀,移热效果好,但产品固液分离较为困难;流化床反应器可以在高温下运行,生产高价值的轻烃产物,但催化剂消耗较大。研究认为,如果目标产品是以分子质量较大的柴油和石蜡为主,建议选择浆态床反应器;如果目标产品是生产烯烃等化学品,建议选择固定流化床反应器。     

费托合成铁基催化剂浆态床反应性能的研究

为了获得工艺参数对铁基催化剂费托合成产品分布的影响规律,在浆态床反应器中考察了反应温度、反应压力、氢碳比、空速对铁基催化剂费托合成反应性能的影响。结果表明,温度升高时,催化剂活性、CO_2和CH_4选择性均升高,产物向轻组分分布;压力增大时,催化剂活性和CO_2选择性升高,CH_4选择性下降,产物向重组分分布;随氢碳比的增加,催化剂活性和CH_4选择性升高,CO_2选择性下降,C_(5+)呈下降趋势;随空速增加,催化剂的活性和CO_2选择性下降,CH_4选择性上升,C_(5+)向轻质烃分布。选择合适的工艺条件,可有效改善铁基催化剂的费托合成反应性能,控制碳链长度和产物的分布,提高费托合成反应的经济性。     

Fischer-Tropsch synthesis over iron catalysts

Because of the decreased profitability of making synthetic fuels, Sasol intends expanding its production of the higher valued chemicals, in particular waxes and olefins. The advantages and disadvantages of using Fe, Co and Ru catalysts are discussed from the point of view of costs, availability, product selectivity, activity and sensitivity to poisons.The loss of activity and selectivity of iron based catalysts in both fixed and fluidized bed reactors is discussed. The main contributing factors are sulfur poisoning, oxidation and coke fouling. In fixed bed reactors sulfur poisoning and coke laydown deactivates the front end of the bed while hydrothermal sintering/oxidation deactivates the back end. In fluidized beds the deposition of large amounts of Boudouard carbon doesnot markedly lower the activity. The smaller catalyst particles end up consisting of small iron carbide entities embedded in a matrix of carbon. The larger catalyst particles consist of cores of inert magnetite surrounded by the carbide/carbon matrix.FT reactor development at Sasol is briefly reviewed.     

An active iron catalyst containing sulfur for Fischer-Tropsch synthesis

A precipitated iron catalyst containing sulfur for Fischer-Tropsch (F-T) synthesis was prepared by means of a novel method using a ferrous sulfate as precursor. Both fixed bed reactor (FBR) and continues stirred tank slurry reactor (STSR) were used to test long-term F-T reaction behaviors over the catalyst. A stability test (1600 h) in FBR showed that the catalyst was active even after 1500 h of time-on-stream with CO conversion of 78% and with C₅⁺ hydrocarbon selectivity of 72 wt% at 250 °C, 2.0 MPa, 2.0 NL/g-cat/h, and H₂/CO=2.0. The test (550 h) in STSR indicated that the catalyst exhibited relatively high activity with CO conversion of 70-76% and C₅⁺ selectivity of 83-86 wt% in hydrocarbon products under the conditions of 260 °C, 2.0 MPa, 2.0 NL/g-cat/h, and H₂/CO=0.67. The deactivation rate of the catalyst was low, accompanied by surprisingly low methane selectivity of 2.0-2.9 wt%. It is shown that a small amount of sulfur (existing as SO₄²⁻) may promote the catalyst by increasing activity and improving the heavier hydrocarbon selectivity. It is also comparable with other typical iron catalysts for F-T synthesis.     

MnOx promotional effects on olefins synthesis directly from syngas over bimetallic Fe‐MnOx/SiO2 catalysts

The direct synthesis of lower olefins via the Fischer‐Tropsch reaction (FTO) has been performed over a series of Fe‐MnO_x/SiO₂ catalysts. The addition of MnO_x could improve the dispersion of iron species, and promote the reduction of iron oxide during the activation and subsequent carburization. Moreover, the results of characterization demonstrated that MnO_x could enhance the surface basicity of the catalysts due to electronic effects and promote the formation of iron carbides. For the first time, the intrinsic power‐law kinetics for FTO was obtained for both Fe₂₀/SiO₂ and Fe₂₀‐Mn₁/SiO₂ catalysts. Kinetic parameters and structure characterizations indicated that MnO_x could facilitate the CO dissociation on the catalyst surface, thus enhancing the adsorption strength and capacity of surface carbonaceous intermediates. The weak hydrogenation of carbonaceous species would boost the selectivities toward lower olefins. Finally, a plausible mechanism for FTO, involving the promotional effects of MnO_x on Fe, has been proposed. © 2017 American Institute of Chemical Engineers AIChE J, 63: 4451–4464, 2017